JPH02155951A - Polyethylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition having excellent rigidity in a high- temperature region by mixing a polyphenylene sulfide with an epoxidized polyphenylene oxide. CONSTITUTION:100pts.wt. polyphenylene sulfide [desirably a polyphenylene sulfide having 70mol% or above, desirably 90mol% or above repeating units of formula I (wherein Ar is an arylene, desirably a p-phenylene)] is mixed with 5-100pts.wt. epoxidized polyphenylene oxide (e.g. a compound of formula II). In this way, a polyphenylene sulfide resin composition improved in rigidity in a high-temperature region without detriment to the excellent properties such as heat resistance, chemical resistance, abrasion resistance, flame retardancy, rigidity and electrical insulation properties inherent in polyphenylene sulfide can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a polyphenylene sulfide resin composition, and more particularly to a polyphenylene sulfide resin composition that has excellent rigidity in a high temperature range.

(Conventional technology and its issues) Polyphenylene sulfide resin is attracting attention as an engineering plastic with excellent heat resistance, flame retardance, chemical resistance, rigidity, electrical insulation, abrasion resistance, etc., and is used for various purposes. . In particular, in the fields of electrical and electronic parts, automobile parts, etc., they have gradually come to be actively used in parts that require heat resistance.

However, although polyphenylene sulfide resin has superior properties compared to general-purpose engineering plastics, it is not necessarily sufficient for parts that require heat resistance. Since the temperature is generally in the range of 80 to 100°C, when used in a high temperature range of 100°C or higher, the glass transition temperature is exceeded, resulting in a rapid decrease in rigidity.

Conventionally, in order to suppress the decrease in rigidity at temperatures above the glass transition temperature, reinforcing materials such as glass fibers and carbon fibers have been blended with polyphenylene sulfide. However, this method did not lead to a fundamental solution and could not necessarily improve the rigidity to a satisfactory degree.

On the other hand, attempts to mix polyphenylene ether to improve certain properties of polyphenylene sulfide
This has already been done, for example, in Japanese Patent Publication No. 56-34032 and Japanese Patent Publication No. 60-11063. However, with the mixtures of polyphenylene sulfide and polyphenylene ether disclosed in these documents, it is difficult to simultaneously improve rigidity at high temperatures and impact resistance at temperatures below room temperature, or to simultaneously improve mechanical properties and appearance of molded products. is difficult, and it has not yet been possible to provide a material suitable for industrial parts.

Therefore, one object of the present invention is to improve the quality of polyphenylene sulfide, which has not been achieved in the past, and particularly to provide a polyphenylene sulfide resin composition that has sufficient rigidity even in a high temperature range.

(Means for Solving the Problems) As a result of intensive studies to achieve the above object, the present inventors have found that polyphenylene sulfide is blended with polyphenylene ether having an epoxy group, and obtained by melt-kneading. The present invention was achieved by discovering that the resin composition has significantly improved rigidity in a high temperature range.

That is, the polyphenylene sulfide resin composition of the present invention includes (a) 100 parts by weight of polyphenylene sulfide.

and (b) polyphenylene ether having an epoxy group 5
~100 parts by weight.

Polyphenylene sulfide used in the present invention (
a) is the following formula: −+−A r −S−←− (wherein A
r represents an arylene group)
70 mol% or more of the structural unit,
Preferably it has 90 mol% or more.

As the arylene group in the above formula, p-phenylene group, m-phenylene group, 0-phenylene group, carbon number 1
%p of phenylene groups substituted with ~4 alkyl groups,
p' - Diphenylene sulfone group (-(=S← Tamekai
), p, p'-biphenylene group
), p, p diphenylene ether group (-@-o combination
1,p,p-diphenylenecarbonyl group

The arylene group is preferably one consisting of p-phenylene group or one having p-] dinylene group as the main component.

The molecular weight of polyphenylene sulfide (a) is usually 10,000 or more, and the melting point is preferably about 275 to 290°C.

Next, the polyphenylene ether (b) having an epoxy group used in the present invention will be described.

Component (b) may be modified polyphenylene ether (b-1) alone, in which an epoxy group has been introduced into the polyphenylene ether molecule by chemical reaction, or unmodified polyphenylene ether (b-1) may be used as component (b). b-2) may be added. At this time, the weight ratio (b-2) of unmodified polyphenylene ether (b-2) to modified polyphenylene ether (b-H)
-2/b-1) is 20 or less, preferably 10 or less, the heat resistance effect of the obtained resin composition is remarkable. In addition, from an economical viewpoint, b-2/b-1 is preferably 1 or more and 10 or less.

The concentration of epoxy groups in modified polyphenylene ether (b-1) is 1 per 100 g of polyphenylene ether.
Xl0-' mol or more, preferably lXl0-' mol-l
The concentration of Xl0-' epoxy groups was determined by infrared absorption spectroscopy, N
It can be determined by MR spectral analysis. It is also possible to employ the titration method used for epoxy resins.

As the polyphenylene ether used in the present invention,
The following formula: (wherein, R1-R6 are each independently a hydrogen atom,
It is a homopolymer or a copolymer obtained by oxidative polymerization of one or more monocyclic phenols represented by (representing a hydrocarbon group or a hydrocarbon group substituted with a halogen atom, etc.). Additionally, vinyl aromatic compounds are added to the polyphenylene ether skeleton, e.g.
It is also possible to use a graft copolymer in which a small amount of a styrene polymer or the like is grafted.

Preferred monocyclic phenol compounds represented by the above formula [1F are 2.6-dimethylphenol, 2.6
-diphenylphenol and 2.3.6-drimethylphenol.

The polyphenylene ether used in the present invention has an intrinsic viscosity of 0.0001 measured at 30°C using chloroform as a solvent.
A range of 15 to 0.65 dZ/g is used, preferably a range of 0.30 to 0.60 dl/g. If the intrinsic viscosity is less than 0.15 dl/g, the resulting resin composition will be brittle (and the mechanical strength will be reduced).
If the amount exceeds 65dj77g, good dispersion of the components of the resin composition cannot be obtained and the object of the present invention cannot be achieved.

Next, as a method for introducing an epoxy group into the above-mentioned polyphenylene ether, methods of introduction using the phenolic hydroxyl group of polyphenylene ether can be mentioned. Specifically, examples include addition reaction of epichlorohydrin, 2.2-bis(4
-glycidyl phenyl ether) propane addition reaction, etc. can be used. Moreover, glycidyl methacrylate, monoglycidyl maleate, etc. can also be introduced by a radical reaction using an alkyl side chain.

The resin composition of the present invention comprises the above-mentioned component (a), that is, polyphenylene sulfide, and component (bl).

That is, it is made of polyphenylene ether having an epoxy group, and the blending ratio of components (a) and (b) is (a) 1
00 parts by weight, (b) is 5 to 100 parts by weight, preferably 10 to 75 parts by weight. If the proportion of (b) is less than 5 parts by weight, the resulting composition will not have sufficient rigidity in the high temperature range, while if the proportion of (b) exceeds 100 parts by weight, the resulting composition will have excellent stiffness. Among the various properties, properties such as chemical resistance and flame retardancy are lost.

The resin composition of the present invention comprises the above-mentioned components (a) and (b).
It is obtained by melting and crossing the wires.

That is, the resin composition of the present invention can be manufactured, for example, as follows.

Since components (a) and (b) are mixable in the molten state, a conventional melt molding machine can be used.

That is, the components of one stroke can be mixed in advance at room temperature, and then kneaded using, for example, a Pan Bali mixer, a roll mixer, an extruder, etc., and then pelletized. In addition, the component (a
), then the component (b) may be added and melt-kneaded, or after the component (b) is melted, the component (a) may be added and melt-kneaded.

It is appropriate that the temperature of the melting cross-wire is normally in the range of 270 to 320°C.

Furthermore, various additives such as pigments, stabilizers, inorganic fillers, reinforcing materials such as glass fibers and carbon fibers can be added to the resin composition during melt-kneading. Furthermore, it is also possible to optionally add an elastomer to improve properties such as impact strength.

The pelletized resin composition is shaped into a desired shape using conventional extrusion molding, injection molding, compression molding, or the like.

(Function) The polyphenylene sulfide resin composition of the present invention has improved rigidity in a high temperature range by adding polyphenylene ether having an epoxy group to polyphenylene sulfide.

The reason why the object of the present invention cannot be achieved simply by mixing polyphenylene sulfide with polyphenylene ether (unmodified) is thought to be because the compatibility is poor in a molten mixture of polyphenylene sulfide and polyphenylene ether. . That is, it is considered that by mixing polyphenylene ether having an epoxy group as component (b), the compatibility between the two is improved and the excellent properties of polyphenylene sulfide and polyphenylene ether can be obtained at the same time.

In other words, the polyphenylene sulfide resin composition of the present invention maintains the excellent properties of polyphenylene sulfide such as heat resistance, flame retardance, chemical resistance, rigidity, electrical insulation, and abrasion resistance, while maintaining the thermal deformation of polyphenylene ether. It is an excellent resin composition that has properties such as high temperature and excellent rigidity in the high temperature range.

(Example) Next, the present invention will be explained in more detail with reference to Examples.

In addition, in the following examples, the bending elastic modulus is JIS-
Measured at temperatures of 23℃, 100℃ and 150℃ according to JIS-7203, and the heat distortion temperature is 720℃ according to JIS-7203.
7, the measurement was carried out with a load of 18.5 kg.

Example 1 Toubrene T-3 (
■Torblen) was used.

Polyphenylene ether (b-1) having an epoxy group was produced and used by the reaction shown in the following formula.

That is, (b-1) was manufactured as follows.

Epichlorohydrin 10I2 was placed in a stainless steel autoclave with an internal volume of 3012 mm, and then poly-2,6
-Simethyl-1,4-phenylene ether polymer powder (
300 g of Mitsubishi Yuka ■ (intrinsic viscosity at 30°C in chloroform: 0.48 d12/g) was added.

Next, the temperature was raised through the external jacket, and the mixture was heated for 1 hour while stirring.
After holding at 00°C for about 30 minutes to completely dissolve the polymer, add 50ml of 40% by weight aqueous sodium hydroxide solution! 2 was added thereto, and the mixture was reacted at 100° C. for 3 hours under a nitrogen atmosphere while being dehydrated under reflux.

After the reaction was completed, epichlorohydrin was distilled off under reduced pressure, and the resulting polymer was dissolved in chloroform 5I2. Then, solids floating in the polymer solution (formed NaC
12 and excess Na0H) were removed by filtration. The polymer was reprecipitated by adding a mixed solvent of methanol/water (volume ratio 50150), filtered, washed three times with the above mixed solvent 10β, and dried at 100°C for about 10 hours to obtain glycidylated polyphenylene. Obtained ether.

As a result of titrating the obtained polymer by the perchloric acid-CTAB method, the amount of glycidyl groups contained in 100 g of the polymer was 4XIO-'' moles.
The polystyrene equivalent number average molecular weight determined by the method is 202
It was 00. This confirmed that the obtained polymer had one glycidyl group per molecule.

``Tsu JI ■ 11 As component (a), 100 parts by weight of the polyphenylene sulfide described above, and as component (b), 10 parts by weight of polyphenylene ether (b-1) having an epoxy group produced as described above. The mixture was triblended and melt-kneaded using an extruder to obtain a pellet-shaped polyphenylene sulfide resin composition.

The obtained polyphenylene sulfide resin composition was further molded to a thickness of 4 mm at 300°C using a compression molding machine.
A sheet-like molded product was manufactured and its flexural modulus was measured, and a 6.4 mm sheet-like molded product was manufactured and its heat distortion temperature was measured. The results are shown in the table.

Examples 2 to 4 Using the same components (a) and (b), that is, (b-1) as used in Example 1, (b-1) was added to the table for 100 parts by weight of component (a). A pellet-shaped polyphenylene sulfide resin composition was produced in the same manner as in Example 1 except that the amounts shown were blended.

Furthermore, using this resin composition, sheet-like molded products with thicknesses of 4 mm and 6.4 mm were manufactured in the same manner as in Example 1.

Next, using this molded product, the bending elastic modulus and heat distortion temperature were measured under the same conditions as in Example 1. The results are shown in the table.

Example 5 I'm angry at you The same polyphenylene sulfide as in Example 1 was used.

Components-〇Rho Polyphenylene ether with epoxy groups (b-1) produced in Example 1 and unmodified polyphenylene ether (b-2) (manufactured by Mitsubishi Yuka ■, 30% in chloroform solution)
The intrinsic viscosity measured at °C was 0, 4saj2/g).

1 spoonful and 100 parts by weight of the above-mentioned polyphenylene sulfide as component (a), and 100 parts by weight of the above-mentioned polyphenylene sulfide as component (b).
5 parts by weight of b-1) and 10 parts by weight of (b-2) were triblended and melt-kneaded using an extruder to obtain a pellet-shaped polyphenylene sulfide fat composition.

The obtained polyphenylene sulfide resin composition was further molded to a thickness of 4 mm at 300°C using a compression molding machine.
And a 6.4 mm sheet-like molded product was manufactured. The flexural modulus and heat distortion temperature of each molded product were measured. The results are shown in the table.

Examples 6 to 10 The same components (a) and (b) as used in Example 5 were used, and for 100 parts by weight of component (a), component (b), that is, (b-1) and (b- A pellet-shaped polyphenylene sulfide resin composition was produced in the same manner as in Example 5, except that 2) was blended in the amount shown in the table.

Furthermore, using this resin composition, sheet-like molded products with thicknesses of 4 mm and 6.4 mm were manufactured in the same manner as in Example 5.

Next, using this molded product, the flexural modulus and heat distortion temperature were measured under the same conditions as in Example 5. The results are shown in the table.

Comparative Example 1 A resin was melt-kneaded in the same manner as in Example 1, except that the same component (a) as in Example 1 was used, and component (b) was not used. A sheet-like molded product was obtained. The flexural modulus and heat distortion temperature of the obtained molded product were measured under the same conditions as in Example 1. The results are also listed in the table.

Comparative Example 2 Using the same component (a) as in Example 1, and using only the same unmodified polyphenylene ether (b-2) as component (b) as used in Example 5, 100% by weight of component (a) The resin composition was melted and mixed in the same manner as in Example 1, except that 45 parts by weight was used, and a sheet-like molded product was obtained in the same manner as in Example 1. Regarding the obtained molded product, the 19 flexural modulus and heat distortion temperature were measured under the same conditions as in Example 1. The results are also listed in the table.

Looking at the table, it can be seen that the resin composition of the present invention has a high heat deformation temperature, a high bending elastic modulus in a high temperature range of 100° C. or higher, and has excellent heat resistance.

Moreover, in comparison, the resin or resin composition of the comparative example has a low heat deformation temperature, and a sharp decrease in flexural modulus at 100° C. or higher is observed.

(Effects of the Invention) The polyphenylene sulfide resin composition of the present invention has various outstanding properties originally possessed by polyphenylene sulfide, namely heat resistance, flame retardance, chemical resistance, rigidity, abrasion resistance, and electrical insulation properties. While maintaining these properties, it also has improved rigidity in high-temperature ranges, so it can be used in a wider range of applications than polyphenylene sulfide resins have been used to date, and its industrial value is great. .

Claims (1)

[Scope of Claims] (a) 100 parts by weight of polyphenylene sulfide, and (b) 5 to 5 parts of polyphenylene ether having an epoxy group.
A polyphenylene sulfide resin composition comprising 100 parts by weight.