JP3473186B2 - Polyphenylene sulfide resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to a polyphenylene sulfide resin composition having improved adhesiveness with an epoxy resin and the like, without impairing the thermal stability, melt fluidity, mechanical strength or moldability of the polyphenylene sulfide resin composition. With respect to the polyphenylene sulfide resin composition having a relatively low rate, for example, electricity in a box-shaped molded product of the polyphenylene sulfide resin composition,
The present invention relates to a polyphenylene sulfide resin composition that is particularly suitable for applications such as embedding electronic parts with epoxy resin.

[0002]

2. Description of the Related Art Polyphenylene sulfide resin (hereinafter P
PS resin) has excellent heat resistance, flame retardancy, rigidity, chemical resistance, and other properties suitable for engineering plastics, and is mainly used for injection molding. Is used for.
Taking advantage of such excellent characteristics, application to applications such as embedding electric and electronic parts with epoxy resin in a box-shaped molded body of PPS resin has been studied in recent years. One of the important requirements required for such applications is that peeling does not occur at the interface between the box-shaped molded product and the epoxy resin even when exposed to various temperature conditions. That is, in such applications,
First of all, in the box-shaped molded body where electrical and electronic parts etc. are arranged,
It is used by pouring an uncured epoxy resin and then curing the epoxy resin. Further, it is required that peeling does not occur at the interface between the box-shaped molded product and the epoxy resin even when this component is repeatedly exposed to a temperature of minus several tens of degrees Celsius to plus hundreds of several tens of degrees Celsius. However, the conventional PPS resin cannot be said to be sufficiently excellent in terms of the difficulty of peeling (hereinafter referred to as peel resistance), and its improvement is required.

It is considered that one of the methods for improving the peeling resistance between the PPS resin and the epoxy resin is to increase the adhesiveness between them. PPS with excellent adhesion to epoxy resin
The resin composition has been studied so far, for example, a method of adding a polyalkylene ether to a PPS resin (JP-A-4-275368), a method of blending a fibrous filler and talc with the PPS resin ( Japanese Patent Laid-Open No. Hei 4
-304264) and the like have been proposed.

However, the method described in Japanese Patent Application Laid-Open No. 4-275368 is extremely effective in improving the adhesiveness between the PPS resin and the epoxy resin, but the polyalkylene ether is stable and easy to handle at high temperatures. It is hard to say that this point is sufficient, and there is room for further improvement in this point. The method described in JP-A-4-304264 is also effective in improving the adhesiveness between the PPS resin and the epoxy resin, but the addition of talc deteriorates the melt fluidity and lowers the mechanical strength. However, it may cause problems such as an increase in elastic modulus.

[0005]

Therefore, according to the present invention, the PP
For the purpose of obtaining a PPS resin composition having significantly improved peeling resistance without significantly impairing the excellent heat resistance, melt fluidity, mechanical strength and moldability that the S resin originally possesses, first a thorough study was conducted. C) By incorporating a carboxylic acid amide wax obtained by reacting a higher aliphatic monocarboxylic acid, a polybasic acid and a diamine, P
It was found that the adhesive strength between the PPS resin and the epoxy resin was remarkably improved without substantially impairing the excellent properties inherent to the PS resin, but this alone was not sufficient for the peel resistance. there were.
Therefore, we changed the viewpoint next and lowered the elastic modulus of PPS resin,
It was thought that the peeling resistance would be improved by lowering the stress generated at the interface between the PPS resin and the epoxy resin during the cold heat test, and as a result of further study, (B) or (D) α-olefin And an olefinic copolymer containing an α, β-unsaturated acid glycidyl ester as an essential component, and (C) a carboxylic acid amide wax obtained by reacting a higher aliphatic monocarboxylic acid with a polybasic acid and a diamine at the same time. The inventors have found that the inclusion of the PPS resin composition can provide a PPS resin composition having extremely excellent peeling resistance without significantly impairing the excellent characteristics of the PPS resin, which has been achieved by the present invention.

In the present invention, the olefin copolymer and the (C) carboxylic acid amide containing the glycidyl ester of α-olefin and α, β-unsaturated acid as the component (B) and / or (D) as essential components. It is important to include a system wax at the same time, and the addition of the (C) carboxylic acid amide system wax to the PPS resin improves the adhesive strength as described above, but the peel resistance is insufficient. On the other hand, just by adding the olefinic copolymer (B) or (D) to the PPS resin, the adhesive strength is not sufficient and the peeling resistance becomes insufficient.

When an olefinic (co) polymer not containing a glycidyl ester of an α, β-unsaturated acid is used, a decrease in elastic modulus is recognized, but when (C) a carboxylic acid amide wax is used in combination, The effect of improving the adhesive strength becomes small and the peeling resistance becomes insufficient.

The compound obtained by reacting a higher monocarboxylic acid, a polybasic acid and a diamine is described in JP-A-3.
No. 153793 and Japanese Patent Laid-Open No. 6-145686. However, JP-A-3-153793 does not describe PPS resin as a target resin, and JP-A-6-145686 also describes polyolefin resin and PPS resin as one of many resins to be used. Nothing more than. In addition, α-of (B) or (D)
There is no specific description about an olefin-based copolymer having an glycidyl ester of an olefin and an α, β-unsaturated acid as an essential component, and an olefin-based copolymer containing no glycidyl ester of an α, β-unsaturated acid is used. However, as described above, the desired effect of the present invention cannot be obtained. Further, its effect is only described as a lubricity improver excellent in heat resistance, and as shown in the present invention, (B)
Alternatively, by incorporating the specific olefinic copolymer (D) and the carboxylic acid amide wax obtained by reacting the (C) higher aliphatic monocarboxylic acid with a polybasic acid and a diamine, the PPS resin originally has There is no description that a PPS resin composition having extremely excellent peeling resistance can be obtained with almost no loss of excellent properties.

[0009]

That is, the present invention is as follows.
(A) 60 to 99.5% by weight of α-olefin and 0.5 to 40 of glycidyl ester of α, β-unsaturated acid based on 100 parts by weight of polyphenylene sulfide resin.
An olefin-based copolymer having a main component of wt% or (D) an α-olefin (1) and a glycidyl ester of an α, β-unsaturated acid (2), and a monomer represented by the following general formula ( 3) is an olefin-based copolymer having an essential component, and the copolymerization ratio thereof is (1) / (2) = 60 to 99.
% / 40 to 1% by weight, and (3) 5 to 60% by weight of the monomer represented by the following general formula with respect to the total amount ((1) + (2)) of 95 to 40% by weight. % Of olefinic copolymer, and (C) 0.0% of carboxylic acid amide wax obtained by reacting higher aliphatic monocarboxylic acid with polybasic acid and diamine.
The present invention provides a polyphenylene sulfide resin composition containing 1 to 10 parts by weight.

[0010]

[Chemical 2] (Wherein R ¹ represents hydrogen or a lower alkyl group, X 1
Is one or more groups selected from —COOR ² group, —CN group or aromatic group. R ² has 1 to 10 carbon atoms
Represents the alkyl group of

The polyphenylene sulfide resin used in the present invention has a repeating unit represented by the following structural formula.

[Chemical 3] It is a polymer containing 70 mol% or more, more preferably 90 mol% or more, and if the repeating unit is less than 70 mol%, heat resistance is impaired, which is not preferable. Also PPS
The resin can comprise less than 30 mol% of its repeating unit with a repeating unit having the following structural formula.

[0012]

[Chemical 4]

The melt viscosity of the PPS resin used in the present invention is not particularly limited as long as it can be melt-kneaded, but is usually 5
0-20,000 Poise (320 ° C, shear rate 1000
sec ^-1 ) is used, and the range of 100 to 2000 poise is more preferable.

Such PPS resin is a known method, that is, a method for obtaining a polymer having a relatively small molecular weight as described in JP-B-45-3368, or JP-B-52-12240 and JP-A-61-7332. It can be produced by the method described in the publication for obtaining a polymer having a relatively large molecular weight. In the present invention, the PPS resin obtained as described above is subjected to crosslinking / polymerization by heating in air, heat treatment in an atmosphere of an inert gas such as nitrogen or under reduced pressure, washing with an organic solvent, hot water, an aqueous acid solution, etc., It is of course possible to use it after various treatments such as activation with a functional group-containing compound such as an acid anhydride, an amine, an isocyanate, or a functional group-containing disulfide compound. It is also possible to use a PPS resin into which a functional group such as an amino group or a carboxylic acid group has been introduced by copolymerizing mono-, di- or trihalobenzene substituted with a functional group such as an amino group or a carboxylic acid group. is there.

In the PPS resin composition of the present invention, ASTM D1238-86 (31) is used as the PPS resin.
The use of PPS resin having a melt flow rate value of 30 minutes retention at 5.5 ° C. and a load of 5000 g) of 80% or more of the melt flow rate value after retention for 5 minutes is effective for adhesion with epoxy resin. It is preferable for obtaining a resin composition having more excellent properties, reactivity with an olefin-based copolymer, and resulting peeling resistance.

The olefin-based copolymer (B) in the present invention is an olefin-based copolymer mainly containing glycidyl ester of α-olefin and α, β-unsaturated acid.

Specific examples of (B) the α-olefin which is one of the monomer components of the olefin copolymer are ethylene, propylene, butene-1,4-methylpentene-1, hexene and decene. -1, octene-1 and the like, among which ethylene is preferably used.
Also, two or more of these may be used at the same time.
On the other hand, the glycidyl ester of α, β-unsaturated acid, which is another monomer component of the olefin copolymer (B), has the general formula

[Chemical 5] (Wherein R represents a hydrogen atom or a lower alkyl group), and specific examples thereof include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylic acid. Of these, glycidyl methacrylate is preferably used.

The olefin copolymer (B) may be a random, block or graft copolymer of the above-mentioned α-olefin and glycidyl ester of α, β-unsaturated acid.

(B) α-olefin and α, of the present invention
The copolymerization amount of the glycidyl ester of the α, β-unsaturated acid in the olefin copolymer mainly composed of the glycidyl ester of the β-unsaturated acid is 0.5 to 40% by weight, particularly 3 to 30% by weight. Is preferred. If it is less than 0.5% by weight, the desired effect is insufficient, and if it exceeds 40% by weight, P
Gel is generated during melt-kneading with the PS resin, which adversely affects extrusion stability, moldability, mechanical strength and the like, which is not preferable.

Such (B) α-olefin and α, β
The blending amount of the olefin-based copolymer having a glycidyl ester of an unsaturated acid as a main constituent component is selected in the range of 2 to 70 parts by weight, particularly 3 to 100 parts by weight of the (A) polyphenylene sulfide resin. A range of 50 parts by weight is more preferable. If it is less than 2 parts by weight, the desired effect is insufficient, and if it exceeds 70 parts by weight, the fluidity with the PPS resin, moldability, mechanical strength, etc. are adversely affected, which is not preferable.

In the present invention, in place of the olefin copolymer (B), an α-olefin (1) and a glycidyl ester (2) of an α, β-unsaturated acid, and a monomer represented by the following general formula are further added. The (D) olefin-based copolymer having the monomer (3) as an essential component is also preferably used.

[0022]

[Chemical 6] (Wherein R ¹ represents hydrogen or a lower alkyl group, X 1
Is one or more groups selected from —COOR ² group, —CN group or aromatic group. R ² has 1 to 10 carbon atoms
Represents the alkyl group of

Details of the α-olefin (1) and the glycidyl ester (2) of the α, β-unsaturated acid (D) used in the olefin copolymer (D) are the same as those in the (B) olefin copolymer.

On the other hand, specific examples of the monomer (3) include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, Α, β-unsaturated carboxylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate and isobutyl methacrylate, acrylonitrile, styrene, Examples thereof include α-methylstyrene, styrene in which an aromatic ring is substituted with an alkyl group, and acrylonitrile-styrene copolymer. These can be used in combination of two or more.

The (D) olefin-based copolymer has α
-A random, block or graft copolymer of olefin (1) and glycidyl ester of α, β-unsaturated acid (2) and monomer (3), any copolymerization mode,
For example, there are two or more copolymerization modes in which a monomer (3) is graft-copolymerized to a random copolymer of α-olefin (1) and glycidyl ester (2) of α, β-unsaturated acid. It may be a combined copolymer.

The copolymerization ratio of the (D) olefinic copolymer of the present invention is α from the viewpoint of influence on the desired effect, polymerizability, gelation, heat resistance, fluidity and strength.
A range of olefin (1) / glycidyl ester of α, β-unsaturated acid (2) = 60 to 99% by weight / 40 to 1% by weight is selected. The copolymerization ratio of the monomer (3) is α
A range of 5 to 60% by weight of the monomer (3) is preferably selected with respect to the total amount of 95 to 40% by weight of the olefin (1) and the glycidyl ester (2) of the α, β-unsaturated acid.

The compounding amount of the (D) olefin-based copolymer is such that the (A) polyphenylene sulfide resin 100 is used.
A range of 2 to 70 parts by weight is selected with respect to parts by weight, and a range of 3 to 50 parts by weight is particularly preferable. If it is less than 2 parts by weight, the desired effect is insufficient, and if it exceeds 70 parts by weight, the fluidity with the PPS resin, moldability, mechanical strength, etc. are adversely affected, which is not preferable.

The olefin copolymer (B) and the olefin copolymer (D) may be used in combination.

In the present invention, the combined use of the olefinic copolymer (B) and / or (D) and the elastomer (E) which does not contain an epoxy group is effective in obtaining more excellent peeling resistance and also in fluidity. It is effective in improving the sex.

Examples of the (E) epoxy group-free elastomers include polyolefin elastomers, diene elastomers, acrylic elastomers, and the like. Specific examples of the polyolefin elastomer include ethylene-propylene copolymer, ethylene-butene copolymer, polybutene, ethylene-propylene-diene copolymer, ethylene-vinyl acetate copolymer and the like. Specific examples of the diene elastomer include styrene-butadiene copolymer, polybutadiene, butadiene-acrylonitrile copolymer, polyisoprene, butene-isoprene copolymer, and styrene-ethylene-butadiene-styrene copolymer. Hydrogenated products of Specific examples of the acrylic elastomer include ethylene-methyl acrylate copolymer, ethylene-
Ethyl acrylate copolymer, ethylene-acrylic acid n-
Propyl copolymer, ethylene-isopropyl acrylate copolymer, ethylene-n-butyl acrylate copolymer,
Ethylene-t-butyl acrylate copolymer, ethylene-
Isobutyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-n-propyl methacrylate copolymer,
Olefin- (meth) acrylic acid ester copolymers such as ethylene-isopropyl methacrylate copolymer, ethylene-n-butyl methacrylate copolymer, ethylene-t-butyl methacrylate copolymer, ethylene-isobutyl methacrylate copolymer Polymer, methyl acrylate-acrylonitrile copolymer, methyl methacrylate-acrylonitrile copolymer, propyl acrylate-acrylonitrile copolymer, propyl methacrylate-acrylonitrile copolymer, butyl acrylate-acrylonitrile copolymer, (Meth) acrylic acid ester-acrylonitrile copolymer such as butyl methacrylate-acrylonitrile copolymer, ethylene- (meth) acrylic acid copolymer and metal salts thereof such as Na, Zn, K, Ca and Mg, Butadiene mentioned above Such as acrylonitrile copolymers.

To impart reactivity, unsaturated carboxylic acids such as acrylic acid, (meth) acrylic acid and maleic acid, or unsaturated carboxylic acid anhydrides such as maleic anhydride, methylmaleic anhydride and citraconic anhydride. The above-mentioned elastomer containing no epoxy group may be used as a modifier component.

When (E) the epoxy group-free elastomer is used, its preferable blending amount is in the range of 2 to 70 parts by weight, particularly 3 to 50 parts by weight, relative to 100 parts by weight of (A) polyphenylene sulfide resin. A range of parts by weight is more preferred.

On the other hand, the (C) carboxylic acid amide wax used in the present invention is obtained by dehydration reaction of a higher aliphatic monocarboxylic acid, a polybasic acid and a diamine. The higher aliphatic monocarboxylic acid has 1 carbon atom
Zero or more aliphatic monocarboxylic acids and hydroxycarboxylic acids are preferable, and specific examples thereof include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid,
Examples thereof include linoleic acid, behenic acid, montanic acid and 12-hydroxystearic acid. Among them, saturated aliphatic monocarboxylic acids having 16 or more carbon atoms such as palmitic acid, stearic acid, behenic acid, montanic acid and 12-hydroxystearic acid. And hydroxycarboxylic acid are more preferable, and two or more kinds of these higher aliphatic monocarboxylic acids may be used in combination.

The polybasic acid is a carboxylic acid of dibasic acid or more, and specific examples thereof include aliphatic dicarboxylic acids such as malonic acid, succinic acid, adipic acid, sebacic acid, pimelic acid and azelaic acid, and phthalic acid. Aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and cyclohexylsuccinic acid, and the like. These may be used in combination of two or more, among which succinic acid, Adipic acid, sebacic acid and pimelic acid are particularly preferred.

Specific examples of the diamine include ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, tetramethylenediamine, hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine and metaxylyl. Examples include diamine, paraxylylenediamine, tolylenediamine, phenylenediamine, and isophoronediamine, and these may be used in combination of two or more. Among them, ethylenediamine is particularly suitable.

The mixing ratio of the higher aliphatic monocarboxylic acid, polybasic acid and diamine is 0.18 mol to 1.0 mol of polybasic acid and 1.0 mol of diamine with respect to 2 mol of higher aliphatic monocarboxylic acid. Is preferably in the range of from 0.5 to 2.2 mol, polybasic acid 0.5 to 1.0 mol, diamine 1.5.
The range of mol to 2.0 mol is more preferable.

The carboxylic acid amide type wax (C) used in the present invention can be used in combination with a conventional higher aliphatic amide.

The carboxylic acid amide type wax (C) of the present invention is obtained by the dehydration reaction of a higher aliphatic monocarboxylic acid, a polybasic acid and a diamine as described above, and many products obtained by such dehydration reaction are In this case, it is a mixture of a product composed of a higher aliphatic monocarboxylic acid, a polybasic acid and a diamine and a product composed of a higher aliphatic monocarboxylic acid and a diamine and containing no polybasic acid. The production ratio changes depending on the synthesis conditions such as the molar ratio of each component charged during synthesis. In the present invention, the ratio of the reaction product of the higher aliphatic monocarboxylic acid and the diamine and containing no polybasic acid is 10 to 50% by weight based on the total carboxylic acid amide wax (C ) A carboxylic acid amide wax is more preferably used.

The weight% of the reaction product of the higher aliphatic monocarboxylic acid and the diamine and containing no polybasic acid is determined by using a differential scanning calorimeter. In particular,
(C) Second scan using carboxylic acid amide wax as sample (when temperature is raised, lowered once, and then raised again)
Which is a reaction product of a higher aliphatic monocarboxylic acid and a diamine and which corresponds to a reaction product containing no polybasic acid, and a heat of fusion of a peak, and a separately available higher aliphatic monocarboxylic acid and diamine It can be determined by comparing the amounts of heat of fusion obtained in the same manner by using a pure compound that is a reaction product of the above and does not contain a polybasic acid as a sample.

The carboxylic acid amide wax (C) is excellent not only in the effect of improving the adhesiveness but also in the effect of improving the injection moldability, and it is a reaction product of a higher aliphatic monocarboxylic acid and a diamine, and is a polybasic acid. The ratio of the reaction product not containing is 10 to 50 with respect to the total carboxylic acid amide wax.
By using the (C) carboxylic acid amide type wax in a weight percentage, a PPS resin composition more excellent in this respect can be obtained.

The amount of the carboxylic acid amide wax (C) added is 0.01 with respect to 100 parts by weight of the PPS resin.
The range is from 10 to 10 parts by weight, preferably from 0.1 to 5 parts by weight. If the addition amount is less than 0.01 parts by weight, the effect of improving the adhesiveness with the epoxy resin is insufficient, which is not preferable, and if the addition amount exceeds 10 parts by weight, gas generation during injection molding is induced, which is not preferable.

In the present invention, in order to improve strength, dimensional stability and the like, (F) fibrous and / or
Alternatively, a non-fibrous filler is used. Such (F) fibrous and / or non-fibrous fillers include glass fibers, carbon fibers, potassium titanate whiskers, zinc oxide whiskers, aluminum borate whiskers, aramid fibers, alumina fibers, silicon carbide fibers, ceramic fibers, asbestos fibers. ,
Gypsum fiber, fibrous filler such as metal fiber, wollastonite, zeolite, sericite, kaolin, mica, clay, pyrophyllite, bentonite, asbestos,
Silicates such as talc and alumina silicate, alumina,
Metal compounds such as silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, iron oxide, calcium carbonate, magnesium carbonate, carbonates such as dolomite, calcium sulfate, sulfates such as barium sulfate, glass beads, ceramic beads, boron nitride, Non-fibrous fillers such as silicon carbide, magnesium hydroxide and silica are mentioned, which may be hollow, and further these fillers
It is also possible to use more than one type. Further, these (F) fibrous and / or non-fibrous fillers are used after being pretreated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound or an epoxy compound. Is more preferable in the sense of obtaining better mechanical strength.

When such a (F) fibrous and / or non-fibrous filler is used, its preferable blending amount is
(A) polyphenylene sulfide resin and (B) and /
Alternatively, it is 15 to 250 parts by weight, and more preferably 20 to 150 parts by weight, based on 100 parts by weight of the total of the (D) olefin-based copolymer and the (E) epoxy group-free elastomer.

The PPS resin composition of the present invention contains γ-glycidoxypropyltrimethoxysilane and γ-glycidoxy for the purpose of improving the mechanical strength and moldability of the PPS resin composition so long as the effects of the present invention are not impaired. Epoxy group-containing alkoxysilane compounds such as propyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, mercapto group-containing alkoxy such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane Silane compound, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl)
Ureido group-containing alkoxysilane compounds such as aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane , Γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane and other isocyanato group-containing alkoxysilane compounds, γ-
To add an organic silane compound such as an amino group-containing alkoxysilane compound such as (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, and γ-aminopropyltrimethoxysilane. You can

The PPS resin composition of the present invention contains a plasticizer such as a polyalkylene oxide oligomer compound, a thioether compound, an ester compound, an organic phosphorus compound, talc, kaolin, and an organic compound as long as the effects of the present invention are not impaired. Crystal nucleating agents such as phosphorus compounds, release agents, lubricants,
Ordinary additives such as antioxidants, heat stabilizers, UV inhibitors, colorants, flame retardants and foaming agents can be added. Further, the PPS resin composition of the present invention is a polyester such as polybutylene terephthalate, polyethylene terephthalate, polycyclohexane dimethylene terephthalate, polysulfone, etc. within a range that does not impair the effects of the present invention.
Polytetrafluoroethylene, polyetherimide, polyamideimide, polyimide, polycarbonate, polyethersulfone, polyetherketone, polythioetherketone, polyetheretherketone, epoxy resin, phenol resin, polyamide elastomer, polyester elastomer, polyalkylene oxide, etc. It may contain a resin.

The method for preparing the composition of the present invention is not particularly limited, but the pellet surface obtained by melt pelletizing a PPS resin or a mixture of a PPS resin and an olefinic copolymer, a filler, etc. A method of adhering an acid amide wax and subjecting it to molding or a mixture of raw materials is a single-screw, twin-screw extruder, Banbury mixer, kneader,
As an example, a method of supplying it to a conventionally known melt mixer such as a mixing roll and kneading at a temperature of 280 to 380 ° C. can be mentioned. The order of mixing the raw materials in the case of melt mixing is not particularly limited, and the PPS resin, the olefin copolymer of (B) or (D), the (C) carboxylic acid amide wax, and, if necessary, other A method of dry-blending the compound and then melt-kneading it by the above-mentioned method, or a method of dry-blending a part of the PPS resin and other compound and melt-kneading them and then melt-kneading the rest It is possible.

With the above constitution, the PPS resin composition of the present invention has improved adhesiveness with the epoxy resin and is excellent in peel resistance. The epoxy resin mentioned here is not particularly limited, and examples thereof include bisphenol A, bisphenol F, bisphenol S, bisphenol AF, bisphenol AD,
4,4'-dihydroxybiphenyl, resorcin, saligenin, trihydroxydiphenyldimethylmethane, tetraphenylolethane, halogen-substituted and alkyl-substituted products thereof, butanediol, ethylene glycol, elitsu, novolac, glycerin, polyoxyalkylene Such as glycidyl ether compounds synthesized from compounds containing two or more hydroxyl groups in the molecule and epichlorohydrin, glycidyl ester compounds such as phthalic acid glycidyl ester, aniline, diaminodiphenylmethane, metaxylene diamine, 1,3-bis A glycidylamine system synthesized from primary or secondary amines such as aminimethylcyclohexane and epichlorohydrin,
And the like, non-glycidyl epoxy resins such as glycidyl epoxy resins, epoxidized soybean oil, vinyl cyclohexene dioxide, dicyclopentadiene dioxide and the like. These epoxy resins are used alone or as a mixture of two or more kinds. Further, these epoxy resins are generally used after being cured with a curing agent. Examples of the curing agent include amines, polyamides, amino resins, acid anhydrides, polyphenols, phenol resins, polysulfides, isocyanates and the like.

The polyphenylene sulfide resin composition obtained by the present invention does not significantly deteriorate the heat stability, melt flowability and mechanical strength of the resin composition, and is insufficient in the conventional PPS resin for improving the peel resistance. The resin composition is provided with the new characteristics described above. The resin composition thus obtained can be made into various molded articles such as injection molding, extrusion molding, compression molding and blow molding. The molded product thus obtained has good peeling resistance, and is particularly useful for embedding epoxy resin in electric and electronic parts.
ED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed circuit boards, tuners, speakers,
Microphone, headphones, small motor, magnetic head base, power module, semiconductor, liquid crystal, FDD
Carriage, FDD chassis, motor brush holder, parabolic antenna, electric / electronic parts such as computer related parts; VTR parts, TV parts,
Irons, hair dryers, rice cooker parts, microwave oven parts, audio parts, audio equipment parts such as audio / laser disks / compact disks, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, or water heaters and baths. Household and office electrical product parts represented by water supply equipment parts such as hot water amount and temperature sensor; office computer related parts, telephone related parts, facsimile related parts, copier related parts, cleaning jigs, motor parts , Machine parts such as lighters, typewriters: microscopes, binoculars, cameras,
Optical equipment such as watches, precision machinery related parts; alternator terminal, alternator connector, I
C regulator, potentiometer base for light deer, various valves such as exhaust gas valve, fuel related
Exhaust system / intake system various pipes, air intake nozzle snorkel, intake manifold, fuel pump, engine cooling water joint, carburetor main body,
Carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, air conditioner thermostat base, heating hot air flow control valve, Brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts,
Distributor, starter switch, starter relay, transmission wire harness, window washer nozzle, air conditioner panel switch board, fuel-related electromagnetic valve coil, fuse connector, horn terminal, electrical component insulating plate, step motor rotor, lamp socket, Lamp reflector,
It is also applicable to automobile / vehicle related parts such as lamp housings, brake pistons, solenoid bobbins, engine oil filters, ignition device cases, and various other applications.

[0049]

The present invention will be described in more detail with reference to the following examples.

Various characteristics shown in Examples and Comparative Examples were evaluated according to the following methods.

Tensile shear adhesive strength: ASTM No. 1 tensile test piece is divided into two equal parts, and a spacer (thickness 40 to 50 μm) and an epoxy resin (two-component epoxy resin, XNR5002, XNH5002 manufactured by Nagase Ciba Co., Ltd.) Fixed with a pinch. This was cured and the tensile strength was measured at a speed of 10 mm / min, and the maximum value of the strength was divided by the adhesive area to obtain the tensile shear adhesive strength.

Bending strength, elastic modulus: According to ASTM D790.

Peel resistance test: bottom 100 mm × 70 m
A box-shaped molded product having a rectangular shape of m and a height of 45 mm was injection-molded using the PPS resin composition. After pouring the above-mentioned two-pack type epoxy resin into the box-shaped molded product to a height of 25 mm and curing it, (minus 40 ° C. × 2 hours, plus 140 ° C.)
80 cycles of treatment was performed with 1 cycle of (° C. × 2 hours) as one cycle, and the peeling state between the box-shaped molded product and the epoxy resin interface was visually observed.

Moldability evaluation: length 40 mm x width 15 mm x
A molded piece having a rib with a thickness of 1 mm and a height of 2 mm was molded at a cylinder temperature of 320 ° C., a mold temperature of 135 ° C., and an injection time of 1
Injection molding was performed under the conditions of 0 seconds and a cooling time of 10 seconds, and the judgment was made based on the presence or absence of molding defects such as the molded piece sticking to the fixed side mold, or the molded piece and the sprue were cut.

The compounding materials used in Examples and Comparative Examples are shown below.

(B) Olefin-based copolymer B-1 containing ethylene-glycidyl methacrylate = 88 /, whose main constituent is glycidyl ester of α-olefin and α, β-unsaturated acid
12 (wt%) copolymer B-2: ethylene / glycidyl methacrylate = 91 /
9 (wt%) Copolymer (D) Olefin-based copolymer D-1 containing glycidyl ester of α-olefin, glycidyl ester of α, β-unsaturated acid and other monomer as essential components: ethylene / glycidyl methacrylate ( E / G
MA) = 85/15 (wt%) as the main skeleton, and acrylonitrile / styrene (AS) = 30/70 (wt%) graft-copolymerized, wherein (E / GMA) /
(AS) = 70/30 (wt%) copolymer D-2: ethylene / glycidyl methacrylate / methyl acrylate = 38.7 / 2.3 / 59 (wt%) copolymer (E) containing epoxy group Not Elastomer E-1: Ethylene / Butene-1 = 82/18 (wt%)
Copolymer E-2: Ethylene / ethyl acrylate = 85/15 (wt%) Copolymer Reference Example 1 (PPS resin) PPS-1: Sodium sulfide 3.26 in autoclave.
Kg (25 mol, containing 40% of water of crystallization), sodium hydroxide 4 g, sodium acetate trihydrate 1.19 Kg (about 8.8 mol) and NMP 7.9 Kg were charged and gradually heated to 205 ° C. with stirring. After warming, about 1.5 liters of distilled water containing 1.36 kg of water was removed. 3.72 kg (25.3 mol) of 1,4-dichlorobenzene and 2 kg of NMP were added to the residual mixture, and the mixture was heated at 265 ° C for 3 hours. The reaction product was washed 5 times with warm water at 80 ° C.
After being washed twice with an acetic acid aqueous solution having a pH of 4 at 0 ° C., washed again with warm water, dried under reduced pressure at 80 ° C. for 24 hours, and powdered polyphenylene having a melt viscosity of about 650 poise (310 ° C., shear rate 1000 sec ⁻¹ ). Sulfide (PPS-1) about 2Kg
Got The melt flow rate value of this PPS resin at the time of 30 minutes residence is 110 of the melt flow rate value at the time of 5 minutes residence.
%Met.

Reference Example 2 (PPS Resin) PPS-2: The above PPS-1 was melted at 220 ° C. in an air atmosphere and had a melt viscosity of about 950 poise (310 ° C., shear rate 1).
The heat treatment was performed until it reached 000 sec- ¹ ). The melt flow rate value of this PPS resin after retaining for 30 minutes was 70% of the melt flow rate value after retaining for 5 minutes.

Reference Example 3 (Synthesis of Carboxylic Acid Amide Wax) PA-1: 1.97 mol of stearic acid and 0.32 mol of sebacic acid were charged in a reactor, heated and dissolved, and 1.37 mol of ethylenediamine was gradually added. In addition, a dehydration reaction was started at 160 ° C. in a nitrogen stream, and after reaction at 250 ° C. until the amine value became 5 or less, a wax-like substance (PA-1) was obtained. When this wax was used as a sample and measured by a differential scanning calorimeter under the following conditions, an endothermic peak was recognized at 143 ° C., and the calorific value was 79 J / g. On the other hand, a differential scanning calorimeter was similarly prepared using ethylene bis-stearyl amide (corresponding to a reaction product of a higher aliphatic monocarboxylic acid and a diamine in the case of using the above raw materials, which does not contain a polybasic acid) as a sample. When an endothermic peak was observed at 145 ° C., the calorific value was 125 J / g. Since the endothermic peak temperatures are almost the same, 143 of PA-1
The endothermic peak at ° C is considered to correspond to ethylene bis-stearyl amide, and from the calorific ratio, ethylene bis-stearyl amide in PA-1 is about 63% by weight. The differential scanning calorimeter analysis showed that both the rate of temperature increase and the rate of temperature decrease were 20
° C / min, scanning range 50 ° C to 170 ° C, sample volume about 4 m
The melting peak value for the second time was used by scanning at two consecutive scans.

Reference Example 4 (Synthesis of Carboxylic Acid Amide Wax) PA-2: 2 mol of stearic acid and 1 sebacic acid in a reactor.
After adding 2 mol of ethylenediamine and heating and dissolving, 2 mol of ethylenediamine was added, and the dehydration reaction was started at 160 ° C. in a nitrogen stream.
After the reaction at 0 to 260 ° C. until the amine value becomes 5 or less,
A waxy product was obtained (PA-2). When measured with a differential scanning calorimeter in the same manner as above, an endothermic peak was observed at 143 ° C., and the calorific value was 37.5 J / g. Therefore, from the calorific ratio, the ethylenebisstearylamide of PA-2 is about 30% by weight.

Examples 1 to 8 PPS resin, glycidyl group-containing olefin copolymer,
After carboxylic acid amide wax and other compounding ingredients were dry blended in the proportions shown in Table 1, 280 to 32
The mixture was melt-kneaded and pelletized by a screw type extruder set to a temperature condition of 0 ° C. Bending strength, bending elastic modulus, tensile shearing adhesive strength, peeling resistance, and moldability measurement evaluation test pieces were molded using the obtained pellets. Table 1 shows the measurement results of the flexural strength, flexural modulus, tensile shear adhesive strength, peel resistance, and moldability of the obtained test pieces.

Comparative Example 1 Example 1 except that the carboxylic acid amide wax and the glycidyl group-containing olefin copolymer were not blended.
Dry blending, melt kneading, and pelletizing were performed in the same manner as in. Bending strength, bending elastic modulus, tensile shearing adhesive strength, peeling resistance, and moldability measurement evaluation test pieces were molded using the obtained pellets. Table 2 shows the measurement results of the flexural strength, flexural modulus, tensile shear adhesive strength, peel resistance, and moldability of the obtained test pieces.

Comparative Example 2 Dry blending, melt kneading, and pelletization were carried out in the same manner as in Example 1 except that the glycidyl group-containing olefin copolymer was not blended. Bending strength, bending elastic modulus, tensile shearing adhesive strength, peeling resistance, and moldability measurement evaluation test pieces were molded using the obtained pellets. Flexural strength, flexural modulus, tensile shear adhesive strength measured on the obtained test piece,
Table 2 shows the results of measurement of peeling resistance and moldability.

As can be seen from Comparative Examples 1 and 2, the addition of the carboxylic acid amide wax is effective in improving the tensile shear adhesive strength, but the peel resistance is insufficient by itself.

Comparative Example 3 Dry blending, melt kneading, and pelletization were performed in the same manner as in Example 1 except that the carboxylic acid amide wax was not added. Bending strength, bending elastic modulus, tensile shearing adhesive strength, peeling resistance, and moldability measurement evaluation test pieces were molded using the obtained pellets. Flexural strength, flexural modulus, tensile shear adhesive strength, peel resistance measured on the obtained test pieces,
The results of moldability measurement are shown in Table 2.

When the carboxylic acid amide type wax is not added in this way, the tensile shear adhesive strength is low and the peel resistance is insufficient.

Comparative Example 4 Dry blending, melt-kneading, and pelletizing were carried out in the same manner as in Example 1 except that only the elastomer containing no epoxy group was used instead of the glycidyl group-containing olefin copolymer. Bending strength using the obtained pellets,
Bending elastic modulus, tensile shear adhesive strength, peeling resistance, and moldability measurement evaluation test pieces were molded. Table 2 shows the measurement results of the flexural strength, flexural modulus, tensile shear adhesive strength, peel resistance, and moldability of the obtained test pieces.

As described above, when an epoxy group-free elastomer is used instead of the glycidyl group-containing olefin copolymer, even if a carboxylic acid amide wax is added, the tensile shear adhesive strength is low and the peeling resistance is poor. Will be enough.

[0068]

[Table 1]

[0069]

[Table 2]

[0070]

INDUSTRIAL APPLICABILITY The polyphenylene sulfide resin composition of the present invention relates to a polyphenylene sulfide resin composition having improved adhesiveness with an epoxy resin and a relatively low elastic modulus, for example, box-shaped molding of the polyphenylene sulfide resin composition. Suitable for applications such as embedding electrical and electronic parts in the body with epoxy resin.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI // (C08L 81/02 C08L 23:02 23:02 101: 00 101: 00) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08L 81/00-81/02 C08L 23/00-23/24 C08K 5/20 C08K 3/00-3/20 C08K 7/02-7/14

Claims (8)

(57) [Claims] 1. A polyphenylene sulfide resin (A) 10
(B) α-olefin 60 to 99.
2 to 70 parts by weight of an olefinic copolymer containing 5% by weight and 0.5 to 40% by weight of a glycidyl ester of an α, β-unsaturated acid as a main constituent, and (C) a higher aliphatic monocarboxylic acid A polyphenylene sulfide resin composition, which comprises 0.01 to 10 parts by weight of a carboxylic acid amide wax obtained by reacting a polybasic acid and a diamine. 2. A polyphenylene sulfide resin (A) 10
0 parts by weight of (D) α-olefin (1) and α,
An olefin-based copolymer having a glycidyl ester of a β-unsaturated acid (2) and a monomer (3) represented by the following general formula as essential components, and the copolymerization ratio is (1) /
(2) = 60 to 99% by weight / 40 to 1% by weight, and their total amount ((1) + (2)) 95 to 40% by weight
In contrast, the monomer (3) represented by the following general formula is 5 to 60
0.0% by weight of an olefin copolymer and (C) a carboxylic acid amide wax obtained by reacting a higher aliphatic monocarboxylic acid with a polybasic acid and a diamine.
A polyphenylene sulfide resin composition comprising 1 to 10 parts by weight. [Chemical 1] (Wherein R ¹ represents hydrogen or a lower alkyl group, X 1
Is one or more groups selected from —COOR ² group, —CN group or aromatic group. R ² has 1 to 10 carbon atoms
Represents the alkyl group of 3. A carboxylic acid amide wax, wherein the proportion of the reaction product of the higher aliphatic monocarboxylic acid and the diamine in the (C) carboxylic acid amide wax does not contain a polybasic acid. To 10 to 50% by weight
The polyphenylene sulfide resin composition according to claim 1 or 2, wherein the carboxylic acid amide wax (C) is used. 4. The (A) polyphenylene sulfide resin comprises:
ASTM D1238-86 (315.5 ° C, 5000
A polyphenylene sulfide resin having a melt flow rate value after 30 minutes retention defined by g load) of 80% or more of the melt flow rate value after 5 minutes retention.
The polyphenylene sulfide resin composition according to any one of 3 above. 5. The polyphenylene sulfide resin composition according to claim 1, further comprising 2 to 70 parts by weight of (E) an epoxy group-free elastomer based on 100 parts by weight of the (A) polyphenylene sulfide resin. 6. (E) The epoxy group-free elastomer is an ethylene-propylene copolymer, an ethylene-butene copolymer, an ethylene-propylene-diene copolymer, an ethylene-ethyl acrylate copolymer, an ethylene-ethylene copolymer. The polyphenylene sulfide resin composition according to claim 5, which is an elastomer selected from a butyl acrylate copolymer. 7. (F) a fibrous and / or non-fibrous filler, further comprising (A) a polyphenylene sulfide resin, (B) and / or (D) an olefin copolymer and (E) an epoxy group. Not a total of 10 elastomers
The polyphenylene sulfide resin composition according to any one of claims 1 to 6, which is blended in an amount of 15 to 250 parts by weight with respect to 0 parts by weight. 8. A molded product obtained by molding the polyphenylene sulfide resin composition according to any one of claims 1 to 7 and used by adhering an epoxy resin.