JPH1095926A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition extremely excellent in heat resistance, chemical resistance, fluidity, adherent strength to an epoxy resin, etc., and useful for a direct ignition system by making physical properties such as deflection temperature under load, breakdown voltage, spiral flow, etc., within respectively a specific range. SOLUTION: This resin composition has >=150 deg.C deflection temperature under load (measured under 4.6kg load according to JIS K7202), >=72hrs a time for cracking and breaking of a test piece after giving 1% of forced strain and respectively dipping in a gasoline and an engine oil at a normal temperature, >=20kV breakdown voltage (according to a short-time breakdown test of JIS K2110), >=13kg/cm<2> adherent strength to an epoxy resin and Z50 mm spiral flow (measured at 280 deg.C cylinder temperature, 120'C mold temperature and 0.5mm thickness). This composition can be obtained by using (A) 90-40 pts.wt. of a crystalline resin and (B) 10-60 pts.wt. of an amorphous resin and dispersing the component B having <=5μm particle diameter in the component A forming a continuous phase.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition having excellent heat resistance, chemical resistance, dielectric breakdown voltage, epoxy adhesion and fluidity, and more particularly to a resin composition particularly useful in the automobile industry. About.

[0002]

2. Description of the Related Art Polyphenylene sulfide (hereinafter referred to as PP)
S may be abbreviated as S), is a crystalline polymer having a high melting point of 250 ° C. or more and excellent in chemical resistance, and has high fluidity, and thus has been widely used in thin injection molded products. However, PPS has poor adhesion to other resins, especially epoxy resins. Therefore, semiconductor modules, flyback transformers,
It was not suitable for applications such as solenoids, ignition coils, sensors, and relays.

On the other hand, polyphenylene ether (hereinafter referred to as P
PE) is a resin having a high glass transition temperature (T _g ) of about 210 ° C. and excellent heat resistance. Furthermore, because of its excellent adhesion to epoxy resin, it is used for internal applications of home appliances and automobiles such as flyback transformers and ignition coils. However, PP
E is a non-crystalline resin and has poor chemical resistance, and thus is not suitable for applications that are exposed to the outside such as being in contact with an organic solvent.
Further, in recent years, such external uses tend to be lighter. Therefore, in order to achieve further thinning, a resin is required to have high fluidity, but PPE generally has poor fluidity, and at present it is difficult to reduce the thickness. In order to improve the fluidity of such PPE, it is common practice to incorporate polystyrene, a hydrocarbon fluidity modifier, and the like. However, these methods have the disadvantage of lowering the high glass transition temperature of PPE.

In recent years, especially in automobiles, weight reduction and computerization have progressed, and various plastic materials have been used instead of metal materials.
For example, in the case of ignition coil systems, we will move from the conventional mechanical distributor ignition system to the direct ignition system (a method in which a small ignition coil is mounted directly on the engine plug and the ignition timing is optimally controlled by a computer). It is said that. Therefore,
It is desired to develop a plastic material suitable for the system.

The characteristics of the plastic material required for the direct ignition system are as follows: 1: the ignition coil itself is directly attached to the engine plug and is directly exposed to high heat from the engine, so that high heat resistance is required; : High chemical resistance is required due to the possibility of contact with organic solvents such as gasoline and engine oil. 3: Two coils to which high voltage and low voltage are applied inside the ignition coil molded product. enter. Therefore, the molded product must have a high dielectric breakdown voltage enough to withstand high voltage. 4: Since the inside of the coil is sealed with epoxy resin, if the adhesiveness with epoxy resin is insufficient, the molded product is used. In addition, air gaps occur at the interface with the epoxy resin, which causes leakage and dielectric breakdown and hinders the running of automobiles, so high epoxy adhesion is required. 5: Ignition coil molded products are extremely miniaturized. In addition, since a complicated mechanism such as a high-voltage coil and a low-voltage coil is required inside, it is necessary to reduce the thickness of the plastic molded product to about 0.5 mm. Therefore, in order to produce a thin molded article, the resin used needs to have extremely high fluidity.

[0006] For the above reasons, it is extremely difficult to develop a resin that can be used in a direct ignition system, and no resin having such characteristics is known at present.

[0007]

SUMMARY OF THE INVENTION The present invention provides a resin composition for a direct ignition system which is remarkably excellent in all of heat resistance, chemical resistance, breakdown voltage, epoxy adhesion and fluidity. .

[0008]

Means for Solving the Problems In order to solve the above problems, the present inventors have studied various resins. Further, the present inventors focused on two kinds of resins, PPS and PPE, which were considered to be unsuitable for the above-mentioned reasons, and further studied. As a result, when PPS and PE are blended as described below, surprisingly, only the advantages of both resins can be effectively obtained, and the disadvantages can be eliminated, and heat resistance, chemical resistance, The present inventors have found that a resin composition having remarkably excellent dielectric breakdown voltage, epoxy adhesion, and fluidity can be obtained, and have completed the present invention.

That is, the present invention provides: (1) a heat distortion temperature (HDT) of 150 ° C. or more (JIS K72
The value was measured under a load of 4.6 kg in accordance with C.02, and a test piece with a 1.0% forced strain was immersed in gasoline and engine oil, respectively, at room temperature. Time of 72 hours or more, breakdown voltage of 20 kv or more (measured in accordance with JIS C2110 short and long-term breakdown test method), epoxy adhesion strength of 13.0 kg / cm ² or more (the test piece shown in FIG. 1) Then, as shown in FIG. 1, an epoxy resin adhesive is applied to the surfaces a and b and bonded (bonding area 3.7).
5 cm ² ), and then a tensile tester was used to pull the adhesive surface at a crosshead speed of 10 mm / min to separate the load when the adhesive surface was peeled off, and the spiral flow was 50 mm or more (a cylinder temperature of 28 mm).
0 ° C., a mold temperature of 120 ° C. and a thickness of 0.5 mm). As a preferred embodiment, (2) a test piece having a 1.0% forced strain is immersed in an engine oil and ethylene glycol at a temperature of 80 ° C., respectively. (3) a flexural modulus of 30 × 10 ³ kg / cm ² or more, a flexural strength of 1200 kg / cm ² or more, and a bending SS The resin composition according to the above (1) or (2), which has an energy of 10 kgfcm or more, can be mentioned.

Further, the present invention relates to (4) (A) 90 to 40 parts by weight of a crystalline resin and (B)
A resin composition containing 10 to 60 parts by weight of an amorphous resin, wherein (A) forms a continuous phase, (B) is dispersed in the continuous phase, and the particle size of (B) is 5 μm. The following is a resin composition for a direct ignition system.

In a preferred embodiment, (5) the resin composition according to the above (4), wherein (A) the crystalline resin is polyphenylene sulfide and (B) the non-crystalline resin is polyphenylene ether; ) And (B) for a total of 100 parts by weight,
(C) The resin composition according to the above (4) or (5), which contains 0 to 70 parts by weight of an inorganic filler. (7) For the total of 100 parts by weight of (A) and (B),
(D) The resin composition according to any one of the above (4) to (6), which contains 0 to 20 parts by weight of a thermoplastic elastomer,
(8) For a total of 100 parts by weight of (A) and (B),
(E) The above (4) containing 0.01 to 10 parts by weight of a compatibilizer.
To (7).

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition of the present invention has the following characteristics. That is, (1) heat distortion temperature [(HDT) JI
SK7202, a value measured under a load of 4.6 kg] is 150 ° C. or more, preferably 150 to 300 ° C., and (2) a test piece having a 1.0% forced strain was applied to gasoline and an engine, respectively. It is immersed in oil at normal temperature, and the time required for cracking after the immersion and cracking of the test piece is 72 hours or more, and preferably 72 to 500 hours. (3) Dielectric breakdown voltage (short and long term breakdown test method of JIS C2110) 20 kv or more, preferably 20 to 6
0 kv, and (4) epoxy adhesion strength (using the test piece shown in FIG. 1 and applying an epoxy resin adhesive to surfaces a and b as shown in FIG. 1 and bonding them together (bonding area 3.75 cm)
² ) Then, by pulling at a crosshead speed of 10 mm / min using a tensile tester, the value obtained by dividing the load when the bonded surface was separated by the bonded area) was 13.0 kg / cm.
² or more, preferably 13.0 to 110 kg, and (5) spiral flow (measured at a cylinder temperature of 280 ° C., a mold temperature of 120 ° C. and a thickness of 0.5 mm) of 50
mm or more, preferably 50 to 400 mm.

Further, the resin composition of the present invention is prepared by immersing a test piece having a 1.0% forced strain in engine oil and ethylene glycol at a temperature of 80.degree. More than 72 hours to crack,
Preferably, it is 72 to 500 hours.

Further, the resin composition of the present invention has a flexural modulus of 30 × 10 ³ kg / cm ² or more, preferably 30 × 10 ³ kg / cm ² or more.
× 10 ^{3 to} 150 × 10 ³ kg / cm ² and a flexural strength of 1200 kg / cm ² or more, preferably 1200 to 1000 kg / cm ^2.
4000 kg / cm ² , and the bending SS energy is 10 kgfcm or more, preferably 10 to 80 kgf
cm. Here, the flexural modulus, flexural strength and flexural SS energy are all JIS K
It is a value measured according to 7203. Where the bending S
-S energy is a value obtained by calculating the area from the SS curve up to the fracture.

Because of these excellent properties, the resin composition of the present invention requires high heat resistance and chemical resistance, is required to have excellent adhesion to an epoxy resin, and has a thin molding property. It is extremely suitable for use as a direct ignition system that is required to be a product. Furthermore, applications that require sealing or bonding with epoxy resin, such as normal type ignition coils, relay boxes,
Also suitable for use in flyback transformers, solenoids, semiconductor modules, sensors, etc.

The present invention also relates to (A) crystalline resin 90
(A) forms a continuous phase, (B) is dispersed in the continuous phase, and (B) the amorphous resin comprises 10 to 60 parts by weight. (B) A resin composition for a direct ignition system having a particle size of 5 μm or less.

The resin composition of the present invention having the above structure is
It is a resin composition having the various characteristics described above at the beginning of “Embodiments of the Invention”.

In the resin composition, the compounding ratio of component (A) crystalline resin to component (B) non-crystalline resin is (A) 9
10 to 60 parts by weight of (B) to 90 to 45 parts by weight of (B), preferably 10 to 55 parts by weight of (B) to 90 to 45 parts by weight, particularly preferably 90 to 50 parts by weight of (A). (B) 10 to 50 parts by weight with respect to parts by weight. When the component (A) exceeds the above range and the component (B) is below the above range, the adhesion to the epoxy resin is poor. When the component (A) is less than the above range and the component (B) exceeds the above range, the chemical resistance and the moldability are poor.

In the resin composition of the present invention, the crystalline resin of component (A) forms a continuous phase and the resin of component (B)
The non-crystalline resin is present as a dispersed phase in component (A).
Here, the particle diameter of the component (B) non-crystalline resin present as a dispersed phase is 5 μm or less, preferably 5 to 0.3 μm. When the component (A) and the component (B) are present as described above, the excellent effects of the present invention can be achieved.

Examples of the crystalline resin (A) used in the present invention include polyphenylene sulfide, polybutylene terephthalate, polyamide, polyethylene terephthalate, and liquid crystal polymer (LCP). Preferably, polyphenylene sulfide is used.

The polyphenylene sulfide used as the component (A) is represented by the general formula

[0022]

Embedded image The one containing 70 mol% or more of the structural unit represented by the formula (1) is preferable because it provides a composition having excellent characteristics. Examples of the polymerization method of PPS include a method in which p-dichlorobenzene is polymerized in the presence of sulfur and sodium carbonate, and a method in which sodium sulfide or sodium hydrosulfide and sodium hydroxide or hydrogen sulfide and sodium hydroxide are used in a polar solvent. Polymerization method, p
Self-condensation of -chlorothiophenol, etc.
A suitable method is to react sodium sulfide with p-dichlorobenzene in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone solvent such as sulfolane. At this time, it is preferable to add an alkali metal salt of carboxylic acid or sulfonic acid or to add an alkali hydroxide in order to adjust the degree of polymerization. If the amount of the copolymer component is less than 30 mol%, a meta bond (1), an ortho bond (2), an ether bond (3), a sulfone bond (4), a biphenyl bond (5), a substituted phenyl sulfide represented by the following formula: Bond (6), trifunctional phenyl sulfide bond (7), etc.

[0023]

Embedded image (Where R represents an alkyl, nitro, phenyl, alkoxy, carboxylic acid or a metal base of a carboxylic acid) as long as it does not significantly affect the crystallinity of the polymer. Is preferably 10 mol% or less. In particular, trifunctional or higher phenyl, biphenyl,
When a naphthyl sulfide bond or the like is selected for copolymerization, it is preferably at most 3 mol%, more preferably at most 1 mol%.

Such a PPS can be produced by a general production method, for example, (1) reaction of a halogen-substituted aromatic compound with an alkali sulfide (US Pat. No. 2,513,188, Japanese Patent Publication No. 44-1988).
No. 27671 and Japanese Patent Publication No. 45-3368), and (2) a condensation reaction of thiophenols in the presence of an alkali catalyst or a copper salt (US Pat. No. 327416).
No. 5, specification of British Patent No. 1160660),
(3) It is synthesized by a condensation reaction between an aromatic compound and sulfur chloride in the presence of a Lewis acid catalyst (see Japanese Patent Publication No. 46-27255, Belgian Patent No. 29437), and the like. Can be selected.

PPS is currently available on the market from Philips Petroleum Co., Ltd., Tosoh Sastille Co., Ltd., Topren Co., Ltd. and Kureha Chemical Co., Ltd. There are various grades depending on the crosslink density and viscosity,
In the present invention, any of a linear type, a branched type, a cross-linked type, a semi-cross-linked type and the like can be used.

The component (B) non-crystalline resin used in the present invention includes polyphenylene ether, polystyrene, polycarbonate, polyetherimide, ABS
Resins. Preferably, polyphenylene ether is used.

Known polyphenylene ethers can be used as the component (B). PPE is, for example, a general formula:

[0028]

Embedded image (Wherein Q ₁ , Q ₂ , Q ₃ and Q ₄ each independently have a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group and at least two carbon atoms between the halogen atom and the phenyl ring Represents a monovalent substituent selected from haloalkyl groups or haloalkoxy groups containing no tertiary α-carbon, and q is an integer representing the degree of polymerization. The polymer represented by the general formula may be a single type or a copolymer of two or more types.

The method for producing PPE is not particularly limited. For example, US Pat. No. 3,306,874 and US Pat.
It can be prepared by the reaction of phenols according to the procedures described in 257,357 and 3,257,358. These phenols include 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-dibutylphenol, 2,6-dilaurylphenol, 2,6-dipropylphenol, 2,6-diphenylphenol, 2-methyl-6-
Ethylphenol, 2-methyl-6-cyclohexylphenol, 2-methyl-6-tolylphenol, 2-methyl-6-methoxyphenol, 2-methyl-6-butylphenol, 2,
This includes, but is not limited to, 6-dimethoxyphenol, 2,3,6-trimethylphenol, 2,3,5,6-tetramethylphenol and 2,6-diethoxyphenol. Each of these may be reacted alone to the corresponding homopolymer, or reacted with another phenol to the corresponding copolymer having different units encompassed by the above formula.

In a preferred embodiment, Q ₁ and Q ₂ are an alkyl group having 1 to 4 carbon atoms, and Q ₃ and Q ₄ are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. For example, poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1, 4-phenylene) ether, poly (2-methyl-6-propyl-1,4
-Phenylene) ether, poly (2,6-dipropyl-1,4
-Phenylene) ether, poly (2-ethyl-6-propyl-1,4-phenylene) ether and the like. Further, as the PPE copolymer, an alkyl tri-substituted phenol in the above-mentioned polyphenylene ether repeating unit, for example,
Copolymers partially containing 2,3,6-trimethylphenol can be mentioned. Further, a copolymer in which a styrene-based compound is grafted on these PPEs may be used.
The styrene-based compound-grafted polyphenylene ether is a copolymer obtained by graft-polymerizing a styrene-based compound, such as styrene, α-methylstyrene, vinyltoluene, or chlorostyrene, with the above PPE.

The resin composition of the present invention may contain an optional component (C) an inorganic filler as an optional component. The amount of component (C) is preferably 70 parts by weight or less, particularly preferably 50 parts by weight or less, based on 100 parts by weight of the total of component (A) crystalline resin and component (B) non-crystalline resin. . If (C) exceeds the above upper limit, the moldability of the resin composition deteriorates. Further, in order to increase mechanical strength such as flexural modulus and flexural strength, it is preferable to add 10 parts by weight or more. As the component (C) inorganic filler, a commonly used inorganic filler can be used. For example, a powdery / flaky filler, a fibrous filler and the like can be used. Examples of the powdery / flaky filler include alumina, talc, mica, kaolin, clay, titanium oxide, calcium carbonate,
Calcium silicate, calcium phosphate, calcium sulfate, magnesium oxide, magnesium phosphate, silicon nitride, glass, hydrotalcite, zirconium oxide,
Glass beads, carbon black and the like can be mentioned. Examples of the fibrous filler include glass fiber, asbestos fiber, carbon fiber, silica fiber, silica / alumina fiber, potassium titanate fiber, and polyaramid fiber. These can be used alone or in combination of two or more. Further, the surface of the inorganic filler may be treated with a silane coupling agent or a titanate coupling agent.

The resin composition of the present invention may contain (D) a thermoplastic elastomer as an optional component in order to further improve mechanical strength such as flexural modulus and flexural strength. Component (D) is preferably hydrogenated styrene-ethylene-butadiene-styrene copolymer (SEB
S), hydrogenated styrene-ethylene-propylene-styrene copolymer (SEPS), styrene-ethylene-butadiene copolymer (SEB), styrene-ethylene-propylene copolymer (SEP), hydrogenated styrene-butadiene-styrene A rubbery polymer having a glass transition temperature T _g of an amorphous component such as a copolymer (SBS) of 0 ° C. or less can be given. The amount of component (D) is preferably at most 20 parts by weight, particularly preferably at most 15 parts by weight, based on 100 parts by weight of the total of component (A) crystalline resin and component (B) non-crystalline resin. . If it exceeds the above upper limit, the morphology and moldability of the resin composition deteriorate. Further, in order to increase mechanical strength such as flexural modulus and flexural strength, it is preferable to add 4 parts by weight or more. In order to promote the compatibilization between the component (A) and the component (B), it is preferable to further add a compatibilizer (E) to the resin composition of the present invention. As the compatibilizer, for example, any of the known compatibilizers for PPS and PPE can be used. Preferred examples of such compatibilizers include (a) citric acid, malic acid, agaric acid and derivatives thereof. (B) (a) a carbon-carbon double or triple bond and (b) carboxylic acid in the molecule. A compound having an acid group, an acid anhydride group, an acid amide group, an imide group, a carboxylic ester group, an epoxy group, an amino group or a hydroxyl group, and (c) a compound having a carboxyl group or an acid anhydride group and an acid halide group At least one compound selected.

The above-mentioned (a) citric acid, malic acid, agaric acid and derivatives thereof are described in JP-T-61-502195, and the compounds represented by the general formula in this publication are used in the present invention. However, the above-mentioned ones are particularly preferable. Derivatives include ester compounds, amide compounds, anhydrides,
Examples include hydrates and salts. Examples of the acid ester compound include an acetyl ester of citric acid, a mono- or distearyl ester, and the like. Acid amide compounds include citric acid N, N'-diethylamide, N, N'-dipropylamide, N-phenylamide, N-dodecylamide,
N, N'-didodecylamide, N-dodecylamide of malic acid and the like can be mentioned. Examples of the salt include calcium malate, calcium citrate, calcium malate, potassium citrate and the like.

The compound (b) is described in JP-A-56-49753. Specific examples thereof include maleic anhydride, maleic acid, fumaric acid, maleimide, maleic hydrazide, and maleic anhydride. A reactant with a diamine, for example:

[0035]

Embedded image (Where R represents an aliphatic or aromatic group), methylnadic anhydride, dichloromaleic anhydride, maleic amide, soybean oil, tung oil, castor oil, linseed oil, etc. Hempseed oil, cottonseed oil, sesame oil, rapeseed oil,
Natural oils such as peanut oil, camellia oil, olive oil, coconut oil, sardine oil, epoxidized natural oils such as epoxidized soybean oil, acrylic acid, butenoic acid, crotonic acid, vinyl acetic acid,
Methacrylic acid, pentenoic acid, angelic acid, tiglic acid, 2-pentenoic acid, 3-pentenoic acid, α-ethylacrylic acid, β-methylcrotonic acid, 4-pentenoic acid, 2-
Hexenoic acid, 2-methyl-2-pentenoic acid, 3-methyl-2-pentenoic acid, α-ethylcrotonic acid, 2,2-dimethyl-3-butenoic acid, 2-heptenoic acid, 2-octenoic acid, 4- Decenoic acid, 9-undecenoic acid, 10-undecenoic acid, 4-dodecenoic acid, 5-dodecenoic acid, 4-tetradecenoic acid, 9-tetradecenoic acid, 9-hexadecenoic acid, 2-
Octadecenoic acid, 9-octadecenoic acid, eicosenoic acid,
Docosenoic acid, erucic acid, tetracosenoic acid, mycolipenoic acid, 2,4-pentadienoic acid, 2,4-hexadienoic acid, diallylacetic acid, geranic acid, 2,4-decadienoic acid, 2,4
-Dodecadienoic acid, 9,12-Hexadecadienoic acid, 9,12-
Octadecadienoic acid, hexadecatrienoic acid, linoleic acid, linolenic acid, octadecatrienoic acid, eicosadienoic acid, eicosatrienoic acid, eicosatetraenoic acid, ricinoleic acid, eleostearic acid, oleic acid, eicosapentaenoic acid, Unsaturated carboxylic acids such as erucic acid, docosadienoic acid, docosatrienoic acid, docosatetraenoic acid, docosapentaenoic acid, tetracosenoic acid, hexacosenoic acid, hexacodienoic acid, octacosenoic acid, and traaconthenic acid, or esters of these unsaturated carboxylic acids,
Acid amides, anhydrides, or allyl alcohol, crotyl alcohol, methyl vinyl carbinol, allyl carbinol, methyl propenyl carbinol, 4-penten-1-ol, 10-undecene-1-ol, propargyl alcohol, 1,4 -Pentadien-3-ol,
1,4-hexadien-3-ol, 3,5-hexadien-2-ol, 2,4-hexadien-1-ol, general formula C _n H _2n-5 OH, C _n H _2n-7 OH, C _n Alcohol represented by H _2n-9 OH (where n is a positive integer), 3-butene-1,2-diol, 2,5-dimethyl-3-hexene-2,
5-diol, 1,5-hexadiene-3,4-diol,
Unsaturated alcohols such as 2,6-octadiene-4,5-diol or unsaturated polymers in which the OH group of such an unsaturated alcohol is replaced by -NH ₂ group, or a low polymer such as butadiene or isoprene (For example, if the average molecular weight is
About 500 to 10,000) or high molecular weight polymer (for example, those having an average molecular weight of 10,000 or more) to which maleic anhydride and phenols are added, or amino group, carboxylic acid group, hydroxyl group, epoxy group, etc. are introduced. And the like. The compound (b) also includes a compound containing two or more functional groups in the group (a) and two or more (same or different) functional groups in the group (b).

As the compound (c), trimellitic anhydride chloride is particularly mentioned, which is described in JP-T-62-50056.

Another example of the compatibilizer of the component (F) is an unsaturated monomer and / or polymer containing an epoxy group and / or an oxazolinyl group.

Examples of the unsaturated monomer having an epoxy group or an oxazolinyl group include the following.

First, preferred epoxy group-containing unsaturated monomers include glycidyl methacrylate (hereinafter referred to as GMA).
Glycidyl acrylate, vinyl glycidyl ether, glycidyl ether of hydroxyalkyl (meth) acrylate, glycidyl ether of polyalkylene glycol (meth) acrylate, and glycidyl itaconate.

Next, preferred oxazolinyl group-containing unsaturated monomers include those represented by the general formula:

[0041]

Embedded image Wherein Z contains a polymerizable double bond. Preferred substituents Z are:

[0042]

Embedded image In these formulas, R is a hydrogen atom or an alkyl or alkoxy group having 1 to 6 carbon atoms, for example a methyl group, i
-And n-propyl or butyl.

Particularly preferred compounds have the general formula:

[0044]

Embedded image Wherein R has the above-mentioned meaning, and is preferably a hydrogen atom or a methyl group.

Examples of the polymer having an epoxy group or an oxazolinyl group include a homopolymer of the above unsaturated monomer, a copolymer of two or more of the above unsaturated monomers, and a copolymer of one or more of the above unsaturated monomers. And other unsaturated monomers. Other unsaturated monomers include aromatic vinyl monomers such as styrene (hereinafter sometimes abbreviated as St),
Vinyl cyanide monomer such as acrylonitrile, vinyl acetate, acrylic acid (salt); methacrylic acid (salt), acrylic acid ester, methacrylic acid ester, (anhydride) maleic acid, maleic acid ester, 2-norbornene-5,6 -
Unsaturated carboxylic acids such as dicarboxylic acids (anhydrides) or derivatives thereof, ethylene, propylene, 1-butene, 1-
Pentene, 4-methyl-1-pentene, 1-hexene,
Α such as 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene
-Diene components such as olefin, butadiene, isoprene, 1,4-hexadiene, 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene.

Examples of copolymers include, for example, GMA / St,
GMA / St / MMA (methyl methacrylate) / M
A, GMA / St / acrylonitrile, GMA / MMA
/ Acrylonitrile, GMA / MMA, GMA / MMA
/ St, vinyl oxazoline / St, vinyl oxazoline / MMA, ethylene / GMA, ethylene / vinyl acetate / GMA, and the like. Of course, copolymers other than those described above can also be used in the present invention.

Further, as the component (E), a styrene-maleic acid copolymer can be used.

The compatibilizers described above may be used alone or in combination of two or more.

The amount of the component (E) compatibilizer to be added is a total of 1 (a) the crystalline resin and (b) the non-crystalline resin.
The upper limit is preferably 10 parts by weight, more preferably 5 parts by weight, particularly preferably 2 parts by weight, and the lower limit is preferably 0.01 parts by weight, more preferably 0.05 parts by weight, relative to 00 parts by weight. Particularly preferred is 0.1 part by weight.
Exceeding the above upper limit is not preferred because the heat resistance is lowered, and below the lower limit is not preferred because the compatibilizing effect is insufficient.

Further, resins such as polystyrene (PS), rubber-modified polystyrene (HIPS), ABS, polyester, polycarbonate and the like can be appropriately included according to the purpose.

In the resin composition of the present invention, various additives known to those skilled in the art besides the above-mentioned components at the time of mixing and molding the resin, such as pigments, as long as the effects of the present invention are not impaired Dyes, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, plasticizers, plasticizers, antistatic agents and flame retardants can be added.

In producing the resin composition of the present invention, each component can be mixed by a conventionally known method. For example, a method in which each component is dispersed and mixed in a high-speed mixer represented by a turntable mixer or a Henschel mixer in the form of pellets, powders, and pieces, and then melt-kneaded with a single-screw or multi-screw extruder, a Banbury mixer, a roll, or the like. Is appropriately selected.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0054]

The following compounds were used in the following Examples and Comparative Examples. <Component (A)> Polyphenylene sulfide (Sastile B070, trademark, manufactured by Tosoh Corporation) was used as the crystalline resin. <Component (B)> Polyphenylene ether (manufactured by Gem Polymer Co., Ltd.) was used as the non-crystalline resin. The intrinsic viscosity of the resin is 0.31 g / dl. <Component (C)>-Glass fiber: CS-3PE-454S, trademark, manufactured by Asahi Fiber Co., Ltd.-Talc: LMS-100, trademark, manufactured by Tsuchiya Kaolin Co., Ltd.-Mica: 200-HK, trademark, manufactured by Kuraray Co., Ltd. <Component (D)>-SEBS: KL8006, trademark, manufactured by Kuraray Co., Ltd.-SEPS: KL2006, trademark, manufactured by Kuraray Co., Ltd. <Component (E)>-Compatibilizer (a): Bond Fast-E, trademark, Sumitomo Epoxy-modified polyolefin manufactured by Chemical Co., Ltd.-Compatibilizer (b): RPS-1005, trademark, manufactured by Nippon Shokubai Chemical Co., Ltd., oxazoline-modified polystyrene <Others>-Polystyrene (PS): CR3500, trademark, Dainippon Ink Co., Ltd.・ High Impact Polystyrene (HIPS): 870S
T, trademark, Mitsui Toatsu Co., Ltd.

[0055]

Examples 1 to 5, Comparative Examples 1 to 3 The components (parts by weight) shown in Table 1 were blended and mixed with a blender to give a mixture of 53 mm.
Using a twin-screw extruder (TEM-50, trade name, manufactured by Toshiba Machine Co., Ltd.), set the barrel temperature at 300 ° C. and rotate at 20 rpm.
Pellets were prepared by kneading and extruding at 0 rpm. The pellets were supplied to Plastar Ti-80G2 (trademark, manufactured by Toyo Kikai Metal Co., Ltd.), and the cylinder temperature was 280 ° C.
125 × 12.5 × 6 mm (used for heat resistance evaluation), 6.4 × 12.5 × 3 mm (used for chemical resistance) at a mold temperature of 120 ° C. and a test piece as shown in FIG. 1 (epoxy adhesion) (Used for strength).

The properties shown in Table 1 were evaluated by the following test methods. <Heat resistance (HDT)> 125 x 12.5 x 6 mm
The HDT (heat deformation temperature) was measured and evaluated under the load of 4.6 kg according to JIS K7202 by using the test piece of (1). <Chemical resistance (normal temperature)> The above 6.4 × 12.5 × 3 mm
Was forcibly attached and fixed to an aluminum jig, and a 1.0% forced strain was applied to the test piece. The test pieces thus fixed were immersed in gasoline (regular gasoline, manufactured by Nippon Oil Co., Ltd.) and engine oil (Nissan genuine motor oil SG-Xtra Save X, trademark, manufactured by Nissan Motor Co., Ltd.) at room temperature, and after immersion. The time until the test piece cracked and cracked was measured and evaluated.

The symbols shown in Table 1 indicate the following contents. ：: Cracks did not occur in either gasoline or engine oil after 72 hours of immersion. X: Cracks occurred in either gasoline or engine oil within 72 hours of immersion. <Chemical resistance (80 ° C.)> Specimens fixed as well as chemical resistance (normal temperature) were immersed in engine oil (same as above) and ethylene glycol, respectively, and placed in an oven at 80 ° C. and kept at that temperature. The time until cracking was measured and evaluated.

The symbols shown in Table 1 indicate the following contents. ：: No cracking occurred in either the engine oil or ethylene glycol after 72 hours of immersion. ×: Cracking occurred in either the engine oil or ethylene glycol within 72 hours of immersion. <Epoxy adhesion> FIG. 1 and epoxy resin adhesive (base agent:
KE 5523-7A, trademark, curing agent: KE 5523
-7B, trademark, both manufactured by Hitachi Chemical Co., Ltd .; main agent / hardener compounding ratio (weight) = 100/26)
Cured at 30 ° C for 2 hours and bonded (bonded area 3.75cm
² ) Then, a tensile tester (UCT-1T TENSI)
LON (trademark, manufactured by Orientic) at a crosshead speed of 10 mm / min, and the load when the adhesive surface was peeled was measured. In addition, the value at that time was measured for the material in which the adhesive surface did not peel and the base material was broken.
The epoxy adhesion strength is shown in Table 1 as a value obtained by dividing the load by the adhesion area. Further, the state of peeling was observed.

The symbols shown in Table 1 indicate the following contents. ：: good adhesion, not peeling off from the epoxy resin bonded part,
Destruction of base material ×: Peeled from epoxy resin adhesive part with epoxy adhesion strength of less than 13.0 kg / cm ² <Moldability> The above pellets are Plastar Ti-8
0G2 (trademark, manufactured by Toyo Machine Metal Co., Ltd.), 0.5 mm at a cylinder temperature of 280 ° C. and a mold temperature of 120 ° C.
The thick spiral flow was measured.

The symbols shown in Table 1 indicate the following contents. ：: The flow was 50 mm or more. X: The flow was less than 50 mm. Further, the delamination phenomenon during molding was visually observed.

The symbols shown in Table 1 indicate the following contents. ：: No delamination occurred X: Delamination occurred <Dielectric breakdown voltage> Measured in accordance with JIS C2110 short and long term breakdown test method. <Overall evaluation> The symbols shown in Table 1 indicate the following contents. ：: Very good ：: Good ×: Poor These evaluation results are shown in Table 1.

[0062]

[Table 1] In Examples 1 to 5, the amounts of (A) PPS and (B) PPE were changed within the scope of the present invention. As the amount of PPE was increased, heat resistance, epoxy adhesion strength, and dielectric breakdown voltage were increased, and the moldability was all good. In Example 5, a decrease in chemical resistance at 80 ° C. and delamination were observed, but did not impair the effects of the present invention. Both were found to be suitable for direct ignition systems.

On the other hand, Comparative Example 1 is only PPS. Heat resistance, epoxy adhesion strength and moldability were all extremely poor. Comparative Examples 2 and 3 have a PPS less than the scope of the present invention. All were inferior in chemical resistance and moldability. It is presumed that the decrease in chemical resistance is due to the fact that PPS can no longer form a continuous phase at this mixing ratio, and PPE having poor chemical resistance has been attacked by gasoline and the like.

Further, Examples 1 to 3 and Comparative Example 1 were observed with an electron microscope. Each of the test pieces for which the above-mentioned epoxy adhesion was evaluated was subjected to a microtome (Sup
per NOVA (trademark, manufactured by LBK)), the thin film was stained with ruthenium oxide, and the epoxy adhesion surface was observed with a transmission electron microscope (JEM1200EX-2, tradename, manufactured by JEOL). The results are shown in FIGS. In the resin compositions of Examples 1 to 3 (FIGS. 2 to 4), it was found that PPS formed a continuous phase and PPE formed a dispersed phase, and that the particle size of PPE as a dispersed phase was 5 μm or less. . In addition, the moldability was good, and no delamination was observed. On the other hand, in the resin of Comparative Example 1 (FIG. 5),
Laminar exfoliation was observed.

[0065]

Examples 6 to 15 Using the components shown in Table 2 (parts by weight), the respective properties were evaluated in the same manner as in Example 1. The flexural modulus, flexural strength, and flexural SS energy were measured using TENSILON (trademark, crosshead speed 10 mm / min, manufactured by Toyo Baldwin Co., Ltd.) using a 125 × 12.5 × 6 mm test piece. JIS K7
203).

Table 3 shows the results of these evaluations. In addition,
Each symbol in Table 3 has the same contents as those shown in Table 1.

[0067]

[Table 2]

[0068]

[Table 3] Example 6 is a resin composition of the present invention composed of (A) PPS and (B) PPE. Examples 7 and 8 are the same as the PPS and PPE of Example 6, respectively. And talc. Examples 7 and 8 show significantly higher flexural modulus, flexural strength and flex SS
Had energy. In addition, the heat resistance and epoxy adhesion strength also increased significantly. Examples 9 to 15 relate to the resin composition of the present invention in which other optional components are appropriately blended. Each characteristic value was remarkably good. According to these examples, when optional components (C), (D), (E) and the like are further blended, all of the properties of heat resistance, chemical resistance, dielectric breakdown voltage, epoxy adhesion strength and fluidity can be improved. It has been found that the mechanical strength of the molded article can be further increased while holding the molded article.

[0069]

The present invention provides a resin composition having remarkably excellent heat resistance, chemical resistance, dielectric breakdown voltage, epoxy adhesion and fluidity.

[Brief description of the drawings]

FIG. 1 shows the shape of a test piece for evaluating epoxy adhesion and the state of the test piece when bonded with an epoxy resin (the state before breaking).

FIG. 2 is an electron micrograph (about 5,000) showing the particle structure of a test piece evaluated for epoxy adhesion in Example 1.
0 times).

FIG. 3 is an electron micrograph (about 5,000) showing the particle structure of a test piece evaluated for epoxy adhesion in Example 2.
0 times).

FIG. 4 is an electron micrograph (about 5,000) showing the particle structure of a test piece evaluated for epoxy adhesion in Example 3.
0 times).

FIG. 5 is an electron micrograph (about 5,000) showing the particle structure of a test piece evaluated for epoxy adhesion in Comparative Example 1.
0 times).

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Terumasa Hirata 2-2 Kinugaoka, Moka City, Tochigi Prefecture Inside Japan Plastics Co., Ltd.

Claims (3)

[Claims] 1. A test piece having (1) a heat distortion temperature (HDT) of 150 ° C. or higher (measured under a load of 4.6 kg according to JIS K7202), and (2) a 1.0% forced strain. Immersed in gasoline and engine oil at room temperature, respectively.
The time required for cracking and cracking of the test piece after immersion is 72 hours.
Time or more, (3) breakdown voltage 20 kv or more (JIS
(4) epoxy adhesion strength of 13.0 kg / cm ² or more, and (5) spiral flow of 50 mm or more (cylinder temperature 280 ° C., mold temperature 120 ° C.) And a value measured at a thickness of 0.5 mm). 2. A resin composition comprising (A) 90 to 40 parts by weight of a crystalline resin and (B) 10 to 60 parts by weight of a non-crystalline resin, wherein (A) forms a continuous phase, A resin composition for a direct ignition system, wherein (B) is dispersed in a phase and the particle size of (B) is 5 μm or less. 3. The resin composition according to claim 2, wherein (A) the crystalline resin is polyphenylene sulfide, and (B) the non-crystalline resin is polyphenylene ether.