JP2002235002A - Heat resistant polyarylene sulfide resin composition having improved adhesion property with epoxy resin, and conjugated molded article with epoxy resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyarylene sulfide-based resin material having a strong adhesion property especially with an epoxy resin as a molded article to become a base plate, container and other exterior article for holding or internally containing the epoxy resin, and also excellent mechanical properties, heat resistance, chemical resistance and flame retardant property, and a conjugated molded article strongly adhered with the epoxy resin by a simple method. SOLUTION: The polysrylene sulfide resin composition having an improved adhesion property with the epoxy resin is obtained by blending (A) 100 pts.wt. polyarylene sulfide resin, (B) 10-60 pt.wt. α-olefin copolymer consisting mainly of an α-olefin and an alkyl ester of an α,β-unsaturated acid, (C) 5-115 pt.wt. fibrous filler and (D) 1-15 pt.wt. epoxy resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyarylene sulfide resin composition which is excellent in adhesion to an epoxy resin and is suitable for holding or embedding an epoxy resin or an epoxy resin product closely, and molded from such a resin material. The present invention relates to a composite molded product in which an epoxy resin is adhered or held or provided inside.

[0002]

2. Description of the Related Art Polyarylene sulfide resin (hereinafter abbreviated as PAS) represented by polyphenylene sulfide (hereinafter abbreviated as PPS) resin has heat resistance, mechanical properties, chemical resistance, and the like. Because of its excellent dimensional stability and flame retardancy, it is widely used in electrical and electronic equipment parts materials, automotive equipment parts materials, chemical equipment parts materials and the like. In particular, for various electronic components, electrical insulation, maintenance of mechanical strength, and internal protection from external environments such as temperature and floating impurities are indispensable for maintaining their performance, and therefore, they are sealed using a synthetic resin. The so-called sealing is generally performed. Although epoxy resin is exclusively used as such a sealing resin material, it is necessary to closely incorporate or fix it in a support such as a substrate or a container for supporting and fixing the epoxy resin. As a substrate or package material for holding or incorporating such an epoxy resin body, firstly, it has excellent heat resistance, flame retardancy, mechanical properties, and the like that have excellent adhesiveness to the epoxy resin and can withstand a severe use environment. Although a material having such a performance is required, a resin material having such performance has not yet been obtained. PAS
The resin is suitable as a protective material in terms of excellent mechanical properties, heat resistance, chemical resistance, flame retardancy and chemical resistance by blending an appropriate reinforcing agent or filler, but is generally an epoxy resin. Adhesion was poor. The adhesiveness of this resin is slightly improved by mechanical roughening of the adhesive surface of the molded product, physical treatment such as plasma treatment, chemical treatment such as chemical etching, etc., but such means leads to an increase in cost, Not only is it economically undesirable, but its adhesiveness is not always sufficient.

In order to solve the above-mentioned problem, the applicant of the present application has proposed a composition in Japanese Patent Application Laid-Open No. 4-304264 in which a fibrous filler, talc, and, in some cases, a polyolefin-based elastomer are further added to a PAS resin. Such a composition is excellent in mechanical properties and also excellent in adhesion to an epoxy resin, but has a problem in that the releasability of a molded product is poor at the time of molding.

[0004]

Means for Solving the Problems The present inventors have aimed to provide a PAS resin material which has good mechanical properties and adhesiveness (adhesion) with an epoxy resin, and also has excellent mold release properties during molding. As a result of intensive studies, it has been found that by combining a specific α-olefin copolymer and an epoxy resin in combination with the PAS resin, a PAS resin material having strong adhesiveness to the epoxy resin and good moldability can be obtained. The present inventors have found that a composite molded article firmly adhered to an epoxy resin can be obtained by a simple method, and have completed the present invention.

That is, the present invention relates to (A) 100 parts by weight of a polyarylene sulfide resin, (B) an α-olefin and α, β-
1 to 60 parts by weight of an α-olefin copolymer mainly containing an alkyl ester of an unsaturated acid, (C) 5 to 115 parts by weight of a fibrous filler, and (D) 1 to 15 parts by weight of an epoxy resin. A resin composition having improved adhesion with an epoxy resin,
The present invention also relates to a composite molded article obtained by joining a molded article molded with such a composition and an epoxy resin body.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The PAS resin as the component (A) in the epoxy adhesive composition of the present invention has a main repeating unit composed of-(-Ar-S-)-(where Ar is an arylene group). Examples of the arylene group (—Ar—) include a p-phenylene group, m
- phenylene, o- phenylene group, substituted phenylene group (wherein the substituent is an alkyl group, preferably an alkyl group of C ₁ -C _5, or a phenyl group), p, p'-di polyphenylene sulfone groups, p, p ' -A biphenylene group, a p, p'-diphenylene ether group, a p, p'-diphenylenecarbonyl group, a naphthalene group and the like can be used. In this case, in the arylene sulfide group composed of the above-mentioned arylene group, a polymer using the same repeating unit, that is, a homopolymer can be used, and from the viewpoint of processability of the composition, a heterogeneous repeating unit is used. In some cases are preferred.

As the homopolymer, those having a p-phenylene sulfide group as a repeating unit using a p-phenylene group as an arylene group are particularly preferably used. Further, as the copolymer, among the arylene sulfide groups composed of the above-mentioned arylene groups, two or more different combinations can be used. Particularly preferably used. Among them, those containing a p-phenylene sulfide group in an amount of 70 mol% or more, more preferably 80 mol% or more are suitable from the viewpoint of physical properties such as heat resistance, moldability, and mechanical properties. Among these PAS 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 a PAS resin having a structure, a polymer having a partially branched or cross-linked structure formed by using a small amount of a monomer such as a polyhalo aromatic compound having three or more halogen substituents at the time of condensation polymerization can be used. A polymer having a low molecular weight linear structure polymer heated 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 the moldability can also be used.

[0008] The PAS resin of the component (A) is a linear resin.
PAS (310 ° C, shear speed 1200 sec ^-1Viscosity at 10
~ 300 Pa · s), and part of it (1-30% by weight,
Preferably 2 to 25% by weight) but relatively high viscosity (300 to 30%).
00 Pa · s, preferably 500 to 2000 Pa · s)
Mixtures with bridge PAS resins are also suitable. Also used in the present invention
Some PAS resins are polymerized, washed with acid, washed with hot water, organic solvent
Wash (or a combination of these) to remove by-product impurities, etc.
It is preferable to remove and purify it.

Next, the α-olefin copolymer used as the component (B) in the present invention is mainly composed of an α-olefin and an alkyl ester of an α, β-unsaturated acid. Examples of the α-olefin, which is one of the components, include ethylene, propylene, and butylene, and ethylene is preferable. Further, as the alkyl ester of α-olefin and α, β-unsaturated acid, which are other components constituting the copolymer, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate,
Examples thereof include butyl acrylate and butyl methacrylate, and ethyl acrylate is particularly preferable. Further, acrylic acid, methyl acrylate, and the like are added to the alkyl ester of the α-olefin and the α, β-unsaturated acid.
Either ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, acrylonitrile, styrene or the like is a graft copolymer obtained by chemically bonding in a branched or cross-linked structure. I don't care.

As the α-olefin copolymer as the component (B), ethylene-ethylene copolymer is particularly preferred because it exhibits not only an effect of improving the adhesiveness but also a particularly excellent effect on the mold releasability during molding.
Ethyl acrylate is particularly preferred.

The α-olefin copolymer (B) has a melt flow rate at 190 ° C. of 5 g / 10 min.
It is appropriate that the amount is at least 10 g / 10 min.
That is all. If the melt flow rate is less than 5 g / 10 min, the effect of improving the adhesion to the epoxy resin will be reduced.

The amount of the α-olefin copolymer (B) to be added is 1 to 60 parts by weight based on 100 parts by weight of the (A) PAS resin.

Next, the fibrous filler (C) constituting the composition of the present invention is effective for lowering the molding shrinkage and the coefficient of linear expansion of the molded article and improving the mechanical properties. Is a metal such as 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, copper, brass, etc. A fibrous substance is mentioned, and glass fiber is particularly preferably used.

In using these fibrous fillers, it is desirable to use a sizing agent or a surface treatment agent if necessary. This example is a functional compound such as an epoxy compound, an isocyanate compound, a silane compound and a titanate compound. These compounds may be used after being subjected to a surface treatment or a convergence treatment in advance, or may be added simultaneously with the preparation of the material.

The amount of the fibrous filler (C) is PAS resin
(A) 5 to 115 parts by weight per 100 parts by weight is suitable. If the amount is too small, the mechanical strength of the molded article decreases.If the amount is too large, the moldability deteriorates, and distortion, deformation, etc. occur, which may cause a problem in the adhesiveness to the epoxy resin, which is not preferable. .

Next, in the present invention, it is necessary to mix an epoxy resin as the component (D). Examples of such epoxy resins include those containing two or more epoxy groups, for example, bisphenol A, catechol, resorcinol, hydroquinone, bisphenol F, bisphenol S,
Glycidyl ethers such as 1,3,5-trihydroxybenzene, 4,4-dihydroxybenzene, diglycidyl ether of bisphenol such as 1,5-dihydroxynaphthalene, halogenated bisphenol and diglycidyl ether of butanediol, novolak epoxy, etc. Glycidyl ethers, glycidyl esters such as glycidyl phthalate, glycidyl epoxy resins such as glycidylamines such as N-glycidylaniline, epoxidized polyolefins, linear systems such as epoxidized soybean oil and vinylcyclohexenedi. A cyclic non-glycidyl epoxy resin such as an oxide is exemplified, and a particularly preferable one is a bisphenol A type epoxy resin.
The epoxy equivalent of the epoxy resin (D) is suitably 5000 or less. When the epoxy equivalent exceeds 5,000, the effect of improving the adhesiveness with the epoxy resin is reduced.

The amount of component (D) added is (A) PAS resin 100
The amount is suitably 1 to 15 parts by weight, preferably 3 to 10 parts by weight based on parts by weight. If the amount is too large, the mechanical properties of the material may be reduced.

The composition of the present invention may further contain other powdery or plate-like fillers as long as the effects of the present invention are not impaired. For example, as a granular filler, carbon black, graphite, silica, quartz powder, glass beads,
Glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, silicates such as wollastonite, oxides of metals such as iron oxide, titanium oxide and alumina, carbonates of metals such as calcium carbonate and magnesium carbonate And metal sulfates such as calcium sulfate, barium sulfate, silicon carbide, silicon nitride, and various metal powders. Particularly typical ones are carbon black, silica, glass beads or glass powder, calcium carbonate, talc and the like. Examples of the plate-like filler include mica, glass flake, various metal foils, and the like. These fillers can be used alone or in combination of two or more. or,
When using these fillers, if necessary, treatment with a sizing agent or a surface treatment agent can be performed as described above.

Further, the composition of the present invention may contain a silane compound in an amount of 0.05 to 3 parts by weight per 100 parts by weight of the PAS resin (A) for the purpose of improving burrs and the like as long as the effects of the present invention are not impaired.
It can be added in an amount of about parts by weight. 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, Examples include, but are not limited to, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, and the like.

The composition of the present invention contains known substances which are generally added to a thermoplastic resin according to the purpose, that is, an antioxidant, a heat stabilizer, a lubricant, a crystal nucleating agent, an ultraviolet absorber,
A coloring agent, a release agent, a flame retardant, and the like can be appropriately added. The composition of the present invention may additionally contain other thermoplastic resins or organic fillers for the purpose of improving and supplementing its properties. As the thermoplastic resin blended for this purpose, polyethylene, polypropylene or a polyolefin-based polymer or copolymer mainly containing a polyolefin such as a modified polymer thereof, nylon 6, nylon 66, other polyamide-based polymers or Polyester polymers or copolymers mainly composed of copolymers, polyethylene terephthalate, polybutylene terephthalate, etc., liquid crystalline polyester polymers, styrene polymers such as polystyrene, polystyrene acrylonitrile, ABS, etc., and acrylics such as polyalkyl acrylate Examples include polymers, polycarbonate, polyphenylene oxide, polyacetal, polysulfone, polyethersulfone, polyetherimide, polyetherketone, and the like. These thermoplastic resins can be used as a mixture of two or more kinds. Examples of the organic filler include a high melting point fibrous or granular polymer such as an aromatic polyamide.

The resin composition of the present invention can be prepared by equipment and a method generally used for preparing a synthetic resin composition. Generally, necessary components are mixed, and one or two
It can be melt-kneaded using a shaft extruder and extruded to form molding pellets. The resin temperature during the melt-kneading is preferably 360 ° C. or lower to prevent the (B) α-olefin copolymer from being thermally degraded. It is also a preferable method to melt-extrude a resin component and add and mix an inorganic component such as glass fiber during the extrusion.

The material pellets thus obtained can be molded by a generally known thermoplastic resin molding method such as injection molding, extrusion molding, vacuum molding, compression molding, etc., but the most preferable is the injection molding. It is a molding method.

The composite molded article supporting or embedding the epoxy resin of the present invention is, for example, a substrate or a container molded with the PAS composition of the present invention, and a functional part to be supported is set thereon.
A thermosetting epoxy resin as described below is injected and cured, and the functional parts and the like are sealed with the epoxy resin.
It is prepared by adhesively fixing the AS composition molded article. In addition, functional parts, etc. are sealed in advance with epoxy resin, and the cured epoxy resin body is set in a mold, insert-molded by injection molding, and the exterior support is molded with the PAS resin composition to form a composite molded part. May be.

The molded product of the PAS resin composition of the present invention has a practically sufficient adhesiveness with an epoxy resin without special surface treatments such as mechanical surface roughening, physical treatment such as plasma treatment, and chemical etching. However, if strong adhesiveness is particularly required, such a surface treatment may be used in combination, and a further effect can be obtained.

The epoxy resin to be bonded to the molded PAS resin composition of the present invention is not particularly limited, and is a curable epoxy resin which is usually used as a sealant or adhesive for functional parts, a paint, and the like. In general, an organic compound having an epoxy group obtained by a reaction between an active hydrogen compound such as bisphenol A and epichlorohydrin, or an oxidation of a double bond compound or the like can be carried out in the presence of a curing agent or a catalyst. Is a substance that reacts and cures when left or heated at room temperature at room temperature, and can be of various viscosities depending on the purpose. Further, the PAS resin composition molded article of the present invention has an effect on the adhesiveness even when coated with an epoxy or paint as in the upper part.

[0026]

As described in the above description and Examples, the molded article made of the PAS resin composition of the present invention is excellent not only in adhesiveness and adhesion to an epoxy resin, but also has a high adhesive strength and a low temperature. It has excellent peel resistance against thermal shock due to repeated high temperatures, and has excellent mechanical properties, heat resistance, flame retardancy, chemical resistance, and excellent mold release properties during molding. Further, the composite molded article bonded to the epoxy resin has a performance capable of withstanding severe conditions, and is suitable as a support for a substrate or a container or the like that supports or houses the epoxy resin that encapsulates the functional component used under such conditions. Yes,
Excellent as a coated product with epoxy resin paint.

[0027]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. Examples 1 to 4 (A) For polyphenylene sulfide resin, (B)
(D) The components were added in the amounts shown in Table 1 and mixed for 5 minutes with a Henschel mixer.
It was fed to a screw extruder. (C) The fibrous filler is added separately from the side feed section of the extruder, and the resin temperature is increased in the twin-screw extruder.
The mixture was melt-kneaded at 350 ° C. to form pellets of the polyphenylene sulfide resin composition.

Next, various test pieces were molded from the pellets by an injection molding machine at a cylinder temperature of 320 ° C. and a mold temperature of 150 ° C., and the following various tests were performed. Comparative Examples 1 to 6 For comparison, as shown in Table 1, when one or both of the components (B) and (D) were not blended, when the blending amount of the component (D) was out of the range of the present invention, (B In the case where a copolymer not falling under the present invention was used as a component, pellets were prepared in the same manner as in the above Examples, and the results of similar tests were also shown in Table 1. Tensile test: Tensile strength was measured according to ASTM D-638. Adhesive strength to epoxy resin: The above-mentioned ASTM test piece was cut at almost the center, washed with acetone, and then subjected to an epoxy resin-based adhesive (XN1244, manufactured by Ciba Geigy K.K.
mm × 6.5 mm), and cured at 120 ° C. for 1 hour. After standing at 23 ° C. for 1 day, a peeling test was performed in a direction perpendicular to the bonded surface to measure the adhesive strength. . Mold release resistance; cylinder temperature 320 using an injection molding machine
When the injection molding is performed using the mold for measuring the release resistance to obtain the molded article shown in FIG. 1 under the condition of 150 ° C. and the mold temperature of 150 ° C., the molded article is released from the mold. The pressure was measured to obtain a mold release resistance value.

(A) to (D) used in Examples and Comparative Examples
Are as follows. (A) Polyphenylene sulfide (PPS) resin; manufactured by Kureha Chemical Industry Co., Ltd., FORTRON KPS (melt viscosity at 310 ° C., shear rate 1200 sec ⁻¹ 140 Pa · s) (B) α-olefin copolymer B -1; ethylene-ethyl acrylate copolymer (melt flow rate = 20 g / 10 min) B-2; ethylene-ethyl acrylate copolymer (melt flow rate = 250 g / 10 min) B-3; ethylene-ethyl acrylate copolymer B-4: ethylene-ethyl acrylate copolymer grafted with methyl methacrylate polymer (melt flow rate = 10 g / 10 min) B-5; ethylene-glycidyl A copolymer obtained by grafting a methyl methacrylate polymer onto a methacrylate copolymer (melt flow rate = 10 g / 10 min). It was determined by ASTM D-1238. (C) Fibrous filler glass fiber; 13 μm φ chopped strand (fiber length 3 mm) (D) Epoxy resin D-1; bisphenol A type epoxy resin (epoxy equivalent = 800 to 1000) D-2; bisphenol A type epoxy Resin (epoxy equivalent = 1700-2200)

[0030]

[Table 1]

[Brief description of the drawings]

FIG. 1 is a view showing a shape of a molded product used for evaluation of a mold release resistance used in Examples, (a) is a top view, and (b) is a front view.

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08L 63:00) C08L 63:00) Z B29K 81:00 B29K 81:00 F term (reference) 4F211 AA03E AA20E AA34 AB11 AG03 TA03 TC01 TC08 TC20 TD07 TD11 TN46 4J002 BB002 BB072 BB253 CD003 CD013 CD023 CD053 CD063 CD123 CD133 CD163 CN011 DA016 DA076 DA096 DA116 DC006 DE096 DE146 DE186 DJ016 DJ026 DK006 DL006 FA046 FD016 GF00

Claims (5)

[Claims] (A) Polyarylene sulfide resin 100
Parts by weight, (B) 1 to 60 parts by weight of an α-olefin copolymer mainly containing an alkyl ester of an α-olefin and an α, β-unsaturated acid, (C) 5 to 115 parts by weight of a fibrous filler, (D) A polyarylene sulfide resin composition having improved adhesion to an epoxy resin, which is obtained by mixing 1 to 15 parts by weight of an epoxy resin. 2. The epoxy equivalent of the epoxy resin (D) is 5,000.
The polyarylene sulfide resin composition according to claim 1, which is: 3. The polyarylene sulfide resin composition according to claim 1, wherein the melt flow rate of the (B) α-olefin copolymer at 190 ° C. is 5 g / 10 min or more. 4. The polyarylene sulfide resin composition according to claim 1, wherein the fibrous filler (C) is glass fiber. 5. A composite molded article obtained by joining a molded article obtained by molding the polyarylene sulfide resin composition according to claim 1 with an epoxy resin body.