JP2636805B2 - 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 resin composition which is excellent in mechanical strength, in particular, in falling weight impact strength, oil resistance and molding workability of a plate-like molded product. Specifically, the center of the drop weight impact strength of a plate-like molded product made of a polyphenylene ether resin, a crystalline polyamide resin, an amorphous or low-crystalline polyamide resin, and, if desired, a compound having both an unsaturated group and a polar group. The present invention relates to a resin composition suitable for injection molding, extrusion molding, and hollow molding, which has excellent mechanical strength balance, moldability and organic solvent resistance.

[0002]

2. Description of the Related Art Polyphenylene ether resins are attracting attention as useful resins having excellent mechanical properties and heat resistance.
For example, it is blended with a styrene resin, but the solvent resistance is remarkably poor. To improve this point, polyamide (JP-B-59-41663, etc.) and polyester (JP-B-51-21662, etc.) are used. Have been proposed. Further, for the purpose of improving the impact strength of these blends, a composition comprising a combination of a polyphenylene ether and a polyamide and a compound containing a group such as a carboxylic acid, an imide or an epoxy and a rubber material (Japanese Patent Application Laid-Open No.
No. 49753) has been proposed. On the other hand, with the expansion of applications of plastics, plastic materials have been required to have a higher level of performance than ever before, for example, heat resistance, the above-mentioned blends with excellent organic solvent resistance, In order to respond to the demand for a high level of impact strength, the present inventors have developed a specific range of combinations of polyphenylene ether resin, polyamide resin, and a compound having both an unsaturated group and a polar group in the same molecule. A composition comprising an alkenyl aromatic compound-conjugated diene block copolymer (Japanese Patent Application No. 60-265358).
No.). However, in the field of industrial parts, there is a case where the surface impact strength, which is an important performance, is unsatisfactory for large flat plate parts, and there is room for improvement in this aspect.

[Summary of the Invention] The present invention solves the above-mentioned problems and shows a particularly high level of balance of mechanical properties required in the field of industrial parts, particularly a falling weight impact strength of a flat plate portion, and an organic resistance. It is intended to provide a resin composition having good solvent properties and moldability. For this reason, as a result of examining various compounding components, the main crystalline polyamide resin was used in a combination of a polyphenylene ether resin, a polyamide resin, and a compound having an unsaturated group and a polar group in the same molecule as desired. By replacing a part of the component with a non-crystalline or low-crystalline polyamide resin component, by sharing the crystalline polyamide component and the non-crystalline or low-crystalline polyamide resin component,
It has been found that a very high level of falling weight impact strength of a flat molded product can be obtained, and the present invention has been completed. Therefore, the gist of the present invention is:

Component (a): 20-70% by weight of polyphenylene ether resin Component (b): 29-79% by weight of crystalline polyamide resin Component (c): Non-crystalline or low-crystalline having a glass transition temperature of 70-210 ° C. A cyclic hydrocarbon-based copolymerized polyamide in an amount of 1 to 55% by weight.

According to the present invention, a polyphenylene ether-polyamide system which has a high level of falling weight impact strength of a plate-like molded product, has a good level of other mechanical properties, and is suitable as an industrial component material having a flat plate-like portion A resin composition is obtained.

[Detailed Description of the Invention] Constituents (1) Polyphenylene ether resin (a) The polyphenylene ether used in the present invention has a general formula

[0007]

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Wherein the ether oxygen atom of one unit is connected to the benzene nucleus of the next adjacent unit, n is at least 50, and Q is independently hydrogen A halogen, a hydrocarbon group containing no tertiary α-carbon atom, a halohydrocarbon group having at least two carbon atoms between the halogen atom and the phenyl nucleus, a hydrocarbonoxy group, and a halogen atom and the phenyl nucleus. A monovalent substituent selected from the group consisting of halohydrocarbonoxy groups having at least two carbon atoms between
May be the same or different.

Further, 2,6-dimethylphenol and 2,6-dimethylphenol
3,6-trimethylphenol copolymer, 2,6-dimethylphenol and 2,3,5,6-tetramethylphenol copolymer, 2,6-diethylphenol and 2,
Copolymers such as a copolymer of 3,6-trimethylphenol can also be mentioned. Further, the polyphenylene ether used in the present invention is a styrene-based monomer (e.g.,
Styrene, p-methylstyrene, α-methylstyrene, etc.) and modified polyphenylene ethers.

Processes for the preparation of polyphenylene ethers corresponding to the above are known and are described, for example, in US Pat. No. 3,306,687.
No. 4, No. 3,300,875, No. 3,257,357 and No. 3,257,358, and Japanese Patent Publication No. Sho 52
17880 and JP-A-50-51197. A group of preferred polyphenylene ethers for the purposes of the present invention is those having two groups per ether oxygen atom.
Having an alkyl substituent at one of the ortho positions and 2,
It is a copolymer of 6-dialkylphenol and 2,3,6-trialkylphenol.

(2) Crystalline polyamide resin (b) The crystalline polyamide resin used in the present invention has a polymer main chain.

[0012]

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It has a bond and can be heated and melted;
It also has a distinct melting point with a measurable heat of fusion. The melting point and heat of fusion can be measured using a differential scanning calorimeter. For example, PERKIN-E
There is a DSC-II manufactured by LMER. Using this apparatus, the heat of fusion can be measured, for example, at a rate of temperature increase of 10 ° C. per minute. Heat the sample to a temperature above the expected melting point, then cool the sample at a rate of 10 ° C. per minute,
It can be measured by cooling to 0 ° C., allowing the mixture to stand for about 1 minute, and then heating at a rate of 10 ° C. per minute. The heat of fusion that is constant within the experimental error range even when measured in any of the subsequent cycles of temperature rise and temperature fall is adopted. The crystalline polyamide in the present invention is defined as having a heat of fusion exceeding 1 Cal / g by the above method. According to this method, commercially available nylon-6 has a heat of fusion of about 16 Cal / g.

Representative examples of the crystalline polyamide resin include nylon-4, nylon-6 (hereinafter, sometimes referred to as polyamide-6), nylon-12, and nylon-6,6 (hereinafter, polyamide-6). , 6), nylon-4,6, nylon-6,10, nylon-6,12 and nylon-6, T (polyamide comprising hexamethylenediamine and terephthalic acid), nylon-MXD, 6 ( Polyamide consisting of meta-xylylenediamine and adipic acid), nylon-6 and nylon-
6,6, a copolymer of hexamethylenediamine, adipic acid and caprolactam, etc. Among them, aliphatic polyamide polymers are more preferable, and nylon-6,6 and nylon- are more preferable. 6, which are commercially available. As an example, there is a product sold by BASF, West Germany under the trade name of Ultramid.

(3) Non-crystalline or low-crystalline cyclic carbonization
Hydrogen-based copolymer polyamide resin (c) The non-crystalline or low-crystalline cyclic hydrocarbon-based copolymer resin used in the present invention has a glass transition temperature of 70 ° C to 210 ° C,
More preferably 80 ° C or more and 170 ° C or less, further preferably 90 ° C or more and 170 ° C or less, particularly preferably 90 ° C or less
It is in a range of not less than 150 ° C and not less than 150 ° C. Non-crystalline and low-crystalline generally indicate that it does not have a definite melting point or measurable heat of fusion.However, in the present invention, it is possible to gradually cool from a molten state or to perform some heat treatment in a solid state by sufficient heat treatment. Includes those that produce crystals. The glass transition temperature, melting point and heat of fusion can be measured by the method described in the section of “Crystalline polyamide resin (b)”. The non-crystalline or low-crystalline cyclic hydrocarbons according to the present invention
The copolymerized polyamide resin is 1 Cal by the method described above.
/ G or less. It is also possible to know the melting point and the glass transition temperature from the viscoelastic temperature change behavior measured by a mechanical spectrometer or the like. These non-crystalline or low crystalline cyclic hydrocarbon-based copolymerized polyamide resin has an amide bond structural unit,
It mainly consists of those selected from the following structural formulas I to VI having a chain structure or a cyclic structure, and is configured to satisfy the above range of glass transition temperature and non-crystallinity or low crystallinity. .

It should be noted that these non-crystalline or low-crystalline
Copolymerized polyamide resin is a copolymer polyamide resin containing a cyclic structure in the repeating units of the molecular chain.

[0017]

Embedded image I-HN—W—NH— (W is at least one selected from linear or branched aliphatic groups having 2 to 12 carbon atoms)

[0018]

[ Image Omitted ] II- HN-X-NH- (X is at least one selected from a metaxylylene group or an aliphatic group having at least one alicyclic hydrocarbon skeleton having a carbon number of 5 to 22)

[0019]

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(R is each independently hydrogen or carbon atom 1
At least one selected from aliphatic groups in the range of 1 to 6, wherein each R may be the same or different)

[0021]

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(R is each independently hydrogen or carbon atom 1
And R is the same or different.)

[0023]

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(Y is an aliphatic group having 4 to 22 carbon atoms,
At least one selected from aliphatic groups containing alicyclic hydrocarbon groups)

[0025]

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(Z is an aliphatic group having 4 to 14 carbon atoms;
At least one selected from aromatic groups) Specific examples of W in the structural unit I include a butylene group,
Hexylene, octylene, decanylene, 2,2
A 4-trimethylhexylene group, a 2,4,4-trimethylhexylene group, a 3-methylhexylene group, a pentylene group and the like, more preferably a butylene group, a hexylene group and a 2,4,4-trimethylhexylene Group, 2,4,4
-A trimethylhexylene group.

Specific examples of X in the structural unit II include:
Meta-xylylene group (Xa), 4,4'-methylenedicyclohexane-1,1'-diyl group (Xb), 2,2'-
Dimethyl-4,4'-methylenedicyclohexane-1,
1'-diyl group (Xc), 1,5,5-trimethyl-
1,3-cyclohexylene-1-methylene group (Xd),
Cyclohexylene-1,4-dimethylene group (Xe), 4
-Thymylenecyclohexylene group (Xf), 3-methylenecyclohexylene group (Xg), cyclohexylene-1,
3-dimethylene group (Xh) and the like. The structural formula of each specific example of X is shown below.

[0028]

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Specific examples of R in the structural units III and IV include a hydrogen atom, a methyl group, a tertiary butyl group, an isopropyl group and an ethyl group, more preferably a hydrogen atom, a methyl group, and still more preferably a hydrogen atom. It is. Specific examples of Y in the structural unit V include ethylene, propylene, butylene, hexylene, octylene, decanylene, 1,4-cyclohexylene, 1,3-cyclohexylene, and structural unit II ( Xa), (Xb), (Xc), (Xd), (Xe),
(Xf), (Xg), (Xh) and the like, and more preferably an ethylene group, a propylene group, a butylene group, an octylene group, a 1,4-cyclohexylene group, a 1,3-cyclohexylene group, Preferred are an ethylene group, a propylene group and a butylene group.

Specific examples of Z in the structural unit VI include:
Examples thereof include a butylene group, a pentylene group, a hexylene group, a decanylene group, an undecaneylene group, and a paraphenylene group, more preferably a pentylene group, a hexylene group, and an undecaneylene group, and further preferably a pentylene group.

In the above structural units I to VI,
Those mainly comprising I, III and IV are more preferred. The relative viscosity of the polyamide resin (c) (in 98% concentrated sulfuric acid,
(Concentration 1 g / dl, measurement temperature 25 ° C) is 1.0 to 5.0 d
1 / g, more preferably from 1.4 to 3.5 dl / g, even more preferably from 1.6 to 3.0 dl / g. Methods for producing these non-crystalline or low-crystalline cyclic hydrocarbon copolymers are known.
The ones disclosed in JP-A-8-38751, JP-A-60-217237, JP-A-60-219227 and the like are applicable.

In the present invention, the compatibilizer (d)
For example, a compound having both an unsaturated group and a polar group in the same molecule can be blended in the composition. Compounds having both an unsaturated group and a polar group include an unsaturated group, ie, a carbon-carbon double bond or a carbon-carbon triple bond, and a polar group, ie, an amide bond contained in a polyamide resin, a carboxyl group present at a chain end, It is a compound having a functional group showing affinity and chemical reactivity with amino groups and the like in the same molecule.
Examples of such a functional group include a carboxylic acid group, a group derived from a carboxylic acid, that is, various salts and esters substituted with a hydrogen atom or a hydroxyl group of a carboxyl group, an acid amide, an acid anhydride, an imide, an acid azide, an acid halide, Alternatively, a functional group such as oxazoline and nitrile, an epoxy group,
Examples thereof include an amino group, a hydroxyl group, and an isocyanate group. Compounds having both an unsaturated group and a polar group include unsaturated carboxylic acids, unsaturated carboxylic acid derivatives, unsaturated epoxy compounds, unsaturated alcohols, unsaturated amines,
Unsaturated isocyanates are mainly used.

Needless to say, the compound having both an unsaturated group and a polar group in the same molecule includes a compound containing two or more unsaturated groups and two or more (same or different) polar groups. Alternatively, it is also possible to use two or more specific compounds. Among them, more preferably maleic anhydride, maleic acid, itaconic anhydride, unsaturated dicarboxylic acids such as itaconic acid and its anhydrides, unsaturated alcohols such as oleyl alcohol, epoxidized soybean oils and other epoxidized natural fats and oils. And more preferably maleic anhydride, maleic acid, oleyl alcohol, epoxidized soybean oil and epoxidized linseed oil, and particularly preferably maleic anhydride.

In the present invention, when such a compatibilizer is added, a resin composition having further improved impact strength can be obtained. On the other hand, the color tone of a molded article tends to cause difficulty. When the color tone does not matter, the component (d) can be used.

2. Composition ratio of constituent components The mixing ratio of the components (a) to (c) as described above is (a)
+ (B) + (c) in the total weight respectively: (a) component: 20 to 70% by weight, preferably 30 to 60%
% By weight, more preferably 40 to 60% by weight. Component (b): 29 to 79% by weight, preferably 34 to 69%
% By weight, particularly preferably 39-59% by weight. Component (c): 1 to 55% by weight, preferably 2 to 39% by weight, particularly preferably 2 to 32% by weight;
The component (c) is preferably 70% by weight or less, more preferably 60% by weight or less, in the total amount of the components (b) and (c).

When the compound of the component (d) is blended with the components (a), (b) and (c),
The total amount of the components (a), (b) and (c) is set to 100 parts by weight, and the amount of the component (d) to be added as an external number is 0.1 part.
The amount is preferably from 0.1 to 10 parts by weight, preferably from 0.05 to 10 parts by weight.
The amount is preferably 5 parts by weight, particularly preferably 0.1 to 2 parts by weight, more preferably 0.2 to 1.5 parts by weight, and further preferably 0.2 to 1 part by weight.

With respect to the above composition, if the component (a) is less than 20% by weight, the heat stiffness is insufficient, and if it exceeds 70% by weight, the organic solvent resistance is unsatisfactory, which is not preferable. If the component (b) exceeds 79% by weight, the heat resistance is unsatisfactory, which is not preferable. The effect of the present invention, that is, for the purpose of obtaining a resin composition having a high level of falling weight impact strength of a plate-shaped molded product,
The amount of the component (c) is 1% by weight or more and 55% by weight or less, and 70% by weight of the total weight of the components (b) and (c).
The following is sufficient. If the content of the component (c) is less than 1% by weight, the impact strength level is unsatisfactory, which is not preferable. When the proportion of the component (c) in the total amount of the components (b) + (c) exceeds 70% by weight, the level of the falling weight impact strength of the plate-shaped molded article tends to be insufficient. When the component (d) is used, if the component (d) is more than 10 parts by weight, the impact strength level and the appearance of the molded article tend to have difficulty.

The composition according to the present invention may contain, if necessary, a thermoplastic or thermosetting resin other than the above-mentioned polymer component, a rubber component, an antioxidant, or the like, as long as the object of the present invention is not impaired.
Components such as a weather resistance improver, a nucleating agent, a slip agent, an inorganic or organic filler and a reinforcing agent, a flame retardant, various colorants, an antistatic agent, and a release agent can also be added.

For example, the polymer component ((a),
Examples other than (b) and (c) components) include random (especially, styrene-butadiene rubber), graft, and block (especially, styrene-butadiene rubber) containing an alkenyl aromatic compound and a conjugated diene as main monomer components. (Butadiene block-based polymer) and other copolymers that form a bonding mode and partially include a crosslinked structure, or those in which a part of aliphatic unsaturated bonds derived from a conjugated diene is hydrogenated. .

When a composition having a higher Izod impact strength is required, such a copolymer can be added, but the color tends to change when used in a high temperature environment. . Also, as an example of an antioxidant,
Highly sterically hindered phenolic, thioether, phosphorous,
An amine-based stabilizer or the like can be used. In addition, glass fiber,
Addition of wollastonite, calcium carbonate, barium sulfate, titanium oxide, and zinc oxide is remarkably effective in improving heat resistance and the like.

3. Blending Method The composition of the present invention can be produced by using a usual kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a roll, a Brabender plastograph, a kneader and the like.
Usually, the mixture is kneaded with an extruder or the like to form a pellet-shaped compound, and then subjected to processing. In a special case, it is also possible to directly supply all the components to various molding machines and perform molding while kneading with the molding machine. In addition, fillers and other components are kneaded at a high concentration (with various additives as necessary) in advance to form a masterbatch, which is separately diluted with another polymer or the like, and then blend-compounded or molded. You can also. Further, at the time of kneading, an additional filler component may be kneaded with a crystalline polyamide resin in advance and used.

4. Application of the resin composition according to the present invention The molding method using the composition of the present invention is not particularly limited, and is a molding method generally applied to thermoplastic resins, that is, extrusion molding, hollow molding, injection molding, sheet molding, heat molding. It can be easily molded by molding methods such as molding, rotational molding, and lamination molding, but is most suitable for injection molding. Because of its good mechanical properties and dimensional stability, it is suitable for interior and exterior parts of automobiles, exterior parts of electric equipment, and parts such as so-called office automation equipment.

[IV] Experimental Example Measurement and Evaluation Methods The physical property values and various properties in the following Examples and Comparative Examples were measured and evaluated under the following conditions.

1) Flexural modulus ISO R178-1974 Procedure 12
It was measured using an Instron tester according to (JIS K7203). 2) Izod impact strength ISO R180-1969 (JIS K7110)
According to (Izod impact strength with notch), it was measured using an Izod impact tester manufactured by Toyo Seiki Seisaku-sho.

3) Drop weight impact strength A test piece (120 m) set on a support (hole diameter 40 mm)
A dart, which is a load sensor, was dropped (m × 80 mm, thickness 2 mm) (2 m × 7 kgf), and the deformation and fracture behavior of the test piece under an impact load was measured. The dart was absorbed up to the crack generation point in the obtained impact pattern. The impact energy was calculated and used as the impact strength of the material. The measurement atmosphere temperature is 23 ° C and -30 ° C.

4) Organic solvent resistant injection molded specimen (129 mm × 125 mm, thickness 4 mm)
Was immersed in a commercially available gasoline at room temperature for 7 days, and changes in appearance were observed. The case where there was no change in the appearance was rated as ○, the case where surface roughness or whitening occurred, and Δ when the surface roughness or whitening was remarkable.

2. Mixing and kneading of the resin composition A predetermined amount of each component shown in Table 1 was sufficiently mixed and stirred with a super-kimiser, and then melted at a set temperature of 280 ° C. using a PCM twin-screw extruder manufactured by Ikegai Iron Works Co., Ltd. After kneading to obtain a composition, the mixture was extruded in a strand shape and pelletized by a cutter.

3. Preparation of Test Specimen for Measurement and Evaluation of Physical Properties Using an in-line screw type injection molding machine, Model IS-90B manufactured by Toshiba Machine Co., Ltd., injection molding was performed at a cylinder temperature of 280 ° C. and a mold cooling temperature of 60 ° C. to prepare a test piece. Immediately before the injection molding, drying was performed for 48 hours under conditions of 0.1 mmHg and 80 ° C. using a reduced-pressure drier immediately before the injection molding. The injection-molded specimen was placed in a desiccator immediately after molding, left at 23 ° C. for 4 to 6 days, and then measured for physical properties.

4. Description of each component 1) Polyphenylene ether resin (a) Poly (2,6-dimethyl-1,4-phenylene) ether having an intrinsic viscosity of 0.52 dl / g (in chloroform at 30 ° C.) was used. 2) Crystalline polyamide resin (b) Nylon-6,6 (trade name Ultramid A4) and Nylon-6 (trade name Ultramid B4) manufactured by Birdie Shearling Und Soda Acthun Gesellschaft (West Germany) did. 3) Non-crystalline or low-crystalline cyclic hydrocarbon-based copolymer polyamide resin (c) As a cyclic hydrocarbon-based non-crystalline or low-crystalline copolymerized polyamide resin, Novamid X21 manufactured by Mitsubishi Chemical Corporation (glass transition temperature 125 ° C, JIS K6810
A relative viscosity by reference of 2.1 dl / g) was used.

4) Compatibilizer (d) (1) Compound having both an unsaturated group and a polar group in the same molecule Commercially available maleic anhydride (reagent grade) is used (2) Polyethylene oxide wax (PE WAX oxide) Hoechst (3) Using citric acid reagent grade (4) Styrene-maleic anhydride copolymer (St-Mah copolymer) Using Alarco Polymer's Dairak 230

[0051]

[Table 1]

[0052]

[Table 2]

5. Description of Examples and Comparative Examples From the comparison between the respective Examples and Comparative Examples, in a resin composition comprising a combination of polyphenylene ether and polyamide, as a polyamide component, a crystalline polyamide and a non-crystalline or low-crystalline cyclic hydrocarbon as a polyamide component The resin composition formed by combining the copolymerized polyamide is a crystalline polyamide or a non-crystalline or low -crystalline polyamide component.
Compared with each of the resin compositions using a crystalline cyclic hydrocarbon-based copolymer alone, the impact of the present invention is remarkably high, and the effect of the present invention is clear, and the Izod impact The strength level is not significantly reduced when both polyamides are used together. The actual values in Table 1
As is clear from the comparison between Example 1 and Comparative Example 5,
(C) Amorphous aliphatic copolymerized polyamide resin as component
When used, the impact strength is poor and the effect of the present invention
Is not expressed.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Kiyoji Takagi 1 Tohocho, Yokkaichi City, Mie Prefecture Mitsubishi Chemical Research Institute, Inc. (72) Inventor Hironari Sano 1 Tohocho, Yokkaichi City, Mie Prefecture Mitsubishi Chemical Corporation (56) References JP-A-62-270654 (JP, A) JP-A-58-38751 (JP, A) JP-A-57-42761 (JP, A) JP-A-50-108355 (JP, A) , A) Patent 2512450 (JP, B2)

Claims (1)

(57) [Claims] 1. A resin composition comprising the following components (a) to (c). Component (a): 20 to 70% by weight of polyphenylene ether resin Component (b): 29 to 79% by weight of crystalline polyamide resin Component (c): Non-crystalline or low-crystalline ring having a glass transition temperature of 70 to 210 ° C. Hydrocarbon copolymerized polyamide resin 1 to 55% by weight