JPH05230369A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, comprising a polyphenylene sulfide resin, other polyphenylene sulfide resins and a polycarbonate-based resin and excellent in mechanical characteristics such as impact resistance with hardly any deterioration in heat resistance. CONSTITUTION:The objective composition is obtained by blending (A) a polyphenylene sulfide resin (having preferably 300-3000 P melt viscosity) with (B) a polyphenylene sulfide resin having a melt viscosity (preferably <=20000 P at 300 deg.C and 200sec<-1>) of >=3 times that of the component (A), (C) a polycarbonate-based resin having >=3000 P melt viscosity and further (D) a thermal processing stabilizer composed of a phenolic, a phosphorus-based or a sulfur-based stabilizer. Furthermore, the polyphenylene sulfide resin with <=4000ppm chlorine content is used as the components (A) and/or (B).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition comprising a polyphenylene sulfide resin (hereinafter abbreviated as PPS) and a polycarbonate resin (hereinafter abbreviated as PC) having excellent mechanical properties. The composition is used for injection-molded products, extrusion-molded products and the like, and is used for various electric / electronic parts, machine parts, precision machine parts, automobile parts, sporting goods, sundries and the like.

[0002]

2. Description of the Related Art PPS is a crystalline engineering plastic excellent in heat resistance, flame retardancy, high rigidity, chemical resistance, dimensional stability, molding processability, etc., and is used for electrical parts, precision machine parts, automobile parts. It is used in various fields such as.

However, the resin is poor in flexibility,
Since it is very brittle, it is usually used in a form reinforced with glass fiber, and its field of use as a material is limited. It has also been pointed out that there are drawbacks in weather resistance and burr characteristics of molded products. Furthermore, since the glass transition temperature is relatively low at 80 to 90 ° C., there is a drawback that the elastic modulus sharply decreases in the temperature range exceeding the glass transition temperature.

Many attempts have been made so far to improve the defects of PPS or to impart the excellent properties of PPS to PC by blending PPS and PC. However, in either case, because the affinity between PPS and PC is insufficient, the desired effects (in particular, mechanical properties such as impact resistance) may not be sufficiently manifested, or in some cases, the characteristics may be rather reversed. There was a problem such as the decrease.

For example, in JP-A-51-100150, PPS is blended with PC, and flame resistance, which is a defect of PC,
We are improving the hydrolyzability. However, in this case, although these objects are achieved, there is a problem that mechanical properties such as impact resistance are not improved or rather deteriorated due to insufficient affinity. Further, in JP-A-2-283763, mechanical properties are improved by mixing PPS modified with a carboxylic acid anhydride with PC. However, in this case, the heat resistance of the carboxylic acid anhydride was inferior to that of PPS, so that the heat resistance of the molded product was lowered, and the improvement of impact resistance was also unsatisfactory. On the other hand, JP-A-2-180962 proposes to improve the molding stability of PPS by mixing and using two or more kinds of PPS having different viscosities. PC is mentioned as an example of a resin that can be used within the scope of the invention. However, even if PC is simply mixed with two or more kinds of PPS having different viscosities, improvement in mechanical properties cannot be expected.

[0006]

As described above, in any of the conventional techniques, the resin composition of PPS and PC was insufficient in improving the mechanical properties.

An object of the present invention is to provide a resin composition comprising PPS and PC which has improved mechanical properties such as impact resistance without impairing heat resistance.

[0008]

[Means for Solving the Problems] As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention firstly found that PPS which is hardly compatible with other engineering plastics.
Among them, it was found that PPS having a relatively low molecular weight has a good affinity with PC. Although there is a general rule in polymer chemistry that a compound having a small molecular weight is advantageous for compatibilization, the present inventors have found that a low molecular weight PP in the reactivity with PC.
It is speculated that S is active and reacting. At this time, the PC is PP
It tends to decompose by reaction with S, which means that P
Although it increases the compatibility with PS, it also causes the mechanical properties to be impaired. The present inventors not only improve the affinity of the phase-separated interface between PPS and PC, but also improve the brittleness of PPS and PC themselves in the resin composition together with this, if mechanical properties are improved several times. Was considered to improve further.

Based on the above findings, further intensive investigations have been carried out to obtain a low molecular weight PPS having a good affinity and a high molecular weight PPS having a relatively good brittleness, and melting the PPS (A) and the resin (A) three times or more. It was found that a resin composition having improved mechanical properties can be obtained by using PPS (B) having viscosity and mixing it with PC having a relatively high molecular weight, and completed the present invention. .

That is, the present invention relates to a polyphenylene sulfide resin (A) and the polyphenylene sulfide resin (A).
Containing a polyphenylene sulfide resin (B) having a melt viscosity three times or more of the above (melt viscosity at 300 ° C., 200 sec-1; the same applies below) and a polycarbonate resin (C) having a melt viscosity of 3000 poise or more. And a thermoplastic resin composition.

The PPS used in the present invention is (-φ-
S-) (provided that -φ- is a p-phenylene group and the same shall apply hereinafter), 70 mol% of a structural unit represented by
Particularly preferred is a polymer containing 90 mol% or more. The arylene sulfide structural unit contained in addition to (-φ-S-) is mainly an arylene group having a group shown below. That is, a divalent aromatic residue such as m-phenylene, o-phenylene, 2,6-naphthalene, 4,4'-biphenylene, or (-φ-O-φ-), (-φ
-CO-φ-), (-φ-CH ₂ -φ-), (-φ-S
O ₂ -φ-), (-φ-C (CH ₃ ) ₂ -φ-) and the like, which is a divalent aromatic residue containing at least two aromatic rings having 6 carbon atoms, and each aromatic group. F, Cl, Br, CH in the ring
Substituents such as ₃ , COOH, NH ₂ , OH, CN and NO ₂ may be introduced. These PPS may be a homopolymer, a random copolymer or a block copolymer.

A general method for producing such PPS is, for example, (1) a reaction between a halogen-substituted aromatic compound and an alkali metal sulfide (US Pat. No. 2,513,188, JP-B 4).
No. 4-27671 and Japanese Patent Publication No. 45-3368), (2) Condensation reaction of thiophenols in the coexistence of an alkali catalyst or a copper salt (US Pat.
4165, British Patent No. 1160660),
(3) It is synthesized by a condensation reaction of an aromatic compound and sulfur chloride in the presence of a Lewis acid catalyst (see Japanese Patent Publication No. 46-27255 and Belgian Patent No. 29437), and is arbitrarily selected according to the purpose. You can

Even if the viscosity of PPS (A) is relatively low, PP
When the viscosity of S (B) is less than 3 times that of PPS (A), PPS and PC exhibit good dispersibility, but the mechanical properties of the resin composition are extremely insufficient. In addition, even if the viscosity of PPS (A) is relatively high, PPS
If the viscosity of (B) is less than 3 times that of PPS (A), the affinity of the interface is insufficient, and the effect of improving the mechanical properties is also small.

Therefore, in the composition of the present invention, 3000
PP used with PC having melt viscosity higher than poise
S combines PPS (A) with PPS (B) having a melt viscosity three times or more that of PPS (A). Only when PPS made of such a combination is used, the affinity between PPS and PC is improved, and it is sufficient to dramatically increase the brittleness of the composition containing PC.

The melt viscosity range of the PPS (A) used is selected as a range in which the brittleness of PPS itself is not deteriorated while maintaining the affinity with PC as described above, but it is 100 to 100.
00 poise is more preferably 300 to 3000 poise. On the other hand, the melt viscosity range of PPS (B) is PPS (A)
Is selected as a range that compensates for brittleness and does not deteriorate moldability, and is preferably 3 times or more to 100,000 poises or less, more preferably 20,000 poises or less of the viscosity of PPS (A).

The mixing ratio of PPS (A) and PPS (B) varies depending on the absolute value of these viscosities and the magnitude relationship of the viscosities and cannot be specified unconditionally, but is generally PPS.
(A) 5 to 50% by weight, PPS (B) 95 to 50% by weight, and more preferably 5 to 30% by weight PPS (A) and PPS (B) 95 to 70% by weight.

The PC used in the present invention can be a homogeneous polycarbonate or a polycarbonate copolymer based on, for example, one or more of the following bisphenols. Hydroquinone, resorcin, dihydroxydiphenyl, bis- (hydroxyphenyl) -alkane,
Bis- (hydroxyphenyl) -cycloalkane, bis- (hydroxyphenyl) -sulfide, bis- (hydroxyphenyl) -ketone, bis- (hydroxyphenyl) -ether, bis- (hydroxyphenyl) -sulfoxide, bis- (hydroxy) Phenyl) -sulfone and α, α'-bis- (hydroxyphenyl)-
Diisopropylbenzene and those compounds in which the nucleus is substituted with alkyl or halogen.

Of these, specific examples of suitable bisphenols include 4,4-dihydroxydiphenyl,
2,2-bis- (4-hydroxyphenyl) -propane, 2,4-bis- (4-hydroxyphenyl) -2-
Methyl butane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, α, α′-bis- (4-hydroxyphenyl) -p-diisopropylbenzene, 2,2
-Bis- (3-methyl-4-hydroxyphenyl) -propane, 2,2-bis- (3-chloro-4-hydroxyphenyl) -propane, bis- (3,5-dimethyl-4)
-Hydroxyphenyl) -methane, 2,2-bis-
(3,5-Dimethyl-4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) -sulfone, 2,4-bis- (3,5
-Dimethyl-4-hydroxyphenyl) -2-mercaptan, 1,1-bis- (3,5-dimethyl-4-hydroxyphenyl) -cyclohexane, α, α'-bis-
(3,5-Dimethyl-4-hydroxyphenyl) -p-
Diisopropylbenzene, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) -propane and the like can be mentioned, preferably. Is 2, 2
-Bis- (4-hydroxyphenyl) propane, 2,2
-Bis- (3,5-dimethyl-4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-
4-hydroxyphenyl) -propane, 2,2-bis-
(3,5-Dibromo-4-hydroxyphenyl) propane and 1,1-bis- (4-hydroxyphenyl)-
Cyclohexane is mentioned.

Preferred PCs are based on the preferred bisphenols mentioned above. A particularly preferred polycarbonate copolymer is the copolymer of 2,2-bis- (4-hydroxyphenyl) -propane with one of the other particularly preferred other bisphenols mentioned above.

Another particularly suitable PC is 2,2-bis-
(4-hydroxyphenyl) -propane or 2,2-
Bis- (3,5-dimethyl-4-hydroxyphenyl)
-Based solely on propane.

The PC can be produced by a known method such as a melt transesterification reaction of bisphenol and diphenyl carbonate, a two-phase interfacial polymerization method of bisphenol and phosgene, and the like.

Since PC tends to be decomposed by mixing with PPS as described above, it is necessary to use a high molecular weight PC in advance. In the present invention, the melt viscosity is 3
000 poises or more, more preferably 5000 poises or more are remarkably excellent in improving the impact resistance of the composition of the present invention.

The mixing ratio of PPS and PC is determined in consideration of the balance between heat resistance and mechanical properties of the resin composition to be obtained, and is not generally determined, but PP
PC 5 for S-total amount (A + B) 50-90 parts by weight
The preferred range is 0 to 10 parts by weight. However, the total weight is 100 parts by weight.

As described above, PC has a tendency to decompose when mixed with PPS, and therefore it is very important to add a heat-resistant processing stabilizer to the resin composition. Phenol-based, sulfur-based, phosphorus-based, or the like is used as the heat-resistant processing stabilizer. The stabilizer is usually added in the range of 0.1 to 1.0% by weight.

As the phenolic heat-resistant processing stabilizer, butylated hydroxytoluene, butylated hydroxyanisole, n.octadecyl-β- (4'.hydroxy-
3'-5'.di.t.butylphenyl) propionate, 1,1,3.tris (2-methyl.4hydroxy-)
5-t.butylphenyl) 'butane 1,3,5 trimethyl.2,4,6.tris (3,5.di.t.butyl 4-hydroxybenzyl) benzene, tetrakis {methylene.
3 * (3 '* 5'-di.t.butyl-4.hydroxyphenyl) propionate} methane and the like are preferably used.

As the sulfur-based heat-resistant processing stabilizer, dilauryl 3,3 'thiodipropionate, di-myristyl 3,3' thiodipropionate, di-stearyl 3,3 'thiodipropionate, etc. Is preferably used.

Examples of phosphorus-based heat-resistant processing stabilizers include trisnonylphenyl phosphite, tris (mixed, mono- and dinonylphenyl) phosphite, tris (2,4di.t.butylphenyl) phosphite, 4,
4'-butylidene bis (3.methyl 6-t.butylphenyl) di tridecyl phosphite, 4,4'-biphenylenediphosphinic acid tetrakis (2,4 di-t-butylphenyl), tris (cyclohexylphenyl) phosphite, cyclic Neopentane tetraylbis (2,4
-Di.t.butylphenylphosphite), cyclic neopentanetetraylbis (2,6-di.t.butyl 4-methylphenylphosphite) and the like are preferably used. These may be used as a mixture of several kinds.

Since hydrolysis of PC is accelerated by residual chlorine in the system, caution should be exercised when the above stabilizer is used, but the same applies to PPS. That is, in PPS, an oligomer component of PPS generated in the synthesis process,
Or, there may be impurities such as unreacted components, and especially chlorine components may be contained as impurities such as NaCl, or may be contained in the molecular end groups. These accelerate the hydrolysis of PC when mixed with PC. However, it lowers the mechanical properties and heat resistance of the resin composition.

The inventors of the present invention used PPS with hot water, acetone,
As a result of sufficiently purifying with various alcohols and using various PPS with a small amount of impurities and oligomers, chlorine content is 4000 ppm or less, particularly preferably 1500 pp.
It was further found that a resin composition excellent in mechanical properties and heat resistance can be obtained by using a specific PPS having a m or less.

The chlorine content present in PPS can be measured by a known analysis method, but the chlorine ion concentration generated by thermally decomposing the PPS polymer in acid or oxygen is analyzed by ion chromatography or The method of determining by argentometry is preferable.

The resin composition of the present invention, if necessary,
It is possible to add a fibrous or granular reinforcing agent, and usually 3 to 300 parts by weight with respect to 100 parts by weight of the resin composition.
By blending in the range of parts by weight, strength, rigidity, heat resistance and dimensional stability can be further improved. Examples of the fibrous reinforcing agent include glass fiber, carbon fiber, silane glass fiber, boron fiber, whiskers, potassium titanate, asbestos, silicon carbide, aramid fiber, ceramic fiber and metal fiber. Examples of the granular reinforcing material include silicates such as mica and talc, carbonates, sulfates, metal oxides, glass beads, and silica. Two or more of these may be used in combination, and these inorganic fillers may be treated with a silane-based or titanium-based coupling agent which is usually used as a treating agent for the filler.

In the composition of the present invention, a small amount of a releasing agent, a colorant, an ultraviolet stabilizer, a foaming agent, a flame retardant, a flame retardant aid, a rust preventive agent, or a small amount is used within the range not departing from the object of the present invention. A thermosetting resin such as an epoxy resin, a phenol resin, or a polyimide can be contained.

The composition of the present invention can be prepared by various known methods. For example, there is a method in which the raw materials are mixed with a mixer such as a tumbler or a Henschel mixer, then fed to a uniaxial or biaxial extruder, melt-kneaded at 280 to 400 ° C., and then adjusted as pellets.

[0034]

EXAMPLES The present invention will be specifically described below with reference to examples. The present invention is not limited to these examples.

[Synthesis Example 1] 9.55 kg of sodium hydrosulfide (NaSH.2H ₂ O), 4.05 kg and 50.0 kg of sodium hydroxide were placed in an autoclave equipped with a distillation outlet, a monomer solution charging inlet and a nitrogen gas inlet. While stirring nitrogen gas while stirring n-methylpyrrolidone, 190
Dehydration operation was performed at ℃ for 1 hour. Then, the autoclave was closed, and a solution of 14.7 kg of p-dichlorobenzene and 10 kg of N-methylpyrrolidone was press-fitted into the system obtained by the dehydration operation heated to 200 ° C. over about 40 minutes, and under pressure. The temperature was raised to 240 ° C., the reaction was carried out for 4 hours, and the polymer was separated to obtain PPS-0.

[Post-treatment example] PPS-0 of Synthesis Example 1 was washed twice with warm water and twice with acetone to obtain PPS-1. This PPS-1 was heat-treated at 260 ° C. for 3 hours in an air atmosphere to obtain PPS-2. In addition, this PPS-1
And heat-treated in an air atmosphere for 2 hours to obtain PPS-3.
PPS-0 with warm water 3 times and isopropyl alcohol with 2 times.
Once, washed twice with acetone, and heat-treated at 260 ° C. for 4 hours, 5 hours, and 6 hours in an air atmosphere to obtain PPS-4, PPS-5, and PPS-6, respectively. PPS
-0 was washed once with warm water and then heat-treated at 260 ° C for 30 minutes in an air atmosphere to obtain PPS-7.

The melt viscosity of the obtained PPS, the chlorine content and the melt viscosity of the PC used are shown in Table 1. The melt viscosity was measured with a flow tester (CFT-500, manufactured by Shimadzu Corporation) under different loads, and the shear rate was 200 sec-1.
Extrapolated to. Chlorine content is measured by chlorine-sulfur analyzer (TS
X-10 model, manufactured by Mitsubishi Kasei).

[Examples 1 to 5 and Comparative Examples 1 and 2] The combinations shown in Table 2 below were preliminarily mixed in a powder state and pelletized at 300 ° C using an extruder. This was injection molded at 300 ° C. to obtain a sample piece. These are shown together in Table 2 together with their physical properties.

The Izod impact test is ASTM-D-
256 (notched, unit: Kg · cm / cm), bending strain at break by bending test is JIS-K7055 (unit:%), heat distortion temperature is ASTM-D648 (18.6).
Kgf / cm ² , unit: ° C).

[0040]

[Table 1] Note) S-1000, S-3000, and H-3000 are polycarbonates manufactured by Mitsubishi Gas Chemical Co., Inc. "Eupiron"

[0041]

[Table 2] * 1 Iupilon manufactured by Mitsubishi Gas Chemical Co., Ltd. * 2 Proportion (% by weight) in the entire resin composition * 3 IRGAFOS 168 (phosphorus-based) IRGANOX manufactured by Ciba-Geigy Co., Ltd.
1010 (phenolic) to the resin component, 0.0
Add 5wt%, 0.5wt%

[Example 6] A sample piece was prepared in the same manner as in Example 1 except that 0.5 wt% of MARK AO-23 (sulfur-based) manufactured by Adeka Argus Co., which was a heat-resistant processing stabilizer, was added to the resin component. Obtained. This product had an Izod impact value of 17 kg · cm / cm, a bending strain at break of 6.0% by a bending test, and a heat distortion temperature of 195 ° C.

[0043]

The composition of the present invention has remarkably improved mechanical properties such as impact resistance. Therefore, the resin composition of the present invention includes, for example, electrical / electronic parts such as connectors / printed boards / encapsulation molded products, automobile parts such as lamp reflectors / various electrical component parts, various buildings and aircraft /
Interior materials such as automobiles, leisure and sports equipment such as tennis rackets, skis, golf clubs, fishing rods, acoustic materials such as enclosures such as speakers and back decks of stringed instruments, OA equipment parts, camera parts, clock parts, etc. Molding materials or fibers or films with excellent mechanical properties such as heat resistance and impact resistance in various molding processing fields such as injection molding and compression molding of precision parts, extrusion molding and pultrusion molding of composites, sheets, pipes, etc. Used as.

Claims (5)

[Claims] 1. A polyphenylene sulfide resin (A)
And a polyphenylene sulfide resin (B) having a melt viscosity three times or more that of the polyphenylene sulfide resin (A) (melt viscosity at 300 ° C., 200 sec−1, and the same below), and a melt viscosity of 3000 poise or more. A thermoplastic resin composition comprising a polycarbonate resin (C). 2. The composition according to claim 1, wherein the polyphenylene sulfide resin (A) has a melt viscosity of 300 to 3000 poise. 3. The composition according to claim 2, wherein the polyphenylene sulfide resin (B) has a melt viscosity of 20000 poise or less. 4. The composition according to claim 1, further comprising at least one heat-resistant processing stabilizer selected from a phenol type, a phosphorus type and a sulfur type. 5. The composition according to claim 1, wherein a polyphenylene sulfide resin having a chlorine content of 4000 ppm or less is used as (A) and / or (B).