JPH1143604A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition improved in the ability to give moldings improved in tensile strength and adhesion to epoxy resins without detriment to the properties inherent in the constituent PPS resin by mixing a polyphenylene resin with a copolyamide resin containing a dimerized fatty acid as a comonomer, an epoxy resin and a filler in a specified ratio. SOLUTION: This composition is prepared by mixing 100 pts.wt. polyphenylene sulfide resin with 0.5-30 pts.wt. copolyamide resin containing a dimerized fatty acid as a comonomer, 0.1-10 pts.wt. epoxy resin and 0-400 pts.wt. filler. The polyphenylene sulfide resin is desirably a linear PPS being a polyphenylene sulfide resin comprising at least 70 mol.% paraphenylene sulfide skeleton. The copolyamide resin includes a polyamide component prepared by the polymerization of a dimerized fatty acid with a diamine and a polyamide component prepared by the polymerization of a three-membered or larger-ring lactam. The epoxy resin is desirably e.g. an epibis-type epoxy resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyphenylene sulfide resin composition, and more particularly, to a polyphenylene sulfide resin composition having excellent adhesion to an epoxy resin.

[0002]

2. Description of the Related Art Polyphenylene sulfide resin (hereinafter, referred to as polyphenylene sulfide resin)
Also called PPS resin. ) Is used as an engineering plastic having excellent heat resistance, flame retardancy, mechanical properties, chemical resistance, water resistance, and dimensional stability in the fields of electric, electronic parts, automobile parts, industrial machine parts, and the like. However, PPS resin has low adhesive strength with epoxy resin,
For example, when sealing with an epoxy resin for protection when used in a storage case for circuits and electronic components, the adhesiveness was insufficient.

[0003] PP with improved adhesion to epoxy resin
As the S resin, for example, a resin composition containing a carbana wax is disclosed in Japanese Patent Application Laid-Open No. 2-272603, which is a resin composition containing a copolymer of an aromatic vinyl compound and an unsaturated carboxylic acid or an acid anhydride thereof. Is disclosed in JP-A-3-7446.
No. 2 discloses this. Further, a resin composition containing a polyalkylene ether compound is disclosed in JP-A-4-275.
JP-A-368-368 discloses a resin composition containing an aromatic sulfone compound, and JP-A-6-57136 discloses a resin composition containing an aliphatic polyester.
No. 46 discloses this. However, in any of these compositions, since the heat resistance of the compound is insufficient, there is a problem that thermal decomposition easily occurs when molding using the resin composition, and strength is reduced.

[0004]

SUMMARY OF THE INVENTION The object of the present invention is
Provides polyphenylene sulfide resin composition with excellent tensile strength, impact strength, moldability, and excellent adhesion to epoxy resin, without impairing the inherent properties of S resin such as heat resistance, chemical resistance, water resistance, etc. Is to do.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and its gist is as follows.
(A) 100 parts by weight of polyphenylene sulfide resin,
(B) 0.5 to 30 parts by weight of a copolymerized polyamide resin containing a dimerized fatty acid as a copolymerization component, (C) 0.1 to 10 parts by weight of an epoxy resin, and (D) 0 to 400 parts by weight of a filler. The polyphenylene sulfide resin composition is contained.

Hereinafter, the present invention will be described in detail. Examples of the polyphenylene sulfide resin in the present invention include a polyphenylene sulfide resin having a paraphenylene sulfide skeleton of at least 70 mol%, preferably at least 90 mol%. As an example of polyphenylene sulfide resin, for example, a relatively low molecular weight PPS obtained from paradichlorobenzene and sodium sulfide described in Japanese Patent Publication No. 45-3368 was subjected to high temperature heat treatment in an oxygen atmosphere to increase the molecular weight. Cross-linked PPS, high-molecular-weight linear PPS obtained from paradichlorobenzene and sodium sulfide in the presence of an alkali metal salt of an organic acid described in JP-B-52-12240, JP-B-02-67
No. 74, a linear PPS obtained from paradichlorobenzene and sodium sulfide in the presence of a small amount of water,
Further, a semi-crosslinked PPS obtained by an intermediate production method between a crosslinked PPS and a linear PPS may be used.

In producing PPS from paradichlorobenzene and sodium sulfide, various solvent removal methods and polymer washing methods (water washing, solvent washing, acid washing, etc.) have been proposed in the polymer recovery process. As the polyphenylene sulfide resin in the present invention, PPS obtained by any of these methods can be used.
A linear type PPS is exemplified.

In the present invention, the copolymerized polyamide resin containing a dimerized fatty acid component as a copolymerized component includes a polyamide component obtained by polymerizing a dimerized fatty acid and a diamine, a lactam having three or more membered rings, and a polymerizable polymer. And a copolyamide resin containing a polyamide component obtained by polymerizing a suitable ω-amino acid or a dibasic acid and a diamine.

Examples of the lactam having three or more rings include ε-caprolactam, unantholactam, capryllactam, lauryl lactam, α-pyrrolidone, α-piperidone and the like. Examples of the ω-amino acids include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, and 11-aminoundecanoic acid.

The dibasic acids include adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sabacic acid, undecandionic acid, dodecadionic acid, hexadecadionic acid, hexadecenedionic acid, eicosandioic acid, eicosadiacid Endionic acid, diglycolic acid, 2,
Examples include 2,4-trimethyladipic acid, xylylenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, and isophthalic acid.

The diamines preferably have 2 carbon atoms.
To 22 diamines, specific examples of which include ethylene diamine, trimethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine,
Undecamethylenediamine, dodecamethylenediamine,
Aliphatic diamines such as tridecamethylenediamine, hexadecamethylenediamine, 2,2,4- (or 2,4,4-) trimethylhexamethylenediamine, cyclohexanediamine, bis- (4,4'-aminocyclohexyl) methane And diamines having an aromatic ring such as meta-xylylenediamine.

Specific examples of the polyamide component obtained by polymerizing a lactam having three or more ring members, a polymerizable ω-amino acid, or a dibasic acid and a diamine include, for example, polyamide 4, polyamide 6, polyamide 7, polyamide 8, Polyamide 11, polyamide 12, polyamide 6,6, polyamide 6,9, polyamide 6,10, polyamide 6,1
1, polyamide 6,12, polyamide 6T, polyamide 6 / 6,6, polyamide 6 / 6T and the like.

The dimerized fatty acid contained as a copolymer component is, for example, a monobasic fatty acid derived from natural fats or oils having 8 to 24 carbon atoms and having at least one double bond or triple bond, or a synthetic fatty acid. A polymerized fatty acid obtained by polymerizing a basic fatty acid is used. Specific examples include dimers such as linoleic acid, linolenic acid and oleic acid.
Commercially available polymerized fatty acids usually contain a dimerized fatty acid as a main component, and also contain a raw material fatty acid and a trimerized fatty acid, and have a dimerized fatty acid content of 70% by weight or more, preferably It is desirable that the content is 95% by weight or more, more preferably 98% by weight or more. Commercial products are also called dimer acids. In addition, commercially available polymerized fatty acids may be used by increasing the content of dimerized fatty acids by distilling the same, or may be used by reducing the degree of unsaturation by hydrogenation in some cases.

The diamine used to prepare the polymer with the dimerized fatty acid includes ethylene diamine,
Aliphatic diamines such as 1,4-diaminobutane, hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, and 2,4,4-trimethylhexamethylenediamine , Alicyclic diamines such as bis (4,4'-aminocyclohexyl) methane, and aromatic diamines such as meta-xylylenediamine;
Preferably, hexamethylene diamine is used.

In the present invention, a method for producing a copolymerized polyamide resin containing a dimerized fatty acid component as a copolymerized component includes, for example, polycondensation of a dimerized fatty acid and a diamine,
Further, a lactam having three or more rings, a polymerizable ω-amino acid,
Alternatively, a method in which a dibasic acid and a diamine are present and polycondensation is performed under heating and reduced pressure may be used.

In the present invention, the content of the dimerized fatty acid component in the copolymerized polyamide is 10 to 80% by weight,
Preferably it is 20 to 60% by weight. If the content is too small, the adhesion and impact resistance tend to be insufficient, and if it is too large, the heat resistance and chemical resistance tend to decrease.

The compounding amount of the copolymerized polyamide resin containing a dimerized fatty acid as a copolymerizing component in the polyphenylene sulfide resin composition of the present invention is 0.5 to 30 parts by weight based on 100 parts by weight of the polyphenylene sulfide resin. , Preferably 1 to 20 parts by weight. If the content of the copolymerized polyamide resin containing a dimerized fatty acid as the copolymerization component is too small, the adhesiveness and impact resistance become insufficient, and if it is too large, the inherent rigidity, heat resistance, water resistance, and chemical resistance of the PPS resin are obtained. Easily deteriorates.

The epoxy resin used in the present invention is a so-called epoxy resin containing a glycidyl group derived from various bisphenols, polyhydric phenols, polyhydric alcohols, polyalkylene oxide polyols and the like. Further, an epoxy resin compound obtained by oxidizing a compound having an intramolecular double bond with hydrogen peroxide or peracetic acid is also included.

Specific examples of the epoxy resin include an epoxy resin derived from bisphenol A and epichlorohydrin and having an epoxy equivalent of 180 to 5000 (epibis epoxy resin), an epoxy resin derived from bisphenol F and epichlorohydrin, a phenol novolak resin or cresol. Epoxy resin derived from a novolak resin and epichlorohydrin and having an epoxy equivalent of 170 to 1500 (novolak type epoxy resin); an alicyclic epoxy resin obtained by epoxidizing an alicyclic compound having an unsaturated double bond; 1,4-butane Examples thereof include diglycidyl ether obtained from diol or neopentyl glycol and epichlorohydrin, and preferably include epibis epoxy resin and novolak epoxy resin. The epoxy equivalent is a value obtained by dividing the molecular weight of the epoxy resin by the number of epoxy groups, and is represented by the number of grams of resin containing 1 gram equivalent of epoxy group.

The compounding amount of the epoxy resin in the polyphenylene sulfide resin composition of the present invention is 0.1 to 10 parts by weight, preferably 0.2 to 8 parts by weight based on 100 parts by weight of the polyphenylene sulfide resin. If the amount of the epoxy resin is too small, the adhesiveness tends to decrease, and if it is too large, the mechanical strength tends to decrease. The mixing ratio of the epoxy resin and the copolymerized polyamide resin containing a dimerized fatty acid as a copolymerization component is preferably 2/1 to 1/20 (weight ratio).

The filler in the present invention includes a fibrous filler and a non-fibrous filler. The amount of the filler in the polyphenylene sulfide resin composition of the present invention is 400 parts by weight or less, preferably 5 to 300 parts by weight, more preferably 10 to 200 parts by weight, based on 100 parts by weight of the polyphenylene sulfide resin. It is.

Examples of the fibrous filler include glass fiber, carbon fiber, wollastonite, alumina fiber, silicon nitride fiber,
Boron fiber, potassium titanate whiskers, stainless steel fiber,
Aluminum fibers and the like are preferable, and glass fibers and carbon fibers are preferable from the viewpoint of improving the thermal deflection temperature of PPS and improving mechanical strength.

Examples of the non-fibrous filler include calcium carbonate, magnesium carbonate, talc, mica, glass powder, glass flake, glass beads, kaolin, clay, silica, barium sulfate, calcium sulfate, alumina, graphite, antimony oxide, oxide Titanium and the like,
Preferably, calcium carbonate, talc, mica, glass flake and the like are used. The non-fibrous filler improves dimensional accuracy, and is preferably used in combination with glass fiber.

When the polyphenylene sulfide resin composition of the present invention contains a non-fibrous filler in addition to the fibrous filler, the mixing ratio (weight ratio) of the fibrous filler and the non-fibrous filler is preferably , Fibrous filler / non-fibrous filler is 99-10 / 1 to 90.

Various additives can be added in small amounts to the resin composition of the present invention. Examples of additives include an external lubricant such as a metal stearate, a heat stabilizer such as a hindered phenol compound and an organic phosphite compound, an ultraviolet absorber such as a triazine compound, a hindered amine light stabilizer, and hydrotalcite. Examples include a site, a corrosion inhibitor such as lithium carbonate, and various coloring pigments.

The method for producing the resin composition of the present invention is not particularly limited, and is usually kneaded with an extruder. For example, PP
S, copolymerized polyamide resin and epoxy resin are mixed by a mixer such as a Henschel mixer or a tumbler, and are quantitatively supplied from a main supply port of an extrusion kneader, and kneaded at a temperature equal to or higher than the melting point of PPS. By side-feeding, it becomes a compound, it is taken up as a strand,
Cut with a pelletizer to obtain pellets. The kneading temperature is usually 280 to 340 ° C. If it is lower than 280 ° C., the melting of PPS becomes insufficient, and if it exceeds 340 ° C.,
Copolyamide resin, epoxy resin, etc. are prone to thermal degradation and thermal decomposition.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.

The following components were used in these Examples and Comparative Examples. (1) Polyphenylene sulfide resin: Linear PPS
Resin, melt viscosity 1200 poise (316 ° C, 100 sec
c ^-1 ). (PPS-1)

(2) Copolymerized polyamide containing a dimerized fatty acid as a copolymerization component: ε-caprolactam, starting from ε-caprolactam, hexamethylenediamine and dimerized fatty acid (linolenic acid dimer) A copolymerized polyamide having a polyamide component / polyamide component comprising hexamethylenediamine and a dimerized fatty acid in a ratio of 60/40 (weight ratio) and a dimerized fatty acid content of 33.2%. (Copolymer PA-1)

(3) Copolymerized polyamide containing a dimerized fatty acid as a copolymerization component: ε-caprolactam, starting from ε-caprolactam, hexamethylenediamine and dimerized fatty acid (linolenic acid dimer) A copolymerized polyamide having a polyamide component / polyamide component composed of hexamethylenediamine and a dimerized fatty acid in a ratio of 33/67 (weight ratio) and a dimerized fatty acid content of 55% by weight. (Copolymer PA-2)

(4) Epoxy resin: epoxy equivalent 650
(5) Glass fiber: chopped glass fiber, diameter 13 μm, length 3 mm.

(6) Tensile strength: ASTM D-63
8 was measured. (7) Izod impact strength: measured according to ASTM D-256. (8) Adhesive strength: A test piece having a width of 1/2 inch, a length of 5 inches and a thickness of 1/8 inch was formed as an adhesive test piece, joined with the following adhesive at a distance between laps of 15 mm, and cured under predetermined conditions. The adhesive strength test was conducted at a pulling speed of 5 mm / mi.
The shear bond strength was measured at n. Adhesive thickness is 0.1mm
Met. The adhesive strength test was performed at a measurement atmosphere temperature of 23 ° C.

(9) Adhesive-A: One-component epoxy resin adhesive Technodyne AH3052K (manufactured by Taoka Chemical Co., Ltd.), curing conditions 100 ° C. × 45 minutes. (10) Adhesive-B: polyamideamine-curable epoxy resin Origin Bond E-100 (Origin Electric)
Curing conditions 80 ° C x 60 minutes. (11) Adhesive-C: acid anhydride-curable epoxy resin (W
Epibisepoxy of PE182 + hexahydrophthalic anhydride + 30% by weight of calcium carbonate, catalyst BDMA0.5
wt%), curing conditions: 120 ° C. × 120 minutes.

Examples 1 to 6 As shown in Table 1, P
PS resin, dry blended copolymerized polyamide and epoxy resin containing a dimerized fatty acid as a copolymer component,
After melt-kneading with a twin screw extruder (L / D = 28) set at 300 ° C., the mixture was taken up in a strand form and pelletized with a pelletizer to obtain a resin composition pellet.
The obtained pellets were dried, and a test piece for mechanical strength measurement and a test piece for adhesive strength test were formed at a mold temperature of 140 ° C. by an injection molding machine set at 300 ° C., and various evaluations were performed. Was. Table 1 shows the measurement results.

[0034]

[Table 1]

Comparative Examples 1 to 3 Pellets were obtained in the same manner as in Example 1 using the components shown in Table 2, and various evaluations were performed in the same manner as in Example 1. Table 2 shows the measurement results.

[0036]

[Table 2]

Examples 7 to 11 As shown in Table 3,
A PPS resin, a copolymerized polyamide containing a dimerized fatty acid as a copolymerization component, an epoxy resin and glass fiber were used, and the glass fiber was kneaded in the same manner as in Example 1 except that the glass fiber was side-fed from the middle of the extruder cylinder to obtain a pellet. ,
Molding was performed in the same manner as in Example 1 except that the molding temperature was set to 310 ° C., and various evaluations were performed. Table 3 shows the measurement results.

[0038]

[Table 3]

Comparative Examples 4 to 6 Using the components shown in Table 4, pellets were obtained in the same manner as in Example 7, and molding and various evaluations were performed in the same manner as in Example 7. Table 4 shows the measurement results.
Shown in

[0040]

[Table 4]

[0041]

The polyphenylene sulfide resin composition of the present invention has excellent tensile strength and impact resistance, and has excellent adhesion to various epoxy resin adhesives having different curing systems. Accordingly, it is a material that is required for heat resistance, chemical resistance, water resistance and adhesion to metal or epoxy resin, and is useful for molded articles in the electric and electronic fields, automotive parts, and the like. In addition, the polyphenylene sulfide resin composition containing the filler is excellent in adhesiveness, impact strength, tensile strength, and excellent dimensional accuracy,
It is useful for molded products in the fields of electricity and electronics, automotive-related parts, precision molded products, precision machinery and equipment.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI // C08G59 / 44 C08G59 / 44 (C08L 81/02 77:08 77:00 63:00)

Claims (8)

[Claims] (A) Polyphenylene sulfide resin 1
(B) 0.5 to 30 parts by weight of a copolymerized polyamide resin containing a dimerized fatty acid as a copolymerization component,
A polyphenylene sulfide resin composition comprising (C) 0.1 to 10 parts by weight of an epoxy resin and (D) 0 to 400 parts by weight of a filler. 2. A polyamide component comprising a copolymerized polyamide resin obtained by polymerizing a dimerized fatty acid and a diamine.
The polyphenylene sulfide resin composition according to claim 1, which is a copolymerized polyamide resin containing a polyamide component obtained by polymerizing a lactam having at least two membered rings. 3. The polyphenylene sulfide resin composition according to claim 1, wherein the dimerized fatty acid is a dimerized fatty acid derived from linoleic acid, linolenic acid, or oleic acid. 4. The composition according to claim 1, wherein the content of the dimerized fatty acid is 10 to 80% by weight in the copolymerized polyamide resin containing the dimerized fatty acid component as a copolymerization component. The polyphenylene sulfide resin composition according to any one of the above. 5. The polyphenylene sulfide resin composition according to claim 2, wherein the lactam having three or more rings is ε-caprolactam. 6. The polyphenylene sulfide resin composition according to claim 2, wherein the diamine is hexamethylene diamine. 7. An epoxy resin having an epoxy equivalent of 180 to 180.
5000 bisphenol A-epichlorohydrin epoxy resin, phenol novolak resin having an epoxy equivalent of 170 to 1500-epichlorohydrin epoxy resin or cresol novolak resin having an epoxy equivalent of 170 to 1500-epichlorohydrin epoxy resin. Item 7. The polyphenylene sulfide resin composition according to any one of Items 1 to 6. 8. The polyphenylene sulfide resin composition according to claim 1, wherein the filler is a fibrous filler.