JPH02202947A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition retaining heat resistance inherent in nylon 46 resin and having an impact strength higher than that of this resin by mixing a nylon 46 resin with a modified polyphenylene oxide resin and a polymer having rubber elasticity in a specified ratio. CONSTITUTION:This resin composition comprises 100 pts.wt. nylon 46 resin, 5-300 pts.wt. polyphenylene oxide resin of formula I (wherein R1, R2, R3 and R4 are each a hydrogen atom, a halogen atom, a hydrocarbon group or a substituted hydrocarbon group; and n is an integer >=50), and 5-200 pts.wt. polymer having rubber elasticity. The polyphenylene oxide resin is one modified with 0.05-10 pts.wt., per 100 pts.wt. resin, compound having at least one group selected from among carboxyl, metal carboxylate, carboxylic ester, carboxylic anhydride and imide groups and a C-C double bond and 0.005-2 pts.wt., per 100 pts.wt. resin, 2,3-dimethyl-2,3-diphenylbutane.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a resin composition, and more particularly to a nylon 46 resin that exhibits excellent heat resistance and high impact strength.

[Prior art] Nylon 46 obtained from tetramethylene diamine or its functional derivative and adipic acid or its functional derivative
resin is known.

This nylon 46 resin has excellent mechanical strength such as tensile strength 2 bending strength, as well as excellent heat resistance and sliding properties, and is therefore considered to have great utility as a useful engineering plastic. However, nylon 4
Similar to other polyamide resins such as nylon 6 resin and nylon 66 resin, the impact strength of 6 resin shows very excellent properties when moisture is absorbed, but the properties when dry are not necessarily at a satisfactory level. This is a particularly important issue, for example, in applications where the excellent heat resistance of nylon 46 resin is utilized in high-temperature atmospheres, or when post-processing is performed on molded products immediately after injection molding of nylon 46 resin. This is undesirable because it requires a humidity conditioning process for the molded product, making it complicated to handle during production and processing.

Separately from this problem, it is known that as a means to improve the impact strength of polyamide resins, it is possible to incorporate various components having impact absorption ability. These include modified polyolefins, such as ionomer resins made by ionizing ethylene-methacrylic acid copolymers with Ha, Zri, Mg, etc. (U.S. Pat. No. 3,845,163), and ethylene-methacrylic acid copolymers.
A method of blending EPDM (US Pat. No. 4,174,358 M) in which maleic anhydride is grafted onto a propylene-diene copolymer, or a method of modifying polyolefin and polyamide,
A method of alloying to increase compatibility with rubber components, for example, a method of grafting maleic anhydride to an ethylene-propyl non-diene copolymer (Japanese Patent Application Laid-Open No. 70254/1982)
.

Polypropylene mixed with maleic anhydride in graph 1 (Japanese Patent Publication No. 55-20500), acrylic ester copolymer (Japanese Patent Publication No. 47-6284), and rubber-modified styrene-maleic anhydride copolymer and polyamide graft copolymer (JP-A No. 56-50931, No. 56-53
Many studies have been made, including methods using methods such as No. 134).

When trying to increase the impact strength by blending these modified polyolefins into nylon 46 resin,
Nylon 46 resin has a melting point of approximately 290°C, and its molding temperature is as high as 300°C or higher, so the heat resistance of the modified polyolefin is insufficient, causing the modified polyolefin to decompose, and the melt viscosity is high. Because of the difference, there are problems such as difficulty in uniformly dispersing them in the nylon 46 resin, so there are major restrictions on their types and amounts. Furthermore, even when it can be blended into nylon 46 resin, it has the disadvantage that the excellent properties of nylon 46 resin, such as heat resistance and elastic modulus expressed by heat distortion temperature, are significantly reduced.

Recently, attempts have been made to obtain materials with excellent mechanical properties and heat resistance by blending polyphenylene ether resins and rubber components with ordinary polyamide resins such as nylon 6 and nylon 66. 62-2469
57.62-232455.62-209165.62
-177085゜62-187747.62-2706
54.62-273254.62-277465゜62
-257957.83-130658.63-1306
59.63-33471゜63-10655.63-1
0656.63-24()345.63-202651
．． 63-202652.63-205350.63-2
t)7849.63-207850.63-21576
6, 63-215767, 63-161053.63-
178161.63-26775.63-89567,
63-95262.63-108056.63-686
63, 63-8139.63-48358.63-54
427.63-61047゜63-61049.63-
It is recognized in many publications such as Publication No. 27557. However, although the compositions disclosed in these documents are improved to some extent in impact strength, they cannot be said to be satisfactory in heat resistance as expressed by heat distortion temperature. For example, when attempting to utilize the impact strength of these compositions to apply them to automobile exterior panels, it is hard to say that they have resin performance that allows on-line coating on the premise of integral coating with steel plates.

Also, an example of blending polyphenylene ether resin and modified rubber component with nylon 46 resin (Japanese Patent Application Laid-Open No. 62-25365
Although the high heat resistance of nylon 46 resin has been demonstrated, there is still room for improvement in its impact strength.

[Object of the invention] The present invention was made against the background of the above-mentioned circumstances, and
The purpose is to maintain the excellent heat resistance of nylon 46 resin while improving its impact strength.

[Structure of the Invention] As a result of intensive research to improve the impact strength of nylon 46 resin, the present inventors blended a specific amount of polyphenylene ether modified with a specific compound and a polymer with rubber elasticity into nylon 46 resin. The present invention was achieved based on the finding that the above-mentioned composition meets the above-mentioned objectives.

That is, the resin composition of the present invention includes (A) nylon 46 resin 1
00 parts by weight, (B) 5 to 300 parts by weight of the polyphenylene ether resin represented by maximum (1) above, and (
C) In a composition consisting of 5 to 200 parts by weight of a polymer having rubber elasticity, 100 parts by weight of polyphenylene ether resin
Per part by weight, 0.05 to 1011 parts of a compound having at least one of a carboxylic acid group, a carboxylic acid metal base, a carboxylic ester group, a carboxylic acid anhydride group, and an imide group and a carbon-carbon double bond. and 2,3-dimethyl-2
, 3-diphenylbutane o, oos to 2 parts by weight.

The nylon 46 resin as component (A) used in the present invention is mainly intended for polyamides obtained by a condensation reaction using adipic acid or a functional derivative thereof as an acid component and tetramethylene diamine or a functional derivative thereof as an amine component. However, a part of the adipic acid component or tetramethylene diamine component may be replaced with another copolymer component.

A preferred embodiment of the method for producing nylon 46 resin is disclosed in JP-A-56
-149430 publication and JP-A-56-149431
It is stated in the No.

The intrinsic viscosity of the nylon 46 resin used in the present invention is m-
1.00 to 1 when measured at 35°C using cresol
．． 90, more preferably in the range of 1.10 to 1.50.

When a nylon 46 resin with an intrinsic viscosity exceeding 1.90 is used, the effect of improving the fluidity of the composition is weak, and the resulting molded product not only loses its luster in appearance but also suffers from variations in its mechanical and thermal properties. This is not preferable because it increases the size.

On the other hand, if the intrinsic viscosity is lower than i, oo, the mechanical strength of the composition becomes low.

The polyphenylene ether resin as component (B) used in the present invention is a polymer represented by the above-mentioned -maximum (I>), which is obtained by condensation polymerization of monocyclic phenols represented by the following formula (n>). It may be a homopolymer or a copolymer obtained by using two or more of the above monocyclic phenols.

Examples of the monocyclic phenol represented by maximum (I) include 2,6-dimethylphenol, 2゜6-diethylphenol, 2,6-dipropylphenol, 2-methyl-6-ethylphenol, 2-methyl -6-propylphenol, 2-ethyl-6-propylphenol,
m-cresol, 2゜3-dimethylphenol, 2,3
-diethylphenol, 2,3-dipropylphenol, 2-methyl-3-ethylphenol, 2-methyl-3
-propylphenol, 2-ethyl-3-methylphenol, 2-ethyl-3-propylphenol, 2-propyl-3-methylphenol, 2-propyl-3-ethylphenol, 2,3.6-trimethylphenol,
Examples include 2,3.6-triethylphenol, 23.6-doliprobylphenol, 22,6-dimethyl-3-ethylphenol, and 2,6-dimethyl-3-propylphenol. Polyphenylene ethers obtained by condensation polymerization of these monocyclic phenols include poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene)
Ether, poly(2,6-diprobyl-1,4-phenylene)ether, poly(2-methyl-6-ethyl-1,
4-phenylene) ether, poly(2-methyl-6-broby-1,4-phenylene) ether, poly(2-ethyl-6-broby-1,4-phenylene) ether,
2,6-dimethylphenol/2,3.6-trimethylphenol copolymer, 2,6-dimethylphenol/
2,3.6-driethylphenol copolymer, 2.15
-diethylphenol/2.3.6-trimethylphenol copolymer, 2,6-diprobylphenol/2,3
．． Illustrative examples include 6-drimethylphenoful copolymer.

The degree of polymerization of this polyphenylene ether resin is 50 or more. The compositions obtained with a degree of polymerization lower than this do not exhibit sufficient mechanical properties.

The polyphenylene ether resin of component (B) is a compound having at least one of a carboxylic acid group, a carboxylic acid metal base, a carboxylic ester group, a carboxylic acid anhydride group, and an imide group and a carbon-carbon double bond. It is modified with 2,3-dimethyl-2,3-diphenylbutane. Examples of the former include maleic anhydride, maleic acid,
fumaric acid.

Maleimide, maleic hydrazide, reaction product of maleic anhydride and diamine, maleic acid amide.

Natural oils and fats such as soybean oil, sesame oil, rapeseed oil, peanut oil, camellia oil, olive oil, coconut oil, sardine oil, acrylic acid, butenoic acid, crotonic acid, vinyl acetic acid.

Methacrylic acid, pentenoic acid, angelic acid, tibric acid, 2-pentenoic acid, 3-pentenoic acid, α-ethyl acrylic acid, β-methylcrotonic acid, 4-pentenoic acid, 2-hexenoic acid, 2-methyl-2- Pentenoic acid, 3-methyl-
2-pentenoic acid, α-ethylcitonic 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-tetradecenoic acid, 9-hexadenoic acid.

2-octadecenoic acid, 9-octadecenoic acid, icosenoic acid, tocosenoic acid, erucic acid, tetracosenoic acid, mycolibenic acid, 2.4-pentadienoic acid, 2゜4-hexadienoic acid, diallylacetic acid, geranic acid, 2.4- Decadienoic acid, 2,4-dodecadienoic acid.

9.12-Hexadecadienoic acid, 9j2-octadecadienoic acid, hexadecatrienoic acid, linoleic acid, lylunic acid, octadecatrienoic acid, icosadienoic acid, icosaterienoic acid, icosatetraenoic acid, ricinoleic acid, eleo Unsaturated carboxylic acids such as stearic acid, oleic acid, icosapentaenoic acid, erucic acid, docosadienoic acid, docosatrienoic acid, docosatetraenoic acid, docosapentaenoic acid, tetracosenoic acid, hexacosenoic acid, hexacosenoic acid, oftacosenoic acid, traaconthenic acid, and their esters, acid amides, anhydrides, etc.

Further, these compounds may contain two or more of the above-mentioned functional groups and/or carbon-carbon double bonds,
Furthermore, two or more types of compounds may be used simultaneously.

Any method can be used for modification with one or more compounds selected from these compounds and 2,3-dimethyl-2,3-diphenylbutane, but usually these compounds are melted in an extruder. This can be easily done by kneading.

Peroxides are often used to modify polyphenylene ethers and olefin-based polymers for similar purposes. This peroxide can efficiently achieve its purpose under relatively mild conditions of 150 to 250°C, but when modifying polyphenylene ether resin or compounding with nylon 46 resin, the temperature of the molten resin is low. 300℃
As a result, at such high temperatures, highly reactive peroxides not only decompose in an extremely short time, but the generated radical species also attack polymers, causing crosslinking and gelation. . In addition, peroxide itself has many problems, including the need to be careful when handling it because it has the risk of explosion.

In contrast, the 2,3-dimethyl-
2,3-diphenylbutane starts the reaction at a high temperature of 200°C or higher and does not cause side reactions.

Carboxylic acid groups, carboxylic acid metal bases, carboxylic acid ester groups used for modifying polyphenylene ether resins,
The compounding amount of the compound having both a carbon-carbon double bond and at least one of a carboxylic acid anhydride group and an imide group and 2,3-dimethyl-2,3-diphenylbutane is 10 (weight) of the polyphenylene ether resin. Per department, the former is O, OS
~10 parts by weight, the latter being ~2 parts by weight.

The former compound is not preferred because when the amount is less than 0 parts by weight of O, OS, the effect of modification is small, and when it exceeds 10 parts by weight, it causes a decrease in the molecular weight of the polymer, including polyphenylene ether resin and nylon 46 resin. . Furthermore, if the amount of 2,3-dimethyl-2,31 diphenylbutane is less than o or oos parts by weight, the modification will not be carried out at all, and if it exceeds 2 parts by weight, the effect will no longer be promoted by increasing the amount. It is no longer necessary because it will no longer occur.

The amount of polyphenylene ether resin modified by such means is 5 parts per 100 parts by weight of nylon 46 resin.
~300 parts by weight. Heat resistance of the composition obtained when the blending amount is less than 5 parts by weight.

In particular, the heat deformation temperature decreases and the excellent characteristics of nylon 46 resin are lost, and when the amount exceeds 300 parts by weight, the melt viscosity of the composition increases, resulting in disadvantages such as decreased moldability.

In the present invention, the polymer having rubber elasticity as component (C) is ethylene-α-olefin copolymer, ethylene-α-
Olefin-polyene copolymer, ethylene-acrylic copolymer, styrene-isoprene copolymer, acrylonitrile-butadiene copolymer, styrene-butadiene block copolymer.

Examples include styrene-isoprene block copolymers, hydrogenated styrene-butadiene block copolymers, styrene craft ethylene-propylene elastomers, ethylene ionomers, and derivatives thereof. These polymers, of course, have carboxylic acid groups, carboxylic acid metal bases, and carboxylic ester groups.

It may be modified with a compound having at least one of a carboxylic acid anhydride group and an imide group and a carbon-carbon double bond, and examples of modification methods include copolymerization and the above-mentioned modification of polyphenylene ether resin. There are similar methods.

The amount of component (C), a polymer having rubber elasticity, is 5 to 200 parts by weight per 100 parts by weight of nylon 46 resin. When the amount is less than 5 parts by weight, no effect of improving impact resistance is exhibited, and when it exceeds 200 parts by weight, the heat resistance of the composition is significantly lowered.

By blending component (C), a polymer with rubber elasticity, into the nylon 46 resin, its impact resistance is greatly improved, but when it is blended alone, the heat resistance, especially the heat distortion temperature, decreases. Nylon 46 resin has an extremely high heat distortion temperature of approximately 230°C, and can be distinguished from general polyamide resins (nylon 6, nylon 66, etc.), so a decrease in this heat distortion temperature indicates its characteristics. You will lose it. However, by blending a modified polyphenylene ether resin, the high heat distortion temperature can be recovered while maintaining the impact resistance. This is a higher level than that achieved with a similar composition using general polyamide, resulting in a composition that takes advantage of the excellent heat resistance of nylon 46 resin.

Pigments and other compounding agents may be added to the resin composition of the present invention in the desired amount. Such additives include fillers such as glass fibers.

Fibrous materials such as carbon fibers, aromatic polyamide fibers, potassium titanate fibers, steel fibers, ceramic fibers, boron whiskers, etc.: fibers, silica, talc, calcium carbonate, glass peas, glass flakes, clay,
Examples include inorganic fillers in the form of a single powder or a plate, such as wollastonite.

These fillers are usually blended as surface modifiers of the reinforcing material 2 or for the purpose of modifying electrical, thermal, and other properties, but adding them to the minimum amount to achieve effects and adding too much to the original composition It should be blended within a range that does not impair the excellent properties and molding advantages.

Furthermore, flame retardants such as halogen-containing compounds such as brominated biphenyl ether, brominated bisphenol-A diglycidyl ether and their oligomers, such as polycarbonate oligomers prepared from dibrominated bisphenol-A as raw materials; red phosphorus.

It is possible to add phosphorus compounds such as triphenyl phosphate; phosphorus-nitrogen compounds such as phosphonic acid amides; flame retardant aids such as antimony trioxide, zinc borate, etc. In addition, for the purpose of improving heat resistance, antioxidants or heat stabilizers such as hindered phenol compounds, organic phosphorus compounds, sulfur compounds, etc. can also be added. Furthermore, various epoxy compounds may be added for the purpose of improving melt viscosity stability and hydrolysis resistance. Epoxy compounds include, for example, bisphenol A type epoxy compounds obtained by reacting bisphenol A and epichlorohydrin, various glycols, aliphatic glycidyl ethers obtained by reacting glycerol and epichlorohydrin, novolak type epoxy compounds, aromatic or aliphatic carbon Acid type epoxy compounds and alicyclic compound type epoxy compounds obtained from alicyclic compounds are preferred, and particularly preferred epoxy compounds include bisphenol A type epoxy compounds and diglycidyl ether of low molecular weight polyethylene glycol.

Other stabilizers 9 Colorants, antioxidants, lubricants, ultraviolet absorbers, and antistatic agents can also be added.

In addition, other thermoplastic resins such as styrene resin, acrylic resin, polyethylene, polypropylene,
Fluoroplastics and other polyamide resins.

Polycarbonate 1 - Resin, polysulfone, etc.: Thermosetting resin, such as phenol resin, melamine resin.

Unsaturated polyester resins, silicone resins, etc. may also be added.

Any blending method can be used to obtain the resin composition of the present invention.

Generally, it is preferable to disperse these ingredients more uniformly, all or part of them simultaneously or separately, for example, in a blender, kneader, or roll. A method of mixing and homogenizing using a mixer such as an extruder, or a method of mixing some of the mixed components simultaneously or separately using a blender, kneader roll, extruder, etc., and then adding the remaining components using these mixers or A method of mixing and homogenizing using an extruder can be used. Furthermore, there is a method in which a pre-triblended composition is melt-kneaded in a heated extruder to homogenize it, and a method in which it is extruded into a wire shape and then cut into a desired length and granulated. The molding composition thus prepared is normally kept in a sufficiently dry state before being put into a molding machine hopper and subjected to molding. Furthermore, it is also possible to tri-blend the constituent raw materials of the composition, directly charge the mixture into the hopper of a molding machine, and melt-knead the mixture in the molding machine.

[Example] The present invention will be explained in detail with reference to Examples below.

In addition, various characteristics in the examples were measured by the following methods.

(1) Static strength: Bending test...AST) I 0-790 or equivalent to Vi
j! ,.

Impact strength...AST) D-256 (with isotnotch) (2) Heat distortion temperature: Measured with ASTHD...648 at a load of 264 psi.

Polyphenylene ether anhydrous cuprous chloride 3.8g and di-n-butylamine 54g,
A toluene solution of 55% 2,6-xylenol was placed in a polymerization tank containing 500% toluene solution of 2,6-xylenol.
1 was added thereto, and the mixed solution kept at 30°C was stirred while blowing oxygen to carry out oxidative polymerization of 2,6-xylenol. After polymerization, a moderating acid aqueous solution was added to deactivate the catalyst and stop the reaction.

This reaction solution was concentrated and methanol was added to precipitate the polymer. The precipitated polymer was filtered, washed, and dried to produce polyphenylene ether. The intrinsic viscosity was 0.49.

Polyphenylene ether 100 parts by weight of the above polyphenylene ether dried at 130° C. for 5 hours, 0.6 parts by weight of anhydrous maleic M, and 2.
0.1 part by weight of 3-dimethyl-2,3-diphenylbutane was melt-kneaded at 280 DEG C. using an extruder with a diameter of 68 mm, and then pelletized.

PDM Tafmer A4085 (manufactured by Mikata Petrochemical) was used.

Maleic anhydride 0 per 100 parts by weight of Tafmer^4085
．． 6 parts by weight and 0.1 parts by weight of 2,3-dimethyl-2,3-diphenicibutane were melt-kneaded at 220 DEG C. in the same manner as in the production of modified polyphenylene ether, and then pelletized.

Examples 1-2 and Comparative Examples 1-4 Nylon 46 resin (rsTANYLJ Netherlands DSM
company).

Modified or unmodified polyphenylene ether resin dried at 130°C for 5 hours and modified or unmodified EPDM were mixed uniformly in a tumbler in the proportions shown in Table 1, and then mixed in a 44 mm diameter twin screw extruder. Barrel temperature used: 32
The mixture was melted and kneaded at 0° C. while drawing a vacuum from the vent, and the thread discharged from the die was cooled and cut to obtain a pellet for molding.

Next, this pellet was used in an ounce injection molding machine at a cylinder temperature of 300°C and an injection pressure of 800 Kg/Cm2.
A test piece for measuring characteristics was molded under the following conditions: a mold temperature of 120° C., a cooling time of 15 seconds, and a total cycle time of 35 seconds.

Static strength and heat distortion temperature were measured using this test piece. After molding, the test piece was stored in a desiccator and used for testing.

These results are shown in Table-1.

Nylon 46 resin itself has a high heat distortion temperature, but when EPDM is added to increase its impact strength, the heat distortion temperature is significantly lowered (Comparative Examples 1 to 3). When a polyphenylene ether resin is added to this system, the heat distortion temperature recovers when it is unmodified, but the impact strength is extremely low (Comparative Example 4)aHowever, when a modified polyphenylene ether resin is used, the impact strength is greatly improved; The effect is further expanded by modifying EPDM (Examples 1 and 2).

Comparative Example 5 Pellets 1 to 1 were prepared in the same manner as in Examples 1 and 2, except that the extrusion and molding temperature was 280°C using nylon 66 resin (Leona 13003 J Asahi Kasei Kogyo ■!l).

Characteristics were measured.

When Filon 66 is used, its heat resistance is comparable to that of Nylon 4.
Since it is inferior to No. 6, only compositions with low heat distortion temperatures can be obtained (Table 1).

Claims (1)

[Claims] (A) per 100 parts by weight of nylon 46 resin, (B) 5 to 300 parts by weight of polyphenylene ether resin represented by the following general formula (I), and ▲numerical formula, chemical formula, table, etc.▼... (I) [wherein R_1, R_2, R_3, and R_4 are each independently selected from hydrogen, halogen, a hydrocarbon group, and a substituted hydrocarbon group, and n is an integer of 50 or more. ](
C) A composition comprising 5 to 200 parts by weight of a polymer having rubber elasticity, the composition comprising 100 parts by weight of a polyphenylene ether resin.
0.05 to 10 parts by weight of a compound having at least one of a carboxylic acid group, a carboxylic acid metal base, a carboxylic ester group, a carboxylic acid anhydride group, and an imide group and a carbon-carbon double bond and 2,3-dimethyl-2,
A resin composition modified with 0.005 to 2 parts by weight of 3-diphenylbutane.