JPH0524177B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on thermoplastic polyester (hereinafter referred to as polyester), polyphenylene sulfide (hereinafter referred to as polyester), and polyphenylene sulfide (hereinafter referred to as
The present invention relates to a resin composition consisting of a non-volatile epoxy resin (abbreviated as PPS) and a ``non-novolagic epoxy resin containing no halogen atoms in the molecule''. Polyesters, such as polybutylene terephthalate (hereinafter abbreviated as PBT), have excellent heat resistance, chemical resistance, and electrical properties, and are used in various applications as engineering plastics. However, polyester is easily hydrolyzed and cannot be used in parts that come into contact with hot water or steam. In addition, polyester has a low heat distortion temperature when used alone, and a high heat distortion temperature can be achieved only when reinforced with a reinforcing agent such as glass fiber, but its long-term heat resistance is not sufficient, and when a reinforcing agent is used, the molded product may It has disadvantages such as warping and a decrease in the molding fluidity of the composition, resulting in a rough appearance of the molded product. A method of blending PPS is known as a method to improve the above drawbacks. However, most of these compositions have insufficient compatibility, resulting in problems such as no improvement in hydrolysis resistance, a significant decrease in mechanical strength, and deterioration in the appearance of molded products. As a result of intensive study, the present inventors found that polyester,
A composition consisting of PPS and a non-novolac type epoxy resin that does not contain halogen atoms in the molecule (hereinafter simply referred to as non-novolac type epoxy resin) has little decrease in mechanical strength, has excellent compatibility, and has excellent hydrolysis resistance and heat resistance of polyester. The inventors have discovered that this material has high practicality, such as greatly improved properties and excellent moldability, and has thus arrived at the present invention. That is, the present invention contains (A) 99 to 60 parts by weight of polyester;
(B) 1 to 40 parts by weight of PPS, (C) 0.1 to 20 parts by weight of non-novolagic epoxy resin (total of 100 parts by weight of (A) and (B)), and (D) 0 to 300 parts by weight of fibrous reinforcing agent. Parts by weight ((A) and
(B) based on a total of 100 parts by weight). Polyesters used in the present invention include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalene dicarboxylic acid, 4,4'-diphenyl dicarboxylic acid, diphenyl ether dicarboxylic acid, α,
β-bis(4-carboxyphenoxy)ethane,
Dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, and dimer acid, or their ester-forming derivatives, and ethylene glycol, propylene glycol, butanediol, pentanediol, neopentyl glycol, Hexanediol, octanediol, decanediol, cyclohexanedimethanol, hydroquinone, bisphenol A, 2,2-bis(4-hydroxyethoxyphenyl)propane,
It is a polyester obtained from glycols such as xylylene glycol, polyethylene ether glycol, polytetramethylene ether glycol, and aliphatic polyester oligomers having hydroxyl groups at both ends, and is usually a 6:4 mixture of phenol and tetrachloroethane. At 30℃ in a mixed solvent with a weight ratio of
The one having an intrinsic viscosity [η] of 0.3 to 1.5 dl/g as measured by . In addition, as a comonomer component, glycolic acid,
Hydroxycarboxylic acids such as hydroxybutyric acid, hydroxybenzoic acid, hydroxyphenylacetic acid, and naphthylglycolic acid, lactone compounds such as propiolactone, butyrolactone, valerolactone, and caprolactone, or trimethylolpropane within a range that can maintain thermoplasticity. , trimethylolethane, glycerin, pentaerythritol, trimellitic acid, trimesic acid, and pyromellitic acid. Also, dibromoterephthalic acid, tetrabromoterephthalic acid, tetrabromophthalic acid, dichloroterephthalic acid, tetrachloroterephthalic acid, 1,4
- An aromatic nucleus such as dimethyloltetrabromobenzene, tetrabromobisphenol A, or an ethylene oxide adduct of tetrabromobisphenol A has a halogen compound such as chlorine or bromine as a substituent, and an ester-forming group. Also included is a thermoplastic polyester resin copolymerized with a halogen compound. Particularly preferred polyesters include polybutylene terephthalate, polyhexamethylene terephthalate, poly(ethylene butylene terephthalate), poly(cyclohexane dimethylene terephthalate), poly(butylene tetramethylene terephthalate), and poly(butylene tetramethylene terephthalate).
terephthalate), 2,2-bis(β-hydroxyethoxytetrabromophenyl)propane copolymerized polybutylene terephthalate, and the like. In addition, the PPS used in the present invention has the general formula

It is preferable that the composition contains 70 mol% or more of the structural unit represented by the formula; if the amount is less than 70 mol%, it is difficult to obtain a composition with excellent properties. The polymerization method for this polymer includes a method of polymerizing p-dichlorobenzene in the presence of sulfur and soda carbonate;
Methods include polymerization in the presence of sodium sulfide or sodium bisulfide and sodium hydroxide or hydrogen sulfide and sodium hydroxide in a polar solvent, self-condensation of p-chlorothiophenol, etc. N-methylpyrrolidone, dimethylacetamide, etc. A suitable method is to react sodium sulfide with p-dichlorobenzene in an amide solvent such as sulfolane or a sulfone solvent such as sulfolane. At this time, in order to adjust the degree of polymerization, it is a preferable method to add an alkali metal salt of carboxylic acid or sulfonic acid, or to add alkali hydroxide. If it is less than 30 mol% as a copolymer component, it is a meta bond.

[Formula] Ortho bond

[Formula] Ether bond

[Formula] Sulfone bond

[Formula] biphenyl join

[Formula] Substituted Feni Rusulfide bond

[Formula] where R represents an alkyl group, a nitro group, a phenyl group, an alkoxy group, a carboxylic acid group or a metal base of a carboxylic acid), trifunctional bond

[Formula] etc. may be contained as long as it does not significantly affect the crystallinity of the polymer, but preferably the copolymerization component is
It is preferably 10 mol% or less. In particular, when trifunctional or more functional phenyl, biphenyl, naphthyl sulfide bonds, etc. are selected for copolymerization, the amount is preferably 3 mol% or less, more preferably 1 mol% or less. As a specific method for producing such PPS, for example,
(1) Reaction of halogen-substituted aromatic compound with alkali sulfide (U.S. Patent No. 2513188, Japanese Patent Publication No. 1973-
27671 and Japanese Patent Publication No. 45-3368) (2) Condensation reaction of thiophenols in the presence of an alkali catalyst or copper salt, etc. (see US Pat. No. 3,274,165, British Patent No. 1,160,660) (3) Aromatic compounds Condensation reaction of sulfur chloride with sulfur chloride in the presence of a Lewis acid catalyst (see Japanese Patent Publication No. 46-27255 and Belgian Patent No. 29437). In order to facilitate the compatibility of the compositions, which is the main objective of the present invention, it is preferable that the blended resins have the same viscosity and have a small amount of crosslinked structure.
PPS is currently available on the market as Ryton PPS from Phillips Petroleum. Ryton PPS has V-
There are grades 1, P-2, P-3, P-4, and R-6. With conventional technology, Ryton V-1 has a low degree of crosslinking, but its viscosity is too low, and Ryton R-6, P-
Although No. 4 had a high viscosity, the degree of crosslinking was too high and good blend compatibility could not be obtained. In the present invention, the non-novolac type epoxy resin is effective in increasing the molecular weight of PPS and is thought to react with polyester, and it is possible to omit the oxidative crosslinking step, which could not be used due to its low viscosity, and to reduce the degree of coloring. PPS can be suitably used.
The degree of crosslinking of PPS can be expressed by the relationship between the melt viscosity of the polymer and the non-Newtonian coefficient (N), and generally, the larger N is, the higher the degree of crosslinking is. In other words, the PPS used in the present invention plots the respective logarithms of the shear rate and shear stress obtained during viscosity measurement, and calculates the slope of the tangent at a shear rate of 200 (1/sec) at 300°C as the non-Newtonian coefficient N. When defined, it is particularly preferred that N is between 0.8 and 1.33 + 0.000047 x (melt viscosity). Furthermore, in the present invention, high molecular weight PPS with a low degree of crosslinking, which is known from JP-A-50-84698 and JP-A-51-144495, can also be suitably used. The non-novolac type epoxy resin, which is an essential component to improve the compatibility between PPS and polyester, is an epoxy resin that does not contain halogen atoms in the molecule and whose constituent components are not novolacic, and which has two epoxy groups. or more,
For example, diglycidyl ether of bisphenol A, halogenated bisphenol instead of bisphenol A, glycidyl ethers such as butanediol diglycidyl ether, glycidyl esters such as phthalic acid glycidyl ester, N-diglycidylaniline, etc. Examples include glycidyl epoxy resins such as glycidyl amine type, linear type non-glycidyl epoxy resins such as epoxidized polyolefin and epoxidized soybean oil, and cyclic type non-glycidyl epoxy resins such as vinyl cyclohexene dioxide and dicyclopentadiene dioxide. These non-novolac type epoxy resins may be used alone and/or as a mixture of two or more. Further, the non-novolac type epoxy resin may be used in combination with a sulfurizing agent such as general amines, acid anhydrides, phenols, polysulfides, and the like. It is preferable that the amount of such curing agent used is smaller than that for ordinary purposes; if it is used in a large amount, the melt flowability of the composition of the present invention may be significantly reduced. In addition, as an effect of combined use with a curing agent, it can be expected that deterioration in bleedability, thermal properties, etc. due to the addition of a non-novolac type epoxy resin can be prevented. The non-novolac type epoxy resin may be added simultaneously with the other raw materials (PPS and polyester) constituting the composition of the present invention. , further polyester or
It is preferable to mix and knead PPS in consideration of the possibility of reaction between the non-novolac type epoxy resin and PPS and/or polyester. Alternatively, the non-novolac type epoxy resin may be added after PPS and polyester are kneaded in advance. The mixing ratio of polyester and PPS is polyester
99 to 6 parts by weight and 1 to 40 parts by weight of PPS,
Preferably for 95-60 parts by weight of polyester
PPS is 5 to 40 parts by weight. The amount of non-novolac type epoxy resin added is 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of PPS and polyester. If the amount is less than 0.1 part by weight, the effect will be small, and if it exceeds 20 parts by weight, the mechanical properties may be lost, and if added, it may cause bleeding to the surface of the molded product or significantly reduce the melt flowability of the composition. This is not desirable because it causes In addition to the above-mentioned components, the composition of the present invention includes:
Additionally, reinforcing fillers such as those described below may also be included.
Such reinforcing fillers include fibrous reinforcing agents such as glass fiber, carbon fiber, potassium titanate, asbestos, silicon carbide, ceramic fiber, metal fiber, and silicon nitride; barium sulfate, calcium sulfate, kaolin, clay, and pyrofluorite. , bentonite, sericite, zeolite, mica, mica, nephelinsinite, talc, attalpalgite, wollastonite, processed mineral fiber (PMF), ferrite, calcium silicate, calcium carbonate, magnesium carbonate, dolomite, Inorganic materials such as antimony trioxide, zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass powder, glass beads, glass balloons, quartz glass, etc.
Examples include organic reinforcing fillers such as aramid fibers. Among these, glass fiber is preferred from the viewpoint of economy, reinforcing effect, etc. These fillers have γ-
It is more effective to use a coupling agent such as an aminosilane such as aminopropyltriethoxysilane or an epoxysilane such as γ-glycidoxypropyltrimethoxysilane. The amount of the reinforcing filler added is usually 1 to 300 parts by weight, preferably 5 to 200 parts by weight, based on 100 parts by weight of the resin components (PPS, polyester, and non-novolac type epoxy resin). If the amount added exceeds 300 parts by weight, there are problems such as poor melt flowability of the composition and impaired appearance of molded products. A mixture of thermoplastic resins can be used.The thermoplastic resins include ethylene, propylene, butylene, pentene, butadiene, isoprene, chloroprene, styrene, α-methylstyrene, vinyl acetate, vinyl chloride, acrylic ester, and methacrylic acid. Homopolymers or copolymers of vinyl monomers such as esters and (meth)acrylonitrile, polyurethane polymers, polyamide polymers, polyester elastomers, polycarbonates, polyacetals, polysulfones, polyarylsulfones, polyethersulfones, Homopolymers such as polyarylate, polyphenylene oxide, polyether ether ketone, polyimide, polyamideimide, silicone resin, phenoxy resin, fluororesin, polyaryl ether,
Mention may be made of copolymers or block and graft polymers. In addition, a small amount of a mold release agent, a coupling agent, a coloring agent, a lubricant, a heat-resistant stabilizer, a weather-resistant stabilizer, a foaming agent, a flame retardant, a flame retardant aid such as antimony trioxide, etc. may be added. In the present invention, the composition of the invention can be prepared by various known methods. For example, there is a method in which the raw materials are uniformly mixed in advance in a mixer such as a tumbler or a Henschel mixer, and then fed into a single-screw or twin-screw extruder for melt-kneading and then pellets are prepared. EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples. Examples 1 to 8, Comparative Examples 1 to 5 In the formulation shown in Table 1, PPS and epoxy resin (Epicron 7050, manufactured by Dainippon Ink and Chemicals Co., Ltd., bisphenol A type epoxy resin) were mixed in advance.
Mix the pellets, PBT and glass fibers according to the composition shown in Table 1 by kneading them at 280℃ using a 30m/m twin-screw extruder, and then mix them using a 40m/m single-screw extruder.
The mixture was kneaded at 280°C to obtain pellets. Using this pellet, a test piece was made using a 3-ounce injection molding machine (cylinder temperature: 270°C, mold temperature: 80°C), and the bending strength and heat distortion temperature were measured. Furthermore, the hydrolysis resistance and appearance of the molded product were evaluated based on the following test methods. Table 1 shows the results.
are summarized in (Appearance condition of molded product) Γ Compatibility evaluation; Visual judgment 〇...Excellent compatibility, good appearance ×...Poor compatibility, exhibits pearly luster and poor appearance (hydrolysis resistance (PCT test)) Bending strength The test piece for measurement is left in pressurized steam at 123°C for 50 hours, and then the retention of bending strength is measured.

【table】

[Table] As is clear from the results shown in Table 1, the composition obtained according to the present invention has good compatibility with little decrease in mechanical strength, exhibits an excellent appearance, and is superior to PBT. It was confirmed that hydrolysis resistance and heat distortion temperature were significantly improved. On the other hand, in a comparative example in which a non-novolac type epoxy resin was not added, the compatibility was poor and it was not practical, the mechanical strength was greatly reduced, and there was almost no improvement in hydrolysis resistance.

Claims (1)

[Claims] 1 99 to 60 parts by weight of thermoplastic polyester, (B) 1 to 40 parts by weight of polyphenylene sulfide, and (C) 0.1 to 20 parts by weight of non-novolac type epoxy resin containing no halogen atoms in the molecule ((A) and (B), based on a total of 100 parts by weight).