JP3168714B2 - Polyphenylene sulfide resin composition - 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.

[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 joining the PPS resins with each other using an epoxy adhesive, joining the PPS resin with another material, or sealing an electric or electronic component with the epoxy resin, this PP is used.
Poor bonding strength between the S resin and the epoxy resin often causes a problem, which is one of the factors that hinders an increase in demand for the PPS resin.

As an example of studying the improvement of the adhesiveness between a PPS resin and an epoxy resin, there is a method of adding carnauba wax to a PPS resin (Japanese Patent Laid-Open No. 2-27263). On the other hand, JP-A-4-130159 discloses that
A composition in which an aromatic sulfone compound is added to a PS resin is disclosed.

[0005]

However, in the method described in Japanese Patent Application Laid-Open No. 2-272603, the effect of adding carnauba wax on the improvement of the tensile shear adhesive strength is at most about 20% as compared with the case where no carnauba wax is added. It is hard to say that it is a level. On the other hand, Japanese Unexamined Patent Publication No.
Japanese Patent Application Laid-Open Publication No. H11-139,086 discloses a composition in which an aromatic sulfone compound is added to a PPS resin, but the purpose is to improve the crystallization speed, and does not mention any effect of improving the adhesiveness with an epoxy resin. . Further, the patent mentions an aromatic sulfone derivative in which a hydrogen atom of an aromatic ring is substituted by an alkoxy group having a short carbon chain such as a methoxy group, an ethoxy group or an allyloxy group, No mention is made of an aromatic sulfone derivative substituted with an alkoxy group having a long carbon group.
No mention is made of the fact that a PPS resin composition having particularly excellent adhesion to an epoxy resin and excellent heat resistance can be obtained by adding it to a PS resin.

[0006] Therefore, the present invention provides P
PPS with sufficiently improved adhesion to epoxy resin without significantly impairing the excellent properties inherent in PS resin
An object is to obtain a resin composition.

[0007]

That is, according to the present invention, an aromatic sulfone compound represented by the following structural formula is used in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of a polyphenylene sulfide resin.
20 parts by weight, fibrous and / or non-fibrous filler
An object of the present invention is to provide a polyphenylene sulfide resin composition mixed with 400 parts by weight.

[0008]

Embedded image (Here, R and R ′ are hydrocarbon groups having 6 to 22 carbon atoms, which may be the same or different.
A ′ is an aromatic group, which may be the same or different. The polyphenylene sulfide resin used in the present invention is 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.

[0009]

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 can be prepared by a generally known method, that is, a method of obtaining a polymer having a relatively small molecular weight as 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 activated by a functional group-containing compound such as an acid anhydride and isocyanate. Of course, it is also possible to use after performing various treatments such as conversion.

The aromatic sulfone compound used in the present invention has the general formula

Embedded image It is represented by Here, R and R ′ have 6 carbon atoms.
To 22 hydrocarbon groups, which may be any of an aliphatic group, an alicyclic group and an aromatic group, but an aliphatic group is more preferred. In the present invention, the number of carbon atoms of the R and R 'groups has an important meaning, and is preferably in the range of 6 to 22 carbon atoms, and more preferably 8 to 18 carbon atoms. When the number of carbon atoms of the R and R 'groups is 5 or less, the heat resistance of the aromatic sulfone compound is remarkably reduced, and the effect of improving the adhesion is poor.
If it is 3 or more, the effect of improving the adhesion to the epoxy resin is impaired, which is not preferable.

Specific examples of the R and R 'groups include linear or branched aliphatic groups such as hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and octadecyl, and cyclohexyl and cyclohexylmethyl. Examples include alicyclic groups and aromatic groups such as phenyl, benzyl, and naphthyl. Among them, aliphatic groups such as hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and octadecyl are more preferred. R and R 'may be the same or different.

A and A 'are aromatic groups. Specific examples thereof include divalent aromatic groups derived from aromatics such as phenylene, naphthalene, biphenylene and their alkyl and halogen-substituted products, and among them, p-phenylene,
m-phenylene and o-phenylene are preferred, especially p-
Phenylene is preferred. A and A 'may also be the same or different.

The amount of the aromatic sulfone compound added is
It is in the range of 0.1 to 20 parts by weight, preferably 0.2 to 15 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the PPS resin. When the amount of the aromatic sulfone compound added is O. When the amount is less than 1 part by weight, the effect of improving the adhesion to the epoxy resin is insufficient, which is not preferable. Conversely, when the amount of the aromatic sulfone compound exceeds 20 parts by weight, the mechanical strength and the mechanical strength of the PPS resin composition are reduced. It is not preferable because characteristics such as heat resistance deteriorate.

[0015] Fibrous and / or compounded in the present invention.
Or, as the non-fibrous filler, fibrous filler such as glass fiber, carbon fiber, potassium whisker, zinc oxide whisker, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, masonry fiber, metal fiber, straw Metal compounds such as silicate such as austenitic, sericite, kaolin, mica, clay, bentonite, asbestos, talc, alumina silicate, zeolite, alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, iron oxide, calcium carbonate, Carbonates such as magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, glass beads, ceramic beads
And non-fibrous fillers such as boron nitride, silicon carbide, zeolite, and silica. These fillers may be hollow, and two or more of these fillers may be used in combination. It is more preferable to use these fibrous and / or non-fibrous fillers after pretreatment with a silane-based or titanate-based coupling agent from the viewpoint of mechanical strength and the like.

In the present invention, the amount of the fibrous and / or non-fibrous filler is 2 parts per 100 parts by weight of the PPS resin.
0 to 400 parts by weight, in order to obtain higher adhesive strength, mechanical properties, dimensional stability, etc., fibrous and / or non-fibrous filler is added to 100 parts by weight of PPS resin.
It is preferable to mix the powder in an amount of 350 parts by weight. If the amount of the fibrous and / or non-fibrous filler exceeds 400 parts by weight, the fluidity of the PPS resin composition is significantly impaired, and if it is less than 20 parts by weight, the resin composition has high mechanical strength. However, it is not preferable in terms of obtaining dimensional stability.

With the above structure, the PPS resin composition of the present invention has improved adhesiveness to an epoxy resin. The epoxy resin referred to here is not particularly limited, and for example, bisphenol A, bisphenol F, bisphenol S, bisphenol AF, bisphenol AD, 4,4′-dihydroxybiphenyl, resorcin, saligenin, trihydroxydiphenyldimethylmethane, tetraphenylol Ethane These halogen-substituted and alkyl-substituted compounds, glycidyl synthesized from a compound containing two or more hydroxyl groups in a molecule such as butanediol, ethylene glycol, erythrit, novolak, glycerin, polyoxyalkylene and epichlorohydrin, etc. Ethers, glycidyl esters such as glycidyl phthalate, and aniline, diaminodiphenylmethane, metaxylenediamine, 1,3-bisaminimethylcyclohexane, etc. Glycidylamine resins synthesized from primary or secondary amines and epichlorohydrin, etc., glycidyl epoxy resins, epoxidized soybean oil, epoxidized polyolefins, non-glycidyl epoxy resins such as vinylcyclohexene dioxide, dicyclopentadiene dioxide, etc. Is mentioned. 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,
Examples include polysulfides and isocyanates.

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, 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-aminopropyltrimethoxysilane, γ- (2
An organic silane compound such as an amino group-containing alkoxysilane compound such as -aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, and γ-aminopropyltrimethoxysilane can be added. .

In the PPS resin composition of the present invention, plasticizers such as polyalkylene oxide oligomer compounds, ester compounds, thioether compounds, and organic phosphorus compounds, talc, kaolin, and organic compounds are used as long as the effects of the present invention are not impaired. Ordinary additives such as nucleating agents such as phosphorus compounds, release agents such as polyolefin compounds, ester compounds and silicone compounds, antioxidants, heat stabilizers, lubricants, UV inhibitors, coloring agents and flame retardants Can be added. Further, the PPS resin composition of the present invention may be polyamide, polyphenylene oxide, polysulfone, polyethylene tetrafluoride, polyetherimide, polyamideimide, polyimide, polycarbonate, polyethersulfone as long as the effects of the present invention are not impaired. , Polyether ketone, polythioether ketone, polyether ether ketone, epoxy resin, phenol resin, polyethylene, polystyrene, polypropylene, ABS resin, polyester, polyamide elastomer, polyester elastomer, polyalkylene oxide, or acid anhydride group, A resin such as an olefin copolymer containing a carboxyl group, an epoxy group or the like may be included.

The method of preparing the composition of the present invention is not particularly limited, and 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 mixing glass. 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,
A method in which an aromatic sulfone compound and a filler are dry-blended and then melt-kneaded by the method described above or PP.
A typical method is to dry blend two of the S resin, the aromatic sulfone compound, and the filler, melt-knead, and then melt-knead the rest.

The polyphenylene sulfide resin composition obtained according to the present invention has a new property, which is not enough in the conventional PPS resin, such as improved adhesion to an epoxy resin or the like, without significantly impairing the excellent properties inherent in the PPS resin. , A resin composition provided with a sensor, an LED lamp, a connector, a socket, a resistor, a relay case, a switch, a coil bobbin, a capacitor, a variable condenser case, an optical pickup, an oscillator, various terminal boards, a transformer, a plug, and a print. Substrate, tuner, speaker, microphone, headphones, small motor, magnetic head base, power module, semiconductor, liquid crystal, 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 by way of examples.

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

Flexural strength: ASTM-D790 Tensile shear adhesive strength: ASTM No. 1 dumbbell pieces were divided into two equal parts, fixed with spacers (1 mm thick) in between, and poured with epoxy resin. After curing, the tensile strength was measured at a speed of 1 mm / min, and the maximum value of the strength was divided by the bonding area to obtain the tensile shear bonding strength.

Reference Example 1 (Synthesis of polyphenylene sulfide) PPS-1: Sodium sulfide 3.26 in an 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
About 2 kg of powdered polyphenylene sulfide (PPS-1) at 10 ° C. and a shear rate of 1000 sec ^-1 ) was obtained.

Further, as PPS-2 and PPS-3, PPS resin manufactured by Toray-Phillips Petroleum Co., Ltd.
2100 and M2900 were used.

Examples 1-4 After the PPS resin, the aromatic sulfone compound and the filler were dry-blended at the ratios shown in Table 1, 280-320
The mixture was melt-kneaded by a screw-type extruder set to a temperature condition of ° C. and then pelletized. Using the obtained pellets, test specimens for measuring mechanical properties and tensile shear adhesive strength were formed.

Table 2 shows the bending strength, tensile shear adhesive strength, and volatile gas generation during melt-kneading of the obtained test pieces.

Comparative Examples 1-2 After dry blending was carried out in the same manner as in the Example except that no aromatic sulfone compound was added, the mixture was melt-kneaded with a screw type extruder set at a temperature of 280-320 ° C., and then pelletized. . Using the obtained pellets, test specimens for measuring mechanical properties and tensile shear adhesive strength were formed.

Table 2 shows the flexural strength, tensile shear adhesive strength, and volatile gas generation state during melt-kneading, which were measured for the obtained test pieces.

As described above, when the aromatic sulfone compound is not added, high adhesiveness to the epoxy resin cannot be obtained.

Comparative Examples 3 and 4 A-3 and A-4 were used as aromatic sulfone compounds, and after dry blending, melt kneading was performed by a screw type extruder set at a temperature of 280 to 320 ° C. and then pelletized. Using the obtained pellets, test specimens for measuring mechanical properties and tensile shear adhesive strength were formed.

Table 2 shows the measured bending strength, tensile shear adhesive strength, and volatile gas generation during melt-kneading of the obtained test pieces.

As described above, in the aromatic sulfone compound substituted with a methoxy group, a volatile gas is generated at the time of melt-kneading, and the effect of improving the adhesiveness to the epoxy resin is also improved by A-1 or A-1.
Inferior to -2. Also, the alkoxy group has 23 carbon atoms.
The aromatic sulfone compound (A-4) described above has a small effect of improving the adhesiveness to the epoxy resin.

[0035]

[Table 1]

[Table 2]

[0036]

The polyarylene sulfide resin composition of the present invention is a polyphenylene sulfide resin composition having improved adhesion to an epoxy resin without substantially impairing mechanical strength. It is suitable when secondary processing such as sealing of electric / electronic parts with an epoxy resin is involved.

Claims (1)

(57) [Claims] 1. An aromatic sulfone compound represented by the following structural formula of 0.1 to 20 parts by weight and a fibrous and / or non-fibrous filler of 20 to 400 parts by weight based on 100 parts by weight of a polyphenylene sulfide resin. A polyphenylene sulfide resin composition that is blended. Embedded image (Here, R and R ′ are a hydrocarbon group having 6 to 22 carbon atoms, which may be the same or different.
A ′ is an aromatic group, which may be the same or different. )