JPH0420567A - Resin composition - Google Patents

Abstract

PURPOSE:To prepare a thermoplastic resin compsn. excellent in strengths, dimensional stability, resistance to heat and chemicals, flame retardance, and melt flowability by compounding a polyphenylene sulfide resin having specified mol.wt. distribution and melt viscosity behavior with a polyarylene sulfide sulfone resin. CONSTITUTION:A thermoplastic resin compsn. is prepd. by compounding 95-1wt.% polyphenylene sulfide resin having such a mol.wt. distribution that the ratio of the wt.-average mol.wt. (Mw) to the number-average mol.wt. (Mn), each determined by gel permeation chromatography using 1-chloronaphthalene as a solvent, satisfies formula I, a melt flow rate according to ASTM D1238-86 (at 315.5 deg.C under 5000g load) satisfying formula II, and a retention of melt flow rate satisfying formula III (wherein MF5 and MF15 are the melt flow rates at a dwell time of 5min and 15min, respectively) with 5-99wt.% polyarylene sulfide sulfone resin.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a thermoplastic resin composition having excellent properties such as strength, heat resistance, dimensional stability, chemical resistance, flammability, and melt flowability. More specifically, polyphenylene sulfide resin (hereinafter abbreviated as PPS resin) and polyarylene sulfide sulfone resin (hereinafter abbreviated as PASS resin) having a specific molecular weight distribution and melt viscosity behavior.
The present invention relates to a resin composition comprising:

<Conventional technology> PPS resin has a high melting point and has excellent melt moldability, moisture resistance, and flammability, so demand for it is increasing in the electrical/electronic field, automobile field, general machinery field, etc. .

However, PPS resin is hard and brittle, and its glass transition point is 90.
Due to its low C, the strength and heat resistance of resins alone are insufficient, and their normal use is limited to those reinforced with glass fiber, carbon fiber, or other inorganic fillers. In order to improve the heat resistance and strength, which are insufficient when using PPS resin alone, research has been conducted on methods of blending non-grade polymers with high glass transition points. method (for example, Japanese Patent Publication No. 56-34032), method of blending PPS resin and polycarbonate (for example, Japanese Patent Publication No. 5313468), method of blending PPS resin with polysulfone or polyether sulfone (for example, Japanese Patent Publication No. 59-198). 164360 or Japanese Unexamined Patent Publication No. 61-34068), PP5tIJ
A method of blending fat and polythioethersulfone or polyethersulfone/polythioethersulfone copolymer (for example, JP-A-63-256653)
etc. have been proposed. However, in the resin compositions obtained by these conventional techniques, the chemical resistance and flame retardance of the resin composition are insufficient because the polymer blended with the PPS resin has extremely low chemical resistance and flame retardancy. In addition, the mechanical strength is low due to poor compatibility between PPS resin and polymer, and at present, no material truly useful as a molding resin material has yet been obtained.

<Problems to be Solved by the Invention> Therefore, the present inventors have developed a combination of PP5vfJ resin and amorphous polymer to improve mechanical strength, heat resistance, dimensional stability, chemical resistance, B flammability, and melt fluidity. As a result of intensive studies to obtain a resin composition that satisfies all of the various properties required for resin molding materials, we have developed a resin composition consisting of a PPS resin with a specific molecular weight distribution and melt viscosity behavior, and a polyarylene sulfide sulfone resin. The inventors have discovered that the above objects can be solved at once, and have arrived at the present invention.

Means for Solving the Problems> That is, the present invention provides (8) a number average molecule M (M n ) and a weight average molecule jt (M w ) determined by gel permeation chromatography using 1-chloronaphthalene as a solvent.
) has a molecular weight distribution that satisfies the following formula (1), and has a molecular weight distribution that satisfies the following formula (1).
Polyphenylene sulfide resin 95 to 1% by weight and (B) polyarylene sulfide sulfone resin 5 to 1% by weight whose melt flow rate value and retention rate determined by
99% by weight of the resin composition.

Mw/Mn<10 (1) MF5
<1000 g/10 min (2) 50<MFs
/MP+5xlOO<120 f3) (here MP5
, MF15 represent melt flow rate values at residence times of 5 minutes and 15 minutes, respectively. ) The PPS resin used in the present invention is a polymer containing a structural formula of % or more, more preferably 90 mol% or more, and whose molecular weight distribution and melt viscosity behavior are specified as described above.

Generally, pps is a polymer with a relatively small molecular weight obtained by a production method typified by Japanese Patent Publication No. 45-3368, and an essentially linear polymer obtained by a production method typified by a production method typified by Japanese Patent Publication No. 52-12240. There are polymers with relatively high molecular weight, and in the polymer obtained by the method described in Japanese Patent Publication No. 45-3368, it is possible to cure the polymer by heating in an oxygen atmosphere after polymerization or by crosslinking with peroxide etc. It may be used after increasing the degree of polymerization by adding an agent and heating.

However, among these various PPSs, those that can provide a useful resin composition that satisfies various requirements such as heat resistance, strength, and dimensional stability as in the present invention must be extremely specific. Must be. That is, if PPS, which is obtained by heating a relatively low molecular weight polymer obtained by the method disclosed in Japanese Patent Publication No. 453368 mentioned above and increasing the degree of polymerization by heating in the presence of oxygen, is used, a partial crosslinked structure may be present. Therefore, only a hard and brittle composition can be obtained, and as in the present invention, a specific PPS resin whose molecular weight distribution and melt viscosity behavior of PPS satisfy all of formulas f1) - (2) and (3) is used. By doing so, a high-performance resin composition with high practical value can be obtained for the first time.

Furthermore, less than 30 mol% of the repeating units of PPS can be composed of repeating units having the following structural formula.

The PPS used in the present invention is preferably produced through the above polymerization step and then subjected to acid treatment, hot water treatment, or washing with an organic solvent.

Examples of PPS resins suitably used in the present invention include M2888, M2588, E2280, and E248 manufactured and sold by Toshi Phillips Vetroleum Co., Ltd.
0, etc., but is not limited to these products.

The polyarylene sulfide sulfone resin (PASS resin) as the component (B) used in the present invention is a polymer mainly composed of i-shaped units represented by the following formula (3),
Such RASSm fat is, for example,
It can be produced by the method described in Japanese Patent Publication No. 5699 and Japanese Patent Publication No. 52-155700.

Here, Ar1 and Ar2 each represent a divalent aromatic hydrocarbon group, such as a p-phenylene group, m-phenylene group, 0-phenylene group, methyl-substituted phenylene group,
Ethyl substituted phenylene group, dimethyl monosubstituted phenylene group,
Examples include trimethyl monosubstituted phenylene group, tetramethyl substituted phenylene group, naphthylene group, alkyl substituted naphthylene group, among which p
i or m-phenylene groups and naphthylene groups, and particularly preferred is a polymer in which both Arl and Ar2 are p-phenylene groups. There is no particular restriction on the degree of polymerization of this PASS resin, and ASTM D1238
86 (340°C, 5,000g load) with a melt flow rate value of 05 to 100.
0 (+r/10 min), preferably 1 to 800 (g/10
minutes) can be used.

In the present invention, the composition ratio of PPS resin and PASS resin is in the range of PPS/PASS = 95 to 115 to 99% by weight, preferably 90 to 3/10 to 97% by weight, more preferably 80 to 5/20. The range is 95% by weight. If the amount of PPS resin exceeds 95% by weight, the resulting resin composition will lack heat resistance and dimensional stability, which is undesirable. On the other hand, if the amount of PASS resin exceeds 99% by weight, the melt flow of the resin composition will deteriorate. This is not preferable because it reduces the properties, that is, the moldability.

The method for preparing the resin composition of the present invention is not particularly limited, and PPS
After tri-blending the resin and PASSVIJ fat powder, pellets, and strips using a ribbon blender, Henschel mixer, ■blender, etc., the mixture is processed using a Banbury mixer, mixing roll, single- or twin-screw extruder, kneader, etc. Examples include a method of melt-kneading using Especially using a single-screw or twin-screw extruder with sufficient kneading power? A typical method is to knead 8 enemies.

In addition, the PPS resin composition used in the present invention may contain conventional additives such as antioxidants, heat stabilizers, lubricants, crystal nucleating agents, ultraviolet inhibitors, coloring agents, and female combustion agents, to the extent that the effects of the present invention are not impaired. Additives and small amounts of various polymers can be added, and in addition, for the purpose of controlling the degree of crosslinking of PPS, ordinary peroxidants and thiophosphinic acid metal salts described in JP-A-59-131650 can be added. crosslinking accelerator or JP-A-58-204045, JP-A-58-20404
It is also possible to incorporate crosslinking inhibitors such as dialkyltin dicarboxylate and aminotriazole described in Publication No. 6 and the like.

In the present invention, the fibrous and/or granular reinforcing agent is not an essential component, but it can be blended in an amount not exceeding 400 parts by weight based on a total of 100 parts by weight of the PPS resin composition, if necessary. It is possible to improve strength, rigidity, heat resistance, dimensional stability, etc. by blending in an amount of usually 10 to 300 parts by weight.

Such fibrous reinforcing agents include glass fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber,
Examples include inorganic fibers such as gypsum fibers and metal fibers, and carbon fibers.

Particulate reinforcing agents include wollastenite, sericite, kaolin, mica, clay, bentonite, asbestos, talc, silicates such as alumina silicate, and metals such as alumina, silicon chloride, magnesium oxide, zirconium oxide, and titanium oxide. Oxides, calcium carbonate, magnesium carbonate, carbonates such as dolomite, calcium sulfate,! ! Examples include sulfates such as barium, glass beads, boron nitride, silicon carbide and silica, which may also be hollow.

These reinforcing agents can be used in combination of two or more,
If necessary, it can be used after being pretreated with a silane-based or titanium-based coupling agent.

<Example> The present invention will be explained in more detail with reference to Examples below.

The properties described in Examples, Reference Examples, and Comparative Examples were measured as follows.

Tensile properties + ASTM D638 Bending properties: ASTM D790 Izot WI impact strength: ASTM D256 Heat distortion temperature (18,6 kgf/-load): ASTM D64
8 Melt flow rate: ASTM D1238-86 (315,5°C 15000sr load and 340°C
15,000+r load) Molecular weight and molecular weight distribution: Measured using a gel permeation chromatography device manufactured by Waters, according to the method disclosed in Kobunshi Ronshu Vol. 44 (1987) February issue 1, pages 39-141. did.

Flame retardance: UL-94 Reference Example 1 PP5t used in this example and comparative example! 1 fat and its characteristic values are shown in Table 1.

Table 1) Manufactured by Azuma Phillips Vetroleum 2) Manufactured by Phillymbs 66 Reference Example 2 3.26 kg (25 kg) of sodium sulfide was placed in an autoclave.
mol, containing 40% water of crystallization), 10 g of sodium hydroxide
and N-methylpyrrolidone (hereinafter abbreviated as NMP) 7
．． 9 kg and P-dichlorodiphenylsulfone7.
After charging 18 kg (25 mol) and purging the system with nitrogen gas, the reaction was carried out under pressure at 200° C. for 5 hours while stirring with a stirrer. The reaction product was washed 5 times with hot water at 90°C and then dried under reduced pressure at 80°C for 24 hours, resulting in a melt float of 840 g/10 minutes (340°C) and a glass transition point of 210°C. 5.9 kg of polyarylene sulfide sulfone resin (RASSL) was obtained and used in the following examples.

Reference Example 3 Sulfolane 10k was used instead of NMP used in Reference Example 2.
The heating reaction was carried out in the same manner as in Reference Example 2 except that g
The produced polymer was recovered and washed, and a polyarylene sulfide sulfone resin (PASS-2>5.5) with a melt flow rate of 200 g/10 minutes (340°C) was performed.
1 qr was obtained and used in the following examples.

Example l 1.8 kg (60% by weight) of PP5-2 log and PAS
After tri-blending 1.2 kg (40% by weight) of S-1 logs using a Henschel mixer, the mixture was fed to a 30-diameter twin-screw extruder feeder, melt-kneaded at a cylinder temperature of 340°C, and the molten guts were cooled with water. , made into pellets using a pelletizer. After drying this pellet with hot air at 140°C for 7/4 hours, molding temperature: 340°C, mold temperature: 150°C.
Injection molding was performed under the following conditions to obtain various test specimens with good appearance. The properties of this molded piece are shown in Table 2, and it was found that it had good heat resistance, strength, and impact resistance, and also had high fluidity of the composition, and was of extremely high practical value.

Comparative Example 1 A single PP5-2 bulk powder was pelletized, injection molded and its properties measured in the same manner as in Example 1. The heat distortion temperature of this product was as low as 124°C, indicating that the heat resistance was insufficient. Ta.

Comparative Example 2 PASS-1 bulk powder was pelletized and injection molding was attempted in the same manner as in Example 1, but the fluidity of this material was insufficient, making it particularly difficult to mold thin test pieces. Ta.

Comparative Example 3 Crosstalk, pelletization, and
Injection molding was performed to obtain a molded piece with an attractive appearance. However, due to the low degree of polymerization of PP53, this product had an extremely low unnotched Izot impact value of 5 kg f-σ7/'d, and was not suitable for practical use.

Comparative Example 4 Kneading and injection molding were carried out in exactly the same manner as in Example 1, except that PP5-4 was used instead of PP5-2 used in Example 1. However, due to the instability of melt retention of PP5-4, the viscosity increases during melt retention, making it difficult to perform stable injection molding, and the unnotched Izo impact strength of the resulting molded piece is 7 kgf Hcx/ cl was insufficient.

Examples 2 to 4 Extrusion kneading and injection molding were carried out in the same manner as in Example 1 except that the types and blending amounts of PPS resin and PASS resin were changed, and in each case, molded pieces with good appearance were stably obtained. was completed. The characteristic values of these molded pieces are summarized in Table 2, and all were excellent in heat resistance, moldability, strength, etc. in a well-balanced manner.

Examples 5 to 8 PPS resin, PASS resin and inorganic reinforcing material were blended in the proportions shown in Table 2, and then 401 mφ, L/D = 25
The mixture was kneaded at 340°C using a single-screw extruder, then turned into a berent, and then injection molded under the same conditions as in Example 1.

The properties of the molded pieces obtained here are as shown in Table 2, and all had high practical value.

<Effect of the invention> PP5v! By selecting PPs resin with a specific molecular weight distribution and melt viscosity behavior as the J resin and combining it with PASIIM resin, which is non-grade and has a high glass transition point, it has excellent heat resistance, strength, chemical resistance, and flame retardancy. A resin composition with excellent moldability was obtained. This resin composition is suitable for applications such as electrical/electronic parts, automobile parts, and general mechanical parts.

Claims (1)

[Claims] (A) Number average molecular weight (@Mn@) determined by gel permeation chromatography using 1-chloronaphthalene as a solvent.
) and weight average molecular weight (@Mw@) has a molecular weight distribution that satisfies the following formula (1), and ASTM D1238-8
6 (315.5℃, 5,000g load) and its retention rate are as follows (2)
and a resin composition comprising 95 to 1% by weight of a polyphenylene sulfide resin satisfying formula (3) and 5 to 99% by weight of (B) a polyarylene sulfide sulfone resin. @Mw@/@Mn@<10(1) MF_5<1000g/10min(2) 50<MF_5/MF_1_5×100<120(3)
(Here, MF_5 and MF_1_5 represent melt flow rate values at residence times of 5 minutes and 15 minutes, respectively.)