JPH0579701B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to polyphenylene sulfide (hereinafter referred to as
This relates to improving the compatibility between polyamide (hereinafter referred to as PPS) and polyamide. Many compositions of PPS and polyamide are known. However, most of these compositions have poor compatibility, and therefore have problems such as a significant decrease in mechanical strength and deterioration of the surface condition of molded products. As a result of extensive studies, the present inventors have found that a composition consisting of PPS, polyamide, and epoxy resin has excellent compatibility, improves the hard but brittle properties of PPS to hard and tough properties, and improves the properties of polyamide by water absorption. The inventors have discovered that it is possible to provide a highly practical molding material by exhibiting the features of both polymer components, such as improving the wide decrease in strength, and have arrived at the present invention. That is, the present invention uses 1 to 99 parts by weight of PPS and polyamide.
The present invention provides a thermoplastic resin composition characterized in that it contains 1 to 20 parts by weight of an epoxy resin to 100 parts by weight of a mixture consisting of 99 to 1 parts by weight. The general formula for PPS used in the present invention is

It is preferable to use a composition containing 70 mol% or more of the structural unit represented by the formula because it provides a composition with excellent properties. The polymerization method for PPS is p-
A method for polymerizing dichlorobenzene in the presence of sulfur and sodium carbonate, a method for polymerizing dichlorobenzene in the presence of sodium sulfide or sodium bisulfide and sodium hydroxide or hydrogen sulfide and sodium hydroxide in a polar solvent, p-chlorothiophenol Examples include self-condensation of sodium sulfide and p-
A method of reacting dichlorobenzene is suitable. 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 phenylus rufiid bond

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

[Formula] and the like may be contained as long as they do not significantly affect the crystallinity of the polymer, but preferably the copolymerization component is 10 mol% or less. Especially trifunctional or more phenyl,
When biphenyl, naphthyl sulfide bonds, etc. are selected for copolymerization, the amount is preferably 3 mol% or less, more preferably 1 mol% or less. Such PPS can be produced by common manufacturing methods, such as (1) reaction of a halogen-substituted aromatic compound with an alkali sulfide (see U.S. Pat. No. 2,513,188, Japanese Patent Publication No. 44-27671 and Japanese Patent Publication No. 45-3368) (2) ) Condensation reaction of thiophenols in the presence of an alkali catalyst or copper salt (US Patent No. 3274165, British Patent No. 1160660)
(3) Condensation reaction of aromatic compounds with sulfur chloride in the coexistence of a Lewis acid catalyst (Special Publication No. 46-27255)
(see Belgian Patent No. 29437), and can be arbitrarily selected depending on the purpose. PPS is currently on the market as Ryton PPS from Philips Petroleum. Ryton PPS has V-
There are grades 1, P-2, P-3, P-4, and R-6. When blended with only polyamide, Ryton V-1 has a low degree of crosslinking, too low viscosity, and
Light R-6 and P-4 had a high viscosity and a degree of crosslinking that was too high, making it impossible to obtain good blend compatibility. In order to further improve blend compatibility, which is the main objective of the present invention, PPS with fewer crosslinked structures is preferred. When polyamide and epoxy resin are blended with such PPS, the epoxy resin is thought to help increase the molecular weight of PPS and also react with the polyamide. PPS with a low degree of coloration can be suitably used without the oxidative cross-linking step, which was conventionally unsuitable due to its low viscosity. 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. That is, the PPS used in the present invention is obtained by plotting the respective logarithms of the shear rate and shear stress obtained during viscosity measurement, and calculating the shear rate of 200 at 300°C.
If the slope of the tangent at the point (1/sec) is defined as the non-Newtonian coefficient N, then N is 0.8 and 1.33+
It is particularly preferable that it is between 0.000047×(melt viscosity). Furthermore, in the present invention, Japanese Patent Application Laid-open No. 50-84698,
High molecular weight PPS with a low degree of crosslinking, which is known from JP-A-51-144495, can also be suitably used. On the other hand, various well-known polyamides can be mentioned. For example, dicarboxylic acids such as oxalic acid, adipic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, 1,4-cyclohexyldicarboxylic acid and ethylenediamine, pentamethylenediamine, hexamethylenediamine, decamethylenediamine, 1,4- Polyamides obtained by polycondensing diamines such as cyclohexyldiamine and m-xylylenediamine; polyamides obtained by polymerizing cyclic lactams such as caprolactam and laurinlactam; or polyamides obtained by polymerizing cyclic lactams, dicarboxylic acids, and diamines. Examples include polyamides obtained by copolymerizing salts. Among these polyamides, 6-nylon, 66 nylon, 6.10 nylon,
Examples include 66/6/10 nylon, 6/66 nylon, 12 nylon, 11 nylon, 6/6T nylon (copolymer of salts of caprolactam, terephthalic acid, and hexamethylene diamine), and particularly preferred ones include 6 nylon and 66 nylon. The epoxy resin used in the present invention contains one or more epoxy groups, and can be in liquid or solid form. For example, bisphenol A, resorcinol, hydroquinone, pyrocatechol, bisphenol F,
Saligenin, 1,3,5-trihydroxybenzene, bisphenol S, trihydroxy-diphenyldimethylmethane, 4,4'-dihydroxybiphenyl, 1,5-dihydroxynaphthalene, casyuphenol, 2,2,5, Glycidyl ethers of bisphenols such as 5-tetrakis(4-hydroxyphenyl)hexane, halogenated bisphenols instead of bisphenols, glycidyl ethers such as diglycidyl ether of butanediol, and glycidyl esters such as phthalic acid glycidyl ester. , glycidyl epoxy resins such as glycidylamine type such as N-glycidylaniline, linear type such as epoxidized polyolefin and epoxidized soybean oil, and cyclic type non-glycidyl epoxy resins such as vinyl cyclohexene dioxide and dicyclopentadiene dioxide. Illustrated. A particularly preferred epoxy resin in the present invention is a novolak type epoxy resin. A novolak type epoxy resin contains two or more epoxy groups and is usually obtained by reacting a novolak type phenolic resin with epichlorohydrin. Further, a novolak type phenolic resin can be obtained by a condensation reaction between phenols and formaldehyde. The phenols used as this raw material are not particularly limited, but include phenol, o-cresol, m-cresol, and p-cresol.
Cresol, bisphenol A, resorcinol, p-tert-butylphenol, bisphenol F, bisphenol S and mixtures thereof are particularly preferably used. Furthermore, poly-p-
Vinylphenol epoxides can also be used in the same way as novolac type epoxy resins. still,
These novolak type epoxy resins may have halogen, hydroxyl groups, etc., and may be used alone or in a mixture of two or more. Generally, epoxy resins are molded by blending curing agents such as amines, acid anhydrides, polysulfides, and phenolic resins, but in the present invention, no curing agents are used at all, or even if they are used, their activity is It is desirable that the amount of hydrogen be at a molar ratio of half or less of that of the epoxy group component. If a normal amount of curing agent is used together, not only will the reaction between the epoxy resin and PPS be inhibited, but a stable increase in melt viscosity cannot be expected due to the formation of a crosslinked network due to the reaction between the epoxy resin and the curing agent. It is from. The effect of the combined use of a curing agent can be expected to be to prevent deterioration in bleeding properties and thermal properties due to the addition of an epoxy resin. The mixing ratio of each of the above components varies depending on the desired properties, but is 1 to 99 parts by weight of PPS to 99 to 1 part by weight of polyamide. If the addition ratio of PPS and polyamide is less than 1 part by weight each, the desired effects of the present invention will be small. Preferably, the amount of polyamide is 10 to 90 parts by weight based on 90 to 10 parts by weight of PPS. The amount of epoxy resin added is 0.1 to 20 parts by weight based on 100 parts by weight of the total weight of PPS and polyamide, preferably
0.5 to 15 parts by weight. The preferred amount of epoxy resin to be added varies depending on the molecular weight of PPS and the intended use, and generally a relatively large amount of epoxy resin is required for low molecular weight PPS or for extrusion molding compositions that require high viscosity. If it 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 depending on the type of epoxy resin added, it may bleed onto the surface of the molded product or the composition may become unstable in melt flow. This is undesirable because it can significantly reduce the performance. The composition of the present invention includes fibrous reinforcing agents such as glass fiber, carbon fiber, potassium titanate, asbestos, silicon carbide, ceramic fiber, metal fiber, silicon nitride, and aramid fiber; barium sulfate, calcium sulfate, kaolin, clay, and pyrofiber. Light, bentonite, sericite, zeolite, mica, mica, nephelinsinite, talc, attalpargite, wollastonite, PMF, ferrite,
Calcium silicate, calcium carbonate, magnesium carbonate, dolomite, ammonium trioxide, zinc oxide,
Inorganic fillers such as titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass beads, glass balloons, and quartz powder are included in the composition.
It can be contained up to 80% by weight. When adding these reinforcing agents or fillers, known silane coupling agents can be used in combination. In addition, the composition of the present invention may contain small amounts of a mold release agent, a coloring agent, a heat stabilizer, an ultraviolet stabilizer, a blowing agent, a flame retardant, a flame retardant aid, and the like, without departing from the purpose of the present invention.
It can contain a rust preventive agent. Furthermore, the following polymers can be mixed and used in the same manner. These polymers include monomers such as ethylene, butylene, pentene, butadiene, isoprene, chloroprene, styrene, α-methylstyrene, vinyl acetate, vinyl chloride, acrylic esters, methacrylic esters, and (meth)acrylonitrile. Coalescing or copolymers, polyurethanes, polyesters, polycarbonates, polyacetals, polysulfones, polyarylsulfones, polyethersulfones, polyarylates,
Polyphenylene oxide, polyphenylene ether, polyether ether ketone, polyimide,
Examples include homopolymers, random copolymers, block copolymers, graft copolymers, etc. of polyamideimide, silicone resins, phenoxy resins, fluorine resins, and polyaryl ethers. The composition of the present invention can be prepared by various known methods. For example, the raw materials are mixed uniformly in advance using a mixer such as a tumbler or Henschel mixer, and then fed to a single-screw or twin-screw extruder at a temperature of 230 to 400°C.
There is a method of melting and kneading the mixture and then preparing it as pellets. When extruding and kneading, it is preferable to divide the epoxy resin into two or more portions and perform the extrusion operation two or more times in order to promote the reaction between PPS and the epoxy resin. It is also possible to dry blend PPS and novolak type epoxy resin and melt-knead them in an injection molding machine. EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples. Example 1 50 parts by weight of PPS (Ryton V-1, manufactured by Philips Petroleum), 66 nylon (Leona
1300, manufactured by Asahi Kasei Industries, Ltd.), and 5 parts by weight of a novolac type epoxy resin (Epicron N-695, manufactured by Dainippon Ink and Chemicals, Ltd.) were uniformly premixed. The mixture was then kneaded into pellets using a vented 40 mm extruder heated to 300°C. A test piece was made from this pellet using an injection molding machine. The appearance was cream-colored and had excellent compatibility. When the physical properties were measured, the bending strength was 960Kg/cm ² ,
Izotsu impact strength (with notch) is 4.2Kg・cm/
cm and flame retardant (UL-94 standard, 1/16 inch thick)
It was V-1. Furthermore, when 0.3 parts by weight of a coloring pigment (cyanine blue) was mixed with 100 parts by weight of the pellets and molded, the pellets were colored bright blue. Comparative Example 1 Molding was carried out in Example 1 without adding any epoxy resin. The resulting molded product had a pearl-like appearance due to poor compatibility between PPS and polyamide. Further, its bending strength was 570 Kg/cm ² and its Izot impact strength was as low as 2.5. Furthermore, an attempt was made to color the molded product with cyanine blue in the same manner as in Example 1, but the molded product had a pearl-like appearance and was not colored bright blue. Examples 2 to 3 In Example 1, the mixing ratio of PPS and 66 nylon was changed to 70/30 and 30/70. The results are summarized in Table 1, and the same results as in Example 1 were obtained. Examples 4 to 6 In Examples 1 to 3, 45% of glass fiber (Glaslon CS03 MA411, manufactured by Asahi Glass Co., Ltd.) was used.
Part by weight was added. The results are summarized in Table-1. Comparative Example 2 Comparative Example 1 was carried out by adding 43 parts by weight of glass fiber. The results are summarized in Table-1. Example 7 Example 4 was carried out by changing the PPS to Ryton P-4 (manufactured by Philips Petroleum). The results are summarized in Table-2. Comparative Example 3 Comparative Example 2 was carried out by changing PPS to Ryton P-4. The results are summarized in Table-2. Test Example In order to evaluate the water resistance of the compositions of each Example and Comparative Example, specimens of each composition were left under 50% humidity (23°C), and the bending strength was measured when the weight became constant. did. The results are shown in Table-1 and Table-2. As is clear from the results shown in Tables 1 and 2, the compositions of Examples have good compatibility, exhibit excellent appearance, and exhibit excellent mechanical properties. On the other hand, the compositions of comparative examples had poor compatibility, poor appearance, and poor mechanical properties.

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Claims (1)

[Claims] 1. A thermoplastic resin composition comprising 1 to 20 parts by weight of an epoxy resin to 100 parts by weight of a mixture consisting of 1 to 99 parts by weight of polyphenylene sulfide and 99 to 1 parts by weight of polyamide.