JPH07122018B2 - Polyphenylene sulfide resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polyphenylene sulfide resin composition, and in particular, the fragility of a polyphenylene sulfide (hereinafter sometimes referred to as PPS) resin to impact is improved, and a good appearance and The present invention relates to a resin composition having heat resistance.

[Prior Art] PPS resin has excellent heat resistance, flame resistance, chemical resistance, and high rigidity.
Although it is a resin that is extremely useful as an engineering plastic, it also has the drawback of being brittle against impact. Therefore, there have been proposed resin compositions that attempt to utilize the excellent properties of PPS, or resin compositions that attempt to improve the drawbacks thereof.

For example, JP-A-53-69255 discloses a polyphenylene resin composition containing PPS and polyamide. This is intended to improve the brittleness of PPS. JP-A-5
8-154757 discloses blending PPS with an epoxy-modified polyolefin and aims at improving the brittleness of PPS.

Further, JP-A-50-156561 discloses a resin composition comprising PPE and PPS, to which PPS is added in order to improve the moldability and flame retardancy of polyphenylene ether (hereinafter sometimes referred to as PPE). Is disclosed.

Further, JP-A-59-213758 discloses that in order to improve the compatibility of PPS and PPE, a polyamide resin and an epoxy resin are added to PP.
A resin composition mixed with a blend of S and PPE is proposed.

[Problems to be Solved by the Invention] In a resin composition containing a polyamide resin to improve the brittleness of PPS, the compatibility between PPS and polyamide is not originally good, and thus the brittleness is not sufficiently improved. In addition, the appearance becomes uneven.

When PPS is blended with an olefin resin, heat resistance and flame retardancy are lowered.

On the other hand, in the blend of PPE and PPS, the moldability of PPE is improved and the flame retardancy is good, but the compatibility with PPS and PPE is poor, so it is brittle and the appearance is not good.

The present invention, without impairing the heat resistance and flame retardancy inherent in PPS,
An object is to provide a PPS resin composition having improved brittleness.

[Means for Solving the Problem] The present invention comprises (A) 30 to 70 parts by weight of a polyphenylene sulfide resin, (B) 30 to 70 parts by weight of a polyamide resin, (C) a carboxyl group, an acid anhydride group and an epoxy group. 1 to 30 parts by weight of a polyolefin modified with at least one selected functional group, and (D) 5 to 30 parts by weight based on 100 parts by weight of the total of (A), (B) and (C). A resin composition containing a polyphenylene ether resin modified with at least one functional group selected from a carboxyl group, an acid anhydride group, and an epoxy group.

The PPS used in the present invention has a general formula Those containing 70 mol% or more of the structural unit represented by are preferable because they provide a composition with excellent properties. PPS can be polymerized by polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate, or in a polar solvent in the presence of sodium sulfide or sodium hydrosulfide and sodium hydroxide or hydrogen sulfide and sodium hydroxide. Method of polymerizing, p
Examples include self-condensation of chlorothiophenol, and a method of reacting sodium sulfide with p-dichlorobenzene in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone solvent such as sulfolane is suitable. . At this time, it is a preferable method to add an alkali metal salt of carboxylic acid or sulfonic acid or to add an alkali hydroxide in order to adjust the degree of polymerization. If less than 30 mol% as a copolymerization component, meta bond Ortho coupling Ether bond Sulfone bond Biphenyl bond Substituted phenyl sulfide bond Where R is alkyl, nitro, phenyl, alkoxy,
Carboxylic acid or metal base of carboxylic acid) trifunctional phenyl sulfide bond Although it may be contained within a range that does not significantly affect the crystallinity of the polymer, the content of the copolymerization component is preferably 10 mol% or less. Particularly, when a phenyl, biphenyl, naphthyl sulfide bond or the like having a functionality of 3 or more is selected for the copolymerization, the content is preferably 3 mol% or less, more preferably 1 mol% or less.

Such PPS is produced by a general method, for example, (1) reaction of a halogen-substituted aromatic compound with alkali sulfide (US Pat.
No. 13188, JP-B-44-27671 and JP-B-45-3368
(2) Condensation reaction of thiophenols in the presence of an alkali catalyst or a copper salt (US Pat. No. 3,274,165).
No. 1160660), (3) Aromatic compounds are synthesized by condensation reaction with sulfur chloride in the presence of a Lewis acid catalyst (see Japanese Patent Publication No. 46-27255 and Belgian Patent No. 29437). It can be arbitrarily selected according to the purpose.

PPS is currently marketed by Phillips Petroleum Co., Ltd., Tosoh Sustain Co., Ltd., Topren Co., Ltd. and Kureha Chemical Co., Ltd. There are various grades depending on the crosslink density and viscosity, and PPS having a small crosslink structure is preferred in the present invention.

Various known polyamide resins can be used as the polyamide used in the present invention. As an example, nylon-4, nylon-6, nylon-6,6, nylon-1
2, nylon-6,10 and the like, but not limited to these. Here, it is preferable to use a polyamide having a larger amount of terminal amino groups than the amount of terminal carboxyl groups. Such a polyamide can be obtained by adding an extra compound such as a diamine having a group that reacts with a carboxyl group during polymerization of the polyamide. Alternatively, it can also be obtained by, for example, reacting with a compound having a group reactive with a carboxyl group after the polymerization of polyamide. Generally, the polyamide resin has a terminal group ratio of 1 or less. In polyamide for injection molding, an end-capping agent is added to the polymerization component in order to appropriately adjust the melt viscosity, but the end group ratio of such polyamide is less than 1. In the present invention, the ratio of the terminal amino group to the terminal carboxyl group is preferably 1.01 or more, more preferably 1.1 or more, and particularly 1.3 or more.

The third component of the resin composition of the present invention is a carboxyl group,
It is a polyolefin modified with at least one functional group selected from an acid anhydride group and an epoxy group. These modified polyolefins are known per se. The polyolefin used here is ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-heptene, 1-.
Homopolymers of α-olefins such as octene, random or block copolymers of these α-olefins, and copolymerization weights of a majority of these α-olefins with other unsaturated monomers such as random, block or graft. They are coalesced and at least partially show crystallinity. Examples of the other unsaturated monomer include, but are not limited to, methyl acrylate, ethyl acrylate, methyl methacrylate, vinyl acetate, styrene, and methylstyrene. Here, the α-olefin is preferably 3 to 20.
It is an unsaturated hydrocarbon having 4 carbon atoms. Examples include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 4-methyl-1-butene, 4-methyl-1-pentene and the like, with propylene being particularly preferred. Polyene compounds (e.g. 1,4-pentadiene, 1,5-hexadiene, 2-methyl-1,5-hexadiene, 3,3-dimethyl-1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, 6-methyl-1,5-hexadiene, 1,4-hexadiene, 7-methyl-1,6-octadiene, 9-methyl-1,9-undecane, isoprene, 1,3
-Pentadiene, 1,4,9-decatriene, 4-vinyl-
1-cyclohexene, cyclopentadiene, 2-methyl-2,5-norbornadiene, 5-methyl-2-norbornene, 5-ethylidene-2-norbornene, 5-isopridene-2-norbornene, 5-isopropenyl-2-
Norbornene, dicyclopentadiene, tricyclopentadiene, etc.) can also be used,
It is preferable that the polyene compound is not copolymerized from the viewpoint of processability. In the ethylene-α-olefin used here, the weight ratio of ethylene to α-olefin is 95: 5.
~ 5: 95, preferably 95: 5 to 20:80, more preferably 92: 8
-60: 40, particularly preferably 85: 15-70: 30.

The modified polyolefin is a mixture of an unsaturated compound having a carboxyl group, an acid anhydride group or an epoxy group, a peroxide, and a polyolefin, and is, for example, 100 to 300 ° C (preferably 150 to 260 ° C) for 0.5 to 30 minutes ( It can be obtained by heat treatment (kneading), preferably for 1 to 10 minutes. These reactions can be performed with an extruder, a kneader, a Banbury mixer, or the like. It can also be obtained by dissolving polyolefin, an unsaturated compound and an organic peroxide in an organic solvent and heating. Examples of the solvent used at this time include hydrocarbons having 6 to 12 carbon atoms, halogenated hydrocarbons having 1 to 12 carbon atoms, tetrahydrofuran and the like. The heating temperature varies depending on the type of organic peroxide used, but is usually 40 to 300 ° C., preferably 50 to 200 ° C., and the heating time is 1 minute to 10 hours, preferably 5 minutes to 5 hours. After the completion of the reaction, the polymer is poured into a solvent in which the polymer is insoluble, for example, to coagulate or solidify by steam stripping and then dried.

Examples of the unsaturated carboxylic acid used for modification such as grafting and copolymerization include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid, maleic acid, and the like, with acrylic acid and methacrylic acid being preferred. You may use 2 or more types of these unsaturated acids. Examples of unsaturated acid anhydrides include maleic anhydride, itaconic anhydride, chloromaleic anhydride, citraconic anhydride, butenylsuccinic anhydride, tetrahydrophthalic anhydride, and the like.
Maleic anhydride is preferred. Two or more kinds of these unsaturated acid anhydrides can be used. The epoxy group-containing unsaturated compound, a compound having an unsaturated group and an epoxy group capable of copolymerizing with an olefin in the molecule, for example, glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl esters, butenecarboxylic acid esters,
Allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether, 3,4
-Epoxy butene, 3,4-epoxy-3-methyl-1-
Butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methylpentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide, p-glycidylstyrene and the like can be mentioned. You may use 2 or more types of these.

The resin composition of the present invention preferably contains the above composition components PPS, polyamide and modified polyolefin in the following proportions.

That is, PPS 30-70 parts by weight, preferably 35-75 parts by weight, polyamide 30-70 parts by weight, preferably 35-75 parts by weight, and modified polyolefin 1-30 parts by weight, preferably 5-20 parts by weight, It is contained in the resin composition. PPS is 3
If the amount is less than 0 parts by weight, the rigidity, heat resistance, and flame retardancy derived from the original properties of the PPS resin will be deteriorated, which is not preferable. When the amount of polyamide is less than 30 parts by weight, the fragility, which is a drawback of PPS resin, is not sufficiently improved, and the appearance of the molded product is not good. If the polyamide is more than 70 parts by weight,
This is not preferable because the hygroscopicity of the molded product becomes high. When the amount of the modified polyolefin is less than 1 part by weight, the effect of the present invention, that is, the brittleness of the PPS / polyamide composition is less improved. On the other hand, if the amount is more than 30 parts by weight, the heat resistance will decrease.

The fourth component of the resin composition of the present invention is a carboxyl group,
It is a polyphenylene ether resin modified with at least one functional group selected from an acid anhydride group and an epoxy group.

Here, it is an important requirement of the present invention that the polyphenylene ether resin is previously modified with a functional group such as a carboxyl group, an acid anhydride group and an epoxy group.
When the unmodified polyphenylene ether is used, the resulting composition has a high heat distortion temperature, but becomes brittle to impact. On the other hand, when PPE modified as in the present invention is used, a resin composition having a high heat distortion temperature and high impact resistance can be obtained. This is totally unexpected.

Epoxidation, carboxylation, and acid anhydride conversion of the terminal group of polyphenylene ether can be carried out by known methods. The epoxidation of the terminal group is described, for example, in JP-A-63-125525. The terminal epoxidized polyphenylene ether can be obtained by contacting the polyphenylene ether and a substance having an epoxy group with heating. The compound having an epoxy group is preferably an epoxy compound having a halogen group at one end or an epoxy compound having an epoxy group at both ends. Preferred examples of the epoxidized product at one end include epichlorohydrin and 2-methylepichlorohydrin, and preferred examples of the epoxidized product at both ends include 2,2-bis (4-glycidylphenyl ether) propane and epoxy resin. The one-terminal epoxidized product is particularly preferable because it can suppress the blocking of polyphenylene ethers.

Carbosylation and acid anhydride conversion of the terminal group are described, for example, in JP-A-62-500456. The terminal carboxylated or acid anhydride polyphenylene ether is obtained by reacting an acid chloride having a carboxyl group or an acid anhydride group, for example, trimellitic anhydride chloride with polyphenylene ether.

Further, for the modification of the PPE other than the terminal, a known method can be used as disclosed in JP-A-59-59724. That is, a compound having an unsaturated bond in the molecule, an epoxy group, a carbosyl group, or an acid anhydride group, for example, maleic anhydride,
This is a method of melt-kneading maleic acid, fumaric acid, glycidyl acrylate, glycidyl methacrylate, etc. in the presence or absence of PPE and a radical polymerization initiator.

The polyphenylene ether used in the present invention is
Not all of them need to be modified, and unmodified polyphenylene ether may be mixed.

As an example of the polyphenylene ether resin used here, 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-methyl-6-propyl-1,4-phenylene) Ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-ethyl-6-propyl-1,
4-phenylene) ether and the like can be mentioned, but polyphenylene ether resins other than these can also be used.

The modified polyphenylene ether resin is preferably 5 to 30 parts by weight based on 100 parts by weight of the total of PPS, polyamide and modified polyolefin.

The compositions of the present invention may optionally include styrenic elastomers such as copolymers including random, block and graft copolymers of vinyl aromatic compound conjugated dienes. Examples are hydrogenated or non-hydrogenated block copolymers of the ABA and A-B type (A is polystyrene, B is an elastomeric diene such as polybutadiene), radial teleblock copolymers of styrene and conjugated dienes. And a graft copolymer obtained by graft-copolymerizing a monomer or a monomer mixture containing a styrene compound as a main component with a rubber-like polymer; You can By blending these styrene elastomers with the resin composition of the present invention, physical properties such as impact strength and processing can be further improved.

Further, in the resin composition of the present invention, other resins and additives such as pigments, dyes, and reinforcing agents (glass fiber, carbon fiber, etc.) at the time of mixing of the resin and molding, as long as the preferable properties are not significantly impaired. ), Fillers (silica, calcium carbonate, titanium oxide, etc.), heat-resistant agents, oxidative deterioration inhibitors, weathering agents, lubricants, release agents, crystal nucleating agents, plasticizers, flame retardants, fluidity improvers, antistatic agents. Etc. can be added.

The method for producing the composition of the present invention is not particularly limited, and a commonly used ordinary method can be used, but a melt kneading method is preferable. Any melt-kneading method can be used provided it can process the molten viscous mass. The equipment is especially an extruder,
A Banbury mixer, roller, kneader, etc. can be operated batchwise or continuously. The order of mixing the components is not particularly limited.

Hereinafter, the present invention will be described more specifically with reference to examples.

[Example] As PPS, poly-p-phenylene sulfide having a melt viscosity of 3900 poise under the conditions of 300 ° C and a shear rate of 200 sec ^-1 was used.

As a polyamide, with 8.4 × 10 ^-5 mol / g of terminal amino groups
Molecular weight 1 with 1.8 × 10 ^-5 mol / g of terminal carboxyl groups
3,000 polyamide-6 (PA6-A) was used.

As the modified polyolefin, maleic anhydride modified ethylene-ethyl acrylate (manufactured by Nippon Unicar Co., Ltd., GB
-301) was used.

The modified polyphenylene ether was obtained as follows.

Poly (2,6-dimethyl-1,4-phenylene) with an intrinsic viscosity of 0.46 (measured in chloroform at 30 ° C) in a dry flask
100 parts by weight of ether was 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 with stirring, and dimethyl-
6 parts by weight of n-butylamine was added and reacted for 2 hours.
Next, after cooling until the temperature was around room temperature, methanol was added in an amount twice that of the added toluene to precipitate a polymer. The polymer was separated by filtration, washed with methanol, water, and methanol in this order, and then dried under reduced pressure at 150 ° C. for 8 hours to obtain polyphenylene ether having an acid anhydride group as a terminal group.

The components (parts by weight) shown in Table 1 were mixed and extruded with a twin-screw extruder (screw diameter 50 mm) set at 300 ° C. to prepare pellets. Cylinder temperature 32 after drying this pellet
A test piece was molded using an injection molding machine set at 0 ° C, and Izod impact strength (without notch), bending strength, bending elastic modulus, and heat distortion temperature (heat distortion temperature) were measured.
ure: HDT) was tested. The test results obtained are shown in Table 1.

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Claims (1)

[Claims] 1. (A) Polyphenylene sulfide resin 30
To 70 parts by weight, (B) 30 to 70 parts by weight of polyamide resin, (C) 1 to 30 parts by weight of polyolefin modified with at least one functional group selected from a carboxyl group, an acid anhydride group and an epoxy group, and (D) 5 to 30 parts by weight of a total of 100 parts by weight of (A), (B) and (C), a carboxyl group, an acid anhydride group,
And a resin composition comprising a polyphenylene ether resin modified with at least one functional group selected from epoxy groups.