JPH0586291A - Composition of polyphenylene sulfide resin - Google Patents

Abstract

PURPOSE:To provide a polyphenylene sulfide resin composition having excellent heat-resistance, moldability and solvent resistance. CONSTITUTION:The objective composition is composed of (A) a polyphenylene sulfide, (B) a polyphenylene ether, (C) an organic compound having ethylenic double bond and containing epoxy group, carboxyl group or acid anhydride group in the molecule and (D) a polycarbodiimide.

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 excellent heat resistance, moldability and solvent resistance.

[0002]

2. Description of the Related Art Polyphenylene sulfide has heat resistance,
It is known as a resin having excellent solvent resistance, electrical characteristics, mechanical strength, dimensional stability, flame retardancy, and the like, and has attracted attention in recent years. In particular, polyphenylene sulfide can improve the above performance by being combined with a fibrous reinforcing material such as glass fiber, carbon fiber, etc., and an inorganic filler such as talc, clay, silica, etc. Is used for. However, polyphenylene sulfide has a drawback that it has a low degree of polymerization, is difficult to mold, has no toughness and is brittle, and that glass fiber reinforced polyphenylene sulfide tends to warp a molded product.

On the other hand, polyphenylene ether is a resin excellent in heat resistance, rigidity, electric characteristics and the like, and is a polymer material useful as an engineering plastic. However, it is well known that polyphenylene ether has a major drawback that it has poor solvent resistance and further has poor moldability. As a technique for improving the moldability of polyphenylene ether, for example, Japanese Patent Publication No. 56-34032 discloses blending polyphenylene sulfide. However, although the effect of improving the molding processability is observed, the poor compatibility between the polyphenylene sulfide and the polyphenylene ether causes poor appearance and deterioration of mechanical properties.

Various proposals have been made for improving the compatibility between polyphenylene sulfide and polyphenylene ether (Japanese Patent Publication No. 60-11063, Japanese Patent Laid-Open No. 64-3).
No. 6645, JP-A-2-49023), but the effect is not sufficient, and the impact resistance and solvent resistance of the obtained resin are not sufficient.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to improve the compatibility when a polyphenylene sulfide and a polyphenylene ether are blended and to obtain a composition excellent in impact resistance and solvent resistance. Is.

[0006]

The feature of the present invention is that the composition of the polyphenylene sulfide resin is (A) polyphenylene sulfide, (B) polyphenylene ether,
It consists of (C) an organic compound having an ethylenic double bond having an epoxy group, a carboxyl group or an acid anhydride group in the molecule and (D) a polycarbodiimide.

The present invention will be described in more detail below. The (A) polyphenylene sulfide resin (hereinafter abbreviated as PPS) used in the present invention has a structural formula:

[0008]

[Chemical 1]

It is a polymer containing 70 mol% or more, more preferably 90 mol% or more of the repeating unit represented by: If the repeating unit is less than 70 mol%, heat resistance is impaired, which is not preferable. As a PPS
And a polymer having a relatively small molecular weight obtained by the production method represented by JP-A-3368, and Japanese Examined Patent Publication No. 52-12240.
An essentially linear polymer having a relatively high molecular weight, which is obtained by the production method typified by the publication, can be used. The polymer obtained by the method described in JP-B-45-3368 has a high degree of polymerization by heating after polymerization in an oxygen atmosphere or by adding a crosslinking agent such as peroxide and heating. It can also be used.

Further, PPS can comprise less than 30 mol% of its repeating unit with a repeating unit having the following structural formula.

[0011]

[Chemical 2]

[0012]

[Chemical 3]

[0013]

[Chemical 4]

[0014]

[Chemical 5]

[0015]

[Chemical 6]

[0016]

[Chemical 7]

[0017]

[Chemical 8]

The melt viscosity of PPS used in the present invention is
There is no particular limitation as long as a molded product can be obtained.
In terms of toughness of PS itself, 100 poise or more,
In terms of moldability, those having 10,000 poise or less are more preferably used. Particularly preferably 1,000 to 5,0
The range is 00 poise. In addition, the PPS used in the present invention contains usual additives such as an antioxidant, a heat stabilizer, a lubricant, a crystal nucleating agent, an anti-UV agent and a coloring agent, and a small amount of other additives within a range that does not impair the effects of the present invention. A resinous or rubbery polymer may be added.

Further, for the purpose of controlling the degree of crosslinking of PPS, an ordinary peroxide type crosslinking agent and JP-A-59-13 are used.
1650, a crosslinking accelerator such as a metal salt of thiophosphinic acid, or JP-A-58-204045.
It is also possible to add a crosslinking inhibitor such as dialkyltin dicarboxylate and aminotriazole described in JP-A No. 58-204046.

The component (B), polyphenylene ether (hereinafter abbreviated as PPE), means a bonding unit:

[0021]

[Chemical 9]

(Wherein R ₁ , R ₂ , R ₃ , and R ₄ are each washed from the group consisting of hydrogen, halogen, hydrocarbon, or substituted hydrocarbon groups and may be the same or different from each other. And the reduced viscosity (0.
5 g / dl, chloroform solution, measured at 30 ° C) is 0.1
Range of 5 to 0.70, more preferably 0.20 to 0.6
It is a homopolymer and / or a copolymer in the range of 0. As a specific example, poly (2,6-dimethyl-
1,4-phenylene ether), poly (2-methyl-6)
-Ethyl-1,4-phenylene ether), poly (2,
6-diphenyl-1,4-phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether), and the like, Further, polyphenylene ether copolymers such as copolymers of 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethylphenol and 2-methyl-6-butylphenol) can also be mentioned. Among them, poly (2,6-dimethyl-
1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol is preferable, and further poly (2,6-dimethyl-1,
4-phenylene ether) is preferred.

Such PPE is prepared, for example, by oxidatively polymerizing 2,6-xylenol, for example, by using a complex of cuprous salt and amine by Hay described in US Pat. No. 3,306,874 as a catalyst. Can be easily manufactured. Examples of the organic compound having a carboxyl group, an acid anhydride group or an epoxy group in the molecule which is the component (C) include maleic acid, maleic anhydride, fumaric acid, itaconic acid, acrylic acid, acrylic acid ester and methacrylic acid. Acid, methacrylic acid ester, crotonic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, and its anhydride, endo-cis-bicyclo [2,2,1] -5-heptene-2,3-dicarboxylic acid , And their anhydrides, maleimide compounds, glycidyl acrylate, diricidyl methacrylate, and the like, among which maleic anhydride and glycidyl methacrylate are preferable.

The polycarbodiimide as the component (D) is a compound having a carbodiimide group (-N = C = N-) in the molecule, and any compound can be used as long as it has two or more carbodiimide groups. Can be used. Specific examples of polycarbodiimide include poly (4,
4'-diphenylmethanecarbodiimide), poly (3,
3'-dimethyl-4,4'-biphenylmethanecarbodiimide), poly (tolylcarbodiimide), poly (p-
Phenylenecarbodiimide), poly (m-phenylenecarbodiimide), poly (3,3'-dimethyl-4,4 '
-Diphenylmethanecarbodiimide), poly (naphthylenecarbodiimide), poly (1,6-hexamethylenecarbodiimide), poly (1,4-tetramethylenecarbodiimide), poly (1,3-cyclohexylenecarbodiimide), poly (1,4 -Cyclohexylenecarbodiimide), poly (1,3,5-triethylphenylenecarbodiimide), poly (4,4'-methylenebiscyclohexylcarbodiimide), poly (1,3-diisopropylphenylenecarbodiimide), poly (1-methyl-
3,5-diisopropylphenylenecarbodiimide),
Examples thereof include poly (isopropylphenylene carbodiimide).

In the present invention, these compounds may be used in combination of two kinds or three kinds or more. The composition of the present invention comprises 10 to 90 parts by weight of component (A), 90 to 10 parts by weight of component (B), 0.2 to 10 parts by weight of component (C),
Component (D) is composed of a range of 0.1 to 10 parts by weight.
Preferably, 40 to 85 parts by weight of component (A), 85 to 40 parts by weight of component (B), 0.5 to 5 parts by weight of component (C),
Component (D) is composed of 0.5 to 5 parts by weight.

In the present invention, a fibrous or granular reinforcing material can be blended, if necessary, in a range not exceeding 300 parts by weight with respect to 100 parts by weight of PPS and PPE in total. Usually, by blending in the range of 10 to 300 parts by weight, strength, rigidity, heat resistance, dimensional stability and the like can be improved. As the fibrous reinforcing material, organic or inorganic fibers are used, and examples thereof include glass fibers, shirasu glass fibers, alumina fibers, silicon carbide fibers, ceramic fibers, asbestos fibers, gypsum fibers, metal fibers, and other inorganic fibers and carbon fibers. Is mentioned.

Organic or inorganic fillers are used as the granular reinforcing material, and examples thereof include silicates such as wollastonite, sericite, kaolin, mica, clay, bentonite, asbestos, talc and alumina silicate;
Metal oxides such as alumina, silicon oxide, magnesium oxide, zirconium oxide, and titanium oxide; calcium carbonate,
Carbonates such as magnesium carbonate and dolomite; sulfates such as calcium sulfate and barium sulfate; glass beads,
Examples thereof include boron nitride, silicon carbide, saloyan, silica, and the like, which may be hollow (porous).

These reinforcing materials can be used in combination of two or more kinds, and if necessary, they can be used after pretreatment with a coupling agent such as silane type and titanium type.
The composition of the present invention comprises, for example, (A), (B), (C)
And (D) are obtained by melt-kneading in an extruder. As a preferred method, there is a method in which PPS and polycarbodiimide are melt-kneaded in advance to prepare a modified PPS, and then PPE and an organic compound having an ethylenic double bond are added, and the mixture is melt-kneaded and pelletized. In this case, (A ') modified polyphenylene sulfide modified with polycarbodiimide, (B) PPE, (C) an organic compound having an ethylenic double bond having an epoxy group, a carboxyl group or an acid anhydride group in the molecule The composition is manufactured. This composition comprises (A ') 10-90 parts by weight, preferably 40-85 parts by weight, (B) 90-10 parts by weight, preferably 85-40 parts by weight, (C) 0.2-1.
0 parts by weight, preferably 0.5 to 5 parts by weight.

The melt-kneading temperature is 280 ° C to 340 ° C.
Is preferred. If the temperature is lower than 280 ° C., the melting of PPS may be insufficient, and if the temperature exceeds 340 ° C., thermal deterioration or gelation of PPE may occur. When the reinforcing material is added as required, the components (A) to (D) and the reinforcing material may be melt-kneaded in the extruder at a temperature equal to or higher than the melting point of PPS.

The melt-kneading can be carried out by using a known device such as a kneader, a roll mill, an extruder or the like which is usually used for kneading a resin melt. The type of extruder includes uniaxial, biaxial, and co-kneader, and the composition of the present invention can be obtained by any extruder.

[0031]

The present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the present invention.

[0032]

[Reference Example 1] (Preparation of modified PPS) After drying PPS powder (Toprene T-4) at 150 ° C for 3 hours, the temperature was lowered to 50 ° C to obtain poly (4,4'-).
2 parts by weight of diphenylmethanecarbodiimide) was mixed with 100 parts by weight of PPS and mixed with a Henschel mixer in a nitrogen atmosphere for 30 seconds, and then, using a Werner-Friedler ZSK40 twin-screw extruder, a cylinder temperature: 2
Pelletizing was performed in a nitrogen atmosphere at 90 to 300 ° C.

[0033]

[Reference Example 2] (Preparation of PPE) 2,6 xylenol was polymerized with cupric bromide as a catalyst,
A pale yellowish white powder PPE (reduced viscosity 0.59) was obtained.

[0034]

Example 1 60 parts by weight of PPS powder (Toprene F4), 40 parts by weight of PPE powder of Reference Example 2 (reduced viscosity 0.59), 2 parts by weight of poly (4,4′diphenylmethanecarbodiimide), 2 parts by weight of glycidyl methacrylate. Parts were mixed in a nitrogen atmosphere for 30 seconds with a Henschel mixer, and pelletized in a nitrogen atmosphere at a cylinder temperature of 290 to 300 ° C. with a Werner-Friedler ZSK40 twin-screw extruder.

The obtained pellets were injection-molded to obtain a dumbbell piece for tensile test having a thickness of 1/8 inch, an Izod impact test piece and a test piece for measuring heat distortion temperature having a thickness of 1/4 inch. Using these test pieces, the tensile strength, the Izod impact strength (without notch), and the heat distortion temperature were measured under a load of 18.6 kg. Further, 4 g of the obtained pellet was subjected to Soxhlet extraction with chloroform for 16 hours. The extraction residue was vacuum dried at 80 ° C. for 24 hours, and the ratio of the extraction residue was determined.

The above results are shown in Table 1.

[0037]

Examples 2 to 4 Polyphenylene sulfide, polyphenylene ether, poly (4,4'-diphenylmethanecarbodiimide) of Example 1 and glycidyl methacrylate were used, and the same operation as in Example 1 was performed with the composition shown in Table 1. .. The results are shown in Table 1.

[0038]

Comparative Examples 1 to 4 Using the polyphenylene sulfide, polyphenylene ether, poly (4,4'-diphenylmetacarbodiimide), and glycidyl methacrylate of Example 1, and using the composition shown in Table 1, the same operation as in Example 1 was performed. It was The results are shown in Table 1.

[0039]

Example 5 80 parts by weight of the modified polyphenylene sulfide pellet obtained in Reference Example 1, 20 parts by weight of PPE of Reference Example 2 and 1 part by weight of glycidyl methacrylate were operated under the same conditions as in Example 1. Tensile strength 710Kg / c
m ² , heat distortion temperature 133 ° C., Soxhlet extraction residue 10
0%, Izod strength without notch 75 kg · cm / cm
A polyphenylene sulfide resin having the following physical property values was obtained.

[0040]

Example 6 The same operation as in Example 1 was carried out except that maleic anhydride was used instead of glycidyl methacrylate in Example 1. A polyphenylene sulfide resin having a tensile strength of 710 Kg / cm ² , a heat deformation temperature of 150 ° C., a Soxhlet extraction residue of 99%, and a notched Izod impact strength of 70 Kg · cm / cm was obtained.

[0041]

[Table 1]

[0042]

The composition of the present invention has heat resistance, moldability,
Excellent solvent resistance.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical indication C08K 5/09 5/10 5/29 C08L 71/12 LQM 9167-4J LQP 9167-4J

Claims (1)

[Claims] 1. A polyphenylene sulfide (A),
A composition of a polyphenylene sulfide resin comprising (B) a polyphenylene ether, (C) an organic compound having an ethylenic double bond having an epoxy group, a carboxyl group or an acid anhydride group in a molecule, and (D) a polycarbodiimide.