JPH04266966A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin composition having excellent mechanical properties, heat resistance, oil resistance, moldability and coatability by compounding a resin composition consisting mainly of a polyphenylene ether and a polyamide with a triisocyanate compound. CONSTITUTION:A resin composition 100 pts.wt. of a resin component consisting of (A) 5-75wt.% of a polyphenylene ether [e.g. poly (2,6-dimethyl-1,4-phenylene) ether], (B) 25-95wt.% of a polyamide, preferably nylon-6, nylon-66, etc., and (C) 0-30wt.% of a rubbery polymer, preferably styrene-butadiene block copolymer or its hydrogenated product, (D) 0.02-5 pts.wt., preferably 0.05-3 pts.wt., of a triisocyanate compound, preferably a compound of formula I-IV (M is dihydric alcohol), preferably the components excluding the component D being kneaded with each other and subsequently kneaded with the component D, the components A and B forming a dispersing phase and a continuous phase, respectively, and all of the component C being substantially dispersed in the component A.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention is characterized by mechanical properties, heat resistance,
This invention relates to a resin composition with excellent oil resistance, moldability, and paintability.

0002

[Prior Art] Polyphenylene ether resin is a resin with excellent dimensional stability, electrical properties, heat deformation resistance under high loads, water resistance, etc., and is used industrially in the form of a blend with polystyrene resin. Although it is widely used, it has major drawbacks such as poor oil resistance and moldability.

On the other hand, polyamide resin has excellent mechanical strength, oil resistance, heat resistance, etc., and is used in large quantities as one of the most representative engineering plastics. However, this polyamide resin has the disadvantage that its properties such as dimensional stability, hygroscopicity, resistance to heat deformation under high loads, and impact resistance when dry are lower than those of other plastics.

[0004] For this reason, attempts have been made to blend the above-mentioned resins in order to take advantage of their respective strengths and compensate for their shortcomings, and various compositions have been proposed so far. . For example, a simple blend of both resins, especially a blended resin obtained by melt-mixing them, has been disclosed (Japanese Patent Publication No. 45-997, Japanese Patent Publication No. 59-4166).
Publication No. 3). However, polyphenylene ether and polyamide are inherently difficult to be compatible with each other, and such a simple blend cannot produce a molded article with excellent mechanical strength.

For this purpose, a copolymer of a styrene compound and an α,β-unsaturated dicarboxylic acid anhydride is blended with polyphenylene ether and polyamide as a compatibility improver, and a rubber-like substance is further added as an impact modifier. Along with the added composition (Japanese Patent Publication No. 59-33614), polyphenylene ether, and polyamide, other components include (a) a carbon-carbon double bond or triple bond and (b) a carboxyl group or an acid anhydride group. There is a composition (Japanese Patent Publication No. 11966/1983) obtained by adding a compound having a functional group such as, and melting and kneading the mixture.

[0006] Furthermore, compositions containing a rubber-like substance (JP-A No. 56-49753) and compositions containing a compound having an isocyanate group as a compatibility improver (JP-A-1-213328) is proposed. Resin compositions made of polyphenylene ether resins and polyamide resins obtained by these methods have excellent heat resistance, moldability, oil resistance, organic solvent resistance, and dimensional stability, and are used in automobile parts, electrical parts, etc.・It is expected to be used in many fields such as electronic parts and mechanical parts.

[0007] Molded products obtained from these resin compositions are often used after being painted, and most of the exterior parts of automobiles are painted. However, poor adhesion of the coating has become a practical problem. Many efforts have been made to improve paintability, but currently the surface of molded products is pretreated with alcohol, acid, etc., which limits productivity.

[0008]

[Problems to be Solved by the Invention] The object of the present invention is to improve properties such as mechanical properties, heat resistance, oil resistance, and moldability in resin compositions containing polyphenylene ether, polyamide, and rubber-like polymer as basic components. It is an object of the present invention to provide an excellent resin composition which has greatly improved paintability without impairing the properties.

[0009]

[Means for Solving the Problems] That is, the present invention provides (
A) Polyphenylene ether 5-75% by weight (B)
Polyamide 25-95% by weight
(C) Rubber-like polymer 0-30
Contains 0.02 to 5 parts by weight of a triisocyanate compound (D) with respect to 100 parts by weight of the total amount of resin components (a), (B), and (C) consisting of % by weight, and component (B). forms a continuous phase, component (A) forms a dispersed phase, and substantially all of component (C) forms a continuous phase.
) It is a resin composition formed by dispersing in the component. The present invention will be explained in detail below.

The polyphenylene ether used as component (A) in the present invention has the general formula

[0011]

[Chemical formula 1]

(Here, R1, R2, R3, R4
, R5, R6 are the same or different monovalent residues such as an alkyl group having 1 to 4 carbon atoms, an aryl group, a halogen, and hydrogen, excluding a tert-butyl group;
is not hydrogen at the same time. ) as a repeating unit, and the constituent units are homopolymers or copolymers consisting of (I) or (I) and (II).

Representative examples of homopolymers of polyphenylene ether include poly(2,6-dimethyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1
, 4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene) ether, poly(2-ethyl-
6-n propyl-1,4-phenylene) ether, poly(2-methyl-6-n butyl-1,4-phenylene)
ether, poly(2-ethyl-6-isopropyl-1,
4-phenylene) ether, poly(2-methyl-6-chloro-1,4-phenylene) ether, poly(2-methyl-6-hydroxyethyl-1,4-phenylene) ether, poly(2-methyl-6) -chloroethyl-1,4-
Examples include homopolymers such as phenylene) ether. Polyphenylene ether copolymer is composed of 2,6-dimethylphenol and orthocresol or the general formula

001
4]

[Case 2]

(Here, R3, R4, R5, R6
are the same or different monovalent residues such as an alkyl group having 1 to 4 carbon atoms excluding a tert-butyl group, an aryl group, halogen, hydrogen, and R5 and R6 are not hydrogen at the same time. ) It includes a polyphenylene ether copolymer mainly composed of a polyphenylene ether structure obtained by copolymerizing with an alkyl-substituted phenol such as 2,3,6-trimethylphenol.

Component (A) is present as an island component dispersed in component (B). Although the form and state of dispersion of the island components are not limited, typical examples include substantially particulate ones. The preferred form is 0.1-5μ
The particles are substantially spherical with a particle size of about m. In the present invention, the polyamide used as component (B) has a

[0017]

[Chemical formula 3]

Any material that has a bond and can be heated and melted is possible. Typical examples include 4-nylon, 6-nylon, 6,6-nylon, 12-nylon, 6,10-nylon, polyamides from terephthalic acid and trimethylhexamethylene diamine, adipic acid and metaxylylene diamine. polyamides from adipic acid and azelaic acid and 2,2-bis(p-aminocyclohexyl)-propane, polyamides from terephthalic acid and 4,4-diaminodicyclohexylmethane, and copolymerized nylons thereof. Among these, 6-nylon, 6,6-nylon, and 6-6,6 copolymerized nylon are preferably used alone or in combination.

Rubbery polymers used as component (C) in the present invention include styrene-butadiene block copolymers, hydrogenated styrene-butadiene block copolymers, ethylene-propylene elastomers, ethylene ionomer resins, These include core-shell polymers consisting of a rubbery core and a non-rubberlike polymer shell, and of course two or more types can also be used in combination. Particularly preferred are styrene-butadiene block copolymers and styrene-butadiene block copolymers in which part or all of the butadiene moieties are hydrogenated.

[0020] It is also possible to use rubber-like substances modified with epoxy compounds, unsaturated carboxylic acids, derivatives thereof, and the like. Component (C) is substantially dispersed in component (A) as an island component. The shape and state of dispersion of the island components are not particularly limited, but typical examples include a state in which they are substantially dispersed in the form of particles or short fibers.

A typical example of the triisocyanate compound used as component (D) in the present invention is a modified form of hexamethylene diisocyanate. Among them, a particularly effective compound is a compound represented by the following formula,
Commercially readily available.

[0022]

[C4]

[0023]

[C5]

[0024]

[C6]

[0025]

[C7]

In the present invention, the blending ratio of (A) polyphenylene ether, (B) polyamide, and (C) rubber-like polymer is determined based on the total amount of components (A), (B), and (C). ether 5-75% by weight, preferably 15-60% by weight, polyamide 25% by weight
-95% by weight, preferably 30-65% by weight, and 0-30% by weight of rubbery polymer, preferably 2-20% by weight.

In the present invention, (A), (B), (C)
The reason why the three components are mixed in the above proportions is that if the polyphenylene ether exceeds 75% by weight or the polyamide exceeds 25% by weight, it will be difficult to make the polyamide a continuous phase, and the oil resistance, which is a characteristic of polyamide, will be reduced. This is because molding processability etc. are impaired. In addition, a rubber-like polymer may be added as needed, but it is important for improving impact resistance, and if it exceeds 30% by weight, it is not necessary for improving impact resistance and rigidity. And heat resistance decreases, which is undesirable.

The triisocyanate compound as component (D) added in the composition of the present invention is the same as the resin component (A).
, (B), and (C) in a total amount of 100 parts by weight, 0.
0.02 to 5 parts by weight, preferably 0.05 to 3 parts by weight. If the amount of component (D) added is less than 0.02 parts by weight, the paintability will not be improved, and if it exceeds 5 parts by weight, the appearance will deteriorate.
Heat resistance decreases. Furthermore, when the amount of component (D) added is 0.5 parts by weight or more, the melt viscosity increases and the shear rate dependence of the melt viscosity is large, so that a material suitable for blow molding or sheet molding can be obtained.

If desired, the composition of the present invention may contain a modified block copolymer obtained by modifying a block copolymer of an aromatic vinyl compound and a conjugated compound with an unsaturated dicarboxylic acid and a derivative thereof. can. By incorporating the modified block copolymer into the composition, the balance of mechanical strength such as impact resistance and rigidity is effectively improved. The block copolymer that is the base of the modified block copolymer is
It is composed of one or more polymer blocks of an aromatic vinyl compound and one or more polymer blocks of a conjugated diene compound, and may be linear, branched, radial, or a combination thereof.

The content of the aromatic vinyl compound in this base block copolymer is preferably in the range of 60 to 97% by weight. Specific examples of this base block copolymer include styrene-butadiene block copolymer, styrene-isoprene block copolymer, and the like. Examples of unsaturated dicarboxylic acids and derivatives thereof used to modify this base block copolymer include maleic acid, fumaric acid, chloromaleic acid, cis-
4-cyclohexene-1,2-dicarboxylic acid and their acid anhydrides, esters, semi-alkyl esters, amides,
Examples include imides, and α,β-unsaturated dicarboxylic acids and derivatives thereof, specifically maleic acid and maleic anhydride, are particularly preferred. Unsaturated dicarboxylic acids and derivatives thereof may be used alone or in combination of two or more.

The amount of unsaturated dicarboxylic acid and its derivative added to the modified block copolymer is such that the content of these compound residues is 0.05 parts by weight or more per 100 parts by weight of the base block copolymer. Good. If it is less than 0.05 part by weight, the balance of mechanical properties will not improve. In the composition of the present invention, the modified block copolymer blended as desired is 0.5 to 15 parts by weight based on 100 parts by weight of the total amount of the resin components (A), (B), and (C). , preferably in the range of 1 to 5 parts by weight. If the amount is less than 0.5 parts by weight, the effect of improving impact resistance will hardly be exhibited, and if it exceeds 15 parts by weight, the heat deformation resistance will tend to decrease. If the content of aromatic vinyl compound units in the base block copolymer in the modified block copolymer is less than 60% by weight, the balance of mechanical properties such as impact resistance and rigidity will hardly be improved; If it exceeds 100%, the modification by the unsaturated dicarboxylic acid or its derivatives will not be sufficient and the effect will not be exhibited.

Next, a general method for producing the composition of the present invention will be explained, but of course other production methods can be used as long as the above conditions are satisfied. That is, the composition of the present invention is obtained by melt-mixing polyphenylene ether, polyamide, rubbery polymer, and triisocyanate compound. As for the kneading method, each component may be kneaded all at once, or two or more components may be pre-kneaded and the remaining components may be kneaded into a blend. It is preferable to knead the mixture afterwards.

[0033] Furthermore, as the modified block copolymer to be blended as desired, a block copolymer that has been modified in advance can be used; When kneading and reacting unsaturated dicarboxylic acids and their derivatives in an extruder, the polyphenylene ether (A) component, (
From the viewpoint of simplifying the process, it is preferable to supply the polyamide as component B), the rubbery polymer as component (C), and component (D) and form the composition at once.

During melt-kneading, α,β-unsaturated dicarboxylic acids and derivatives thereof, vinyl silane compounds, saturated aliphatic polycarboxylic acids and derivatives thereof are added to the resin component (A) in order to adjust the dispersed particle size of polyphenylene ether. ), (B
), (C) can be added in an amount of 0.1 to 2% by weight based on the total amount. Representative examples of such compounds include maleic acid, maleic anhydride, maleimide, vinylmethoxysilane, γ-aminopropylmethoxysilane, citric acid, and malic acid.

In place of these compounds, modified polyphenylene ethers to which such compounds have been added can also be blended, and part or all of component (A) polyphenylene ether can be made into modified polyphenylene ethers. The temperature and time for melt-kneading vary depending on the type of polyamide used and the composition ratio of polyamide and polyphenylene ether, but usually the temperature is in the range of 240 to 350°C, preferably 260 to 320°C, or 0.35°C. 2～
A suitable kneading time is about 10 minutes, preferably about 0.5 to 5 minutes. As the melt-kneading device, an extruder, a kneader, a roll, etc. can be used, but an extruder is particularly suitable.

Other polymers, stabilizers, plasticizers, lubricants, flame retardants, inorganic fillers other than those used in the present invention, glass fibers, carbon fibers, etc. may be added to the composition of the present invention as desired. Can be done.

[0037]

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way. The properties of the materials in Examples and Comparative Examples were evaluated by the following test methods. Izod impact strength: JIS K-7110, 23℃
, Notched heating deformation temperature: JIS K-7207, 4.6Kg/
cm2 Weighted coating Properties: Cylinder temperature 270℃, mold temperature 4
75mm x 75m using an injection molding machine set at 0℃
A flat plate of m×3 mm thickness was molded. The obtained flat plate was coated with an acrylic-urethane paint, cured and dried at 80°C for 30 minutes, and further conditioned and humidified at 23°C and 50% humidity.

Next, a checkerboard peel test was conducted according to JIS K5400, and the samples were classified into the following classes. Number of squares that did not peel out of 100 squares: 100
: ◎ (no peeling) 95-99: ○ 80-95: △ 0-80: × Melt viscosity: Apparent melt viscosity at 290°C was measured by changing the shear rate using a Capillograph manufactured by Toyo Seiki Seisakusho Co., Ltd. did.

[0039] Shear rate 10 sec-1, 103 sec
-1, the melt viscosity (poise) and the ratio thereof were compared.

[0040]

[Example 1] 40 parts by weight of poly(2,6-dimethyl-1,4-phenylene)ether having an intrinsic viscosity of 0.54 (in chloroform at 30°C) and a relative viscosity of 2.5 as polyamide (in chloroform at 25°C). 45 parts by weight of 6-nylon (in sulfuric acid),
Styrene-butadiene block copolymer (Asahi Kasei Corporation)
15 parts by weight of Tuffprene 200 (manufactured by Co., Ltd.), 0.5 parts by weight of a triisocyanate compound of formula-VI (Duranate THA-100, manufactured by Asahi Kasei Industries, Ltd.), and 0.5 parts by weight of maleic anhydride as a dispersion particle size control agent. using a twin screw extruder with a screw diameter of 40 mm at 300°C.
The mixture was extruded and kneaded at 300 rpm to form pellets. At that time, the styrene-butadiene block copolymer and triisocyanate compound were added midway through the extruder.

Next, a test piece was prepared by injection molding,
Physical properties and paintability were evaluated. The evaluation results are shown in Table 1.

[0042]

Examples 2 to 6 Evaluations were carried out in the same manner as in Example 1, except that the composition and the amount of triisocyanate compound were as shown in Table 1. The evaluation results are shown in Table 1.

[0043]

[Example 7] Evaluation was carried out in the same manner as in Example 1, except that 2 parts by weight of the modified block copolymer was blended without adding maleic anhydride as a dispersed particle size regulator. The evaluation results are shown in Table 1.

The modified block copolymer is a styrene-butadiene block copolymer (manufactured by Asahi Kasei Corporation,
It was produced by blending 100 parts by weight of Asaflex 810) with 2 parts by weight of maleic anhydride and 0.5 parts by weight of phenothiazine as a stabilizer, and performing melt extrusion at 290°C using a twin-screw extruder. When this modified block copolymer was dissolved in toluene and neutralization titration was performed,
The content of maleic acid residues was about 0.5% by weight.

[0045]

[Comparative Examples 1 and 2] Evaluation was carried out in the same manner as in Example 1 except that the composition was as shown in Table 1. The evaluation results are shown in Table 1.

[0046]

[Comparative Example 3] In Example 1, melt kneading was carried out using a single screw extruder with a screw diameter of 40 mm at 300°C and 75 rpm.
The mixture was extruded and kneaded at pm and pelletized. The evaluation was performed in the same manner as in Example 1 except for the above. The evaluation results are shown in Table 1.

[0047]

Examples 8 to 9 Evaluations were carried out in the same manner as in Example 1, except that the isocyanate compounds were changed as shown in Table 2. The evaluation results are shown in Table 2.

[0048]

[Table 1]

[0049]

[Table 2]

[0050]

[Effect of the invention] The resin composition of the present invention has excellent heat resistance,
It is a material that has good moldability, oil resistance, and mechanical properties, and also has excellent paintability for molded products. Therefore, the composition of the present invention is useful for applications requiring painting, and further expansion of its applications can be expected.

Claims (1)

[Claims] [Claim 1] (A) Polyphenylene ether 5
~75% by weight (B) Polyamide 25~95% by weight (C) Rubber polymer 0~30% by weight Resin components (A), (B)
), (C) contains 0.02 to 5 parts by weight of a triisocyanate compound (D), and the component (B) forms a continuous phase and the component (A) forms a dispersed phase. , and furthermore, substantially all of the component (C) is (A
) A thermoplastic resin composition dispersed in components.