JP3313168B2 - Polyphenylene ether / polyamide resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyphenylene ether (hereinafter sometimes referred to as PPE) / polyamide (hereinafter sometimes referred to as PA) resin composition.

[0002]

2. Description of the Related Art In recent years, resin outer plates have been used instead of metal outer plates. For example, as a resin for a fender, a material mainly composed of a polyphenylene ether resin and a polyamide resin has been put to practical use.

[0003] These resin molded articles have the advantage that they can be simultaneously painted and baked with a metal automobile body, but they are inferior in dimensional stability as compared with metal, so that other parts due to temperature changes and water absorption can be used. There are problems such as interference with the system.

[0004]

Accordingly, the present invention provides a PPE / PA resin having low water absorption and particularly excellent dimensional stability without impairing various properties such as impact strength, tensile elongation, and surface appearance of a molded article. It is intended to provide a composition.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that PPE resin, PA resin, polyphenylene sulfide (hereinafter sometimes referred to as PPS).
The present inventors have found that a resin composition satisfying all of the above characteristics can be provided by combining the system resin and the compatibilizer in a specific ratio, and have reached the present invention.

That is, the resin composition of the present invention comprises (A) a polyphenylene ether resin, (B) a polyamide resin, (C) a polyphenylene sulfide resin, and (D) a compatibilizing agent. ) Is 2
0 to 70 parts by weight, 30 to 60 parts by weight of (B) and 0.1 to 20 parts by weight of (C), and (A) +
(B) + (C) = 100 parts by weight, (D) is 0.0
1 to 10 parts by weight and the polyamide resin is continuous
A polyphenylene ether-based resin in the continuous phase.
Fat and polyphenylene sulfide resin
It is characterized by being dispersed as independent dispersed particles .

PPE resin used in the present invention (component A)
Is, for example, the general formula (A):

[0008]

Embedded image (Wherein R ₁ , R ₂ , R ₃ , and R ₄ are hydrogen, halogen, alkyl, alkoxy, haloalkyl and haloalkoxy having at least two carbon atoms between the halogen atom and the phenyl ring) Is a monovalent substituent selected from those not containing a tertiary α-carbon, and n is an integer representing the degree of polymerization.)
Even one kind of the polymer represented by the above general formula,
A copolymer in which two or more kinds are combined may be used. In a preferred embodiment, R ₁ and R ₂ are an alkyl group having 1 to 4 carbon atoms, and R ₃ and R ₄ are 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-
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. Examples of the PPE copolymer include a copolymer in which an alkyl trisubstituted phenol such as 2,3,6-trimethylphenol is partially contained in the above-mentioned polyphenylene ether repeating unit. Also these P
A copolymer obtained by grafting a styrene compound to PE 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, or chlorostyrene, with the above PPE.

Next, as the polyamide resin (component B) used in the present invention, for example, nylon-4, nylon-
6, nylon-6,6, nylon-12, nylon-6,10,
Nylon-6,12, nylon-6,36 and the like,
It is not limited to these. In the present invention, a polyamide is preferably used in which the amount of terminal amino groups of the polyamide is larger than the amount of terminal carboxyl groups. Such a polyamide can be obtained by adding a compound having a group that reacts with, for example, a carboxyl group during polymerization of the polyamide, for example, an extra diamine. Alternatively, it can also be obtained by reacting a compound having a group that reacts with a carboxyl group after polymerization of the polyamide. In the present invention, the ratio of the terminal amino group amount to the terminal carboxyl group is preferably 1.01 or more, more preferably 1.1 or more, and especially 1.3 or more.

The PPS resin used in the present invention (component C)
Is preferable because a composition containing 70 mol% or more of the structural unit represented by the general formula: -φ-S- (where -φ- represents a phenylene group) results in a composition having excellent characteristics. PP
As the polymerization method of S, p-dichlorobenzene is polymerized in the presence of sulfur and sodium carbonate, and in a polar solvent in the presence of sodium sulfide or sodium hydrosulfide and sodium hydroxide or hydrogen sulfide and sodium hydroxide. Polymerization method, self-condensation of p-chlorothiophenol, etc. can be mentioned, but sodium sulfide and p-dichlorobenzene are reacted in an amide solvent such as N-methylpyrrolidone, dimethylacetamide or a sulfone solvent such as sulfolane. The method is appropriate. At this time, it is preferable 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 the copolymer component is less than 30 mol%, a meta bond (formula (1) below), an ortho bond (formula (2) below),
Ether bond (the following formula (3)), sulfone bond (the following formula (4)), biphenyl bond (the following formula (5)), substituted phenylsulfide bond (the following formula (6), where R is an alkyl , Nitro, phenyl, alkoxy, carboxylic acid, or a metal base of carboxylic acid), even if it contains a trifunctional phenyl sulfide bond (formula (7) below) as long as the crystallinity of the polymer is not significantly affected. However, the content of the copolymer component is preferably 10 mol% or less. In particular, when a phenyl, biphenyl, naphthyl sulfide bond or the like having three or more functionalities is selected for copolymerization, the amount is preferably 3 mol% or less, more preferably 1 mol% or less.

[0011]

Embedded image Such PPS can be produced by a general production method such as (1) the reaction of a halogen-substituted aromatic compound with an alkali sulfide (US Pat. No. 25
13188, JP-B-44-27671 and JP-B-45-276
No. 3368), (2) Condensation reaction of thiophenols in the presence of an alkali catalyst or a copper salt (US Pat.
No. 165, British Patent No. 1160660), (3) Condensation reaction of aromatic compound and sulfur chloride in the presence of Lewis acid catalyst (Japanese Patent Publication No. 46-27255, Belgian Patent No. 29439)
Etc., and can be arbitrarily selected according to the purpose.

In the resin composition of the present invention, it is important that the above three components (A), (B) and (C) are contained in the following proportions. That is, (A) is 20 to
70 parts by weight, (B) is 30 to 60 parts by weight, and (C) is 0.1 to 20 parts by weight. Preferably, (A) is 25 to 65 parts by weight, (B) is 35 to 55 parts by weight, and (C) is 0.5 to 15 parts by weight. If the amount of (C) is too small, the desired improvement in water absorption and dimensional stability is not sufficient, and if it is too large, impact strength and surface appearance deteriorate.

In the present invention, in addition to the above components, a compatibilizing agent for component (D) is further contained. The compatibilizer is
Any of the known compatibilizers for PPS, PPE and polyamide can be used. Preferred examples of such compatibilizers include (a) citric acid, malic acid, agaric acid and derivatives thereof. (B) (a) a carbon-carbon double or triple bond and (b) carboxylic acid in the molecule. Compounds having an acid group, acid anhydride group, acid amide group, imide group, carboxylic acid ester group, epoxy group, amino group or hydroxyl group, and (c) compounds having a carboxyl group or an acid anhydride group and an acid halide group At least one compound selected.

The above-mentioned (a) citric acid, malic acid, agaric acid and their derivatives are described in JP-T-61-502195, and the compounds represented by the general formula in this publication are used in the present invention. However, those described above are particularly preferable. Derivatives include ester compounds, amide compounds, anhydrides, hydrates, and salts. Examples of the acid ester compound include an acetyl ester of citric acid, a mono- or distearyl ester, and the like. As acid amide compounds, citric acid N, N'-diethylamide, N, N'-
Examples include di-propylamide, N-phenylamide, N-dodecylamide, N, N'-didodecylamide, and N-dodecylamide of malic acid. As salt,
Examples include calcium malate, calcium citrate, calcium malate, potassium citrate and the like.

The compound of the above (b) is disclosed in JP-A-56-49753.
Specific examples thereof include maleic anhydride, maleic acid, fumaric acid, maleimide, maleic hydrazide, and a reaction product of maleic anhydride and a diamine, for example, the following formula (Formula 3):

[0016]

Embedded image (Where R represents an aliphatic or aromatic group), methylnadic anhydride, dichloromaleic anhydride, maleic amide, soybean oil, tung oil,
Castor oil, linseed oil, hemp seed oil, cottonseed oil, sesame oil, rapeseed oil, peanut oil, camellia oil, natural oils such as olive oil, coconut oil, sardine oil, epoxidized natural oils such as epoxidized soybean oil, acrylic acid, butenoic acid , Crotonic acid, vinyl acetic acid, methacrylic acid, pentenoic acid, angelic acid, tiglic acid, 2-pentenoic acid, 3-pentenoic acid, α-ethylacrylic acid, β-methylcrotonic acid, 4-pentenoic acid,
2-hexenoic acid, 2-methyl-2-pentenoic acid, 3-methyl-2-pentenoic acid, α-ethylcrotonic acid, 2,2-
Dimethyl-3-butenoic acid, 2-heptenoic acid, 2-octenoic acid, 4-decenoic acid, 9-undecenoic acid, 10-undecenoic acid, 4-dodecenoic acid, 5-dodecenoic acid, 4-tetradecenoic acid, 9-tetradecene Acid, 9-hexadecenoic acid, 2
-Octadecenoic acid, 9-octadecenoic acid, eicosenoic acid, docosenoic acid, erucic acid, tetracosenoic acid, mycolipenoic acid, 2,4-pentadienoic acid, 2,4-hexadienoic acid, diallylacetic acid, geranium acid, 2,4-decadienoic acid , 2,4-dodecadienoic acid, 9,12-hexadecadienoic acid, 9,12-octadecadienoic acid, hexadecatrienoic acid, linoleic acid, linolenic acid, octadecatrienoic acid,
Eicosadienoic acid, eicosatrienoic acid, eicosatetraenoic acid, ricinoleic acid, eleostearic acid, oleic acid, eicosapentaenoic acid, erucic acid, docosadienoic acid, docosatrienoic acid, docosatetraenoic acid, docosapentaenoic acid, tetracosenoic acid Unsaturated carboxylic acids such as hexacosenoic acid, hexacodienoic acid, octacosenic acid, and traacontenic acid, or esters, acid amides, anhydrides of these unsaturated carboxylic acids, or allyl alcohol, crotyl alcohol, methyl vinyl carbinol, allyl carbinol , Methylpropenylcarbinol, 4-penten-1-ol, 10-undecene-1-
All, propargyl alcohol, 1,4-pentadien-3-ol, 1,4-hexadien-3-ol, 3,5
-Hexadiene-2-ol, 2,4-hexadiene-1-
All the general formula _{C n H 2n-5 OH,} C n H 2n-7 OH, C n
Alcohol represented by H _2n-9 OH (where n is a positive integer), 3-butene-1,2-diol, 2,5-dimethyl-3
-Hexene-2,5-diol, 1,5-hexadiene-3,
Unsaturated alcohols such as 4-diol and 2,6-octadiene-4,5-diol, or unsaturated amines, butadiene, isoprene, etc. in which the OH group of such an unsaturated alcohol is replaced by -NH ₂ group Low molecular weight polymers (for example, those having an average molecular weight of about 500 to 10,000) or high molecular weight polymers (for example, those having an average molecular weight of 10,000 or more) to which maleic anhydride or phenols are added, or amino groups or carboxylic acid groups , A hydroxyl group, an epoxy group and the like are introduced. Compound (b)
Include compounds containing two or more (A) group functional groups and two or more (B) group functional groups (same or different).

As the compound (c), trimellitic anhydride chloride is particularly mentioned, and it is described in JP-T-62-50056.

Another example of the compatibilizer of component (D) is an unsaturated monomer and / or polymer containing an epoxy group and / or an oxazolinyl group.

Examples of the unsaturated monomer having an epoxy group or an oxazolinyl group include the following.

First, preferred epoxy group-containing unsaturated monomers include glycidyl methacrylate (hereinafter referred to as GMA).
Glycidyl acrylate, vinyl glycidyl ether, glycidyl ether of hydroxyalkyl (meth) acrylate, glycidyl ether of polyalkylene glycol (meth) acrylate, and glycidyl itaconate.

Next, preferred oxazolinyl group-containing unsaturated monomers include those represented by the following general formula (4).

[0022]

Embedded image Wherein Z contains a polymerizable double bond. Preferred substituents Z are:

[0023]

Embedded image In these formulas R is a hydrogen atom or an alkyl or alkoxy group having 1 to 6 carbon atoms, for example a methyl, i- and n-propyl or butyl group.

Particularly preferred compounds have the general formula:

[0025]

Embedded image Wherein R has the above-mentioned meaning, and is preferably a hydrogen atom or a methyl group.

Examples of the polymer having an epoxy group or an oxazolinyl group include a homopolymer of the above unsaturated monomer, a copolymer of two or more of the above unsaturated monomers, and a copolymer of one or more of the above unsaturated monomers. And other unsaturated monomers. Other unsaturated monomers include aromatic vinyl monomers such as styrene (hereinafter sometimes referred to as St), vinyl cyanide monomers such as acrylonitrile, vinyl acetate, acrylic acid (salt); methacrylic acid. Acid (salt), acrylic ester, methacrylic ester, (anhydride) maleic acid, maleic ester, 2-norbornene-
Unsaturated carboxylic acids such as 5,6-dicarboxylic acid (anhydride) or derivatives thereof, ethylene, propylene, 1-
Butene, 1-pentene, 4-methyl-1-pentene, 1
Α-olefins such as -hexene, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, butadiene, isoprene,
Examples thereof include diene components such as 1,4-hexadiene, 5-ethylidene-2-norbornene, and 5-vinyl-2-norbornene.

Examples of copolymers include, for example, GMA / St,
GMA / St / MMA (methyl methacrylate) / M
A, GMA / St / acrylonitrile, GMA / MMA
/ Acrylonitrile, GMA / MMA, GMA / MMA
/ St, vinyl oxazoline / St, vinyl oxazoline / MMA, ethylene / GMA, ethylene / vinyl acetate / GMA, and the like. Of course, copolymers other than those described above can also be used in the present invention.

The compatibilizer of the component (D) is used in an amount of 0.0 parts by weight based on 100 parts by weight of the component (A) + (B) + (C).
1 to 10 parts by weight, preferably 0.1 to 3 parts by weight is used.
If the amount of the compatibilizer is less than the above range, the intended effect is reduced, and if it is more than this range, undesired results such as a decrease in heat resistance of the molded article and a deterioration in moldability are caused.

The composition of the present invention comprises a rubber-like substance as an optional component for further improving impact strength, PPS,
It can be contained, for example, in an amount of 30 parts by weight or less based on 100 parts by weight of the total of PPE and PA.

Rubbery materials include natural and synthetic polymeric materials that are elastic at room temperature. Specific examples thereof include natural rubber, butadiene polymer, styrene-isoprene copolymer, butadiene-styrene copolymer (including all random copolymers, block copolymers, graft copolymers, etc.), isoprene polymers , Chlorobutadiene polymer, butadiene-acrylonitrile copolymer, isobutylene polymer, isobutylene-butadiene copolymer, isobutylene-isoprene copolymer, acrylate polymer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer Examples thereof include polymers, thiocol rubber, polysulfide rubber, polyurethane rubber, polyether rubber (for example, polypropylene oxide), epichlorohydrin rubber, and the like.

The resin composition of the present invention may be mixed with a resin at the time of molding or molding, as long as the physical properties are not impaired.
Other resins and additives such as pigments, dyes, reinforcing agents (glass fibers, carbon fibers, etc.), fillers (carbon black, silica, titanium oxide, etc.), heat-resistant agents, antioxidant deterioration inhibitors, weathering agents, lubricants , A release agent, a crystal nucleating agent, a plasticizer, a flame retardant, a flow improver, an antistatic agent and the like.

As a method for producing the resin composition of the present invention, a melt kneading method is preferable. The use of small amounts of solvents is possible but generally not necessary. Examples of the apparatus include an extruder, a Banbury mixer, a roller, a kneader, etc., which are operated batchwise or continuously.

[0033]

In the resin composition of the present invention, PPE, PA
And the PPS quantitative ratio, the PPS
By specifying the content of the series resin, a state is obtained in which the polyamide resin forms a continuous phase, and the polyphenylene ether-based resin and the polyphenylene sulfide-based resin are each dispersed as independent dispersed particles in the continuous phase. I was able to. Therefore, the water absorption and the coefficient of linear expansion could be reduced without impairing impact strength, tensile elongation, appearance, and the like.

[0034]

The present invention will be further described with reference to the following examples.
In the following, the amounts of each component are indicated by parts by weight.

In Examples and Comparative Examples, the following were used. Component (A) Intrinsic viscosity (measured in chloroform at 30 ° C) is 0.46 dl / g
Poly (2,6-dimethyl-1,4-phenylene) ether, which is referred to as PPE. Component (B) Nylon-6 having a terminal amino group of 8.4 × 10 ^-5 mol / g and a terminal carboxyl group of 1.8 × 10 ^-5 mol / g, a molecular weight of 13,000, which is called PA. Component (C) Toprene T4 (trademark, manufactured by Toprene Co., Ltd.), which is referred to as PPS. Component (D) Citric acid Optional component Rubbery substance: Kraton G 1651 (trademark, partially hydrogenated styrene-butadiene block copolymer (SEBS), manufactured by Shell Chemical Company) Examples 1-2 and Comparative Examples 1-3 Table 1 Were mixed and extruded with a twin-screw extruder (screw diameter: 30 mm) set at 280 ° C. to produce pellets. After drying, the pellets were injection molded at 280 ° C. to prepare test specimens, and the physical properties shown below were measured to evaluate the appearance. Table 1 shows the results. In addition, when the dispersion state of each component in the molded article was observed with a transmission electron microscope (TEM), in each of the examples, PA formed a continuous phase, and PPE and PPS were independent of each other in this continuous phase. It was dispersed as particles. (1) Izod Impact Strength Notched Izod impact strength of a 1/8 × 1/2 × 2.5 inch test piece was measured according to ASTM D256. (2) Tensile elongation Measured according to ASTM D638. (3) A molded test piece having a water absorption of 50 × 50 × 3 mm was immersed in water at 40 ° C.
The weight after 170 hours was measured, and the rate of increase with respect to the weight immediately after molding was determined. (4) Using the coefficient of linear expansion TMA (manufactured by Seiko Instruments Inc.)
It was measured at 0 ° C to 80 ° C. The sample was measured after annealing at 150 ° C. for 1 hour. (5) Appearance A test piece of 15 cm × 15 cm was formed and evaluated visually. A sample having a uniform and excellent surface gloss was rated as ○, and a sample having a flow mark on the surface and poor gloss was rated as ×.

[0036]

[Table 1]

[0037]

The PPE / PA resin composition of the present invention is
It has low water absorption, is particularly excellent in dimensional stability, and is also excellent in various properties such as impact strength, tensile elongation, and surface appearance of a molded product, so that it is industrially useful.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroshi Kubo 2-2 Kinugaoka, Moka-shi, Tochigi Pref. Japan E-Plastics Co., Ltd. (56) References JP-A-59-213758 (JP, A) (58) Field surveyed (Int.Cl. ⁷ , DB name) C08L 71/12 C08K 5/00-5/59 C08L 77/00-77/12 C08L 81/02

Claims (2)

(57) [Claims] (A) a polyphenylene ether-based resin,
In a resin composition containing (B) a polyamide resin, (C) a polyphenylene sulfide resin and (D) a compatibilizer, (A) is 20 to 70 parts by weight, and (B) is 30 to 6 parts by weight.
0 parts by weight and 0.1 to 20 parts by weight of (C), and 0.01 to 10 parts by weight of (D) based on 100 parts by weight of (A) + (B) + (C). And the polyamid
Resin forms a continuous phase, and polyphenylene is contained in the continuous phase.
Ether resin and polyphenylene sulfide
A resin composition, wherein the resin is dispersed as independent dispersed particles . 2. The resin composition according to claim 1, wherein the polyamide resin is a polyamide resin having a terminal amino group content larger than a terminal carboxyl group content.