JPH0782485A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition having excellent appearance because of improvement in compatibility between resins, showing excellent heat resistance, flame retardance, mechanical properties, by blending a specific polyphenylene sulfide resin with a polyarylene ether-based resin and a specific compatibilizing agent. CONSTITUTION:This composition is obtained by blending 100 pts.wt. of total of (A) a polyphenylene sulfide resin having 5-50mumol/g end thiol group concentration (preferably a resin of a linear structure containing >=70mol% unit of the formula, washed after treatment with an acid) and (B) a polyarylene ether-based resin [preferably poly(2,6-dimethyl-1,4-phenylene) ether, etc.] with (C) 0.1-30 pts.wt. of a cured material of an epoxy resin. A cured material obtained by curing a naphthalene type polyfunctional epoxy resin with a polyamidoamine or a polyethyleneimine is preferable as the component C. Fine powder or powder having <=300mum is preferably used as the component C and is uniformly dispersed into the component A.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a polyarylene sulfide resin (A) having a terminal thiol group concentration within a specific range.
And a polyphenylene ether-based resin (B) and a cured epoxy resin (C). Particularly, the compatibility of the polyarylene sulfide resin (A) and the polyphenylene ether-based resin (B) is dramatically improved. The present invention relates to an improved resin composition.

[0002]

2. Description of the Related Art Conventionally, polyarylene sulfide (hereinafter, referred to as P) having heat resistance, chemical resistance, flame retardancy and mechanical strength.
(Abbreviated as AS) resin and an amorphous resin having a high degree of heat resistance and hot water resistance, which has a small anisotropy and a high glass transition point, resulting in high rigidity at high temperature, Polyphenylene ether with excellent dimensional stability (hereinafter referred to as PP
A technique for obtaining a resin composition having all of the above performances by using a resin together with (abbreviated as E) is disclosed.

For example, Japanese Patent Publication No. 56-34032 discloses PP.
A technique for obtaining a resin composition excellent in molding processability, chemical resistance, mechanical strength, and flame retardancy by using an E resin and a polyphenylene sulfide (hereinafter abbreviated as PPS) resin in combination is disclosed. Further, JP-A-59-164360 discloses a technique for improving the compatibility of a blend composition of a polyphenylene sulfide resin and a polyphenylene oxide by interposing an epoxy resin.

In addition, Japanese Patent Laid-Open No. 2-36261 discloses a PP
A technique for imparting homogeneity in a polymer mixture containing an E resin and a PAS resin by containing a specific homogenizing agent as used for a polyphenylene ether-polyamide polymer mixture is disclosed.

Further, Japanese Patent Laid-Open No. 2-36262 discloses a PP
In a polymer mixture containing E resin and PAS resin, functionalized polyphenylene ether in combination with an epoxy compound.
Techniques for obtaining homogenized polymer blends with improved mechanical properties by using tellurium have been disclosed.

[0006]

However, the PAS
It is difficult to say that the compatibility between the resin and the PPE resin is still at a sufficient level, and the appearance is inferior such as poor dispersion / unevenness on the surface of the molded product, and the performance is not sufficiently satisfactory. is the current situation. .

The problem to be solved by the present invention is that the PAS
A resin composition having small anisotropy, which has improved compatibility between a resin and a poly (arylene ether) -based resin, is excellent in heat resistance, flame retardancy, mechanical properties, and has dimensional stability and a good appearance. To provide.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that the PAS resin (A) and the poly (arylene ether) -based resin having a terminal thiol group concentration in a specific range. It was found that the above problems can be solved by adding a specific amount of a cured epoxy resin (C) as a compatibilizing agent to a resin composition comprising (B), and to complete the present invention. I arrived.

That is, the present invention has a terminal thiol group concentration of 5 μm.
0.1 to 30 parts by weight of an epoxy resin cured product (C) based on 100 parts by weight of the total amount of the polyarylene sulfide resin (A) and the polyphenylene ether-based resin (B) which are mol / g or more and 50 μmol / g or less. The present invention relates to a resin composition containing the same.

It is essential for the PAS resin used in the present invention that the concentration of the terminal thiol group is within a specific range, that is, the concentration of the terminal thiol group is 5 μmol / g or more, 50
A poly (arylene sulfide) resin having a concentration of μmol / g or less is used. When the terminal thiol group concentration is less than 5 μmol / g, the reactivity with the polyphenylene ether resin or the epoxy resin cured product is poor, and when the terminal thiol group concentration exceeds 50 μmol / g, the composition during processing is Color tone and melt viscosity become unstable.

Generally, the terminal thiol group concentration is
It can be quantified by the iodoacetamide method described in No. 187731, etc., but the principle and operation are shown below. (1) Principle (iodoacetamide method)

[0012]

[Chemical 1]

(2) Operation A powdery polymer sample (about 10 mg to 1 g) is precisely weighed and placed in a tightly closed test tube, and an acetone solution containing 2.5 ml of acetone and 50 mmol of iodoacetamide is used.
Add 5 ml, seal tightly, heat at 100 ° C. for 60 minutes, cool with water, open the bottle, separate the liquid phase portion, and measure the absorbance at 450 nm (absorbance of I ₂ ) using an ultraviolet absorptiometer. Advance model thiol compounds "Cl-C ₆ H ₄
The terminal thiol group concentration is calculated from the absorbance using the calibration curve prepared for "-SH". (The sample amount was such that the concentration of thiol groups in the acetone slurry was 0.1 to 0.
It is preferable to select appropriately so as to be in the range of 3 mmol. ) The same powdery sample is measured three times to obtain the average value of the terminal thiol group concentration.

The PAS resin (A) used in the present invention is a random copolymer, a block copolymer, or a copolymer containing a repeating unit having a structure in which a sulfur atom is bonded to an aromatic ring which may have a substituent. Or a mixture with a homopolymer. Typical examples of these resins include polyphenylene sulfide, polyphenylene sulfide ketone, polyphenylene sulfide sulfone, and polyphenylene sulfide ketone sulfone. Among PASs, the bond of the repeating unit preferably has a structure in the para position with respect to the aromatic ring in terms of heat resistance and crystallinity.

In particular, a PPS resin containing 70 mol% or more of a structural unit represented by the following general formula (2) (the aromatic ring does not contain a substituent) is preferable in terms of physical properties and economy. If the amount is less than 70 mol%, it tends to be difficult to obtain a composition having excellent properties.

[0016]

[Chemical 2]

As the method for polymerizing the PPS resin, for example, p-dichlorobenzene and p-dichlorobenzene are polymerized in the presence of sulfur and sodium carbonate, if necessary, and other copolymerization components. Further, if necessary, other copolymerization components are polymerized in a polar solvent in the presence of sodium sulfide or sodium hydrosulfide and sodium hydroxide or in the presence of hydrogen sulfide and sodium hydroxide, p-chlorothiophenol. And, if necessary, a method of self-condensing other copolymerization components, sodium sulfide and p-dichlorobenzene in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone solvent such as sulfolane, Further, if necessary, there may be mentioned a method of reacting with another copolymerization component, among which the method is suitable. At this time, it is preferable to add an alkali metal salt of a carboxylic acid or a sulfonic acid or an alkali hydroxide to adjust the degree of polymerization.

The copolymerization component contained in the PPS resin is, for example, a meta bond represented by the following structural formula 3, an ether bond represented by the structural formula 4, or a structural formula 5.
A sulfone bond shown, a sulfide ketone bond shown in Structural Formula 6, a biphenyl bond shown in Structural Formula 7,
Examples include a substituted phenyl sulfide bond represented by Structural Formula 8, a trifunctional phenyl sulfide bond represented by Structural Formula 9, and a naphthyl bond represented by Structural Formula 10, and the content thereof is preferably less than 30 mol%. Is. However,
When a trifunctional or higher functional bond is contained, the content is usually 5 mol% or less, preferably 3 mol% or less.

[0019]

[Chemical 3]

[0020]

[Chemical 4]

[0021]

[Chemical 5]

[0022]

[Chemical 6]

[0023]

[Chemical 7]

[0024]

[Chemical 8]

[0025]

[Chemical 9]

[0026]

[Chemical 10]

The PAS resin (A) used in the present invention is preferably a PAS resin having a substantially linear structure. PAS resin having a substantially linear structure is disclosed in Japanese Examined Patent Publication No.
It can be manufactured by the manufacturing method represented by JP 2-12240 G, but is not limited to this method.

The PAS resin having a substantially linear structure, which is preferably used in the present invention, is particularly preferably washed after acid treatment. The acid used for this acid treatment is not particularly limited as long as it has no action of decomposing the PAS resin, but acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid,
Examples thereof include silicic acid, carbonic acid and propylic acid, with acetic acid and hydrochloric acid being preferred. Examples of the acid treatment method include a method of immersing the PAS resin in an acid or an acid aqueous solution, and stirring or heating may be performed as necessary.

For example, the case of acid treatment of PPS with acetic acid will be described. A sufficient effect can be obtained by immersing PPS in an aqueous solution of pH 4 heated to 80 to 90 ° C. and stirring for 30 minutes. The acid-treated PPS is
In order to physically remove the remaining acid or salt, it is preferable to wash with water or warm water several times. The water used at this time is preferably distilled water or deionized water.

For the acid treatment which is preferably carried out in the PAS resin preferably used in the present invention, it is also possible to use the PAS resin powder or granules, and the PAS resin in the slurry state after polymerization is directly treated with an acid. It is also possible to use it for processing.

Further, in the present invention, a polyarylene sulfide resin modified with a carboxyl group, that is, a carboxyl group-containing resin (hereinafter, CPAS resin) can be contained. The CPAS-based resin includes, for example, a carboxyl group-containing polyarylene sulfide (CPAS) represented by the following general formula (11), (12) or (13) represented by the following general formula and a polycyclic compound represented by the following chemical formula (2). Examples thereof include a copolymer with arylene sulfide (PAS) and the like, but the production method by copolymerization is not limited.

[0032]

[Chemical 11]

[0033]

[Chemical 12]

(In the formula, Y is --O--, --SO _2- , --CH _{2
-, - C (CH 3)} 2 -, - CO-, C (CF 3) 2 - or an single bond. )

[0035]

[Chemical 13]

The content ratio of the carboxyl group-containing arylene sulfide structural unit represented by the above Chemical formula 11, Chemical formula 12 or Chemical formula 13 cannot be unconditionally specified because it depends on the purpose of use and the like, but it is 0.5 to 0.5 in the CPAS resin. It is 30 mol%, preferably 0.8 to 20 mol%. The CPAS-based resin obtained by such copolymerization may be a random type, a block type, or a graft type. Most typically, the PAS part is PPS and C
There is a copolymer in which the PAS moiety is CPPS represented by Chemical formula 11.

The method for producing a CPAS resin by copolymerization is as follows:
For example, in the case of a random type, JP-A-63-305
131, a method using a dihalogeno aromatic compound, an alkali metal sulfide, a dihalogeno aromatic carboxylic acid and / or an alkali metal salt thereof, and an alkali sulfide used in the production method described in the publication. Instead, a method using an alkali metal hydrosulfide compound and an alkali metal hydroxide can be adopted. In the case of block type, (1) in a polar solvent in which the PAS prepolymer is present,
(2) Polarity of a CPAS prepolymer in which a dihalogenoaromatic carboxylic acid and / or an alkali metal salt thereof is reacted with a sulfidizing agent (alkali sulfide; a combination of an alkali metal hydrosulfide compound and an alkali metal hydroxide) There are methods such as reacting a dihalogeno aromatic compound with a sulfidizing agent in a solvent, and (3) reacting a PAS prepolymer with a CPAS prepolymer in a polar solvent.

Further, in the present invention, an amino group-modified polyarylene sulfide resin (hereinafter, referred to as APAS resin) can be contained. The amino group content in the APAS resin that can be contained in the present invention is preferably 0.1 to 30 mol%. The APAS-based resin that can be contained in the present invention is polymerized in the presence of an amino group-containing aromatic halide when reacting an alkali metal sulfide and dihalobenzene in an amide-based solvent such as N-methylpyrrolidone. ,
Although it can be obtained by a method by copolymerization, it is not limited to the method by copolymerization.

Examples of the amino group-containing aromatic halide which can be used in the production of the APAS resin by copolymerization include the compounds generally represented by the following formula (14).

[0040]

[Chemical 14]

(In the formula, X is halogen, Z is hydrogen, --NH
₂ or halogen, R ₁ is a hydrocarbon group having 1 to 12 carbon atoms, m
Is an integer of 0 to 4. ) Specific examples thereof include m-fluoroaniline, m-chloroaniline, 3,5-dichloroaniline, 2-amino-4-chlorotoluene, 2-amino-6-chlorotoluene, 4-amino-2-chloro. Mention may be made of toluene, 3-chloro-m-phenylenediamine, m-bromoaniline, 3,5-dibromoaniline, m-iodoaniline and mixtures thereof.

As the polyarylene ether resin (B) in the present invention, a polyphenylene ether resin can be used. The polyphenylene ether resin that can be used in the present invention is, for example, a compound represented by the following general formula 15
Is a generic term for homopolymers or copolymers containing one or more units represented by.

[0043]

[Chemical 15]

(In the formula, R ₂ , R ₃ , R ₄ , and R ₅ are each independently hydrogen, halogen, hydrocarbon, halohydrocarbon,
Selected from the group consisting of hydrocarbon oxy and halohydrocarbon oxy, n representing the total number of monomer units, 2
It is an integer of 0 or more. )

The method for producing the above-mentioned polyphenylene ether resin is not particularly limited, but US Pat. Nos. 3,306,874, 3,306,875 and 325 are applicable.
It can be produced by the reaction of phenols by the method described in Nos. 7357 and 3257358. As these phenols, 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-methoxyphenol, 2-methyl-6-butylphenol, 2,6-dimethoxyphenol, 2,3,6-trimethylphenol, 2,3,5,6-tetramethylphenol and 2, Includes, but is not limited to, 6-diethoxyphenol.

The polyphenylene ether resin of the present invention may be a copolymer obtained by grafting a homopolymer or a copolymer represented by the chemical formula 15 with a styrene compound. As the styrene compound-grafted polyphenylene ether resin, a homopolymer or a copolymer represented by the chemical formula 15 can be used as a styrene compound.
For example, it is a copolymer obtained by graft-polymerizing styrene, α-methylstyrene, vinyltoluene, chlorostyrene and the like.

A preferred polyphenylene ether resin that can be used in the present invention is poly (2,6-dimethyl-
1,4-phenylene) ether.

The polyarylene ether resin (B) of the present invention may contain a styrene resin.

The styrenic resin that can be contained in the present invention contains a repeating structural unit derived from a vinyl aromatic compound represented by the following general formula 16 in its polymer.
Must have at least 5% by weight.

[0050]

[Chemical 16]

(Wherein R ₆ is hydrogen or an alkyl group having 1 to 4 carbon atoms, A is a halogen or a substituent group which is an alkyl group having 1 to 4 carbon atoms, and p is an integer of 1 to 5). It is.)

Examples of such styrenic polymers include homopolymers of styrene and its derivatives and polybutadiene, polyisoprene, butyl rubber, EPD.
M, ethylene-propylene copolymer, natural rubber, a mixture of natural or synthetic elastomeric substances such as epichlorohydrin, or a styrene-based polymer modified with these, and a styrene-containing copolymer such as styrene-acrylonitrile copolymer, styrene -Butadiene copolymer, acid modified styrene-hydrogenated butadiene copolymer, epoxy modified styrene-hydrogenated butadiene copolymer, styrene-maleic anhydride copolymer, styrene-acrylonitrile-butadiene copolymer can be mentioned. . Preferred styrenic resins that can be contained in the present invention are homopolystyrene, rubber-reinforced polystyrene, acid-modified-styrene-hydrogenated butadiene copolymer and epoxy-modified-styrene.
It is a hydrogenated butadiene copolymer.

The content ratio of the styrene resin to the polyarylen ether resin (B) is as follows: polyarylen ether resin (B) / styrene resin = 100/0 to 20 /
A range of 80 is preferred.

When the poly (arylene ether) resin (B) contains a styrene resin, the PAS resin (A) and the poly (arylene ether) resin (B) having a terminal thiol group concentration within a specific range. And epoxy cured product (C)
As a method for preparing a resin composition consisting of, a polyarylene ether resin and a styrene resin are melt-kneaded in advance, and then the melt-kneaded product, PAS resin (A) and epoxy cured product (C) are further mixed. However, the method is not limited to this.

The poly (arylene ether) resin (B) of the present invention comprises the group consisting of (a) ethylenic double bond and (b) carboxyl group, acid anhydride group, hydroxyl group and epoxy group in the molecule. A functionalized polyphenylene ether resin obtained by functionalizing with a functionalizing agent selected from organic compounds having simultaneously selected functional groups can be contained.

The functionalized polyphenylene ether resin which can be contained in the present invention is the polyphenylene ether resin described above.
It can be obtained by functionalizing a tell resin with a specific functionalizing agent.

The functionalizing agent used for preparing the functionalized polyphenylene ether resin is composed of (a) an ethylenic double bond and (b) a carboxyl group, an acid anhydride group, a hydroxyl group and an epoxy group in the molecule. An organic compound having simultaneously a functional group selected from the group, specifically, maleic acid,
Α, β-unsaturated dicarboxylic acids exemplified by fumaric acid, chloromaleic acid, citraconic acid, itaconic acid, etc .; exemplified by acrylic acid, planic acid, crotonic acid, vinylacetic acid, methacrylic acid, pentenoic acid, angelic acid, etc. Unsaturated monocarboxylic acids; anhydrides of these α, β-unsaturated dicarboxylic acids and unsaturated monocarboxylic acids; 1 mol of the above α, β-unsaturated dicarboxylic acids and ethylene glycol, propylene glycol, tri Methylene glycol, butane-1,
Aliphatic diols such as 4-diol, tetramethylene glycol, pentaethylene glycol, etc., and hydroquinone, resorcin, catechol, m-xylylene diol
, P-xylylene diol, 4,4'-dihydroxybiphenyl ether, bisphenol A, bisphenol
Dihydroxy-α, β-unsaturated dicarboxylic acid ester having a structure derived from 2 moles of an aromatic diol such as sulfur S and bisphenol F; α, β-unsaturated dicarboxylic acid 1
Hydroxy-α having a structure derived from 1 mol of an aliphatic diol or an aromatic dihydroxy compound,
β-unsaturated dicarboxylic acid ester; derived from α, β-unsaturated dicarboxylic acid and aliphatic polyvalent alcohol such as glycerol, pentaerythritol or aromatic polyphenol such as pyrogallol A hydroxy ester having a structure represented by the formula; a hydroxy unsaturated monocarboxylic acid ester having a structure derived from 1 mol of the above unsaturated monocarboxylic acid and 1 mol of the above aliphatic diol or an aromatic dihydroxy compound; Hydroxypolyunsaturated monocarboxylic acid esters having a structure derived from a saturated monocarboxylic acid and the aforementioned aliphatic polyhydric alcohol or aromatic polyhydric phenol; the aforementioned α, β-unsaturated dicarboxylic acid or Reaction products of unsaturated monocarboxylic acids with epichlorohydrin, which are glycidyl maleates, glycidyl acrylates, glycidyl methates Unsaturated epoxy compounds exemplified by tacrylate and the like can be mentioned.

The functionalized polyphenylene ether resin that can be contained in the present invention is prepared by the following method, but is not particularly limited thereto. For example, as the functionalized polyphenylene ether resin, the polyphenylene ether resin and the functionalizing agent described above are used at 150 to 350 ° C. using a roll mill, a Banbury mixer, an extruder or the like.
Even when prepared by melt-kneading and reacting at a temperature of benzene, toluene, heating the polyphenylene ether resin and the functionalizing agent in a solvent exemplified by xylene,
It may be prepared by reacting. In order to facilitate the functionalization reaction, organic peroxides and azobisisobutyrate such as benzoylper-oxide, di-t-butylperoxide, dicumylperoxide, t-butylperoxybenzoate, etc. are added to the reaction system. The presence of a radical initiator represented by azo compounds exemplified by ronitrile and azobisisovaleronitrile is effective. A more practical functionalization method is melt-kneading in the presence of a radical initiator.

The content of the functionalized polyphenylene ether resin in the poly (arylene ether) resin (B) of the present invention is not limited to a specific range, and PAS may be used.
A resin composition comprising a resin (A), a polyarylene ether resin (B) and an epoxy cured product (C),
Any range may be used as long as it achieves the object of the present invention.

The epoxy cured product (C) to be added in the present invention is produced by a curing reaction between an epoxy resin and a curing agent such as an acid compound, a phenol compound or an amine. The epoxy resin preferably contains one or more, especially two or more epoxy groups. Typical examples thereof include a condensation product of bisphenol A and epichlorohydrin, and a halogen in place of bisphenol A. Bisphenol A, resorcinol, bisphenol F, bisphenol S, 4-4 'diaminodiphenylmethane, hydroxynaphthalene and its derivatives as a glycidyl ether, naphthalene type polyfunctional epoxy resin, or novolac type Examples include epoxy resins and polyvalent alcohol type epoxy resins other than the above. Among them, diglycidyl ether of 1,6-dihydroxynaphthalene represented by the following formula 17 and triglycidyl ether or tetraglycidyl ether of a naphthalene ring-containing hydroxy compound represented by the following formulas 18 and 19 A naphthalene type polyfunctional epoxy resin such as ter is preferably used.

[0061]

[Chemical 17]

[0062]

[Chemical 18]

[0063]

[Chemical 19]

Examples of the curing agent for producing the epoxy cured product (C) to be added in the present invention include acid compounds, phenol compounds and amines as described above.

Examples of the acid compound include aliphatic acids such as adipic acid, azelaic acid and sebacic acid, alicyclic acids such as hexahydrophthalic anhydride and methyltetrahydrophthalic anhydride,
Aromatic acids such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic acid anhydride can be used.

Examples of the phenol compound include a phenol novolac resin and a cresol novolac resin.

The amines include (1) aliphatic polyamines such as alkylenediamines such as ethylenediamine, tetramethylenediamine and hexamethylenediamine, diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine and tetraamine. Polyalkylene polyamines such as ethylene pentamine and pentaethylene hexamine, alkylaminopropylamine, aminoethylethanolamine, alkyl or hydroxylalkylamine compounds such as methyliminobispropylamine, xylylenediamine, tetrachloro-p-xylylenediamine Such as aromatic-containing aliphatic amines such as (2) polyethyleneimine, (3) alicyclic or heterocyclic-containing aliphatic polyamines such as menthanediamine, - aminoethyl piperazine,
(3) 1,3-diaminocyclohexane, isophoronediamine, hydrogenated methylenedianiline, etc. (4) Aromatic polyamines such as phenylenediamine, toluenediamine,
Diaminodiphenylmethane, diaminodiphenyl sulfone, benzidine, 4,4′-bis (o-toluidine),
Thiodianiline, dianisidine, methylenebis (o-chloroaniline), bis (3,4-diaminophenyl) sulfone, diaminoditolylsulfone, 2,6-diaminopyridine, 4-chloro-o-phenylenediamine, 4-
Methoxy-6-methyl-m-phenylenediamine, m-
Aminobenzylamine, 4,4'-diamino-3,3 '
(5) Polyamidoamine such as dimethyldiphenylmethane, for example, long chain aliphatic diamine containing amide bond, which is produced from dimer acid having about 20 to 50 carbon atoms and aliphatic diamine, (6) Benzoacnamine and / or Include alkyl guanamine and its modified products, and (7) dicyandiamide. Among them, polyamidoamine or polyethyleneimine is preferably used.

The curing agents preferably used when producing the epoxy cured product (C) of the present invention are amines. Furthermore, in the case of producing the epoxy cured product (C) of the present invention with amines, the epoxy resin or the amines is used in an amount of 50 mol% more than the equivalent number of moles required for curing, within a range not departing from the object of the present invention. Can be blended in excess.

The epoxy resin cured product to be added in the present invention can be produced by various known methods. For example, the epoxy resin and an acid compound, a phenol compound, or amines, and if necessary, a catalyst such as a tertiary amine are heated and mixed to carry out addition condensation.
It is also possible to produce by cooling and pulverization, and further, a method of obtaining a cured epoxy resin powder by reacting a solution in which an epoxy resin and a curing agent are dispersed or dissolved in a water or a solvent having a relatively low boiling point ( JP-A-53-73249),
It is also possible to produce it by a method of curing reaction of an epoxy resin and an amine-based curing agent in a specific oligomer, and then adding an aliphatic alcohol and fractionating (JP-A-4-249536). It is not limited to these manufacturing methods.

The epoxy cured product (C) in the present invention is
It is preferably uniformly dispersed in the PAS resin, and in this sense, the specific epoxy cured product in the present invention is preferably in the form of fine powder or powder of 300 μm or less in advance. That is, based on the above-described known method, for example, the epoxy cured product after the heat curing reaction is finely pulverized to 300 μm or less by a mill or the like, and the curing reaction is performed in a specific medium such as a solvent to separate the fine particle cured product. As a result, a fine powder or powder-like epoxy cured product of the present invention can be obtained.

In the present invention, the composition ratio of the poly (arylene sulfide) resin (A), the poly (arylene ether) type resin (B) and the epoxy cured product (C) having a terminal thiol group concentration within a specific range is polyary- 1 total of ren sulfide resin (A) and polyarylen ether resin (B)
0.1 to 30 parts by weight of epoxy cured product (C) with respect to 00 parts by weight
It is a range containing parts by weight. If the added amount of the epoxy resin cured product is less than 0.1 part by weight, the effect of the present invention is insufficient, and if it exceeds 30 parts by weight, the strength of the composition tends to decrease.

Various reinforcing materials and fillers can be added to the composition of the present invention in order to improve the mechanical properties. As the reinforcing material and the filler which can be used in the present invention, glass fiber, carbon fiber, calcium titanate, potassium titanate, silicon carbide, aramid fiber, ceramic fiber, metal fiber, silicon nitride, barium sulfate, calcium sulfate, Kaolin, clay, bentonite, sericite, zeolite, mica, mica, talc, wollastonite,
PMF, ferrite, aluminum silicate, calcium silicate, calcium carbonate, dolomite, magnesium oxide,
Magnesium hydroxide, antimony trioxide, titanium oxide,
There are iron oxide, milled glass, glass beads, glass balloons and the like.

Further, the composition of the present invention may contain a lubricant such as graphite, molybdenum disulfide and polytetrafluoroethylene, and a stabilizer thereof. Further, the composition of the present invention, within the range not impairing the object of the present invention, an antioxidant,
There is no restriction due to the addition of heat stabilizers, ultraviolet absorbers, release agents, rust preventives, lubricants, crystal nucleating agents, colorants, silane coupling agents and the like.

Further, in the composition of the present invention, a thermosetting resin and other thermoplastic resins such as epoxy resin, silicone resin, polyimide, polyethylene, polypropylene, polystyrene, styrene butadiene are included as long as the object of the present invention is not impaired. One type of copolymer, polyamide, polycarbonate, polysulfone, polyether sulfone, polyarylate, polyacetal, polyether ketone, polyether ether ketone, polybutylene terephthalate, polyethylene terephthalate, liquid crystal polymer, polyamide imide, polyether imide, etc. The above can be blended.

The composition of the present invention can be prepared by various known methods. For example, after the PAS resin (A) having a terminal thiol group concentration in a specific range, the polyarylene ether resin (B) and the epoxy cured product (C) are mixed in advance with a Henschel mixer or a tumbler, uniaxial or 2 200 ℃ ~ 360 ℃ supplied to the axial extrusion kneader
It can be obtained by kneading with and granulating.

If necessary, other reinforcing materials may be added during mixing.
Fillers and various additives may be added.

[0077]

EXAMPLES The present invention will be further described below with reference to examples. Parts in the examples indicate parts by weight.

Reference Example 1 (Production of PPS-1) 1233 g of N-methylpyrrolidone and 636 g of 2.7 hydrate of sodium sulfide were added to a 5 l autoclave equipped with a stirrer.
(5.0 mol, analysis 61.5%), lithium acetate dihydrate 510 g (5.0 mol) and water 90 g (5.0 mol) were charged, and the amount was about 1 at 205 ° C. under a nitrogen atmosphere.
Distillate containing 257 g of water with stirring for 20 minutes
This resulted in 0 ml.

Then, the reaction system was cooled to 150 ° C. and 750 g (5.1 mol) of p-dichlorobenzene was added to N-.
A solution dissolved in 400 g of methylpyrrolidone was added and the reaction was carried out at 265 ° C. for 3 hours, during which the internal pressure at the end of the polymerization reaction was 9.0 Kg / cm ² .

Thereafter, the autoclave was cooled, the contents were filtered off, the cake was washed with hot water three times, and then with acetone twice, and then with an aqueous HCl solution of pH 1. After soaking at room temperature for 30 minutes, washing with deionized water / drying under reduced pressure at 80 ° C. gave 467 g of PPS. (Yield = 86
%)

The PPS thus obtained had a terminal thiol group concentration of 35 μmol / g, an intrinsic viscosity [η] of 0.25, a melt flow rate of 550 g / 10 minutes, and a total sodium content of 100 ppm. This is called PPS- (1).

The terminal thiol group concentration of PPS, logarithmic viscosity [η], melt flow rate and total sodium content were measured as follows. Terminal thiol group concentration According to the above-mentioned iodoacetamide method.

Logarithmic viscosity [η] The relative viscosity value of an α-methylchloronaphthalene solution of PPS (PPS concentration 0.4 g / 100 ml) at 206 ° C. (400 ° F.) was measured and calculated by the following formula.

[Η] = ln (relative viscosity value) / PPS concentration

Melt flow rate ASTM D1238 according to 316 ° C./5000 g load, orifice; 0.0825 ± 0.002 inch diameter ×
It is a value at a length of 0.315 ± 0.001 inch.

The total sodium content polymer was decomposed with sulfuric acid and measured by an atomic absorption method.

Reference Example 2 (Production of PPS- (2)) N-methylpyrrolidone (7900 g) and sodium sulfide (3260 g) (25 mol, 40% crystallization water) were added to an autoclave.
, Sodium hydroxide 4.0 g and sodium acetate trihydrate 3400 g (25 mol) were charged,
Under nitrogen atmosphere, gradually raise the temperature to 205 ° C. with stirring over about 2 hours, and 1500 m containing 1360 g of water
1 of distilled water was removed. Then, the reaction system was cooled to 150 ° C., and then 3750 g of p-dichlorobenzene (25.
5 mol) and 2000 g of N-methylpyrrolidone,
The reaction was carried out at 230 ° C for 4 hours, and further at 260 ° C for 2 hours. Thereafter, the autoclave was cooled, the contents were filtered off, and the cake was washed 5 times with hot water at 70 ° C. and dried under reduced pressure at 80 ° C. for 24 hours to give about 2200 g.
The granular PPS of was obtained (yield 82%).

Further, the granular PPS resin of about 220
20 g of pH 4 acetic acid aqueous solution heated to 90 ° C.
Pour into the inside, continue stirring for about 30 minutes, then filter, wash with ion-exchanged water at about 90 ° C. until the pH of the filtrate becomes 7,
It was dried at 120 ° C. for 24 hours.

The PPS thus obtained had a terminal thiol group concentration of 40 μmol / g, an intrinsic viscosity [η] of 0.32, a melt flow rate of 100 g / 10 min, and a total sodium content of 250 ppm. This is called PPS- (2).

Reference Example 3 (Production of CPPS) A 2 L autoclave was charged with 540 g of NMP, 139.2 g of sodium hydrosulfide (NaSH) having a purity of 73% by weight, and 72 g of sodium hydroxide, and the mixture was charged to 200 in a nitrogen atmosphere.
The water-NMP mixture was distilled off by raising the temperature to ° C. Furthermore, p-dichlorobenzene 264.
A solution of 6 g in 200 g of NMP was added, and
The reaction was carried out at 0 ° C. for 5 hours under a nitrogen atmosphere. This reaction solution A was cooled to 80 ° C., and 2,4-dichlorobenzoic acid was added to 3
8.2 g, 15.5 g of NaSH, 16.0 g of sodium hydroxide and 80 g of NMP were added, and the mixture was reacted at 220 ° C. for 5 hours and further at 240 ° C. for 1 hour under a nitrogen atmosphere.
The reaction product is washed with hot water, methanol and acetone,
It was dried to obtain a block copolymer type CPPS.

When the infrared absorption spectrum was measured,
Absorption spectra of 1700 and 3000 Kaiser, which are considered to be those of a carboxyl group, were observed, and the content of phenylene sulfide having a carboxyl group with respect to all the phenylene sulfide units determined by elemental analysis was 6.0.
It was mol%. The melting point measured by DSC is 275 ° C.
And melt flow rate; 1000 g / 10 minutes (A
STM D1238, Condition Z).

Reference Example 4 (Production of APPS) NMP 150 ml, N was added to 500 ml autoclave.
0.6 mol of a ² S.2.9H ₂ O was added, the mixture was stirred under a nitrogen atmosphere and the temperature was raised to 200 ° C. to distill a water-based distillate. Thereafter, the mixture was cooled to 150 ° C., p-dichlorobenzene 0.48 mol, 3,5-dichloroaniline 0.2.
After adding 12 mol and 50 ml of NMP and enclosing the system in a nitrogen atmosphere, the temperature was raised to 250 ° C. and the polymerization was carried out for 3 hours. After completion of the polymerization, the mixture was cooled to room temperature, a part of the slurry was sampled, the furnace liquid was sampled, and unreacted dichloroaniline was quantified by a gas chromatogram. As a result, the polymerization rate of dichloroaniline was 85%. The remaining slurry was poured into a large amount of water to precipitate the polymer, which was repeatedly separated by furnace and washed with pure water, and dried by heating under reduced pressure to isolate the polymer.

Reference Example 5 (Polyphenylene ether resin:
Production of PPE-1) 32.2 g of cupric bromide, di-n were charged in a reactor equipped with an oxygen suction device, a cooling coil, and a stirrer, which had been replaced with nitrogen.
-Butylamine (666 g) and toluene (24 liters) dissolved in 2,6-xylenol (5.25 Kg) were mixed and added, and then uniformly dissolved, and then polymerized for 90 minutes while rapidly absorbing oxygen while keeping the inside of the reaction vessel at 30 ° C. did. After the completion of the polymerization, 18 liters of toluene was added, and further, a 20% aqueous solution of ethylenediaminetetraacetic acid was added to stop the reaction. The resulting product mixture was centrifuged, the polymerized solution phase was taken out, and methanol was gradually added while stirring. After fractionation, it was dried and polyphenylene ether with an intrinsic viscosity of “0.50” (measured at 30 ° C. with chloroform as a solvent).
A tell resin was obtained. This is called PPE-1.

Reference Example 6 (Production of functionalized polyphenylene ether resin: FPPE-1) Polyphenylene ether resin synthesized in Reference Example 5: "P
To 1 kg of PE-1 ", 90 g of maleic anhydride was added,
After mixing with a Henschel mixer, use a twin-screw extruder to mix 3
The mixture was melt-kneaded and pelletized at a temperature of 00 to 320 ° C. This is called FPPE-1. After dissolving 2 g of the obtained FPPE-1 pellet in 50 ml of chloroform, the solution was added to 500 ml of methanol to precipitate the polymer. The obtained polymer was separated by filtration and dried (under reduced pressure,
80 ° C / 10 hours). Infrared spectroscopic analysis of the obtained sample was performed, and the weight of the maleic anhydride bonded to the polyphenylene ether resin was determined using a calibration curve prepared in advance from the polyphenylene ether resin and maleic anhydride. % Was calculated and used as the binding amount of maleic anhydride. As a result, the binding amount of maleic anhydride in FPPE-1 was
It was 1.1% by weight.

Reference Example 7 (Production of functionalized polyphenylene ether resin: FPPE-2) Polyphenylene ether resin synthesized in Reference Example 5: "P
PE-1 "3 kg, glycidyl methacrylate 90 g
And 15 g of dicumylper oxide were added and mixed by a Henschel mixer, and then 300 to 3 by a twin-screw extruder.
The mixture was melt-kneaded and pelletized at a temperature of 20 ° C. This is FP
It is called PE-2. 2 g of the obtained FPPE-2 pellets
Was dissolved in 50 ml of chloroform, and this solution was added to 5 ml.
The polymer was precipitated in addition to 00 ml of methanol. The obtained polymer was filtered and dried. (Under reduced pressure, 8
Infrared spectroscopic analysis was performed on the obtained sample, and the sample was bound to the polyphenylene ether resin using a calibration curve prepared in advance from the polyphenylene ether resin and glycidyl methacrylate. The weight% of the glycidyl methacrylate used was calculated and used as the amount of glycidyl methacrylate bound. As a result, the amount of glycidyl methacrylate bonded in FPPE-2 was 1.3% by weight.

Reference Example 8 (Preparation of Various Epoxy Cured Products) (1) Cured Product 1 Epiclon 850 (Bisphenol A type epoxy resin,
Dainippon Ink and Chemicals, Inc., epoxy equivalent 190)
40 parts by weight and laccamide EA-631 (polyamide amine, manufactured by Dainippon Ink and Chemicals, Inc., amine value 28
5) After uniformly mixing 60 parts by weight, the mixture was heated and cured at 150 ° C. for 3 hours, the obtained cured product was coarsely pulverized with a hammer mill, and further finely pulverized with a micro palperizer to obtain a 200 mesh screen pass. An epoxy resin cured product powder was prepared. This is referred to as a cured product 1.

(2) Cured product 2 Epiclon 850 (bisphenol A type epoxy resin,
Dainippon Ink and Chemicals, Inc., epoxy equivalent 190)
35 parts by weight and laccamide EA-631 (polyamide amine, manufactured by Dainippon Ink and Chemicals, Inc., amine value 28
5) After uniformly mixing 65 parts by weight (the amine is 24 mol% excess from the equivalent number of moles), the mixture is heat-cured at 150 ° C. for 3 hours, and the epoxy resin cured product powder is obtained through a crushing step similar to that of the cured product 1. Prepared. This is referred to as a cured product 2.

(3) Cured Product 3 Epicuron HP-4032 (diglycidyl ether of 1,6-dihydroxynaphthalene; Dainippon Ink and Chemicals, Inc., epoxy equivalent 149) 40 parts by weight and laccamide EA-631 (polyamide amine) , Dainippon Ink and Chemicals, Inc., amine value 285 (60 parts by weight) are uniformly mixed (epoxy resin is 27 mol excess over the equivalent number of moles), and then heat cured at 120 ° C./2 hours + 180 ° C./3 hours. Then, the epoxy resin cured product powder was prepared through the same crushing step as the cured product 1. This is referred to as a cured product 3.

(4) Cured Product 4 Epicron 850 (bisphenol A type epoxy resin,
Dainippon Ink and Chemicals, Inc., epoxy equivalent 190)
53 parts by weight and methyltetrahydrophthalic anhydride (acid value 1
67) 47 parts by weight and further 1 part by weight of benzyldimethylamine were uniformly mixed, and then heat-cured at 120 ° C./2 hours + 180 ° C./3 hours, and a pulverization step similar to that of the cured product 1 was performed to prepare a powder of an epoxy resin cured product. did. This is referred to as a cured product 4.

(5) Cured product 5 67 parts by weight of Epicuron N-673 (cresol novolak type epoxy resin, Dainippon Ink and Chemicals, Inc., epoxy equivalent 213) and Barkham TD-2131 (phenol novolac resin) Manufactured by Dainippon Ink and Chemicals, Inc.
33 parts by weight of OH value 103) and 0.1 part by weight of triphenylphosphine are uniformly mixed, and then 120 ° C./2 hours + 1.
The mixture was heated and cured at 80 ° C. for 3 hours, and a pulverization step similar to that of the cured product 1 was performed to prepare an epoxy resin cured product powder. This is referred to as a cured product 5.

The particle size of each cured powder was 10
It was 0 μm or less.

Examples 1 to 5 and Comparative Examples 1 to 5 The various raw materials and other raw materials produced in the reference examples were uniformly mixed at the ratios shown in the table below, and then 320 ° C. in a 35 mmφ twin-screw extruder. And kneaded to obtain pellets. Using these pellets, a cylinder temperature of 320 ° C, a mold temperature of 130 ° C, an injection pressure of 800 by an in-line screw type injection molding machine.
〜1000Kgf / cm ² , 50mm (width) × 100mm (length) by film gate at injection speed medium speed
A × 2 mm (thickness) sheet was formed, and the compatibility was visually evaluated.

The results are shown in the table below.

[0104]

[Table 1]

* 1) Evaluation of compatibility: Good: Compatibility is good and no dispersion unevenness is observed. Δ: The compatibility is insufficient and there is uneven dispersion. X: Poor compatibility, markedly poor dispersion, and delamination phenomenon.

[0106]

[Table 2]

* 1) TGIC; triglycidyl isocyanurate
To N-673; Cresol novolac type epoxy resin, manufactured by Dainippon Ink and Chemicals, Inc. * 2) Compatibility evaluation: Good: Good compatibility and no uneven dispersion is observed.

Δ: Incompatibility is insufficient and dispersion is uneven. X: Poor compatibility, markedly poor dispersion, and delamination phenomenon.

[0109]

According to the present invention, in addition to being excellent in heat resistance, flame retardancy, mechanical properties and dimensional stability, the compatibility of the poly (arylene sulfide) resin and the poly (arylene ether) resin is improved. A resin composition having a good appearance can be provided.

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area C08L 51:04)

Claims (13)

[Claims] 1. A polyarylene sulfide resin (A) having a terminal thiol group concentration of 5 μmol / g or more and 50 μmol / g or less and a polyarylene ether resin (B).
The resin composition is characterized by using 0.1 to 30 parts by weight of the epoxy resin cured product (C) based on 100 parts by weight in total. 2. A polyarylene sulfide resin (A)
The composition according to claim 1, wherein the composition has a substantially linear structure. 3. A polyarylene sulfide resin (A)
The composition according to claim 2, wherein the composition has been acid-treated and then washed. 4. A polyarylene sulfide resin (A)
Is a polyphenylene sulfide resin,
The composition according to 2 or 3. 5. A resin composition, which further comprises a carboxyl group-containing poly (arylene sulfide) resin in the composition according to claim 1. 6. A resin composition which further comprises an amino group-containing poly (arylene sulfide) resin in the composition according to claim 1. 7. The composition according to claim 1, further comprising a polystyrene resin. 8. The composition according to claim 7, wherein the polystyrene resin is provided in the form of a melt-kneaded product of the polyarylene ether resin (B) and the polystyrene resin. 9. A polyarylene ether resin (B)
9. The composition according to claim 1 or 8, wherein is a polyphenylene ether resin. 10. A polyarylene ether resin (B)
Some of them are selected from organic compounds having in the molecule (a) an ethylenic double bond and (b) simultaneously a functional group selected from the group consisting of a carboxyl group, an acid anhydride group, a hydroxyl group and an epoxy group. The composition of claim 1 which may be replaced by a functionalized polyphenylene ether resin obtained by functionalizing with a functionalizing agent. 11. The composition according to claim 1, wherein the cured epoxy resin (C) is produced by a curing reaction between an epoxy resin and amines. 12. The epoxy resin cured product (C) is produced by blending amines in an excess amount up to 50 mol% in the curing reaction between the epoxy resin and amines, which is more than the equivalent number of moles required for curing. Item 11. The composition according to Item 11. 13. The epoxy resin cured product (C) is produced by blending the epoxy resin in an amount of 50 mol% in excess of the equivalent number of moles required for curing in the curing reaction of the epoxy resin and amines. Item 11. The composition according to Item 11.