JPH0619021B2 - Polyphenylene sulfide resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a molding resin composition. More specifically, it relates to a polyphenylene sulfide-based resin composition having excellent heat resistance, chemical resistance, mechanical strength and the like, and excellent moldability.

[Conventional technology]

Conventionally, polyphenylene sulfide has excellent heat resistance, chemical resistance, water resistance, molding processability, electrical characteristics, etc., and is used in fields such as electrical and electronic equipment, aerospace equipment, and transportation equipment. It is expected to be widely used in fields where co-heat resistance is required.

However, polyphenylene sulfide has the drawback of being inferior in mechanical strength, particularly tensile strength, tensile elongation and impact resistance.

[Problems to be solved by the invention]

An object of the present invention is to obtain a polyphenylene sulfide-based resin composition having improved mechanical properties, particularly tensile strength, tensile elongation and impact resistance, in addition to the excellent properties of polyphenylene sulfide.

[Means for solving problems]

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a resin composition comprising polyphenylene sulfide and a specific amount of novel polyetherimide is particularly effective for the above-mentioned purpose. completed.

That is, the present invention is based on 100 parts by weight of polyphenylene sulfide, the formula (I) (In the formula, R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-bonded group in which aromatic groups are directly or cross-linked with each other. A poly (phenylene sulfide) resin composition comprising 1 part by weight or more and less than 100 parts by weight of a polyetherimide resin having a repeating unit represented by the formula (4), which represents a tetravalent group selected from the group consisting of condensed polycyclic aromatic groups. .

The polyphenylene sulfide used in the present invention has the general formula A resin having a repeating structural unit represented by the following formula, and its production method is described in, for example, US Pat.
No. 5-3368, and for example "Ryton" (R
YTON) (trademark of Phillips Petroleum Company, USA) and the like. According to it, polyphenylene sulfide is 160-250 in N-methylpyrrolidone solvent.
It is produced by reacting p-chlorobenzene with sodium sulfide monohydrate under pressure at a temperature of ° C. Polyphenylene sulfide can be freely produced by subjecting polyphenylene sulfides having no degree of cross-linking to those having partial cross-linking to those having various degrees of polymerization in a post heat treatment step. In addition, these are commercially available, and therefore, those having melt viscosity characteristics suitable for the intended blend can be arbitrarily produced or selected on the market.

The polyetherimide resin used together for the purpose of improving the chemical resistance, heat resistance and / or mechanical strength of the polyphenylene sulfide of the present invention has the following formula (I) (Wherein R is the same as the above), it is a polyetherimide, and the present inventor has excellent mechanical properties, thermal properties, electrical properties, solvent resistance, and the like, and has heat resistance. It was found as a polyimide (Japanese Patent Laid-Open No. 62-076095), and an ether diamine represented by the formula (III) as a diamine component, that is,
4,4'-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether is used, and a polyamic acid obtained by reacting these with one or more tetracarboxylic acid dianhydrides is dehydrated and cyclized. The resulting polyetherimide. Moreover, you may use together the well-known diamine used for manufacturing other polyimide in the range which does not impair the characteristic of the polyether imide used by this invention. Examples of diamines that can be used in combination include, for example, metaphenylenediamine, paraphenylenediamine, orthophenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 3,3′-diaminodiphenylmethane, 3,4′- Diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-
Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-
Diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfoxide, 3, 4'-diaminodiphenyl sulfoxide, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfoxide, N, 3,3'-diaminobenzophenone, 3,4'-diamino Benzophenone, 4,4'-diaminobenzophenone, bis [4- (3-aminophenoxy)
Phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4
-Aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, 1,
2-bis [4- (4-aminophenoxy) phenyl] ethane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] Propane, 2,2-bis [4- (3-aminophenoxy) phenyl] butane, 2,2-bis [4-
(4-Aminophenoxy) phenyl] butane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,
3,3,3-hexafluoropropane, 2,2-bis [4- (4
-Aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 4,4'-bis (3-aminophenoxy)
Biphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3 -Aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfoxide, bis [4- (4-
Aminophenoxy) phenyl] sulfoxide, bis [4
-(3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone,
Bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis [4- (3-aminophenoxy) benzoyl) benzene, 1,3- Bis [4- (3-aminophenoxy) benzoyl] benzene, 4,4′-bis [3-
(3-Aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, bis [4
Examples include-(4- (4-amino-α, α-dimethylbenzyl) phenoxy) phenyl] sulfone and bis [4- (4-aminophenoxy) phenoxyphenyl] sulfone.

The polyetherimide used in the present invention is obtained by reacting the diamine and tetracarboxylic dianhydride in an organic solvent and dehydrating and ring-closing.

The tetracarboxylic dianhydride used at this time has the formula (Wherein R is the same as above).

That is, as the tetracarboxylic dianhydride used,
Ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane carboxylic dianhydride,
Pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4, 4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2, 2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride,
Bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1 bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis ( 3,4-dicarboxyphenyl) methane dianhydride, 4,4 '-(p-phenylenedioxy) diphthalic dianhydride, 4,4'-(m-phenylenedioxy) diphthalic dianhydride, 2 , 3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2 , 3,4-benzenetetracarboxylic dianhydride, 3,
4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7
-Anthracene tetracarboxylic dianhydride, 1,2,7,8-
Such as phenanthrene tetracarboxylic dianhydride,
These tetracarboxylic dianhydrides may be used alone or in admixture of two or more.

The polyphenylene sulfide-based resin composition of the present invention is used in the range of 1 part by weight or more and less than 100 parts by weight of the above polyetherimide with respect to 100 parts by weight of the polyphenylene sulfide.

In order to improve the physical properties of polyphenylene sulfide, particularly heat resistance, polyether imide is effective in an amount of 1 part by weight or more, preferably 5 parts by weight or more per 100 parts by weight of polyphenylene sulfide. However, if it is used in an amount of 100 parts by weight or more, the good moldability of the polyphenylene sulfide is lost.

Further, the polyether imide used in the present invention has heat resistance and physical properties that are substantially equivalent to those of conventional polyimides, but since it has excellent flow properties, the above effects can be obtained by using it in combination with polyphenylene sulfide. You can get it.

When the composition according to the present invention is mixed and prepared, it can be produced by a generally known method. For example, the following method is a preferable method.

(1) The polyphenylene sulfide powder and the polyetherimide powder are pre-kneaded into a powder using a mortar, a Henschel mixer, a drum blender, a tumbler blender, a ball mill, a ribbon blender and the like.

(2) Polyetherimide powder is dissolved or suspended in an organic solvent in advance, polyphenylene sulfide is added to this solution or suspension to uniformly disperse or dissolve, and then the solvent is removed to obtain a powder.

(3) Polyether imide precursor of the present invention, in an organic solvent solution of polyamic acid, after dissolving or suspending polyphenylene sulfide, heat treatment at 100 ~ 400 ℃, or a commonly used imidizing agent After chemical imidization using, the solvent is removed to obtain a powder.

The powdery resin composition thus obtained is directly used for various molding applications, that is, injection molding, compression molding, transfer molding, extrusion molding, etc., but it is more preferable to use it after melt blending. is there. Particularly, in mixing and preparing the composition, it is a simple and effective method to mix powders, pellets, or powders and pellets.

For melt blending, the equipment used to melt blend ordinary rubbers or plastics, such as hot rolls,
A Banbury mixer, prabender, extruder, etc. can be used. The melting temperature is set above the melting temperature of the blending system and below the temperature at which the blending system begins to thermally decompose, but the temperature is usually 300 to 420 ° C, preferably 320 to 4
It is 00 ° C.

As a molding method of the resin composition of the present invention, extrusion molding or extrusion molding, which is a molding method of forming a homogeneous melt blend and having high productivity, is preferable, but other transfer molding, compression molding, or sintering molding is performed. There is no problem even if shape or extrusion film molding is applied.

One or more solid lubricants such as molybdenum disulfide, graphite, boron nitride, lead monoxide, and lead powder can be added to the resin composition of the present invention. It is also possible to add one or more reinforcing agents such as glass fiber, carbon fiber, aromatic polyamide, silicon carbide fiber, potassium titanate fiber and glass beads.

With respect to the resin composition of the present invention, within a range that does not impair the object of the present invention, an antioxidant, a heat stabilizer, an ultraviolet absorber, a flame retardant, a flame retardant aid, an antistatic agent, a lubricant, One or more conventional additives such as colorants can be added.

〔Example〕

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

Production Example 1 In a reaction vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 4,4'-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether (5.92 kg, 10 mol) and N,
Charge N-dimethylacetamide 18.8kg, and under room temperature nitrogen atmosphere, pyromellitic dianhydride 2.14kg (9.8mol)
Was added while paying attention to the rise of the solution temperature, and the mixture was stirred at room temperature for about 24 hours to obtain a polyamic acid solution.

To this solution was added 5.37 kg of N, N-dimethylacetamide, and 4.08 kg (40
(Mol) triethylamine and 6.03 kg (60 mol) acetic anhydride were added dropwise. After stirring at room temperature for about 24 hours, add 250
This solution was discharged under vigorous stirring, the precipitate was filtered off, washed with methanol, and dried under reduced pressure at 150 ° C for 24 hours to obtain 7.47 kg (yield about 97.0%) of a pale yellow polyetherimide. A powder was obtained.

The inherent viscosity of this polyetherimide powder was 0.71 ddL / g. Here, the logarithmic viscosity is polyetherimide powder 0.5
g is a mixed solvent of p-chlorophenol and phenol (90:
It is a value measured by heating and dissolving it in 10 weight ratio) and then cooling to 35 ° C.

The glass transition temperature of this polyetherimide powder is 22
7 ℃ (measured by DSC method), 5% weight loss temperature is 540 ℃
(Measured by the DTA-TG method).

Examples 1 to 3 After dry blending the polyetherimide powder obtained in Production Example 1 and the polyphenylene sulfide powder "Ryton P-4" (manufactured by Philips) at various composition ratios as shown in Table-1, 340-380 ℃ using a twin-screw melt extruder
It was extruded and granulated.

Next, the pellets are made into an injection molding machine (cylinder-temperature 340
It was supplied to a mold temperature of ~ 380 ° C and a mold temperature of 150 ° C) to obtain a test piece, and its thermal and mechanical properties were measured. The results are shown in Table-1.

In Table-1, tensile strength and elongation at break are ASTM D-638, flexural strength and flexural modulus are ASTM D-790, and Izod impact values are
ASTM D-256, glass transition temperature was TMA penetration method, heat distortion temperature was ASTM D-648, and moldability was based on minimum injection pressure.

Comparative Examples 1-2 Using compositions outside the scope of the present invention, the thermal and mechanical properties of the molded articles obtained by the same operations as in Examples 1-3 were measured, and the results are shown in Table-1 together with Comparative Examples. Show as.

Production Examples 2 to 5 4,4'-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether in combination with various tetracarboxylic acid dianhydrides, and 4,4'-bis [3- (4-aminophenoxy) ) When other amines were used in combination with benzoyl] diphenyl ether, various polyetherimide powders were obtained in the same manner as in Production Example 1. Table-2
Shows the synthesis conditions, logarithmic viscosity and glass transition temperature of the known polyetherimide.

Examples 4 to 11 and Comparative Examples 2 to 5 Using the various polyetherimide powders obtained in Production Examples 2 to 5, uniform blended pellets were obtained in the same manner as in Examples 1 to 3, and then injection molded in the same manner. Then, the physical and thermal properties of each molded product were measured.

The results of the compositions within the scope of the present invention are Examples 4-11,
The compositions out of the range are shown in Table 3 as Comparative Examples 2 to 5.

〔The invention's effect〕

The polyphenylene sulfide-based resin composition of the present invention has the characteristics inherent to polyphenylene sulfide,
It has significantly improved heat resistance and mechanical strength, and is useful in a wide range of fields such as aerospace equipment, electronic / electrical equipment, automobiles, precision equipment, and general equipment, and its industrial effect is great.

Claims (2)

[Claims] 1. A compound of formula (I) based on 100 parts by weight of polyphenylene sulfide. (In the formula, R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-bonded group in which aromatic groups are directly or cross-linked with each other. A polyphenylene sulfide-based resin composition comprising 1 part by weight or more and less than 100 parts by weight of a polyetherimide resin having a repeating unit represented by the formula (4), which represents a tetravalent group selected from the group consisting of condensed polycyclic aromatic groups. 2. A polyphenylene sulfide has the formula (II) The resin composition according to claim 1, which comprises a repeating unit of