JP2000263586A - Insert molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an insert molded article extremely excellent in high and low temp. impact characteristics and suitably used in various industrial fields requiring these characteristics. SOLUTION: A resin compsn. prepared by compounding 30-89 wt.% of (A) a polyarylene sulfide resin, 1-10 wt.% of (B) an olefinic copolymer based on an α-olefin and a glycidyl ester of an α, βunsaturated acid, 5-45 wt.% of (C) a particulate filler and 5-50 wt. % of (D) a fibrous filler and a metal or inorg. solid are subjected to insert molding.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an insert molded product obtained by insert molding a specific resin composition and a metal or an inorganic solid, and more particularly to an insert molded product having improved high and low temperature impact resistance.

[0002]

2. Description of the Related Art The insert molding method is based on the characteristics of resin and metal or inorganic solid (hereinafter, referred to as "solid").
It is a molding method that embeds metal etc. in resin, taking advantage of the characteristics of the material (abbreviated as metal etc.), such as automobile parts, electric / electronic parts,
It is applied to a wide range of fields such as OA equipment parts, and is now one of the general molding methods. However, since the expansion and contraction rates (so-called linear expansion coefficients) of the resin and the metal due to temperature change are extremely different, the resin part of the molded product is thin or has a portion with a large change in the thickness, and metal. In some cases, such as those having sharp corners, cracks occur immediately after molding, or cracks due to temperature changes during use. For this reason, at present, applications and shapes of molded articles are considerably restricted. In recent years, in the field of automobiles, resinization around the engine has progressed,
Insert molded products have also become important components. In particular, for ignition systems and distributor parts, insert molded products that wrap metal parts such as aluminum, copper, iron, and brass with a thermoplastic resin are being studied. In addition to the fact that there are many portions where the wall thickness changes, the temperature required for use in the vicinity of the engine causes a large change in high and low temperatures, so that the performance required for the insert molded product is higher. Therefore, from these facts, there has recently been a strong demand for a resin that can withstand long-term high / low temperature changes, that is, a resin having excellent high / low temperature impact characteristics. Polyester resins such as polybutylene terephthalate resin are sometimes used as insert molding products in response to the requirement of high-low temperature impact characteristics. Recently, in addition to high-low temperature impact characteristics, in order to improve the reliability of various parts, Flame retardancy is often required at the same time, and it has been difficult to apply polybutylene terephthalate resin to parts requiring such flame retardancy. on the other hand,
Polyarylene sulfide (hereinafter abbreviated as PAS) resin represented by polyphenylene sulfide (hereinafter abbreviated as PPS) has high heat resistance, mechanical properties, chemical resistance,
Because of its dimensional stability and flame retardancy, it is widely used in electrical and electronic equipment parts materials, automotive equipment parts materials, chemical equipment parts materials, etc., but PAS resin has poor toughness and is brittle. There was a drawback that the reliability of the insert molded product against long-term high and low temperature changes was low.

[0003]

Means for Solving the Problems In view of the above problems, the present inventors have intensively studied to obtain an insert molded article having excellent high-temperature and low-temperature impact characteristics. As a result, a composition comprising a PAS resin as a main component, and a specific copolymer and an inorganic filler blended therein, has a high-low-temperature impact characteristic ( In particular, the present invention has been found to be extremely excellent (even when the resin is thin or a metal or the like has sharp corners), and the present invention has been completed. That is, the present invention provides (A) 30 to 89% by weight of a polyarylene sulfide resin, and (B) 1 to 10% by weight of an olefin-based copolymer containing a glycidyl ester of an α-olefin and an α, β-unsaturated acid as main components. % (C) 5 to 45% by weight of a particulate filler (D) 5 to 50% by weight of a fibrous filler and a metal or inorganic solid.

[0004]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the components of the resin material of the present invention will be described in detail. The PAS resin as the component (A) used in the present invention has a repeating unit of-(Ar-S)-
(Where Ar is an arylene group). Examples of the arylene group include a p-phenylene group, an m-phenylene group, an o-phenylene group, a substituted phenylene group, a p, p′-diphenylene sulfone group, a p, p′-biphenylene group, and a p, p′-diphenylene. Ether groups, p, p'-diphenylenecarbonyl groups, naphthalene groups and the like can be used. In this case, among the arylene sulfide groups composed of the above-mentioned arylene groups, in addition to a polymer using the same repeating unit, that is, a homopolymer, a copolymer containing a heterogeneous repeating unit from the viewpoint of processability of the composition. Is sometimes preferred. As the homopolymer, those having a repeating unit of a p-phenylene sulfide group using a p-phenylene group as an arylene group are particularly preferably used. Further, as the copolymer, among the arylene sulfide groups consisting of the above-mentioned arylene groups, two or more different combinations can be used. Among them, a combination containing a p-phenylene sulfide group and an m-phenylene sulfide group is particularly preferably used. Can be In this, p
Those containing 70% by mole or more, preferably 80% by mole or more of a phenylene sulfide group are suitable from the viewpoint of physical properties such as heat resistance, moldability, and mechanical properties. Also, these PAS
Among the resins, a high molecular weight polymer having a substantially linear structure obtained by condensation polymerization from a monomer mainly containing a bifunctional halogen aromatic compound can be particularly preferably used,
In addition to the PAS resin having a linear structure, a polymer having a partially branched or cross-linked structure formed by using a small amount of a monomer such as three or more polyhalogen aromatic compounds at the time of polycondensation can be used. It is also possible to use a polymer obtained by heating a linear polymer having a relatively low molecular weight at a high temperature in the presence of oxygen or an oxidizing agent to increase the melt viscosity by oxidative crosslinking or thermal crosslinking and to improve moldability. As the PAS resin of the component (A), the linear PAS resin (310 ° C.,
The viscosity at a shear rate of 1200 sec ^-1 is mainly 10 to 300 Pa · s), and a part thereof (1 to 30% by weight, preferably 2 to 25
A mixed system with a branched or crosslinked PAS resin having a relatively high viscosity (300 to 3000 Pa · s, preferably 500 to 2000 Pa · s) having a relatively high viscosity (% by weight) is also suitable. The PAS resin used in the present invention is preferably a resin obtained by polymerizing and then performing acid washing, hot water washing, and organic solvent washing (or a combination thereof) to remove by-product impurities and the like.

The olefin copolymer used as the component (B) in the present invention is a copolymer mainly composed of a glycidyl ester of an α-olefin and an α, β-unsaturated acid.
Examples of α-olein, which is one monomer, include ethylene, propylene, and butene-1, and ethylene is preferably used. The glycidyl ester of α, β-unsaturated acid, which is another monomer constituting the olefin copolymer, is represented by the general formula (2)

[0006]

Embedded image

[0007] Examples thereof include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate. Among them, glycidyl methacrylate is particularly preferably used. α-olefin (eg, ethylene) and α, β-
The unsaturated acid glycidyl ester can be obtained by copolymerization by a generally well-known radical polymerization reaction. Olefin copolymer is α-olefin 10
0 to 100 parts by weight, unsaturated acid glycidyl ester 1 to 40
It is preferable to copolymerize using parts by weight. Further, this olefin-based copolymer (B) is one or two of a polymer or a copolymer composed of a repeating unit represented by the following general formula (1) in order to improve impact resistance and heat resistance. The above is preferably a graft copolymer which is chemically bonded in a branched or crosslinked structure.

[0008]

Embedded image

The polymer or copolymer to be graft-polymerized as a branched or crosslinked chain is selected from acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, acrylonitrile and styrene. Alternatively, those obtained by polymerizing or copolymerizing two or more kinds are exemplified. From the viewpoint of moldability, preferably, a methacrylic acid polymer, a copolymer of acrylonitrile and styrene, a copolymer of methyl methacrylate and butyl acrylate, and the like, and particularly preferably a copolymer of methyl methacrylate and butyl acrylate It is a polymer. These polymers or copolymers are prepared by commonly known radical polymerization. Also, the branching or crosslinking reaction of these polymers or copolymers can be easily performed by a radical reaction. For example, by producing free radicals in these polymers or copolymers with peroxides and the like, and melt-kneading the glycidyl ester copolymer of α-olefin and α, β-unsaturated acid, the desired olefin-based Copolymer
(B) can be prepared. The branched or crosslinked chain is α-
It is preferred that 10 to 100 parts by weight be branched or crosslinked with respect to 100 parts by weight of the glycidyl ester copolymer of an olefin and an α, β-unsaturated acid. In the composition of the present invention, the olefin copolymer (B) is blended in an amount of 1 to 10% by weight. (B)
If the amount of the component is less than 1% by weight, the effect of improving the high / low temperature impact resistance, which is the object of the present invention, cannot be obtained. If the amount is more than 10% by weight, the heat deformation temperature is lowered and mechanical properties such as rigidity are impaired. It is not preferable, and the flame retardancy is lowered, which is not preferable.
In order to obtain V-0 having sufficient flame retardancy, the amount of the component (B) is preferably 1 to 6% by weight.

Next, the powdery and particulate filler of the component (C) used in the present invention reduces the molding shrinkage and the anisotropy of the shrinkage of the molded product, and improves the high-temperature impact resistance. Examples of the powdery filler include calcium carbonate, carbonates such as magnesium carbonate, talc, mica, glass beads, plate glass, silica, quartz powder, glass powder, calcium silicate, kaolin,
Clay, diatomaceous earth, silicates such as wollastonite, oxides such as iron oxide, titanium oxide, zinc oxide, alumina, hydroxides such as magnesium hydroxide and barium hydroxide, and sulfuric acids of metals such as calcium sulfate and barium sulfate Oxides, other carbon blacks, granular carbon, silicon carbide, silicon nitride, boron nitride, various metal powders, and metal foils. Calcium carbonate and glass beads are preferably used. These powdery and granular fillers can be used alone or in combination of two or more. In addition, these powdery fillers can be surface-treated with various surface treatment agents such as generally known epoxy compounds, isocyanate compounds, silane compounds, titanate compounds, and fatty acids. It is preferable to improve the adhesiveness with the adhesive. The average particle size of the particulate filler is preferably from 0.1 to 100 μm, more preferably from 1 to 50 μm. The particulate filler (C) is contained in the composition,
The content is 5 to 45% by weight, preferably 10 to 40% by weight.

Next, the fibrous filler of the component (D) used in the present invention has the effects of lowering the molding shrinkage and the coefficient of linear expansion of the molded product, and improving the mechanical properties and the high-temperature impact resistance. . Examples of the fibrous filler include glass fiber, asbestos fiber, carbon fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, stainless steel, aluminum, titanium, Metal fibrous substances such as copper and brass are exemplified, and glass fibers and carbon fibers are particularly preferably used.

The surface treatment of the fibrous filler can be carried out in the same manner as in the case of the powdery and granular fillers. The treating agent may be subjected to a surface treatment or a convergence treatment in advance, or may be added simultaneously with the preparation of the material. May be. The fibrous filler (D) is blended in the composition in an amount of 5 to 50% by weight, preferably 10 to 40% by weight.

In the present invention, a specific olefin-based copolymer is used.
(B), and further, a granular filler (C) and a fibrous filler.
(D) must be used together. The addition of the particulate filler (C) has the effect of reducing the toughness of the weld portion and suppressing the anisotropy of the shrinkage, but has the disadvantage that the reinforcing effect on the strength is small. Is not practical. On the other hand, the compounding of the fibrous filler (D) has a large reinforcing effect, but has a drawback that the anisotropy of the linear expansion coefficient is large and the toughness of the weld portion is greatly reduced, so that sufficient high-temperature impact resistance is obtained. I can't. However, by using a specific combination of the particulate filler (C) and the fibrous filler (D) together with the specific olefin-based copolymer (B), the toughness of the weld portion is improved and the linear expansion coefficient is reduced. In addition, the reduction of the anisotropy of the coefficient of linear expansion and the reinforcing effect are optimized, and as a result, the high and low temperature impact characteristics are remarkably improved.

A silane compound can be added to the resin composition of the insert molded product used in the present invention for the purpose of improving burrs and the like as long as the effects of the present invention are not impaired.
Examples of the silane compound include vinyl silane, methacryloxy silane, epoxy silane, amino silane, and various types such as mercapto silane, for example, vinyl trichlorosilane, γ-methacryloxypropyl trimethoxy silane, γ-glycidoxy propyl trimethoxy silane, γ
-Aminopropyltriethoxysilane, γ-mercaptotrimethoxysilane, and the like, but are not limited thereto.

The resin composition of the insert molded article used in the present invention may optionally contain a small amount of other thermoplastic resin components in addition to the above components, depending on the purpose. Any other thermoplastic resin may be used as long as it is stable at high temperatures. For example, aromatic polyesters such as polyethylene terephthalate and polybutylene terephthalate and aromatic dicarboxylic acid and diol or oxycarboxylic acid, polyamide, polycarbonate, ABS, polyphenylene oxide, polyalkyl acrylate, polysulfone, polyether sulfone, polyetherimide , Polyether ketone, fluorine resin and the like. These thermoplastic resins can be used as a mixture of two or more kinds. Further, the resin composition of the insert molded product used in the present invention, in order to impart desired properties according to the purpose, generally known substances added to thermoplastic resins and thermosetting resins, that is, a flame retardant, Coloring agents such as dyes and pigments,
Lubricants, crystallization promoters, crystal nucleating agents, various antioxidants, heat stabilizers, weathering stabilizers, and the like can be blended according to the required performance.

The resin composition of the insert molded article used in the present invention can be easily prepared using equipment and a method generally used as a conventional method for preparing a resin composition. For example, 1) after mixing each component, kneading and extruding with a single-screw or twin-screw extruder to prepare pellets, and then molding, 2) once preparing pellets having a different composition, and disposing the pellets A method in which the mixture is quantitatively mixed and subjected to molding to obtain a molded article having a desired composition after molding. 3) 1 or 2 of each component is added to a molding machine.
Any of the above methods can be used. Further, a method in which a part of the resin component is added as a fine powder mixed with other components is a preferable method for achieving uniform blending of these components.

The insert molded product is a composite molded product in which a metal or the like is previously mounted on a molding die, and the outside thereof is filled with the above-mentioned resin composition. As a molding method for filling the resin into the mold, there are an injection method, an extrusion compression molding method, and the like, and an injection molding method is generally used. In addition, since the material to be inserted into the resin is used for the purpose of taking advantage of its characteristics and compensating for the defect of the resin, a material that does not change its shape or melt when it comes into contact with the resin during molding is used. Therefore, mainly aluminum, magnesium, copper,
Metals such as iron, brass and their alloys, and inorganic solids such as glass and ceramics which are previously formed into rods, pins, screws, etc. are used.

[0018]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.
In addition, the measuring method of the physical property evaluation shown in the following examples is as follows. High / low temperature impact characteristics Using resin pellets, resin temperature 320 ° C, mold temperature 150 ° C,
Injection time 40 seconds, cooling time 60 seconds, metal pin (14mm × 14
(mm × 24 mm), insert molding was performed so that the minimum thickness of the resin portion was 1 mm, and an insert molded product was manufactured. The obtained insert molded product is heated at 180 ° C. for 2 hours using a thermal shock tester, cooled to -40 ° C., cooled for 2 hours, and further heated to 180 ° C. in one cycle. A low-temperature impact test was performed, and the number of cycles until cracks were formed in the molded product was measured to evaluate high-low temperature impact properties. Flame retardancy Using a 1/16 inch thick flame retardant test piece, UL9
According to the test method of No. 4, it was evaluated whether V-0 could be achieved.場合 indicates that V-0 can be achieved, and X indicates that V-0 cannot be achieved.

Examples 1 to 8 As shown in Table 1, the components (A), (B) and (C) were mixed in a Henschel mixer for 5 minutes, and the mixture was heated at a cylinder temperature of 320 ° C.
(D) The component (D) is added separately from the side feed section of the extruder, melt-kneaded at a resin temperature of 350 ° C in the extruder to form pellets of the resin composition, and the above physical properties are evaluated. went. Table 1 shows the results. Comparative Examples 1 to 7 As shown in Table 2, when one or two of the components (B), (C) and (D) were not added, a copolymer which did not satisfy the requirements of the present invention was used as the component (B). In each case, pellets of the resin composition were prepared in the same manner as in the above examples, and the physical properties were evaluated. Table 2 shows the results. The specific substances of each component used in Examples and Comparative Examples are as follows. (A) Polyphenylene sulfide (PPS) resin Fortron KPS manufactured by Kureha Chemical Industry Co., Ltd. (B) Olefin copolymer B-1 Ethylene / glycidyl methacrylate copolymer B-2 Ethylene / glycidyl methacrylate copolymer with styrene B-3 Copolymer grafted with acrylonitrile copolymer B-3 Copolymer grafted with methyl methacrylate / butyl acrylate copolymer on ethylene / glycidyl methacrylate copolymer B-4 Methyl copolymer on ethylene / ethyl acrylate copolymer Copolymer grafted with methacrylate / butyl acrylate copolymer (C) Granular filler C-1 Calcium carbonate C-2 Talc C-3 Mica C-4 Glass beads C-5 Plate glass (D) Fibrous Filler D-1 Glass fiber (average fiber diameter 13μm) D-2 Carbon fiber (average fiber diameter 6μm)

[0020]

[Table 1]

[0021]

[Table 2]

[0022]

As described above, the insert molded product of the present invention has an extremely high impact characteristic at high and low temperatures, and is particularly suitably used in the field of the automobile industry, for example, in ignition systems and distributor parts.

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Claims (6)

[Claims] (1) a polyarylene sulfide resin (A)
89% by weight; (B) 1 to 10% by weight of an olefin-based copolymer mainly containing a glycidyl ester of an α-olefin and an α, β-unsaturated acid; (C) 5 to 45% by weight of a particulate filler ( D) An insert molded article obtained by insert molding a resin composition containing 5 to 50% by weight of a fibrous filler and a metal or inorganic solid. 2. The olefin copolymer (B) is an olefin copolymer comprising an α-olefin and a glycidyl ester of an α, β-unsaturated acid, and a repeating unit represented by the following general formula (1). The insert molded product according to claim 1, wherein one or more of the constituent polymers or copolymers are graft copolymers that are chemically bonded in a branched or crosslinked structure. Embedded image 3. The olefin copolymer (B) comprising an olefin copolymer comprising an α-olefin and a glycidyl ester of an α, β-unsaturated acid, wherein acrylic acid, methacrylic acid,
A graft copolymer obtained by polymerizing or copolymerizing one or more selected from methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, acrylonitrile and styrene, in a branched or cross-linked structure. The insert molded product according to claim 2, which is a polymer. 4. The insert-molded article according to claim 3, wherein (B) the olefin-based copolymer is a graft copolymer obtained by chemically bonding a copolymer of methyl methacrylate and butyl acrylate as a branched chain. 5. The insert-molded article according to claim 1, wherein (C) the particulate filler is calcium carbonate or glass beads. 6. The insert-molded article according to claim 1, wherein the fibrous filler is glass fiber or carbon fiber.