JPH02127464A - Polyphenylene sulfide resin composition having improved physical property - Google Patents

Abstract

PURPOSE:To obtain a polyphenylene sulfide resin composition, improved in brittleness and excellent in appearance and heat resistance by blending a polyphenylene sulfide resin with a modified polyphenylene ether having specific terminal groups and polyamide having a specified terminal group ratio in specific amounts. CONSTITUTION:A polyphenylene ether resin composition obtained by blending (A) 20-80 pts.wt., preferably 30-70 pts.wt. polyphenylene sulfide resin with (B) 80-20 pts.wt., preferably 70-30 pts.wt. mixture of (B1) 10-90wt.% modified polyphenylene ether resin {e.g., poly(2,6-dimethyl-1,4-phenylene)ether} modified so as to have one or more groups of carboxyl, acid anhydride and epoxy groups in the terminal groups with (B2) 90-10wt.% polyamide resin (e.g., nylon-4) having terminal amino groups in a larger molar amount than that of the terminal carboxyl groups.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a polyphenylene sulfide resin composition, and in particular improves the impact brittleness of polyphenylene sulfide (hereinafter sometimes referred to as PPS) resin, and improves its appearance and heat resistance. The present invention relates to a resin composition having the following.

BACKGROUND ART Although PPS resin has excellent heat resistance, flame retardance, chemical resistance, and high rigidity and is extremely useful as an engineering plastic, it also has the drawback of being brittle against impact. For this reason, resin compositions that utilize the excellent properties of PPS or resin compositions that attempt to improve its drawbacks have been proposed.

For example, JP-A-50-156581 discloses a resin composition consisting of PPE and PPS to which PPS is added to improve the moldability and flame retardancy of polyphenylene ether (hereinafter sometimes referred to as PPE). is disclosed.

Furthermore, Japanese Patent Application Laid-Open No. 53-69255 discloses a polyphenylene resin composition containing PPS and polyamide. This is an attempt to improve the fragility of PPS.

Furthermore, Japanese Patent Application Laid-Open No. 59-21.3758 discloses that PPS
In order to improve the compatibility between PPS and PPE, a resin composition is proposed in which a polyamide resin and an epoxy resin are mixed into a blend of PPS and PPE.

Problems to be Solved by the Invention PPS and PPE are essentially incompatible with each other, and simply mixing them together will result in a resin that is brittle and does not have a good appearance. PPS
Even when polyamide is mixed with PPS, the compatibility between PPS and polyamide is insufficient, and not only is the brittleness of PPS not sufficiently improved, but a new problem of layer separation occurs. Furthermore, when the compatibility between PPS and PPE is improved by adding polyamide and epoxy resin, there is a problem that the epoxy resin reacts with the polyamide and PPS, resulting in inconsistent melt flow characteristics.

Therefore, an object of the present invention is to provide a polyphenylene sulfide resin composition in which PPS, PPE, and polyamide are sufficiently compatibilized and free from the above-mentioned problems.

Means for Solving the Problems The present invention blends PPE having a specific end group and polyamide having a specific end group ratio (terminal amino group mole, inter/terminal carboxyl group mole amount) into PPS to produce each resin component. The purpose is to improve the brittleness of PPS without impairing its excellent properties by sufficiently compatibilizing PPS. That is, the present invention comprises 20 to 80 parts by weight of polyphenylene sulfide resin and the following components (a) and (
A resin composition containing a total amount of 80 to 20 parts by weight of b), (a
) 10 to 90% by weight of a pop-enylene ether resin modified to have at least one group among a carboxyl group, an acid anhydride group, and an epoxy group in the terminal group; (1)) mole of terminal amino group; The amount is 90 to 10% by weight of polyamide resin having more than molar terminal carboxyl groups (the weight % is based on the total amount of components (a) and (b)).

As the PPS used in the present invention, one containing 70 mol % or more of the structural unit represented by the general formula -0-S-1 is preferable because it provides a composition with superior properties. PPS can be polymerized by polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate, or by polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate, or by polymerizing sodium sulfide, sodium hydrosulfide, sodium hydroxide, or hydrogen sulfide, and sulfur hydroxide in a polar solvent. Methods include polymerization in the presence of p-chlorothiophenol, and self-synthesis of p-chlorothiophenol. A method of reacting is suitable. At this time, in order to adjust the degree of polymerization, it is a preferable method to add an alkali metal salt of carboxylic acid or sulfonic acid, or to add alkali hydroxide. If it is less than 30 mol% as a copolymerization component, it is a meta-bond ether bond (80-G-3-), a sulfone bond (-(]Σ-8O2-(■→S-), R is alkyl, nitro, phenyl, Alkoxy, carboxylic acid, or a metal base of carboxylic acid), etc. may be contained within a range that does not significantly affect the crystallinity of the polymer, but preferably the copolymerization component is 10 mol% or less.In particular, 3 3 mol% if phenyl, biphenyl, naphthyl sulfide bonds, etc. with higher functionality are selected for copolymerization.
Below, the content is preferably 1 mol% or less.

Such PPS can be produced by common methods such as) reaction of halogen-substituted aromatic compounds with alkali sulfides (U.S. Pat.
(2) Condensation reaction of thiophenols in the presence of an alkali catalyst or copper salt, etc.
US Patent No. 3,274,165, UK Patent No. 116,066
0), (3) Condensation reaction of aromatic compounds with sulfur chloride in the presence of a Lewis acid catalyst (Japanese Patent Publication No. 46-2725
No. 5, Peruvian Patent No. 29437@), etc., and can be arbitrarily selected depending on the purpose.

PPS is currently owned by Philips Vetrolium ■, Tosoh Sasteel ■, Topren Corporation and Kureha Kagaku fil.
It is offered to the market from There are various grades depending on crosslink density and viscosity, and the present invention uses PP with less crosslinked structure.
S is preferred.

In the present invention, unmodified polyphenylene ether (
(Hereinafter, it may be simply referred to as polyphenylene ether)
A terminal group-modified polyphenylene ether is used in which the terminal end of the polyphenylene ether is modified with at least one of an epoxy group, a carboxyl group, and an acid anhydride group.

Polyphenylene needles, for example, have the general formula (A) (where R1, R2, R3, and R4 are hydrogen, halogen, an alkyl group, an alkoxy group, and at least two carbon atoms are present between the halogen atom and the phenyl ring). is a monovalent substituent selected from haloalkyl groups and haloalkoxy groups that do not contain a tertiary α-carbon, and n is an integer representing the degree of polymerization. One kind of the polymer represented by the general formula may be used alone, or a copolymer of two or more kinds may be used. In a preferred embodiment, R
1 and R2 are alkyl groups having 1 to 4 carbon atoms, and R
3, R4 is hydrogen or an alkyl group having 1 to 4 carbon atoms. For example, poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,6-diethyl-1,4-
phenylene) ether, poly(2-methyl-6-nityl-1,4-phenylene) ether, poly(2-methyl-
6-broby-1,4-phenylene)ether, poly(
2,6-diprobyl-1,4-phenylene) ether,
Poly(2-ethyl-6-broby-1,4phenylene)
Examples include ether. Further, as a polyphenylene ether copolymer, an alkyl trisubstituted phenol such as 2,3.6
- Mention may be made of copolymers partially containing trimethylphenol. Alternatively, a copolymer in which a styrene compound is grafted onto these polyphenylene ethers may be used. The styrene-based compound-grafted polyphenylene ether is a copolymer obtained by graft polymerizing a styrene-based compound such as styrene, α-methylstyrene, vinyltoluene, chlorostyrene, etc. to the above-mentioned polyphenylene ether.

A particularly preferred group of polyphenylene ethers for the present invention includes C1-
Including those with C4 alkyl substituents. Examples of this group include: Poly(2,6-dimethyl-1,4-phenylene) ether: Poly(2,6-diethyl-1,4-phenylene) ether: Poly(2-methyl-6-ethyl-1, 4-phenylene)
Ether: Poly(2,6-diprobyl-1,4-phenylene) ether: Poly(2-ethyl-6-brobyl-1,4-phenylene) ether: etc., and the most preferred is poly(2,6-dimethyl-1). ,4-phenylene) ether having at least one of the terminal groups of formula (8) and formula (C).

Epoxidation of the terminal group of the polyphenylene ether,
Carboxylation or acid anhydride conversion can be performed by a known method.

Regarding epoxidation of terminal groups, for example, JP-A-63-1
It is described in Publication No. 25525. The terminally epoxidized polyphenylene ether can be raised to 1 by bringing the polyphenylene ether into contact with a substance having an epoxy group under heating. As the compound having an epoxy group, an epoxy compound having a halogen group at one end or an epoxy compound having an epoxy group at both ends is preferable. Specifically, preferred epoxidized products at one end include epichlorohydrin, 2-methylepichlorohydrin, and the like, and preferred epoxidized products at both ends include 2,2-bis(4-glycidylphenyl ether) propane, epoxy resin, and the like. From the viewpoint of suppressing blocking of polyphenylene ethers, one end epoxidized product is particularly preferable.

Regarding the carboxylation and acid anhydride conversion of the terminal group, for example, the terminal carboxylated or acid anhydride polyphenylene ether described in Japanese Patent Application Publication No. 62-500458 is an acid chloride having a carboxyl group or an acid anhydride group, For example, it can be obtained by reacting trimellitic anhydride chloride and polyphenylene ether.

The polyphenylene ether used in the present invention does not necessarily all have modified terminal groups, and the resin composition of the present invention can contain polyphenylene ether with unmodified terminal groups. The amount thereof is preferably 30% by weight or less based on the total of components (a) and (b).

The polyamide used in the present invention is not the polyamide normally used for molding, that is, the polyamide with the same amount of terminal amino groups and the amount of terminal carboxyl groups, or the polyamide with a reduced amount of terminal amino groups for stabilization. is a polyamide with more terminal carboxyl fibers.

Examples of the polyamide resin include, but are not limited to, nylon-4, nylon-6, nylon-6,6, nylon-12, and nylon-6,10. What is essential in the present invention is that the amount of terminal amino groups in the polyamide is greater than the amount of terminal carboxyl groups. Such a polyamide can be obtained by adding an extra compound having a group that reacts with a carboxyl group, such as a diamine, during the polymerization of the polyamide.

Alternatively, it can also be obtained by polymerizing polyamide and then reacting it with a compound having a group that reacts with a carboxyl group. Polyamide resins usually have a terminal group ratio of 1 or less. In polyamides for injection molding, a terminal capping agent is added to the polymerization component in order to appropriately control the melt viscosity, but the terminal group ratio of such polyamides is less than 1.

In the present invention, the ratio of the amount of terminal amine groups to the terminal carboxyl group is preferably 1.01 or more, more preferably 1.1 or more. In particular, the end group ratio can be greater than or equal to 1.3.

The resin composition of the present invention preferably contains the composition components PPS, end group-modified PPE, and polyamide in the following proportions.

That is, 320 to 80 parts by weight of PP, preferably 30 to 80 parts by weight.
The total amount of the end group modified PPE and polyamide is 80 to 20 parts by weight, preferably 70 to 30 parts by weight relative to 70 parts by weight, and the end group modified PPE and polyamide are the sum of the end group modified PPE and the polyamide. 10-90% by weight and 90-10% by weight, preferably 20-80% by weight and 80-20% by weight, based on the amount. PP
If S is less than 20 parts by weight, the rigidity, heat resistance, and flame retardance derived from the inherent characteristics of the PPS resin will deteriorate, which is not preferable. If the content of the end group-modified PPE is less than 1011%, the water absorption of the polyamide will have a greater effect on the physical properties, resulting in a decrease in heat resistance and rigidity, which is not preferable. Moreover, if the polyamide content is less than 10% by weight, the appearance will be poor and the brittleness, which is a drawback of PPS resin, will not be sufficiently improved, which is not preferable.

The compositions of the present invention can optionally include styrenic elastomers, such as copolymers, including random, block, and graft copolymers of vinyl aromatic conjugated dienes. Examples of these materials include A-B-A and A-B-A.
- Hydrogenated or non-hydrogenated block copolymers of type B (A is polystyrene and B is an elastomer diene, e.g. polybutadiene), radial teleblock copolymers of styrene and conjugated dienes, acrylic resin modified styrene-butadiene resins and a graft copolymer obtained by graft copolymerizing a monomer or a monomer mixture containing a styrene compound as a main component to a rubber-like polymer. By blending these styrenic elastomers into the resin composition of the present invention in an amount of 50% by weight or less based on the total of components (a) and (b), physical properties such as impact strength and processability can be improved. Further improvements can be made. The resin composition of the present invention may contain other additives such as pigments, dyes, reinforcing agents, fillers, heat resistant agents, oxidative deterioration inhibitors, weathering agents, and lubricants during resin mixing and molding as long as the physical properties are not impaired. , mold release agent, crystal nucleating agent, plasticizer, flame retardant,
A fluidity improver, an antistatic agent, etc. can be added.

There are no particular limitations on the method for producing the resin composition of the present invention, and conventional methods can be used satisfactorily.

However, melt mixing methods are generally preferred. Any melt mixing method can be used provided it can handle the molten viscous mass. The method can be used batchwise or continuously. Particular examples include extruders, Banbury mixers, rollers, and kneaders.

EXAMPLES The present invention will be described in more detail with reference to Examples below.

Example (1) Production of polyphenylene ether (PPE-1) having an acid anhydride group at the end group
100 parts by weight of polyphenylene ether (measured at C) 0.46 were dissolved in 500 parts by weight of toluene.

Next, after adding 3 parts by weight of trimellitic anhydride acid chloride, the temperature was raised to 100'C without stirring, 6 parts by weight of dimethyl-n-butylamine was added, and the mixture was reacted for 2 hours. Next, after cooling until the temperature reached around room temperature, methanol was added in an amount twice as much as the added toluene to precipitate the polymer. The polymer was filtered out and methanol, water,
After washing with methanol in this order, the product was dried at 150°C for 8 hours under reduced pressure to obtain polyphenylene ether having an acid anhydride group at the terminal group.

(2) Production of polyphenylene ether (PPE-2) having an epoxy group at the end group 100 parts by weight of polyphenylene ether with an intrinsic viscosity of 0.46 was mixed with 1500 parts of epichlorohydrin in a dry flask.
It was dissolved in parts by weight. Next, 15 parts by weight of 33.3% caustic soda solution was added, heated to 100"C with stirring, and reacted at this temperature for 4 hours. Next, washed and dried in the same manner as in (1) above, and 1 q of polyphenylene ether having an epoxy group was obtained.

Examples 1 to 6 and Comparative Examples 1 to 4 As terminal group-modified PPE, polyphenylene ether (PPE-1) having an acid anhydride group at the terminal group obtained in (1) and (2) above or epoxy at the terminal group was used. Polyphenylene ether (PPE-2) having groups was used.

As polyamide, polyamide-6 (PA
6-A> was used. Also for comparison, 4.6 X10
' mol/g of terminal amino groups and 7. Ox 10'mol/
Polyamide-6 (PA6-8) having a molecular weight of 13,000 and having 9 terminal carboxyl groups was used.

As PPS, P manufactured by Toprene has a melt viscosity of 3900 poise at 300°C and a shear rate of 200 sec-1.
PS T-4 (trademark) was used.

In addition, novolac type epoxy resin (
Epicron N-695 (trademark, manufactured by Dainippon Ink and Chemicals (t$)) was used.

These components were mixed in the proportions shown in Table 1 and extruded using a twin screw extruder (screw diameter 50M) set at 300°C.
I made a beret. After drying this pellet, a test piece was molded using an injection molding machine set at a cylinder temperature of 32 Ct'G.
Tests were conducted on bending strength, bending modulus, bending breaking energy, heat deformation temperature, and appearance of the molded product. The test results obtained are shown in Table 1.

Examples 7 to 10 and Comparative Examples 5 to 6 The same tests as above were conducted using test pieces obtained in the same manner as in the above examples except that the PPE and polyamide were preextruded and then mixed with PPS. . The test results obtained are shown in Table 2.

The resin compositions (Examples) to 10 of the present invention containing PPS, end group-modified PPE, and polyamide with an end group ratio of >1
Resin compositions containing PS, end group-modified PPE, and polyamide with an end group ratio of >1 (Comparative Examples 1 and 2); Resin compositions containing PPS, end group unmodified PPE, and polyamide with an end group ratio of >1 (Comparative Examples 3 and 5); and a resin composition containing PPS, unmodified PPE, and a polyamide with a terminal group ratio of 1 (Comparative Examples 4 and 6), almost the same or better results in all tests. It shows.

It is also worth noting that the resin composition of the present invention has no particularly inferior properties.

Claims (1)

[Scope of Claims] 1. A resin composition containing 20 to 80 parts by weight of a polyphenylene sulfide resin and a total of 80 to 20 parts by weight of the following components (a) and (b): (a) a carboxyl group at the terminal group; 10 to 90% by weight of a polyphenylene ether resin modified to have at least one of an acid anhydride group and an epoxy group; (b) a polyamide resin in which the molar amount of terminal amino groups is greater than the molar amount of terminal carboxyl groups; 90 to 10% by weight (weight% is based on the total amount of components (a) and (b)).