JPH11228828A - Polyphenylene sulfide resin composition - Google Patents

Abstract

(57) [Problem] To provide a polyphenylene sulfide resin composition which has both excellent adhesion to an epoxy resin and resistance to thermal cycling, and is useful for applications such as electrical components and sealing components. . SOLUTION: (A) Polyphenylene sulfide resin 1
(B) Copolymerized polyester having ethylene terephthalate unit and cyclohexane dimethylene terephthalate unit as main constituent units and having a content of cyclohexane dimethylene terephthalate unit of 20 to 85 mol% with respect to 00 parts by weight. 0.5% polyester
A polyphenylene resin composition comprising (C) 0.5 to 40 parts by weight of (C) an olefin copolymer comprising an α-olefin and an α, β-unsaturated carboxylic acid alkyl ester.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to cracks due to a difference in linear expansion from a metal that is required to have an adhesive property with an epoxy resin, such as an electrical component such as an ignition coil, and is insert-molded during a thermal cycling process. TECHNICAL FIELD The present invention relates to a polyphenylene sulfide resin composition useful for applications in which the generation of heat is difficult to occur (hereinafter referred to as thermal cycling resistance), and a molded article using the same.

[0002]

2. Description of the Related Art Polyphenylene sulfide resin (hereinafter referred to as P
PS resin) is suitable for engineering plastics, such as excellent heat resistance, flame retardancy, rigidity, and electrical insulation. Therefore, various electric parts, machine parts, and automobiles are mainly used for injection molding. Used for parts and other applications.

However, the PPS resin has a relatively low adhesive strength with other resins, particularly with an epoxy resin.
For this reason, for example, when encapsulating an electric / electronic component with an epoxy resin, low adhesion strength between the PPS resin and the epoxy resin often poses a problem, which is one of the factors that hinders an increase in demand for the PPS resin.

[0004] Under such circumstances, several studies have been made so far for the purpose of improving the adhesion between the PPS resin and the epoxy resin. For example, a method of blending a specific polyester with a PPS resin (JP-A-6-166816) is known.

[0005] On the other hand, although the purpose is different, as a composition comprising a PPS resin, a polyester resin and an olefin-based copolymer, JP-A-5-202271 discloses PPS resin, various thermoplastic resins including polyester, and glycidyl group-containing resin. A composition comprising a thermoplastic polymer is disclosed.

[0006]

However, the method described in JP-A-6-166816 has a problem in that when applied to metal insert parts, the thermal cycling resistance is reduced.

In addition, the addition and blending of an olefin copolymer is also described in the details, but no specific example is disclosed. No mention is made of any specific improvement in cyclability and adhesiveness with an epoxy resin.

On the other hand, JP-A-5-202271 describes polyethylene terephthalate and polycyclohexane dimethylene terephthalate. However, copolymer polyesters containing both ethylene terephthalate units and cyclohexane dimethylene terephthalate units as constituent units are disclosed. Is not disclosed.

The glycidyl group-containing thermoplastic polymer is characterized in that it contains a glycidyl group. Examples of the thermoplastic polymer containing an α, β-unsaturated carboxylic acid alkyl ester used in the present invention are listed below. Not been.

The effect is also an improvement in mechanical strength, and is excellent in adhesiveness to epoxy resin and cold heat resistance obtained by adding and blending the specific polyester and the specific olefin copolymer used in the present invention. No mention is made of the cyclability.

Accordingly, an object of the present invention is to obtain a PPS resin composition which has both excellent resistance to thermal cycling and adhesiveness to an epoxy resin.

[0012]

That is, the present invention provides: (B) A copolymerized polyester having (B) an ethylene terephthalate unit and a cyclohexane dimethylene terephthalate unit as main constituent units, and a cyclohexane dimethylene terephthalate unit content of 20 to 8 with respect to 100 parts by weight of a polyphenylene sulfide resin.
0.5 to 40 parts by weight of 5 mol% of a copolyester, and 0.5 to 40 parts by weight of (C) an olefin-based copolymer comprising an α-olefin and an α, β-unsaturated carboxylic acid or / and an alkyl ester thereof. A polyphenylene resin composition obtained by adding and blending 40 parts by weight.

2. (B) The polyphenylene sulfide resin composition according to the above 1, wherein the copolymerized polyester is a copolymerized polyester containing 25 to 50 mol% of cyclohexane dimethylene terephthalate units. (C) The above-mentioned (1) or (2), wherein the olefin-based copolymer is an olefin-based copolymer comprising an α-olefin and an alkyl acrylate, and the content of the alkyl acrylate is 5 to 50% by weight. 3. a polyphenylene sulfide resin composition, 4. The polyphenylene sulfide resin composition according to any one of the above 1 to 3, further comprising (D) a filler in an amount of 5 to 200 parts by weight based on 100 parts by weight of the polyphenylene sulfide resin. 5. A molded article obtained by combining the polyphenylene sulfide resin composition according to any one of the above items 1 to 4 with another material; A composite, wherein the molded article is a molded article comprising the polyphenylene sulfide resin composition according to any one of claims 1 to 4 or a composite molded article according to claim 5, and which has an adhesive surface with an epoxy resin. Molding.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) PPS resin of the present invention is a polymer having a repeating unit represented by the structural formula (1),

Embedded image 70 mol% of the repeating unit represented by the above structural formula (1)
From the viewpoint of heat resistance, a polymer containing 90 mol% or more is particularly preferable. Further, the PPS resin can constitute less than 30 mol% of the repeating unit with a repeating unit having the following structure.

[0015]

Embedded image The melt viscosity of the (A) PPS resin used in the present invention is not particularly limited as long as melt kneading is possible, but is usually 5 to 2
000 Pa · s (320 ° C, shear rate 1000 sec ^-1 )
Is used, and a range of 10 to 300 Pa · s is more preferable.

As for the production method, it can be produced by a generally known method, that is, the method described in JP-B-45-3368 or the method described in JP-B-52-12240. In the present invention, the PPS resin obtained as described above is cross-linked / high molecular weight by heating in air, heat treatment under an atmosphere of an inert gas such as nitrogen or under reduced pressure, washing with an organic solvent, hot water, an acid aqueous solution or the like. It can be used after being subjected to various treatments such as activation with a compound containing a functional group such as an acid anhydride group, an epoxy group or an isocyanate group.

The component (B) copolymerized polyester of the present invention is obtained by converting cis- or trans-isomers of ethylene glycol and 1,4-cyclohexanedimethanol (or a mixture thereof) into terephthalic acid (or an ester-forming derivative thereof). )). The content of the cyclohexane dimethylene terephthalate unit in the copolymerized polyester is from 20 to 85.
Mol%, and more preferably 25-50 mol%.
Is more preferable. When the content of cyclohexane dimethylene terephthalate unit in the copolymerized polyester is 2
Even if less than 0 mol% or more than 85 mol% of copolyester, poly (ethylene terephthalate) homopolymer, or poly (cyclohexane dimethylene terephthalate) homopolymer is added to the PPS resin, a sufficient adhesion improving effect cannot be obtained. .

The copolyester (B) used in the present invention is a copolyester having an ethylene terephthalate unit and a cyclohexane dimethylene terephthalate unit as main constitutional units. However, as long as the effects of the present invention are not impaired, isophthalic acid is used. , Orthophthalic acid, naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid,
Diphenyl ether dicarboxylic acid, α, β-bis (4-
(Carboxyphenoxy) ethane, adipic acid, sebacic acid, azelaic acid, decanedicarbonic acid, dodecanedicarboxylic acid, dicarboxylic acid such as cyclohexanedicarboxylic acid, dimer acid, or propylene glycol, butanediol, pentanediol, neopentylglycol, hexane Diol, octanediol, decanediol, hydroquinone, bisphenol A, 2,2-
Bis (4-hydroxyethoxyphenyl) propane, xylene glycol, polyethylene ether glycol,
Glycols such as polytetramethylene ether glycol, and lactones such as glycolic acid, hydroxyacetic acid, hydroxybenzoic acid, hydroxyphenylbenzoic acid, hydroxycarboxylic acid such as aphthyl glycolic acid, propiolactone, caprolactone, butyrolactone, and valerolactone , Trimethylolpropane, trimethylolethane, glycerin, pentaerythritol,
Trimellitic acid, trimesic acid, polyfunctional components such as pyromellitic acid, dibromoterephthalic acid, tetrabromoterephthalic acid, dichloroterephthalic acid, tetrachloroterephthalic acid, 1,4-dimethyloltetrabromobenzene, tetrabromobisphenol A, etc. A small amount of a halogen-containing ester-forming component or the like may be contained.

Although the molecular weight of the (B) copolymerized polyester is not particularly limited, it is usually in a 60/40 mixed solvent of phenol / tetrachloroethane or a similar solvent.
The intrinsic viscosity measured at 25 to 30 ° C. is 0.
Those having a range of 4 to 2.0 dl / g are used.
Those having a range of 6 to 1.2 dl / g are preferably used.

As the (B) copolymerized polyester used in the present invention, for example, a copolymerized polyester known as poly (cyclohexane dimethylene terephthalate) is available from Toray Industries, Inc. from EASTER GN002, EASTA.
It is commercially available under the trade name R DN003, and these can be used.

The compounding amount of the copolyester (B) used in the present invention is in the range of 0.5 to 40 parts by weight, preferably 1.0 to 40 parts by weight, based on 100 parts by weight of the PPS resin.
The range is 30 parts by weight. If the amount of the (B) copolymerized polyester is less than 0.5 part by weight, the effect of improving the adhesion to the epoxy resin is insufficient, which is not preferable. Conversely, the amount of the (B) copolymerized polyester is 40 parts by weight. Exceeding the part is not preferred because the properties of the PPS resin composition such as mechanical strength and heat resistance are reduced.

The component (C) olefin copolymer of the present invention is a random and / or block copolymer comprising an α-olefin and an α, β-unsaturated carboxylic acid and / or an alkyl ester thereof. Here, specific examples of the α-olefin include ethylene, propylene, butene-1, pentene-1, 4-methylpentene-1, isobutylene, hexene-1, decene-1, octene-1,
Examples thereof include 1,4-hexadiene and dicyclopentadiene, and ethylene, propylene and butene-1 are preferably used. These α-olefins may be used alone or in combination of two or more.

The α, β-unsaturated carboxylic acid and its alkyl ester are, for example, acrylic acid, methacrylic acid and the like and their alkyl esters, and specific examples are acrylic acid, methacrylic acid, methyl acrylate, acrylic acid Ethyl, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-methacrylate Examples thereof include butyl, t-butyl methacrylate, and isobutyl methacrylate. Methyl acrylate, ethyl acrylate, and n-propyl acrylate are preferably used. These α, β-unsaturated carboxylic acid alkyl esters may be used alone or in combination of two or more.

In the olefin copolymer (C) used in the present invention, a glycidyl ester of an α, β-unsaturated acid or an unsaturated acid or an acid anhydride thereof can be further copolymerized as a third component. . Preferred specific examples include glycidyl methacrylate and maleic anhydride.

The content of the α, β-unsaturated carboxylic acid alkyl ester in the olefin copolymer (C) used in the present invention is not limited, but is preferably in the range of 5 to 50% by weight. Preferably, it is in the range of 15 to 40% by weight. (C) When the content of the α, β-unsaturated carboxylic acid alkyl ester in the olefin-based copolymer is less than 5% by weight, the effect of improving the cooling / heat cycling resistance and the adhesion to the epoxy resin is insufficient, which is preferred On the contrary, if it exceeds 50% by weight, the thermal decomposition during melt-kneading becomes severe, which is not preferable.

The olefin copolymer (C) used in the present invention can be used alone or in combination of two or more.
In particular, it is preferable from the viewpoint of fluidity to use the olefin copolymer containing no third component and the olefin copolymer containing the third component in a ratio of 1: 4 to 4: 1 by weight.

The addition amount of the olefin copolymer (C) used in the present invention is in the range of 0.5 to 40 parts by weight, preferably 1.0 to 40 parts by weight, per 100 parts by weight of the PPS resin.
The range is 30 parts by weight. If the addition amount of the (C) olefin copolymer is less than 0.5 parts by weight, the effect of improving the thermal cycling resistance and the adhesion to the epoxy resin is insufficient, which is not preferable. If the addition amount of the system copolymer exceeds 40 parts by weight, the properties of the PPS composition, such as mechanical strength and heat resistance, are undesirably reduced. These (C) olefin copolymers may be used alone or in combination of two or more.

Further, in the present invention, it is possible to further blend (D) a filler, and as the (D) filler, glass fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, alumina fiber, Fibrous filler such as silicon carbide fiber, ceramic fiber, asbestos fiber, stone fiber, metal fiber, etc., silicates such as wollastenite, zeolite, sericite, kaolin, mica, clay, bentonite, asbestos, talc, alumina silicate, etc. Metal compounds such as alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide and iron oxide; carbonates such as calcium carbonate, magnesium carbonate and dolomite; sulfates such as calcium sulfate and barium sulfate; glass flakes; glass beads; Ceramic beads, boron nitride, silicon carbide And non-fibrous fillers are mentioned, such as silica, they may be hollow, it is also possible to further combination of these fillers 2 or more. It is more preferable to use these fibrous and / or non-fibrous fillers after pre-treating them with a silane-based or titanate-based coupling agent from the viewpoint of mechanical strength and the like.

The amount of the filler (D) used in the present invention is not particularly limited, but is preferably 5 to 200 parts by weight based on 100 parts by weight of the PPS resin in view of the balance between fluidity and mechanical strength. Preferably, more preferably, 10 to 100
It is in the range of parts by weight.

The PPS resin composition of the present invention contains 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane for the purpose of improving mechanical strength and moldability such as burrs, etc., within a range not to impair the effects of the present invention. Epoxy group-containing alkoxysilanes such as glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Compound, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3
-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N-phenylaminomethyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, dimethoxymethyl-3-piperazino Amino group-containing alkoxysilane compounds such as propylsilane and 3-piperazinopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) aminopropyltrimethoxy Ureido group-containing alkoxysilane compounds such as silane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanate DOO propyl methyl diethoxy silane, isocyanate group-containing alkoxysilane compounds such as 3-isocyanatopropyl ethyl dimethoxy silane, 3
-An organic silane compound such as a mercapto group-containing alkoxysilane compound such as mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane and 3-mercaptomethyldimethoxysilane can be added and blended.

The PPS resin composition of the present invention contains a releasing agent, an antioxidant, a heat stabilizer, a lubricant, a crystal nucleating agent, an ultraviolet absorber, a coloring agent, a flame retardant, etc. as long as the effects of the present invention are not impaired. The usual additives and small amounts of other polymers can be added. For example, as the release agent, polyethylene,
Examples thereof include polyolefins such as polypropylene, montanic acid waxes, metal soaps such as lithium stearate and aluminum stearate, and polycondensates of ethylenediamine / stearic acid / sebacic acid. As a nucleating agent, polyether ether ketone resin,
Talc and the like can be mentioned.

The method for producing the PPS resin composition of the present invention is not particularly limited, but the mixture of the raw materials is supplied to a generally known melt mixer such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader and a mixing roll. 280
A typical example is a method of melting and kneading at a temperature of 380 ° C. The order of mixing the raw materials is not particularly limited. In addition, as for the small amount additive component, other components can be added before kneading after kneading and pelletizing other components by the above-described method or the like.

The resin composition of the present invention is generally molded by a known thermoplastic resin molding method such as injection molding, extrusion molding, blow molding, transfer molding, and vacuum molding. In particular, injection molding is preferred.

With the above constitution, the PPS resin composition of the present invention has improved cooling / heat cycle resistance and adhesion to the epoxy resin.

The term "cooling / heat cycling resistance" in the present invention means that in a composite molded article combined with another member, a stress is generated with a temperature change due to a difference in linear expansion between the PPS resin and the other member. The durability until cracks occur in the PPS resin composition due to this stress. Here, the material of the other members is not particularly limited, but is an inorganic material such as a metal, a ceramic, or a mineral, and / or an organic material such as a resin. Specific examples of the member include a metal terminal, an iron core, a bolt, a nut, and the like. Gears, bosses, bearings, and the like.

There is no particular limitation on the method of combination with other members, and insert molding, outsert molding,
Examples include press-fitting, thermal caulking, and vibration caulking, and are particularly useful for insert molding and press-fitting combined molded products (composite molded products).

The PPS resin composition of the present invention is excellent in adhesiveness to an epoxy resin, but such an epoxy resin is not particularly limited. For example, bisphenol A, bisphenol F, bisphenol S, bisphenol AF, bisphenol AD, 4,4′-dihydroxybiphenyl, resorcin, saligenin, trihydroxydiphenyldimethylmethane, tetraphenylolethane, halogen-substituted and alkyl-substituted thereof, butanediol, ethylene glycol, erythrit, novolak,
Glycidyl ethers synthesized from compounds containing two or more hydroxyl groups in the molecule such as glycerin and polyoxyalkylene and epichlorohydrin, glycidyl esters such as glycidyl phthalate, aniline, diaminodiphenylmethane, metaxylenediamine, 1 Glycidylamine resins synthesized from primary or secondary amines such as 1,3-bisaminimethylcyclohexane and epichlorohydrin, etc., glycidyl epoxy resins, epoxidized soybean oil, epoxidized polyolefin, vinylcyclohexenedionoxide, Non-glycidyl epoxy resins such as cyclopentadiene oxide and the like. These epoxy resins are used alone or as a mixture of two or more. These epoxy resins are generally used after being cured by a curing agent. Examples of curing agents include amines, polyamides, amino resins, acid anhydrides, polyhydric phenols, phenolic resins, polysulfides,
And isocyanates.

The PPS resin composition of the present invention is excellent in adhesiveness to an epoxy resin as described above, and therefore is suitable for a composite molded article having an epoxy resin adhesive surface with the epoxy resin. Specifically, a composite molded article sealed with an epoxy resin, or a composite molded article obtained by bonding a molded article molded from the same material or a different material to a molded article molded with the PPS resin composition of the present invention with an epoxy resin Goods. The molded article made of the PPS resin composition to be bonded to the epoxy resin may be the above-mentioned combined molded article.

The PPS resin composition obtained by the present invention is a resin composition having excellent resistance to heat and heat cycling and also having high adhesiveness to an epoxy resin.・ Useful for office electrical product parts, machine related parts, optical equipment / precision machine related parts, automobile / vehicle related parts, and various other uses. Among them, it is particularly suitable for applications requiring cold / heat cycling resistance and adhesion to epoxy resin, and specifically includes electrical components such as ignition coils and sensors, insulators, and sealing components such as IC cases. .

[0040]

The present invention will be described in more detail with reference to the following examples. The epoxy adhesive strength, cold cycle resistance and impact strength described in the examples and comparative examples were evaluated and measured according to the following methods.

(1) Measurement of Epoxy Adhesive Strength An ASTM No. 1 dumbbell piece molded under the conditions of a cylinder temperature of 320 ° C. and a mold temperature of 130 ° C. is divided into two equal parts, and a spacer (thickness: 50 mm ²⁾ is used so that the adhesive area becomes 50 mm ² 1.8 to 2.2
mm) and an epoxy resin (manufactured by Nagase Ciba Co., Ltd., two-component epoxy resin, XNR5002, XNH5002). This is cured and the strain rate is 1 mm / mi
n, the tensile strength was measured under the condition of a distance between supporting points of 80 mm, and the value obtained by dividing the maximum value of the strength by the bonding area was used as the epoxy bonding strength.

(2) Evaluation of Cooling / Heat Cycle Resistance The metal insert test piece shown in FIG. 1 in which a metal block was insert-molded under the conditions of a cylinder temperature of 320 ° C. and a mold temperature of 130 ° C. was used. This was treated at 130 ° C. × 1 hr, and then treated at −40 ° C. × 1 hr as one cycle, and subjected to a cooling / heating cycle treatment, and the occurrence of cracks was visually checked every 10 cycles. The number of thermal cycle treatments in which cracks were observed was defined as the thermal cycle resistance.

FIG. 1A is a top view of a metal insert test piece, and FIG. 1B is a side view thereof.

A 47 × 47 × 27 mm insert metal is covered with a resin by injection molding (insert molding). The obtained test piece is a rectangular parallelepiped of 50 × 50 × 30 mm, and the mold thickness is 1.5 ± 0.5 mm.

(3) Measurement of Impact Strength ASTM-D256 Reference Example 1 (Method of synthesizing PPS resin) A 30% aqueous sodium hydrosulfide solution 4.6 was placed in an autoclave.
7 kg (25 mol of sodium hydrosulfide), 2.00 kg of 50% sodium hydroxide (25 mol of sodium hydroxide) and 8 kg of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) are charged and gradually heated to 205 ° C. while stirring. The temperature was raised, and 4.1 l of distillate containing 3.8 kg of water was removed. 3.75 k of 1,4-dichlorobenzene was added to the residual mixture.
g (25.5 mol) and 2 kg of NMP to add
Heat at 0 ° C. for 1 hour and further at 260 ° C. for 2 hours. The reaction product was washed 5 times with warm water and dried under reduced pressure at 80 ° C. for 24 hours to obtain a powdered PPS resin having a weight average molecular weight of 35,000. The PPS resin was used in Examples and Comparative Examples.

Reference Example 2 (Method for synthesizing copolymerized polyester) A-1: 48.9 parts by weight of terephthalic acid, 25.6 parts by weight of ethylene glycol and 25.5 parts by weight of 1,4-cyclohexanedimethanol (molar ratio: 1) /1.4/0.6)
Then, 0.01 parts by weight of tetra-n-butyl titanate was added, and a normal pressure reaction was performed at a temperature of 180 to 220 ° C. for 3 hours under a nitrogen atmosphere. Subsequently, the temperature of the reaction system was gradually shifted to reduced pressure, and simultaneously, the temperature was increased to 250 ° C, and the pressure was reduced to 0.1 mm.
The reaction was performed at Hg and a temperature of 250 ° C. for 1.5 hours. The intrinsic viscosity of the obtained copolymerized polyester was 1.0 dl / g, and the molar ratio of ethylene terephthalate residue / cyclohexane dimethylene terephthalate residue was 7/3.

A-2: 41.0 parts by weight of terephthalic acid, 9.2 parts by weight of ethylene glycol and 49.8 parts by weight of 1,4-cyclohexanedimethanol (molar ratio 1 / 0.6)
/1.4) versus tetra-n-butyl titanate 0.1.
After adding 01 parts by weight, a normal pressure reaction was performed at a temperature of 180 to 220 ° C. for 3 hours under a nitrogen atmosphere. Subsequently, the reaction system was gradually shifted to a reduced pressure, and at the same time, the temperature was raised to 250 ° C., and the reaction was performed at a pressure of 0.1 mmHg and a temperature of 250 ° C. for 1.5 hours. The intrinsic viscosity of the obtained copolyester is 0.9 d.
l / g, the molar ratio of ethylene terephthalate residue / cyclohexane dimethylene terephthalate residue was 3/7.

Examples 1 and 2 PPS resin, copolyester (A-1), olefin copolymer (ethylene / ethyl acrylate = 65 /
35% by weight copolymer and ethylene / methyl acrylate /
(Glycidyl methacrylate = 64/30/6 wt% copolymer blend) and glass fibers were dry-blended at the ratios shown in Table 1, and then melt-kneaded with a screw-type extruder set at a temperature of 320 ° C and pelletized. Using the obtained pellets, cylinder temperature 320 ° C., mold temperature 130
The above-mentioned ASTM No. 1 dumbbell pieces, metal insert test pieces, and test pieces for measuring impact strength were molded under the conditions of ° C.

Table 1 shows the epoxy bond strength, the thermal cycling resistance and the impact strength measured for the obtained test pieces.

Comparative Example 1 Dry blending, melt kneading, pelletizing, molding, and evaluation of physical properties were performed at the ratios shown in Table 2 in the same manner as in Example 1 except that the copolymerized polyester and the olefin-based copolymer were not used. Was. Table 2 shows the results.

Comparative Example 2 Dry blending, melt kneading, pelletizing, molding, and evaluation of physical properties were performed at the ratios shown in Table 2 in the same manner as in Example 1 except that no copolymerized polyester was used. Table 2 shows the results.

Comparative Example 3 Example 1 was repeated except that no olefin copolymer was used.
In the same manner as in the above, dry blending, melt kneading, pelletizing, molding, and physical property evaluation were performed at the ratios shown in Table 2. Table 2 shows the results.

As described above, by adding and blending the copolymerized polyester and the olefin-based copolymer, both excellent epoxy adhesive strength and cold-heat cycle resistance can be achieved.

Example 3 Dry blending, melt kneading, pelletizing, molding, and evaluation of physical properties were performed at the ratios shown in Table 1 in the same manner as in Example 1 except that the type of the copolymerized polyester was changed to (A-2). .
Table 1 shows the results.

The resulting composition was able to achieve both excellent epoxy adhesive strength and resistance to thermal cycling.

Comparative Examples 4 and 5 Dry blending was performed in the same manner as in Example 1 except that poly (ethylene terephthalate) homopolymer and poly (cyclohexane dimethylene terephthalate) homopolymer were used instead of the copolymerized polyester. Melt kneading, pelletizing, molding, and physical property evaluation were performed. Table 2 shows the results.

The composition using the polyester homopolymer did not have satisfactory epoxy adhesive strength.

Examples 4 and 5 Dry blending, melt kneading, pelletizing, molding, and evaluation of physical properties were performed at the ratios shown in Table 1 in the same manner as in Example 1 except that the amount of the olefin copolymer added was changed. Was.
Table 1 shows the results.

The obtained composition was able to achieve both excellent epoxy adhesive strength and thermal cycling resistance.

Example 6 A dry blend was prepared in the same manner as in Example 1 except that the type of the olefin-based copolymer was changed to (ethylene / ethyl acrylate = 65/35% by weight copolymer). Melt kneading, pelletizing, molding, and physical property evaluation were performed.
Table 1 shows the results.

The obtained composition was able to achieve both excellent epoxy adhesive strength and resistance to thermal cycling.

Example 7 The type of olefin copolymer was changed to (ethylene / ethyl acrylate / glycidyl methacrylate = 85/10/5).
(Weight% copolymer), except that dry blending, melt kneading, pelletizing, molding, and evaluation of physical properties were carried out in the same manner as in Example 1 except for changing the ratio to that shown in Table 1. Table 1 shows the results.

The obtained composition was able to achieve both excellent epoxy adhesive strength and resistance to thermal cycling.

Comparative Example 6 Dry blending was performed in the same manner as in Example 1 except that the type of the olefin-based copolymer was changed to (ethylene / glycidyl methacrylate = 94/6% by weight copolymer). Melt kneading, pelletizing, molding, and physical property evaluation were performed. Table 2 shows the results.

When an olefin copolymer containing no α, β-unsaturated carboxylic acid and / or its alkyl ester is used, the impact strength is improved, but the epoxy adhesive strength and the thermal cycling resistance are not satisfactory. Did not.

[0066]

[Table 1]

[0067]

Industrial Applicability The polyphenylene sulfide resin composition of the present invention is excellent in cold-heat cycle resistance and adhesiveness to an epoxy resin, and is useful for applications such as electric parts and sealing parts.

[Brief description of the drawings]

FIG. 1A is a top view of a metal insert test piece, and FIG. 1B is a side view thereof.

[Explanation of symbols]

 1. Insert metal 2. Gate 3. Metal insert test piece

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 67:02 23:02)

Claims (6)

[Claims] (A) Polyphenylene sulfide resin 1
(B) Copolymerized polyester having ethylene terephthalate unit and cyclohexane dimethylene terephthalate unit as main constituent units and having a content of cyclohexane dimethylene terephthalate unit of 20 to 85 mol% with respect to 00 parts by weight. 0.5% polyester
Polyphenylene resin composition obtained by adding and mixing 0.5 to 40 parts by weight of an olefin copolymer comprising (C) an α-olefin and an α, β-unsaturated carboxylic acid or / and an alkyl ester thereof. . 2. The polyphenylene sulfide resin composition according to claim 1, wherein the copolyester (B) is a copolyester containing 25 to 50 mol% of cyclohexane dimethylene terephthalate units. 3. The olefin copolymer (C) is an olefin copolymer comprising an α-olefin and an alkyl acrylate, and the content of the alkyl acrylate is 5 to 50% by weight. Claim 1 or 2
The polyphenylene sulfide resin composition according to the above. 4. The polyphenylene sulfide resin composition according to claim 1, further comprising (D) a filler in an amount of 5 to 200 parts by weight based on 100 parts by weight of the polyphenylene sulfide resin. 5. A composite molded article comprising a combination of the polyphenylene sulfide resin composition according to claim 1 and another material. 6. A molded article comprising the polyphenylene sulfide resin composition according to any one of claims 1 to 4 or a composite molded article according to claim 5, and having an adhesive surface with an epoxy resin. A composite molded article.