JPS642142B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel resin composition, and more specifically, terephthalic acid, isophthalic acid, or functional derivatives thereof, and 2,2-bis(4'-hydroxyphenyl)propane (hereinafter referred to as bisphenol A). Aromatic polyester copolymer obtained from (hereinafter referred to as polyarylate)
, ordinary polyamides, that is, polyamides with amide groups in which hydrogen atoms are not substituted (hereinafter simply referred to as polyamides), and polymers with amide groups in which hydrogen atoms are substituted with hydrocarbon groups (hereinafter simply referred to as polyamides). , simply referred to as N-substituted amide-containing polymer). Polyarylates produced from aromatic dicarboxylic acids or functional derivatives thereof and bisphenols or functional derivatives thereof have been well known for a long time. Known methods for producing such polyarylates include interfacial polymerization, solution polymerization, and melt polymerization. It is also well known that polyarylates obtained by such methods have many excellent properties. In other words, mechanical properties such as tensile strength, bending strength, bending recovery rate, and impact strength, thermal properties such as heat distortion temperature and thermal decomposition temperature, and electrical properties such as specific resistance, dielectric breakdown, arc resistance, dielectric constant, and dielectric loss. General molded products, films, fibers, and coating materials that have excellent properties such as physical properties, flammability, and dimensional stability, and are made by injection molding, extrusion molding, press molding, or various other molding methods. is expected to have a wide range of uses. As mentioned above, polyarylate has many excellent properties and is of great utility value, but its major drawback is poor moldability. When it comes to polymers, especially plastics, moldability plays an important role in the evaluation of the polymer, and even if the material has inherently excellent properties, if the moldability is poor, it will be difficult to manufacture the product economically. Not only is it impossible to do so, but its excellent properties are not fully demonstrated in the product. For example, when making a product by injection molding using a polymer with a high softening temperature and high melt viscosity, a high plasticizing temperature, high injection pressure, and high mold temperature are required, which only causes high costs. In addition, high plasticization temperature induces polymer decomposition, high injection pressure causes distortion in the product, and when such severe conditions are violated, there may be fatal appearance defects such as shot shots, sink marks, and flow marks. This causes mechanical defects and the mechanical properties are significantly deteriorated. Polyarylates also have such high softening temperatures and high melt viscosity, have poor moldability, and have limited uses. Therefore, improvement of its moldability has been desired for a long time. The present applicant previously proposed a resin composition mixed with polyamide in order to improve the moldability of such polyarylate (Japanese Patent Publication No. 14699/1983). Such resin compositions not only have improved moldability of polyarylate, but also have chemical resistance, oil resistance,
Improvements in wear resistance, etc. have been recognized. However, as is well known, polyarylate and polyamide have considerably different solubility indices, so when they are actually mixed, it is difficult to achieve a sufficiently compatible state. Therefore, the mechanical properties of the molded product, especially the impact resistance, were poor.
In addition, mechanical properties such as tensile strength and bending strength vary depending on the manufacturing lot, and results with satisfactory reproducibility cannot be obtained. The present inventor has arrived at the present invention as a result of intensive research aimed at improving the above-mentioned drawbacks of a resin composition composed of polyarylate and polyamide while maintaining its excellent properties. That is, the present invention provides polyarylates obtained from (a) a mixture of terephthalic acid and isophthalic acid or derivatives thereof (provided that the molar ratio of terephthalic acid groups to isophthalic acid groups is 9:1 to 1:9) and bisphenol A; (b) 10 to 150 parts by weight of polyamide, and (c) 3 to 50 parts by weight of N-substituted amide-containing polymer. In this way, by adding an N-substituted amide-containing polymer to a combination of polyarylate and polyamide, which have poor compatibility, it is possible to improve the composition of a resin composition consisting of polyarylate and polyamide while retaining the advantages of polyarylate to a large extent. It is surprising that its mechanical properties have been improved by taking advantage of its excellent moldability, chemical resistance, oil resistance, and abrasion resistance. The polyarylate used in the present invention is
It is obtained from a mixture of terephthalic acid and isophthalic acid or their functional derivatives (the molar ratio of terephthalic acid groups to isophthalic acid groups is 9:1 to 1:9) and bisphenol A. Such polyarylate may be produced by any of interfacial polymerization, solution polymerization, and melt polymerization. In addition, some of the bisphenols (4.
4'-dihydroxydiphenyl)ether, (4.
4′-dihydroxydiphenyl)thioether,
2,2-(4,4'-dihydroxy-3,5,3',
Other bisphenols such as 5'-tetrabromodiphenyl)propane may be substituted. The polyarylate used in the present invention has a concentration of 1 g/dl in a mixed solvent of phenol/tetrachloroethane (6:4, weight ratio), 25
The logarithmic viscosity determined from the solution viscosity measured at °C is
A value of 0.3 to 1.0 is preferred. Examples of the polyamide used in the present invention include a polymer formed by a condensation reaction of a primary diamine and a dibasic acid, a polycondensate formed by a self-condensation reaction of amino acids, and a polymer formed by a polymerization reaction of a lactam. However, the polyamide preferably used in the present invention is a polyamide that melts at a temperature of 170°C or higher, more preferably a temperature of 190°C to 280°C. Particularly preferred polyamides include polyhexamethylene-adipamide, polycaprolactam, polyhexamethylene-sebamide and copolymers thereof. The polyamide used in the present invention preferably has a relative viscosity of 2.4 to 3.4 as determined from the solution viscosity measured in 96% sulfuric acid at a concentration of 1 g/dl at 25°C. The N-substituted amide-containing polymer used in the present invention includes diamines in which at least one of them is a secondary amine and dibasic acids (including acid halide derivatives).
polymers formed by the condensation reaction of amino acids with secondary amines, polymers formed by the ring-opening polymerization of N-alkyl substituted lactams, 2-substituted cyclic imino ethers. A polymer formed by cationic ring-opening polymerization. The substituent is preferably a hydrocarbon group having 10 or less carbon atoms. Moreover, this substituent may form a ring. Specific N-substituted amide-containing polymers include piperazine (including those with various substituents on the piperazine ring), sym-dialkylalkylene diamines, and reaction polymers of diamines and dibasic acids such as sym-dimethylethylenediamine. , ring-opening reactants of N-alkyl-ε-caprolactam, ring-opening polymers of 2-alkyloxazolines, 2-aryloxazolines, 2-alkyloxazines, 2-aryloxazines, and copolymers thereof. The N-substituted amide-containing polymer used in the present invention preferably has a degree of polymerization of 10 to 200 mer. The degree of polymerization is determined by the terminal group determination method using neutralization titration method or the vapor pressure equilibrium method. The blending ratio of polyarylate, polyamide, and N-substituted amide-containing polymer in the resin composition of the present invention is 10 to 150 parts by weight of polyamide and 3 to 3 parts by weight of N-substituted amide-containing polymer per 100 parts by weight of polyarylate. 50 parts by weight. If the polyamide content is less than 10 parts by weight, it is difficult to notice an improvement in moldability;
If it exceeds 150 parts by weight, mechanical properties will deteriorate. N
If the amount of the substituted amide-containing polymer is less than 3 parts by weight, the effect of improving mechanical properties will be poor, while if it exceeds 50 parts by weight, a decrease in mechanical properties, yellowing due to heat, increased hygroscopicity, etc. will be observed, so it is preferable. do not have. In order to prepare the resin composition of the present invention, for example, granules or powders of polyarylate, polyamide, and N-substituted amide-containing polymer are mixed in a V-type blender, super mixer, co-kneader, etc., or by mixing them in an extruder, co-kneader, etc. They may be mixed in a molten state using an intensive mixer or the like to form chips. Alternatively, a method may be adopted in which polyamide powder is mixed with a solution of a polyarylate and an N-substituted amide-containing polymer dissolved in methylene chloride or the like, and then the solvent is removed. In order to improve the heat resistance, light resistance, oxidation resistance, and flame resistance of the resin composition of the present invention, thermal decomposition inhibitors, antioxidants, ultraviolet absorbers, flame retardants, etc. may be present in the resin composition. . In that case, benzotriazole compounds, phosphorus compounds, phenol compounds, benzophenone derivatives, aromatic halogen compounds, and the like are preferably used. These may be present in each polymer before mixing, or may be added at the time of mixing the polymers. Others: plasticizers, pigments,
Lubricants and the like can also be used in conjunction with the resin composition of the present invention. The resin composition of the present invention maintains the excellent moldability, chemical resistance, cold resistance, oil resistance, and abrasion resistance that a resin composition composed of polyarylate and polyamide has, and also has excellent mechanical properties, especially Has impact resistance. Further, the resin composition of the present invention has the advantage that it can be repeatedly and stably prepared and has little variation between lots. Therefore, the resin composition of the present invention can be processed by press molding, injection molding, etc. using powder, chips, or other shapes.
It can be made into various useful products by commonly known plastic molding methods such as extrusion molding. Examples of such products are gears, bearings,
It is used in a wide range of applications, including electrical parts, containers, and other products that require high performance as engineering plastics. In order to further facilitate understanding of the present invention, polyarylate obtained from terephthalic acid, isophthalic acid and bisphenol A, polyamide and N
The present invention will be illustrated by examples using representative combinations of substituted amide-containing polymers. First, a preparation example of the N-substituted amide-containing polymer used in Examples will be shown as a reference example. Reference Example 1 Copolymerized piperazine aramid (hereinafter referred to as PPT/I) using a methylene chloride solution of mixed acid chloride with a molar ratio of terephthalic acid dichloride and isophthalic acid dichloride of 1:1 and an alkaline aqueous solution of piperazine by an interfacial polymerization method. Manufactured. The logarithmic viscosity of this product [1 g/dl in phenol/tetrachloroethane (6:4 weight ratio) at 25°C] was 0.51. Reference Example 2 Copolymerized sym-dimethylethyldiamine aramid (hereinafter referred to as
It is called DMAT/I. ) was manufactured. The logarithmic viscosity of this was measured in the same manner as in Reference Example 1 and was 0.31. Reference Example 3 Poly-N-propionylethyleneimine (hereinafter referred to as PEI) was produced by cationic ring-opening polymerization of 2-ethyl-2-oxazoline in a nitrogen gas atmosphere using methyl p-toluenesulfonate as a catalyst. The molecular weight of this compound was determined to be 9500 by vapor pressure equilibrium method using chloroform solvent. Reference Example 4 Poly-N-benzoylethyleneimine (hereinafter referred to as BEI) was produced in the same manner as Reference Example 3 except that 2-phenyl-2-oxazoline was used instead of 2-ethyl-2-oxazoline. Reference example 3
The molecular weight of this product, measured in the same manner as above, was 12,000. Examples 1 to 4 Polyarylates were produced by an interfacial polymerization method using a methylene chloride solution of a mixed acid chloride with a molar ratio of terephthalic acid dichloride and isophthalic acid dichloride of 1:1 and an alkaline aqueous solution of bisphenol A. Logarithmic viscosity of this [1 g/dl in phenol/tetrachloroethane mixed solvent (6:4 weight ratio),
25℃] was 0.65. 20 parts by weight of this polyarylate powder and polycaprolactam (relative viscosity 2.6)
2 parts by weight and 5 parts by weight of powder of various N-substituted amide-containing polymers shown in Table 1 in a V-type blender.
Mixed for an hour. This was extruded using an extruder of 40 mmφ and L/D=18 and cut to obtain chips. Injection molding was performed using this chip under the conditions shown in Table 1. Polyarylate alone for comparison (Comparative Example 1)
Injection molding was also carried out in the same manner for a material (Comparative Example 2) consisting of 80 parts by weight of polyarylate and 20 parts by weight of polycaprolactam. The injection molding conditions were within the range of normal engineering plastic molding conditions, but in the examples the molded products obtained had a uniform milky white appearance and had no problems such as sink marks or flow marks. In the case of Comparative Example 2, good moldability similar to that in the Examples was shown, but in the case of Comparative Example 1, satisfactory specimens could not be obtained under the same molding conditions as in the Examples, so as shown in Table 1. Strict molding conditions were required. In addition, the properties of the molded products are shown in Table 1, and compared to the comparative examples, the examples showed superior mechanical properties, particularly impact strength.

[Table] Example 5 Logarithmic viscosity was determined by the same interfacial polymerization method as in Example 1 using a methylene chloride solution of mixed acid chloride with a molar ratio of terephthalic acid dichloride and isophthalic acid dichloride of 6:4 and an alkaline aqueous solution of bisphenol A. 0.73 polyarylate was produced. To this methylene chloride solution of polyarylate, polyhexamethylene-azibamide (relative viscosity 2.6) and 20 mesh powder obtained by crushing PPT/I of Reference Example 1 were added to form a mixed slurry, and then While methylene chloride was evaporated in a kneader heated to 0.degree. C., the precipitated polymer mass was ground to obtain a three-part powder mixture. In this case, the mixing ratio of polyarylate, polyhexamethylene-adipamide, and PPT/I was 6:3:1 by weight. Injection molding was performed using the obtained powder under the conditions shown in Table 2, and the properties of the molded products were measured. For comparison, a similar test was conducted on a mixture of polyarylate and polyhexamethylene-adipamide in a weight ratio of 6:4. As shown in Table 2, all three had good moldability, but the present invention had better mechanical properties.

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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 2,2-bis 100 parts by weight of an aromatic polyester copolymer obtained from (4′-hydroxyphenyl)propane, (b) 10 to 150 parts by weight of a polyamide having an amide group in which hydrogen atoms are not substituted, and (c ) A resin composition comprising 3 to 50 parts by weight of a polymer having an amide group in which hydrogen atoms are substituted with hydrocarbon groups.