JPS62943B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel thermoplastic resin composition. More specifically, it is a novel product that is made of (A) aromatic polyester, (B) polyamide, and (C) polyester/polyether block copolymer and has excellent moldability, chemical properties, mechanical properties, heat resistance, and heat aging resistance. The present invention relates to a resin composition. Resin compositions made of aromatic polyester copolymers and polyamides have excellent moldability, chemical properties, mechanical properties, and heat resistance, and are expected to have an extremely wide range of uses as automotive parts, electrical parts, and mechanical parts. However, its heat aging resistance is not necessarily satisfactory. In general, engineering plastics need to have excellent various properties and to maintain these properties even after being exposed to various conditions. The ability to maintain such excellent properties, ie, aging resistance, is an extremely important property in evaluating engineering plastics. Under these circumstances, it has been widely desired to improve the heat aging resistance of resin compositions made of aromatic polyester copolymers and polyamides. As a result of extensive studies aimed at improving the heat aging resistance of such resin compositions, the present inventors have found that by adding a polyester/polyether block copolymer to such resin compositions, the object of the present invention can be achieved. The present invention was completed based on the discovery that this can be achieved and, surprisingly, the impact strength is also significantly improved. That is, the present invention provides (A) a mixture of terephthalic acid and isophthalic acid or functional derivatives thereof (however, the molar ratio of terephthalic acid groups and isophthalic acid groups is 9:
1 to 1:9) and general formula [] Bisphenols represented by ₍ where X is selected from _the group consisting of O, S, SO ₂ , CO, alkylene group and _alkylidene group,
R ₄ , R′ ₁ , R′ ₂ , R′ ₃ and R′ ₄ are selected from the group consisting of hydrogen atoms, halogen atoms and hydrocarbon groups); It consists of polyamide and (C) polyester/polyether block copolymer, and the weight ratio of (A) aromatic polyester copolymer and (B) polyamide is 7 to 3 to 3 to 7, and (A) ) in the total amount of aromatic polyester copolymer, (B) polyamide, and (C) polyester/polyether block copolymer.
(C) A resin composition in which the content of polyester/polyether block copolymer is 1 to 50% by weight. The aromatic polyester copolymer used in the present invention is a mixture of terephthalic acid and isophthalic acid or functional derivatives thereof (provided that the molar ratio of terephthalic acid groups to isophthalic acid groups is 9:1 to 1:
9) and a bisphenol represented by the general formula []. Specific examples of such bisphenols represented by the above 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)-ketone, bis(4-hydroxyphenyl)-methane, bis(4-hydroxyphenyl)-methane,
-hydroxy-3-methylphenyl)-methane,
Bis(4-hydroxy-3,5-dichlorophenyl)-methane, bis(4-hydroxy-3,5-
dibromophenyl)-methane, bis(4-hydroxy-3,5-difluorophenyl)-methane,
1,1-bis(4-hydroxyphenyl)-ethane, 2,2-bis(4-hydroxy-3-methylphenyl)-propane, 2,2-bis(4-hydroxy-3-chlorophenyl)-propane, 2 ，
2-bis(4-hydroxy-3,5-dibromophenyl)-propane, 1,1-bis(4-hydroxyphenyl)-n-butane, bis(4-hydroxyphenyl)-phenylmethane, bis(4-hydroxyphenyl)-phenylmethane, -hydroxyphenyl)-diphenylmethane, bis(4-hydroxyphenyl)-4-methylphenylmethane, 1,1-bis(4-hydroxyphenyl)-2,2,2-trichloroethane, bis(4-hydroxyphenyl)-2,2,2-trichloroethane,
-Hydroxyphenyl)-4-chlorophenyl-
Examples include methane, 1,1-bis(4-hydroxyphenyl)-cyclohexane, bis(4-hydroxyphenyl)-cyclohexylmethane, 2,2-bis(4-hydroxynaphthyl)-propane, but the most commonly used The typical product produced is 2,2-bis(4-hydroxyphenyl)-
It is called propane or bisphenol A. If necessary, mixtures of the bisphenols or bisphenols and small amounts of other divalent compounds such as dihydroxynaphthalenes such as 2,2-dihydroxydiphenyl, 2,6-dihydroxynaphthalene, hydroquinone, resorcinol, 2, 6-dihydroxytoluene, 2,6-dihydroxychlorobenzene,
Mixtures with 3,6-dihydroxytoluene and the like can be used. The functional derivatives of terephthalic acid or isophthalic acid include, for example, halides of these acids such as dichloride, or diesters of alkyl and aryl. Further, the phenylene group of terephthalic acid or isophthalic acid or a functional derivative thereof used in the present invention may be substituted with a halogen atom or an alkyl group. The aromatic polyester copolymer used in the present invention can be synthesized by any method such as an interfacial polymerization method, a solution polymerization method, or a melt polymerization method. The polyamide used in the present invention has the general formula [] or〔〕 It is expressed as Here R ₅ , R ₆ and
R ₇ represents an alkylene group. The polyamide used in the present invention is produced by a condensation reaction of a diamine and a dibasic acid.
It includes polymers formed by self-condensation reactions of amino acids and polymerization reactions of lactams. The polyamide used in the present invention may be any polyamide as long as it is represented by the above general formula, but preferred polyamides include polycaprolactam polyhexamethylene adipamide, polyhexamethylene sebacamide, polyaminoundecanoic acid, polylaurolactam, etc. can be given. The polyester/polyether block copolymer used in the present invention has the following general formula [] and general formula [] It is a block copolymer composed of two types of repeating units represented by [-OR ₉ ]- [] (wherein R _R and R ₉ represent an alkylene group having 2 to 6 carbon atoms). The polyester/polyether block copolymer used in the present invention can be obtained by reacting a polyester-forming component with poly(alkylene oxide) glycol. The average molecular weight for poly(alkylene oxide) glycol is 800~
It is preferable to use 3000. The polyester/polyether block copolymer used in the present invention may be of any type as long as it is composed of repeating units represented by the above general formula, but preferred polyester/polyether block copolymers include, for example: A block copolymer composed of repeating units of and [-OCH ₂ CH ₂ CH ₂ CH ₂ -] (hereinafter referred to as block copolymer). A block copolymer composed of repeating units of and [-OCH ₂ CH ₂ -], Examples include block copolymers (hereinafter referred to as block copolymers) composed of repeating units of and [-OCH ₂ CH ₂ CH ₂ CH ₂ -]. Preferred logarithmic viscosity of the polyester/polyether copolymer used in the present invention (phenol/tetrachloroethane weight ratio 6/4, concentration 1 at 25°C)
g/dl) ranges from 0.4 to 3.0. The blending ratio of the aromatic polyester copolymer and polyamide in the resin composition of the present invention is 3:7 to 7:3 by weight. When the aromatic polyester copolymer is contained in an amount less than this weight ratio range, the heat resistance of the resin composition of the present invention tends to decrease rapidly. Furthermore, if the polyamide content is less than this weight ratio range, the chemical properties, especially the chemical resistance, tend to deteriorate significantly.
The content of polyester/polyether block copolymer in the resin composition of the present invention is 50% by weight.
It is as follows. When the content exceeds 50% by weight, the heat resistance and elastic modulus of the resin composition tend to decrease significantly. Further, the content of the polyester/polyether block copolymer in the resin composition of the present invention is preferably 1% by weight or more in order to sufficiently exhibit heat aging resistance. The resin composition of the present invention contains general heat-resistant agents, such as copper compounds such as cuprous chloride and cuprous iodide, N,
It is also possible to add aromatic amine compounds such as N'-diphenyl-P-phenylenediamine, phenyl-β-naphthylamine, and 4,4'-dioctyldiphenylamine. Although the three components for producing the resin composition of the present invention may be mixed by any method, it is desirable that the three components are substantially uniformly dispersed. If the dispersion is incomplete or non-uniform, relatively macroscopic aggregates will be formed for each component, and these aggregates are undesirable because they impair the mechanical properties of the resin composition. The resin composition of the present invention has excellent moldability, mechanical properties, chemical properties, electrical properties, heat resistance, and heat aging resistance, and can be used in commonly known plastic molding methods such as press molding, injection molding, and extrusion molding. Various useful products can be made using the method. Examples of such products include bearings, electrical connectors, containers, and a wide range of other products, which are used in a wide range of fields requiring high performance as engineering plastics. The present invention will be explained in more detail below using Examples. Examples 1 to 3, Comparative Example 1 A methylene chloride solution of a mixed acid chloride in which the molar ratio of terephthalic acid dichloride and isophthalic acid dichloride is 1:1 and an alkaline aqueous solution of 2,2-bis(4-hydroxyphenyl)propane An aromatic polyester copolymer was produced using an interfacial polymerization method. The logarithmic viscosity of this in phenol/tetrachloroethane (weight ratio) 6/4 at 25°C was 0.70. This aromatic polyester copolymer, a block copolymer [phenol/tetrachloroethane (weight ratio) 6/4, 25°C, logarithmic viscosity 1.32 at a concentration of 1 g/dl], polycaprolactam [manufactured by Unitika, phenol/ Tetrachloroethane (weight ratio)
6/4 with a logarithmic viscosity of 1.07 at 25°C] in the ratio shown in Table 1 and dried in a hot air dryer at 120°C for 16 hours.

[Table] The dried samples were each extruded at 260°C using an extruder and cut into pellets. Good pellets were obtained in all cases. Using the obtained pellets, tensile impact test pieces were produced by injection molding. The obtained test piece was placed in a hot air constant temperature bath at 140°C, and was taken out every time to measure the tensile impact strength. The results obtained were as shown in Table 2.

[Table] As shown in Table 2, the resin composition of the present invention has superior heat aging resistance and initial impact strength compared to the comparative example. Examples 4 and 5, Comparative Examples 2 and 3 The aromatic polyester copolymer used in Examples 1 to 3 and the block copolymer [phenol/tetrachlorocotane (weight ratio) 6/4, 25°C, 1 g/
dl (logarithmic viscosity 1.52) and polyhexamethylene adipamide (manufactured by Toray Industries, logarithmic viscosity 1.3 at 25°C in phenol/tetrachloroethane (weight ratio) 6/4) in the proportions shown in Table 3. In a hot air dryer at 120℃
Dry for 16 hours. Thereafter, it was extruded at 260°C using an extruder and cut into pellets. Good pellets were obtained in all cases. Using the obtained pellets, 1/8" bending test pieces were produced by injection molding. The obtained test pieces were placed in a hot air constant temperature bath at 150°C and taken out at intervals to measure the bending strength. The results were as shown in Table 4.

【table】

[Table] As shown in Table 4, the heat aging resistance of the resin composition of the present invention is significantly superior to that of the comparative example. Comparative Examples 4 to 8 The aromatic polyester copolymers and polycalactams in Examples 1 to 3 and the block copolymers in Examples 4 and 5 were used as individual components as shown in Table 5. Alternatively, a composition consisting of two components is prepared, and each is dried in a hot air dryer at 120°C.
Dry for 16 hours.

[Table] The dried sample was extruded using an extruder to obtain pellets. The extrusion temperature was 310°C for sample 4, 280°C for sample 7, and 250°C for the other samples. The obtained pellets were injection molded into tensile impact test pieces. The test pieces were placed in a hot air constant temperature oven at 140°C, and were taken out at predetermined intervals to measure the tensile impact strength. The results obtained were as shown in Table-6.

【table】

[Table] From Table 6, aromatic polyester copolymers, polyamides, polyester/polyether block copolymers, compositions comprising aromatic polyester copolymers and polyamides, and polyamides and polyester/polyether block copolymers of the present invention are shown in Table 6. It can be seen that all compositions made of copolymers have problems in heat aging resistance.

Claims (1)

[Claims] 1 (A) A mixture of terephthalic acid and isophthalic acid or functional derivatives thereof (provided that the molar ratio of terephthalic acid groups to isophthalic acid groups is 9:1 to 1:
9) and general formula () Bisphenols represented by (where X is O,
selected from the group consisting of S, SO ₂ , CO, alkylene group and alkylidene group, R ₁ , R ₂ , R ₃ , R ₄ ,
R′ ₁ , R′ ₂ , R′ ₃ and R′ ₄ are selected from the group consisting of hydrogen atoms, halogen atoms and hydrocarbon groups), and (B)
It consists of polyamide and (C) polyester/polyether block copolymer, and the blending ratio of (A) aromatic polyester copolymer and (B) polyamide is 7 by weight.
~3 to 3 to 7, and (C) polyester/polyether block copolymer in the total amount of (A) aromatic polyester copolymer, (B) polyamide, and (C) polyester/polyether block copolymer. A resin composition having a combined content of 1 to 50% by weight.