JP3206212B2 - Polyphenylene sulfide resin composition and composite molded article - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyphenylene sulfide resin composition having improved adhesion to an epoxy resin without impairing the weld strength, excellent thermal stability, and melt fluidity of the polyphenylene sulfide resin composition. And a molded product obtained by injection molding the same.

[0002]

2. Description of the Related Art Polyphenylene sulfide resin (hereinafter referred to as P
PS resin) is suitable for engineering plastics, such as excellent heat resistance, flame retardancy, rigidity, chemical resistance, etc., and various electric parts, machine parts and automobile parts mainly for injection molding Used in

However, the PPS resin has a relatively low adhesive strength with other resins, particularly with an epoxy resin.
Therefore, for example, when bonding the PPS resins with each other using an epoxy adhesive, bonding the PPS resin to another material, or sealing or enclosing an electric or electronic component with the epoxy resin, the bonding strength between the PPS resin and the epoxy resin. Is often a problem, which is one of the factors that hinders an increase in demand for PPS resins.

[0004] Improvements in the adhesion between a PPS resin and an epoxy resin have been studied so far. For example, a method of adding a polyalkylene ether to a PPS resin (Japanese Patent Application Laid-Open No. 4-275368), Method of blending fibrous filler and talc (JP-A-4-304)
264) and the like have been proposed.

[0005] On the other hand, although the purpose is different, the composition of a PPS resin and an ester compound is, for example, a highly crystalline and rapidly crystallizing composition obtained by adding a carboxylic acid ester of a monomer to a PPS resin (Japanese Patent Application Laid-Open No. 62-230848). Gazette), P
Composition having excellent tracking resistance obtained by adding a fatty acid saturated carboxylic acid ester to a PS resin (Japanese Patent Application Laid-Open No. 64-6965).
No. 8), a composition comprising a mixture of a PPS resin and a higher fatty acid ester of glycerin having excellent sliding properties (Japanese Patent Application Laid-Open No. 58-1983).
No. 74751) and a composition obtained by adding a tetraester compound to a PPS resin, which is excellent in low gas, releasing property and adhesiveness (Japanese Patent Application Laid-Open No. 4-159369).

As for the composition of a PPS resin and a phenoxy resin, for example, a composition comprising a compound having a phenylene sulfide bond in the molecule and a phenoxy resin (JP-B-54-39856) has excellent flame retardancy. P
A sealing material composition (JP-B-63-11780) in which the adhesiveness between an electronic component molded from a resin composition obtained by mixing a PS resin and a phenoxy resin with an IC circuit or the like is improved. I have.

[0007]

However, the method described in Japanese Patent Application Laid-Open No. 4-275368 is extremely effective in improving the adhesion between the PPS resin and the epoxy resin. However, it is hardly sufficient in terms of stability and handleability in the present invention, and there is room for further improvement in this respect. Also, Japanese Patent Application Laid-Open
The method described in JP-A-304264 is also effective in improving the adhesiveness between the PPS resin and the epoxy resin, but the blending of talc greatly reduces the melt fluidity of the PPS resin composition. Problems such as narrowing or deterioration of the surface appearance occur.

On the other hand, JP-A-62-230848 discloses
JP-A-64-69658 and JP-A-58-7475.
No. 1, JP-B-54-39856 does not mention any effect of improving the adhesion to an epoxy resin for that purpose.

Japanese Patent Application Laid-Open No. 4-159369 discloses a composition in which a tetraester compound is added to a PPS resin, but this tetraester compound is limited to pentaerythritol tetramontanate. Although it is stated that the use of a product improves the adhesion after molding, the addition of a phenoxy resin to the composition comprising the PPS resin and the ester compound significantly improves the adhesion with the epoxy resin. Nothing is mentioned.

On the other hand, Japanese Patent Publication No. 63-11780 discloses a resin composition comprising a PPS resin and a phenoxy resin.
Although it is described that it has good adhesion to metal materials such as circuits and lead wires, it does not mention that the combined use with an ester compound significantly improves the adhesion to an epoxy resin.

Accordingly, an object of the present invention is to obtain a PPS resin composition which is excellent in melt fluidity and has significantly improved adhesion to an epoxy resin while maintaining weld strength.

[0012]

That is, the present invention provides:
(A) 1 to 30 parts by weight of a phenoxy resin and (C) 0.05 to 0.05% of an ester compound comprising an aliphatic carboxylic acid having 12 to 40 carbon atoms and a polyhydric alcohol with respect to 100 parts by weight of a polyphenylene sulfide resin. The present invention provides a polyphenylene sulfide resin composition containing up to 5 parts by weight, and a composite molded article in which a molded article obtained by injection molding the composition and an epoxy resin are in contact with at least a part of the molded article. .

The polyphenylene sulfide resin used in the present invention refers to a repeating unit represented by the structural formula (I).

Embedded image It is a polymer containing 70 mol% or more, more preferably 90 mol% or more, and if the above repeating unit is less than 70 mol%, heat resistance is unfavorably deteriorated. Also PPS
Less than 30 mol% of the repeating unit of the resin can be composed of a repeating unit having the following structural formula.

[0014]

Embedded image The melt viscosity of the PPS resin used in the present invention is not particularly limited as long as melt kneading is possible, but is usually 50 to 20,000.
One having a poise (320 ° C., a shear rate of 10 sec ⁻¹ ) is used.

Such a PPS resin is generally prepared by a known method, that is, a method of obtaining a polymer having a relatively small molecular weight described in JP-B-45-3368, JP-B-52-12240, and JP-A-61-7332. It can be produced by a method for obtaining a polymer having a relatively large molecular weight described in the gazette. In the present invention, the PPS resin obtained as described above is crosslinked / polymerized by heating in air, washed with an organic solvent, hot water, an aqueous acid solution, etc., and functional group-containing compounds such as acid anhydrides, amines and isocyanates. Of course, it is also possible to use it after performing various treatments such as activation by a method.

In the PPS resin composition of the present invention, the residue (hereinafter abbreviated as total ash content) when the raw material PPS resin is baked at a temperature of at least 600 ° C. to volatilize the carbonaceous material is 0.07. By using a PPS resin in the range of 0.90% by weight to 0.90% by weight, the adhesiveness with the epoxy resin is further improved, and when a PPS resin having a total ash content in the range of 0.07% to 0.40% by weight is used, particularly, It is preferable because the effect is remarkable.

The phenoxy resin (B) used in the present invention is a thermoplastic resin having the following structural units as main constituent units.

[0018]

Embedded image That is, it is a polyhydroxyether obtained by the reaction of bisphenol A and epichlorohydrin, and usually has a degree of polymerization (n =) of 70 to 130, preferably 100 to 120.
Particularly preferred is a resin having a high molecular weight of about 100. It is similar in structure to an epoxy resin, but is different from the epoxy resin in that it has no active epoxy group at the molecular terminal and has a much higher molecular weight than the epoxy resin.

The amount of the phenoxy resin added is PPS
It is in the range of 1 to 30 parts by weight, preferably 1 to 20 parts by weight, more preferably 1 to 1 part by weight with respect to 100 parts by weight of resin.
The range is 5 parts by weight. If the amount of the phenoxy resin is less than 1 part by weight, the effect of improving the adhesiveness with the epoxy resin is insufficient, which is not preferable. Conversely, if the amount of the phenoxy resin exceeds 30 parts by weight, the content of the PPS resin composition is reduced. In particular, a decrease in mechanical strength characteristics at high temperatures becomes apparent, which is not preferable.

The (C) ester compound used in the present invention is an ester compound comprising an aliphatic carboxylic acid having 12 to 40 carbon atoms and a polyhydric alcohol. Specific examples of the aliphatic carboxylic acid having 12 to 40 carbon atoms, which is one constituent component of the ester compound, include aliphatic carboxylic acids such as stearic acid, oleic acid, palmitic acid, lauric acid, and montanic acid. Specific examples of the polyhydric alcohol as the other component include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, Examples include polyhydric alcohols such as ethyl-1,3-hexanediol, glycerin, trimethylolpropane, pentaerythritol, and polypentaerythritol.

The amount of the ester compound added is PPS
The range is 0.05 to 5 parts by weight, preferably 0.1 to 4 parts by weight, based on 100 parts by weight of the resin. The amount added is 0.
If the amount is less than 05 parts by weight, the effect of improving the adhesiveness to the epoxy resin is insufficient, which is not preferable. If the amount exceeds 5 parts by weight, gas generation during injection molding is induced, which is not preferable.

In the present invention, a fibrous and / or non-fibrous filler may be added as necessary to improve strength and dimensional stability. Examples of such a fibrous and / or non-fibrous filler include glass fiber, carbon fiber, potassium whisker, titanate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone fiber, metal fiber. Fibrous fillers such as wollastenite, zeolite, sericite,
Kaolin, mica, clay, bentonite, asbestos, talc, silicates such as alumina silicate, alumina, silicon oxide, magnesium oxide, zirconium oxide,
Metal compounds such as titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, glass beads, ceramic beads, boron nitride, silicon carbide and silica. Examples thereof include fibrous fillers, which may be hollow, and two or more of these fillers may be used in combination. In addition, these fibrous and / or non-fibrous fillers are 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 before use. Is more preferable in the sense of obtaining better mechanical strength.

With the above structure, the PPS resin composition of the present invention has improved adhesiveness to an epoxy resin. The epoxy resin referred to herein is not particularly limited, and examples thereof include bisphenol A, bisphenol F, bisphenol S, bisphenol AF, bisphenol AD, 4,4'-dihydroxybiphenyl, resorcin, saligenin, trihydroxydiphenyldimethylmethane, and tetraphenylol. It is synthesized from epichlorohydrin, a compound containing two or more hydroxyl groups in a molecule such as ethane, a halogen-substituted product thereof, an alkyl-substituted product thereof, butanediol, ethylene glycol, erythrit, novolak, glycerin, and polyoxyalkylene. Glycidyl esters such as glycidyl ethers and glycidyl phthalate, aniline, diaminodiphenylmethane, metaxylenediamine, 1,3-bisaminimethylcyclohexane, etc. Glycidylamine resins synthesized from primary or secondary amines and epichlorohydrin, etc., glycidyl epoxy resins, etc., epoxidized soybean oil, non-glycidyl epoxy resins such as vinylcyclohexenedionoxide, dicyclopentadiene dioxide, etc. . These epoxy resins are used alone or as a mixture of two or more. These epoxy resins are generally used after being cured by a curing agent. Examples of curing agents include amines, polyamides, amino resins, acid anhydrides, polyhydric phenols, phenolic resins, polysulfides, isocyanates, and the like.

The PPS resin composition of the present invention is intended to improve γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane and the like for the purpose of improving mechanical strength and moldability such as burrs, etc., within a range not impairing the effects of the present invention. Epoxy group-containing alkoxysilane compounds such as glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and mercapto such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane Group-containing alkoxysilane compounds,
ureido group-containing alkoxysilane compounds such as γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ- Isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyl Isocyanato group-containing alkoxysilane compounds such as trichlorosilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ It may be added to the organic silane compound such as an amino group-containing alkoxysilane compounds such as aminopropyltrimethoxysilane.

In the PPS resin composition of the present invention, plasticizers such as polyalkylene oxide oligomer compounds, thioether compounds and organic phosphorus compounds, talc, kaolin, organic phosphorus compounds and the like can be used as long as the effects of the present invention are not impaired. Additives such as nucleating agents, release agents such as polyolefin compounds and silicone compounds, antioxidants, heat stabilizers, lubricants, UV inhibitors, coloring agents, flame retardants, and foaming agents can be added. it can. Further, the PP of the present invention
S resin composition, polyamide, polyphenylene oxide, polysulfone, polyethylene tetrafluoride, polyetherimide, polyamideimide, polyimide, polycarbonate, polyethersulfone, polyetherketone, as long as the effects of the present invention are not impaired. Polythioetherketone, polyetheretheroketone, epoxy resin, phenolic resin, polyethylene, polystyrene, polypropylene, ABS resin, polyamide elastomer, polyester elastomer, polyalkylene oxide, other polyester or acid anhydride group, carboxyl group, epoxy It may contain a resin such as an olefin copolymer containing a group or the like.

The method of preparing the composition of the present invention is not particularly limited, but the mixture of the raw materials is prepared by a conventional method such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, and a mixingol. For example, a method in which the mixture is supplied to a mixer and kneaded at a temperature of 280 to 380 ° C. can be exemplified. The order of mixing the raw materials is not particularly limited, and PPS resin,
After dry blending the phenoxy resin and the polyhydric alcohol ester compound, a method of melt-kneading by the above-mentioned method or the like, or a dry blending of two of the PPS resin, the phenoxy resin and the ester compound, melt-kneading, and Of course, a method of melting and kneading is also possible.

The polyphenylene sulfide resin composition obtained by the present invention is insufficient for the conventional PPS resin which is said to improve the adhesiveness to an epoxy resin or the like without significantly impairing the thermal stability and melt fluidity of the resin composition. Is a resin composition to which new properties have been added, sensors, LED lamps, connectors, sockets, resistors, relay cases,
Switches, coil bobbins, capacitors, variable condenser cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystals, FDD Carriage, FDD chassis, motor brush holder,
Electrical and electronic parts such as parabolic antennas and computer-related parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts,
Home and office electrical product parts such as audio parts, audio equipment parts such as audio laser discs and compact discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc .; office computer related parts, telephones Related parts, facsimile-related parts, copier-related parts, cleaning jigs, motor parts, machine-related parts represented by lighters, typewriters, etc .: optical equipment represented by microscopes, binoculars, cameras, watches, etc., precision machinery Related parts: alternator terminal, alternator connector, IC regulator,
Potentiometer base for light drier, various valves such as exhaust gas valve, various pipes related to fuel, exhaust system, intake system, 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, radiator motor Brush holder, water pump impeller, turbine vane, wiper motor related parts, dust distributor, starter switch H, starter relay, transmission wire harness, window washer nozzle, air conditioner panel switch board, fuel related electromagnetic valve coil, fuse connector, horn terminal, electrical component insulation board, step motor rotor, lamp socket, lamp reflector, lamp housing ,
It is useful for automobile and vehicle related parts such as brake piston, solenoid bobbin, engine oil filter, ignition device case, and other various uses.

Hereinafter, the present invention will be described in more detail with reference to examples.

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

Tensile shear adhesive strength: An ASTM No. 1 tensile test piece was divided into two equal parts, and a spacer (thickness of 40 to 50 μm) and an epoxy resin (two-part epoxy resin, XNR5002, XNH5002, manufactured by Nagase Ciba Co., Ltd.) Was fixed. After curing, the tensile strength was measured at a speed of 10 mm / min, and the maximum value of the strength was divided by the bonding area to obtain the tensile shear bonding strength.

Weld strength: An ASTM No. 4 test piece having a gate at both ends and a weld line near the center of the test piece was measured for tensile strength at a strain rate of 5 mm / min and a distance between fulcrums of 64 mm.

Reference Example 1 (Synthesis Method of Polyphenylene Sulfide) PPS-1: Sodium sulfide 3.26 in autoclave
Kg (25 mol, containing 40% of water of crystallization), 4 g of sodium hydroxide, 1.19 Kg (about 8.8 mol) of sodium acetate trihydrate and 7.9 kg of NMP were gradually added, and the temperature was gradually raised to 205 ° C. while stirring. Warm and remove about 1.5 liters of distillate containing 1.36 kg of water. 3.75 kg (25.5 mol) of 1,4-dichlorobenzene and 2 kg of NMP were added to the remaining mixture, and the mixture was heated at 265 ° C. for 3 hours. The reaction product was washed 5 times with 70 ° C.
And dried under reduced pressure for 24 hours to obtain a melt viscosity of about 600 poise (3
Powdered polyphenylene sulfide (PPS-1) having a temperature of 10 ° C., a shear rate of 1000 sec ^-1 ) and a total ash content of 0.7% by weight
About 2 kg was obtained.

As PPS-2, PPS-1 was used at pH =
A PPS resin having a total ash content of 0.2% by weight after acid washing with the solution of 5.5 was used.

As PPS-3, a PPS resin having a total ash content of 0.03% by weight was obtained by subjecting PPS-2 to acid washing with a hydrochloric acid aqueous solution having a pH of 2.0 at 180 ° C. under pressure for 3 hours.

As PPS-4, PPS manufactured by Toray PPS Co., Ltd.
Resin, M2900 was used.

Reference Example 2 In the examples, as an example of the phenoxy resin used in the present invention, a weight average molecular weight of about 1 represented by the structural formula (II) is used.
10,000 (B-1) and a weight average molecular weight of about 30,000 (B-
The phenoxy resin of 2) was used.

Reference Example 3 In Examples, the ester compounds used in the present invention were:
The following structural formulas A-1 to A-4

Embedded image Represented by ethylene glycol dimontanate (A
-1), 1,1,1-trimethylolpropane oleate (A-2), pentaerythritol tetrastearate (A-3), and polypentaerythritol montanate (A-4) were used.

Examples 1 to 10 After dry-blending a PPS resin, a phenoxy resin, an ester compound and a filler in the proportions shown in Table 1, 28
The mixture was melt-kneaded by a screw type extruder set at a temperature of 0 to 320 ° C., and then pelletized. Weld strength and tensile shear adhesive strength measurement test piece was molded using the obtained pellet, and the weld strength measured for the obtained test piece,
Tables 1 and 2 show the tensile shear adhesive strength.

As described above, by using a PPS resin in combination with a phenoxy resin and a specific ester compound, the PPS resin can be used.
The adhesiveness of the resin to the epoxy resin is dramatically improved.

Comparative Examples 1, 2, 5, 7, and 8 Dry blending, melt kneading, and pelletizing were performed in the same manner as in Examples 1 to 9 except that the phenoxy resin and the ester compound were not added. Using the obtained pellets, a test piece for measuring the weld strength and the tensile shear adhesive strength was formed, and the weld strength and the tensile shear adhesive strength measured for the obtained test piece are shown in Tables 2 and 3.

Comparative Example 3 Dry blending, melt kneading and pelletizing were carried out in the same manner as in Example 2 except that no ester compound was added. Using the obtained pellets, a test piece for measuring the weld strength and the tensile shear adhesive strength was formed, and the weld strength and the tensile shear adhesive strength measured for the obtained test piece are shown in Table 3.

Comparative Example 4 Dry blending, melt kneading and pelletizing were carried out in the same manner as in Example 2 except that no phenoxy resin was added. Using the obtained pellets, a test piece for measuring the weld strength and the tensile shear adhesive strength was formed, and the weld strength and the tensile shear adhesive strength measured for the obtained test piece are shown in Table 3.

Comparative Example 6 Dry blending, melt kneading, and the like were conducted in the same manner as in Example 6 except that the amount of the ester compound added was less than 0.05 part by weight.
Pelletized. Using the obtained pellets, a test piece for measuring the weld strength and the tensile shear adhesive strength was formed, and the weld strength and the tensile shear adhesive strength measured for the obtained test piece are shown in Table 3.

Comparative Example 7 Dry blending, melt kneading and pelletizing were carried out in the same manner as in Example 6 except that the amount of the phenoxy resin added was less than 1 part by weight. Using the obtained pellets, a test piece for measuring the weld strength and the tensile shear adhesive strength was formed, and the weld strength and the tensile shear adhesive strength measured for the obtained test piece are shown in Table 3.

[0045]

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[0046]

The polyphenylene sulfide resin composition of the present invention is a polyphenylene sulfide resin composition having improved adhesion to an epoxy resin, and is used for bonding with an epoxy-based adhesive or sealing electric / electronic parts with an epoxy resin. Suitable when secondary processing such as is required.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 81/00-81/02 C08L 71/08-71/10 C08K 5/10-5/103

Claims (6)

(57) [Claims] 1. A polyphenylene sulfide resin (A)
(B) 1 to 30 parts by weight of a phenoxy resin and (C) 0.05 to 100 parts by weight of an ester compound comprising an aliphatic carboxylic acid having 12 to 40 carbon atoms and a polyhydric alcohol.
A polyphenylene sulfide resin composition mixed with 5 parts by weight. 2. The (C) ester compound has 12 to 4 carbon atoms.
The polyphenylene sulfide resin composition according to claim 1, which is a mono- or diester compound comprising an aliphatic carboxylic acid of 0 and a dihydric alcohol. 3. The (C) ester compound has 12 to 4 carbon atoms.
Mono aliphatic carboxylic acids and trihydric alcohols,
The polyphenylene sulfide resin composition according to claim 1, which is a di- or triester compound. 4. An ester compound (C) having 12 to 4 carbon atoms.
Mono aliphatic carboxylic acids and tetrahydric alcohols,
2. A di-, tri- or tetraester compound.
The polyphenylene sulfide resin composition according to the above. 5. The method of claim 1, wherein (A) the polyphenylene sulfide resin is
The polyphenylene sulfide resin having a residue in the range of 0.07 to 0.90% by weight when the carbonaceous material is volatilized by firing at a temperature of at least 600 ° C. or more.
The polyphenylene sulfide resin composition according to any one of the above. 6. A composite molded article comprising a molded article obtained by injection-molding the resin composition according to claim 1 and an epoxy resin in contact with at least a part of the molded article.