JPH036185B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a thermoplastic resin composition, and more specifically, thermoplastic resins with poor compatibility are made to be compatible with each other by blending a third component, thereby improving the drawbacks of both resins and making them superior. An object of the present invention is to provide a thermoplastic resin composition that provides a molded article having excellent mechanical properties. (Prior Art) Conventionally, many attempts have been made to solve the drawbacks of each thermoplastic resin by blending thermoplastic resins having different properties.
However, different polymers usually have poor compatibility and do not mix uniformly, forming a so-called "sea-island" structure, and this "sea-island" interface is extremely weak.
For this reason, the resulting composition is brittle, has poor mechanical strength,
The disadvantage is that impact strength is reduced. On the other hand, since blends of polymers with high compatibility have similar properties, characteristic properties cannot usually be expected. In recent years, various modifications of polymers have been investigated in order to uniformly disperse incompatible polymers with different properties, and blends in which modified olefin rubber is finely dispersed in a nylon matrix have been shown to exhibit improved impact resistance. (Refer to Japanese Patent Application Laid-Open No. 143061/1983). However, such blends also tend to deteriorate in other physical properties, and no characteristic properties other than impact resistance have been obtained. (Problems to be solved by the invention) Polyphenylene ether resin has mechanical properties,
It is used in many applications as an engineering plastic because it has excellent electrical properties, excellent heat resistance, and good dimensional stability, all of which are well-balanced. It has major drawbacks of poor moldability, impact strength, and chemical resistance. On the other hand, engineering plastics with excellent chemical resistance include thermoplastic polyester resins (eg, polyethylene terephthalate, polybutylene terephthalate, etc.) and polyamide resins (eg, nylon 6, nylon 66, etc.). The former thermoplastic polyester resin has a high melting point and excellent mechanical strength, but its heat distortion temperature under load is extremely low, so it is usually used as a molding material with a large amount of glass fiber mixed in. . However, thermoplastic polyester resins reinforced with glass fibers have poor surface properties, and glass fiber orientation occurs during molding, resulting in extremely large strength anisotropy and shrinkage anisotropy of the molded product. Therefore, the molded product has disadvantages such as warping and deformation. In order to eliminate these drawbacks of polyphenylene ether and thermoplastic polyester resin, an attempt was made to melt-mix the two.
It is proposed in the Publication No. However, the resulting compositions have significantly different properties (expressed by SP value, etc.) derived from their molecular structures;
Shows typical incompatible properties. In other words, the mechanical properties are significantly lower than expected based on both values, and the molded product obtained from this composition is
The appearance is also worse than when it is used alone. On the other hand, in order to improve the fluidity of polyphenylene ether, it has been proposed in Japanese Patent Publication No. 45-997 to incorporate a polyamide resin.
Polyphenylene ether and polyamide have extremely poor compatibility, and the resulting resin composition has significant deterioration in mechanical properties, and no characteristic properties other than improved fluidity have been obtained. (Means for Solving the Problems) The present inventors created a blend of thermoplastic resins with different properties and poor compatibility, and improved the drawbacks of both resins without reducing the excellent properties of both resins. As a result of intensive research, we have finally completed the present invention. That is, the present invention contains 5 to 99.5% by weight of a thermoplastic resin (A) having at least one polar group selected from a carboxyl group, a hydroxyl group, and an amino group at its terminal and having a melting point of 150 to 300°C and an epoxy group. Polyphenylene ether resin (B) 0.5 to 95 parts by weight,
Epoxy group-free polyphenylene ether resin (C)
0 to 90 parts by weight, and 0 to 90 parts by weight of a styrene resin (D). The thermoplastic resin (A) in the present invention has at least one polar group selected from carboxyl group, hydroxyl group, and amino group at the terminal and has a melting point of 150
~300°C thermoplastic resin, such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexane dimethylene terephthalate, polyoxyethoxybenzoate, polyethylene naphthalate, the above polyester components and other acid components and/or glycol components. , acid components such as isophthalic acid, P-oxybenzoic acid, adipic acid, sebacic acid, glutaric acid, diphenylmethanedicarboxylic acid, dimer acid, hexamethylene glycol, diethylene glycol, neopentyl glycol, bisphenol A, neopentyl Polyesters copolymerized with glycol components such as glycol alkylene oxide adducts, aromatic polyester/polyether block copolymers, aromatic polyester/polylactone block copolymers, polyesters in a broad sense such as polyarylates, nylon 6, nylon 6,6, nylon 6,
9. Nylon 6,10, Nylon 6,12, Nylon 6/6,6, Polyxylylene adipamide, Polyhexamethylene terephthalamide, Polyphenylene phthalamide, Polyxylylene adipamide/Hexamethylene adipamide Polyamides such as polyamide, polyesteramide elastomer, polyetheramide elastomer, polyetheresteramide elastomer, and dimer acid copolymerized polyamide are exemplified, and the resin may be a single resin, a blend of multiple resins, or a copolymer thereof. Especially the melting point is 200
℃ or higher is preferable from the viewpoint of heat resistance. usually,
The polyester resin preferably has an intrinsic viscosity of 0.4 or more, more preferably 0.5 or more, as measured at 30°C in a mixed solvent of phenol/tetrachloroethane (6/4 weight ratio).
In addition, polyamide usually has a relative viscosity (JIS K6810−
(measured in 98% sulfuric acid according to 1970) is preferably 1.8 or more, and particularly preferably 2.0 or more. In addition, as the polyphenylene ether resin (B) containing an epoxy group in the present invention, glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, allyl glycidyl ether, glycidyl ether of hydroxyalkyl (meth)acrylate, polyalkylene glycol (meth) ) glycidyl ether of acrylate,
It is obtained by copolymerizing or graft copolymerizing an epoxy group-containing copolymerizable unsaturated monomer such as glycidyl itaconate with a polyphenylene ether resin consisting of repeating units represented by the following general formula. The content of the epoxy group-containing copolymerizable unsaturated monomer is usually 0.1 to 30% by weight, preferably 0.5 to 20% by weight based on the resin (B). Here, R ₄ , R ₅ , R ₆ and R ₇ are hydrogen, halogen, hydrocarbon group, substituted hydrocarbon group, cyano group, alkoxy group, phenoxy group or nitro group,
n indicates the degree of polymerization. Specific examples of R ₄ , R ₅ , R ₆ and R ₇ include hydrogen, chlorine, bromine, iodine, methyl,
Examples include groups such as ethyl, propyl, allyl, phenyl, benzyl, methylbenzyl, chloromethyl, bromomethyl, cyanoethyl, cyano, methoxy, ethoxy, phenoxy, and nitro.
Specifically, for example, poly-2,6-dimethyl-
1,4-phenylene ether, poly-2,6-diethyl-1,4-phenylene ether, poly-
2,6-dipropyl-1,4-phenylene ether, poly-2,6-dimethoxy-1,4-phenylene ether, poly-2,6-dichloromethyl-
1,4-phenylene ether, poly-2,6-dibromomethyl-1,4-phenylene ether, poly-2,6-diphenyl-1,4-phenylene ether, poly-2,6-ditolyl-1, 4-phenylene ether, poly-2,6-dichloro-1,
4-phenylene ether and poly-2,5-dimethyl-1,4-phenylene ether, poly-
Examples include 2,6-dibenzyl-1,4-phenylene ether. In the preferred polyphenylene ether resin, R ₄ and R ₇ in the general formula are alkyl groups, especially carbon atoms of 1 to 1.
It is a polymer having 4 alkyl groups, and n is usually preferably 50 or more. Various conventionally known methods can be used to produce the epoxy group-containing polyphenylene ether resin (B), but in order to copolymerize efficiently, it is necessary to use a radical generator. Preferably, the reaction is carried out in the presence of. For example, the following method can be adopted. (1) To the solution containing polyphenylene ether resin,
A method in which a radical generator and an epoxy group-containing copolymerizable unsaturated monomer are added and stirred at a temperature of 40°C to 200°C for several tens of minutes to several hours. (2) A method in which each component is melt-kneaded in a system substantially free of solvent at a temperature in the range of 150°C to 350°C for 20 seconds to 30 minutes, preferably 40 seconds to 5 minutes. etc. The epoxy group-free polyphenylene ether resin (C) in the present invention is composed of repeating units represented by the above general formula, and specific examples thereof are also as described above. Next, as the styrene resin (D) in the present invention, polystyrene, polychlorostyrene, poly-
Homopolymers such as α-methylstyrene, styrene-butadiene copolymers, styrene-acrylonitrile-acrylate copolymers, styrene-butadiene rubber-modified polystyrene, FPDM-based rubber-modified polystyrene, acrylic rubber-modified styrene,
Examples include polystyrene thermoplastic elastomers such as acrylonitrile copolymers and hydrogenated styrene-butadiene block copolymers. In the composition of the present invention, a catalyst is used to promote the reactivity between the epoxy group of component (B) and component (A), or to improve the affinity with component (A) by ring opening of the epoxy group. It is preferable. Although the reaction between component (A) and the epoxy group is effective even without a catalyst, the reaction is significantly accelerated when a catalyst is used. Catalysts generally include amines, phosphorus compounds, and carbon atoms.
It is preferable to blend 10 or more monocarboxylic acids and/or dicarboxylic acids with metal salts of groups -a or -a of the periodic table of elements. Particularly preferred are trivalent phosphorus compounds such as tributylphosphine and triphenylphosphine, and metal salts of stearic acid such as calcium stearate and sodium stearate. When using these catalysts, they may be used alone or in combination of two or more.
Further, even if the above catalysts are added all at once, the effect remains the same. There is no particular limitation on the amount of the ingredients, but
(A) It is usually 3 parts by weight or less per 100 parts by weight,
Preferably it is 0.03 to 2 parts by weight. The blending ratio of the above components (A), (B), (C), and (D) can be changed as appropriate depending on the desired physical properties, purpose, cost, etc., but usually component (A) is added to the entire composition. is 5~
99.5% by weight, preferably 20-99% by weight, component (B)
0.5-95% by weight, preferably 1-80% by weight, ingredients
(C) is contained in an amount of 0 to 90% by weight, preferably 0 to 80% by weight, and component (D) is contained in an amount of 0 to 90% by weight, preferably 0 to 75% by weight. If the amount of component (A) added is too low, there will be disadvantages such as a decrease in chemical resistance, and if the amount of component (C) and/or (D) is too low, molding shrinkage will increase and the molded product will have sink marks and warpage. This results in the disadvantage of deterioration of surface properties. Furthermore, when the amount of component (B) is too small, the compatibility between component (A) and component (C) and/or component (D) is poor, resulting in a disadvantage that physical properties are deteriorated. The composition of the present invention may further contain crystal nucleating agents such as talc, mica, titanium oxide, carbon black, etc. and crystallization promoters as component (A), depending on the use, purpose, etc.
For example, when component (A) is an ethylene terephthalate polyester, polyoxyalkylene compounds, polyhydric alcohol derivatives, higher fatty acid esters, higher fatty acid metal salts, polyvalent carboxylic acid esters, high molecular weight aliphatic Polycarboxylic acid salts, polyhydric alcohol esters, etc. may also be blended. Usually, the amount of the crystal nucleating agent is up to about 50% by weight based on the composition, and the amount of the crystallization promoter is preferably up to about 10% by weight based on the composition. In addition, antioxidants, ultraviolet absorbers, stabilizers such as hydrolysis resistance improvers, plasticizers, lubricants, flame retardants, flame retardant aids, antistatic agents, colorants, conductivity imparting agents, and sliding properties. Improvers (solid lubricants, liquid lubricants),
Polyfunctional crosslinkers, impact modifiers (e.g. Tg
0°C or lower, preferably -20°C or lower, more preferably rubber containing a reactive group), inorganic fillers other than the above, fibrous reinforcing agents (for example, glass fibers, carbon fibers, graphite fibers, silicon carbide fibers, silicon nitride fibers, boron nitride fibers, potassium titanate whiskers, heat-resistant organic fibers), conductivity imparting agents (e.g. metal fibers, polyacetylene fibers, metal powders, iron phosphorus, carbon black, organic conductive polymers, etc.) It is also possible to mix additives. When blending inorganic fillers and inorganic fibers, silane couplers, titanium couplers, zircoaluminate couplers, etc. may be used in combination. Additionally, other resins may be blended in amounts and types that do not detract from the objectives of the present invention. The method for producing the composition of the present invention is not particularly limited, and any method may be used. For example, they can be blended by mechanical kneading using an extruder, roll mill, Banbury Misaki, or the like.
Multi-stage kneading may be used, such as kneading component (A) and component (B) and then kneading other components. The composition of the present invention can be widely used for molding various molded parts, films, sheets such as plates, fibrous materials, tubular materials, containers, etc., and can also be used as a coating agent,
It can also be used as an adhesive, a sealant, a modifier for other resins, etc. Further, it can be formed into a film, fiber, etc., and further stretched or formed into a secondary molded product. (Function) The composition of the present invention has a component (A) due to the presence of component (B).
is modified and component (A) and component (C) and/or component
The compatibility with component (D) is improved, resulting in a uniform blend, giving molded products with excellent mechanical properties, and reducing mold shrinkage of component (A), which eliminates problems such as sink marks and warpage. It has the advantages of providing molded products with excellent surface properties and improving the chemical resistance of component (C) and/or (D). (Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. Note that the percentages in the examples are based on weight. Synthesis example of polyphenylene ether resin (B) containing epoxy groups 1 [η] is 0.58 (measured in chloroform at 30°C)
Poly-2,6-dimethylphenylene-1,4-
90 parts of ether powder and 10 parts of glycidyl methacrylate were placed in a flask and dissolved in 170 parts of toluene at 80°C under a nitrogen stream. A solution prepared by dissolving 1.5 parts of benzoyl peroxide in 30 parts of toluene was gradually dropped into the flask using a dropping funnel. After the dropwise addition, the reaction was carried out at 80° C. for 5 hours while stirring while heating. After the reaction was completed, the reaction solution was allowed to cool to room temperature and poured into methanol to precipitate the produced polymer. The precipitate was filtered and dried under reduced pressure to obtain epoxy group-containing polyphenylene ether in a yield of about 96%. The epoxy content in this polymer was determined using the following hydrochloric acid solution.
93% as determined by dimethylformamide method
The reaction rate was . Hydrochloric acid used to quantify the epoxy content in the reaction product.
The dimethylformamide method will be explained in detail below. If the sample is a polymer, accurately weigh the required amount according to Table 1, place it in a 200 ml flask with a seal, add 25 ml of dimethylformamide, and stir well at 40°C or below. Next, add 25 ml of hydrochloric acid/dimethylformamide to the flask at room temperature and shake well. The reaction mixture was left at room temperature for exactly 60 minutes, then
Add 3 drops of bromophenol blue indicator, titrate excess acid with 0.1N NH ₃ OH methanol standard solution, and take the point where the color turns green as the end point. At the same time as this experiment, two blank tests will be conducted. Measure the acidity or alkalinity of a sample. The sample was precisely weighed in approximately the same amount as the titrant, and neutralized in advance using bromophenol blue as an indicator.
Add ml dimethylformamide, if acidity
Titrate with 0.1N・NH ₃ OH・methanol standard solution. For alkalinity, titrate with 0.1N・HCl・methanol standard solution. Acidity or alkalinity = number of cc dropped x titer x 5.61 / sample collection amount (g) Epoxy content (%) = 0.16 x F x (B-A) / S - C x 1.60 / 56.1 However, F: 0.1N methanol Standard solution titer coefficient B: Number of cc dropped in blank test A: Number of cc dropped in main test S: Amount of sample collected (g) C: Acidity or alkalinity The correction term is positive for acidity and negative for alkalinity. do.

[Table] Examples 1 to 8, Comparative Examples 1 to 5 Polyethylene terephthalate with [η] of 0.63 or polybutylene terephthalate with [η] of 1.2,
Powder of epoxy group-containing poly-2,6-dimethylphenylene-1,4-ether modified according to Synthesis Example 1, powder of unmodified poly-2,6-dimethylphenylene-1,4-ether, and styrene Mix the specified amount of the resin in a blender and make a 30mmφ2
The mixture was kneaded and extruded using a shaft extruder (PCM-30, Ikegai Tekko Co., Ltd.) at a cylinder temperature of 300°C to form pellets. The obtained pellets were dried in a vacuum dryer at 120°C for 5 hours, and then placed in an injection molding machine (Nissei Jushi Kogyo Co., Ltd., FS-
75 type) into a molded product. The cylinder temperature at this time was 295°C. Furthermore, the mold temperature was 70°C.
Table 2 shows the physical properties of each of the molded products obtained. In addition, various measurements in the examples were performed by the following methods. (1) Heat distortion temperature According to ASTM D-648, length 126 mm, width 12.6
A bending stress of 18.6 Kg/cm ² was applied to a test piece with a thickness of 6.3 mm, and the temperature of the test piece was raised at a rate of 2°C per minute, and the temperature when the amount of deflection reached 0.254 mm was determined. (2) Bending strength Measured according to ASTM D-790. (3) Surface characteristics The molded product was visually evaluated for sink marks, surface gloss, etc.

[Table] In Table 2 (1) Polyethylene terephthalate (2) Poly-2,6-dimethylphenylene-1,4
-Ether (3) High impact polystyrene (4) Hydrogenated styrene-butadiene block copolymer (5) Polybutylene terephthalate Examples 9 to 11, Comparative Examples 6 to 7 The polyester in Example 1 had a relative viscosity of 2.7
The molded product was molded in the same manner as in Example 1 except that nylon 6 was used and the cylinder temperature was 270°C, and the properties of the molded product were evaluated. The results are shown in Table 3.

[Table] As is clear from Tables 1 and 2, the composition of the present invention containing an epoxy group-containing polyphenylene ether resin can be molded with good surface properties and excellent bending strength. It can be seen that it has an even higher heat distortion temperature. Note that this composition was found to have advantages such as excellent chemical resistance.

Claims (1)

[Claims] 1 5 to 99.5% by weight of thermoplastic resin (A) with a melting point of 150 to 300°C and having at least one polar group selected from carboxyl group, hydroxyl group and amino group at the terminal, polyphenylene containing epoxy group It is characterized by containing ether resin (B) 0.5 to 95% by weight, epoxy group-free polyphenylene ether resin (C) 0 to 90% by weight, and styrene resin (D) 0 to 90% by weight. Thermoplastic resin composition.