JPS62177065A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:A thermoplastic resin composition, obtained by blending a polyphenylene ether resin with polyamide and specific modified polyolefin in a specific proportion and having improved impact, heat, weather and chemical resistance and moldability. CONSTITUTION:A thermoplastic resin composition obtained by uniformly blending and melt kneading (A) 5-90wt%, preferably 15-80wt% polyphenylene ether resin, e.g. poly(2,6-dimethyl-1,4-phenylene)ether, etc., with (B) 5-90wt%, preferably 10-80wt% polyamide, e.g. nylon 6, nylon 11, etc., and copolyamide consisting essentially thereof and (C) 5-60wt%, preferably 8-50wt% polyolefin having one or more functional groups selected from the group consisting of carboxylic acid group and acid anhydride group, preferably a polyolefin graft modified with a vinyl based monomer having carboxylic acid (anhydride) group.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention provides impact resistance typified by Izot impact strength,
The present invention relates to a thermoplastic resin composition that has excellent heat resistance as represented by heat distortion temperature, as well as weather resistance, moldability, and chemical resistance.

<Prior Art> Polyphenylene ether resin is widely known to have excellent mechanical properties, electrical properties, heat resistance, etc., but has low impact resistance and poor chemical resistance. Furthermore, high temperatures are required for molding under melting, which causes various undesirable problems such as discoloration and oxidative deterioration.

For this reason, it is generally not used alone,
It is usually used as a modified polyphenylene ether resin composition (for example, US Pat. No. 3,383,435), which is a composition with polystyrene and rubber-modified polystyrene.

This resin composition has improved molding processability of polyphenylene ether, and has impact resistance at a practical level, although it is not sufficient.

In order to improve the impact resistance of a resin composition of polyphenylene ether and rubber-modified polystyrene resin, a method of blending an elastomer (rubber-like elastic body) has been developed (Japanese Patent Publication No. 57-56941, Kaisho 5:3-73
No. 248<@).

However, although such a composition improved FFJ impact strength, it was inferior in kJ m properties and processability, and was not fully satisfactory.

In addition, for the purpose of increasing the impact of polyamide, resin compositions in which polyamide is blended with an olefin polymer having a carboxylic acid group have also been proposed (Japanese Patent Publication No. 12546/1983, Japanese Patent Publication No. 44108/1983). Such).

Resin compositions containing compounds having specific groups such as polyphenylene ether, polyamide, olefin polymers, and acid anhydride groups typified by maleic anhydride have also been proposed (Japanese Unexamined Patent Application Publication No. 1983-1992). -49753).

<Problems to be solved by the invention> However, polyphenylene ether<SJ fat is
If an attempt is made to increase the impact strength by adding a nidistomer component, the heat resistance will decrease, so a polyphenylene ether resin with high impact strength, high heat resistance, and good moldability has not been obtained.

On the other hand, a resin composition composed of polyamide and a carboxylic acid-containing olefin polymer can obtain high strength, but cannot obtain sufficient heat resistance.

In addition, resin compositions containing compounds (not polymers) with specific groups such as polyphenylene ether, polyamide, unmodified olefin polymers, and acid anhydride groups as typified by maleic anhydride have a high impact strength. Although it has been improved, it was not completely satisfactory.

In other words, polyphenylene ether-based or polyamide-based resins with high impact strength, high heat resistance, and good moldability have not yet been obtained, and there is currently a desire to develop resins that have both of these properties. .

As a result of intensive studies aimed at developing a resin with high impact strength, excellent heat resistance, and moldability, the present inventors found that polyphenylene ether, poIJ'7mid, and a specific modified polyolefin were blended in a specific ratio. The inventors have discovered that the above object can be achieved by doing so, and have arrived at the present invention.

<Means for solving the problem> That is, the present invention provides (A) polyphenylene ether 5
~90% by weight, (13) polyamide 5 having at least one functional group selected from the group consisting of polyamide and at least one functional group selected from the group consisting of a diagonal carboxylic acid group and an acid anhydride group.
60% by weight of a thermoplastic resin composition.

The thermoplastic resin composition of the present invention comprises polyphenylene ether (A), polyamide) and modified polyolefin (A).
0 can be obtained by mixing with any method.

The polyphenylene ether (A) constituting the resin composition of the present invention is a polymer obtained by condensation polymerization of monocyclic phenols represented by the general formula (1), and even if it is a homopolymer, A copolymer obtained using two or more of the above monocyclic phenols may also be used.

(In the formula, R1 means a lower alkyl group having 1 to 3 carbon atoms, and R2 and R1 mean a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms.) A monocyclic phenol represented by the general formula (1) above. For example, 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-dipropylphenol, 2-
Methyl-6-ethylphenol, 2-methyl-6-furobylphenol, 2-ethyl-6-7'ropyruphenol, m-cresol, 2,3-dimethylphenol, 2
, 3-diethylphenol, 2,3-dipropylphenol, 2-methyl-3-ethylphenol, 2-methyl-3-furobylphenol, 2-ethyl-3-methylphenol, 2-ethyl-3-propylphenol , 2-
Propyl-3-methylphenol, 2-7' lobi-3
-Ethylphenol, 2.3.6-) Dimethylphenol, 2゜3,6-) Diethylphenol, 2.3.6-
) Dipropylphenol, 2,6-dimethyl-3-ethyl-phenol, 2,6-dimethyl-3-7'l=1pyruphenol, and the like. Polyphenylene ethers obtained by condensation polymerization of these monocyclic phenols include poly(2,6-dimethyl-1,4-)unicine) ether 1. I-'IJ (2゜6-dinityru 1.
4-phenylene) ether, poly(2-methyl-6-nityl)ether.

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-)
Limethylphenol copolymer, 2,6-dimethylphenol/2,3.6-triethylphenol copolymer, 2
, 6-dinitylphenol/2.3.6-)limethylphenol copolymer, 2,6-dipropylphenol/
2.3.6=trimethylphenol copolymer and the like can be exemplified.

Polyamide 1J3) used in the present invention refers to polyamide obtained by open R polymerization of lactams such as ε-caprolactam and ω-dodecalactam, 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, etc. Polyamides derived from amino acids, ethylenediamine, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2.4-72,4.4-1-limethylhexamethylenediamine, ■, 3- and 1.4~aliphatic, alicyclic, aromatic diamines such as bis(aminomethyl)cyclohexane, bis(A,4'-aminocyclohexyl)methane, meta- and para-xylylene diamine and adipic acid, speric acid, sebacin acids, aliphatic, alicyclic, such as dodecanoic acid, l,3- and 1,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, dimer acid,
Polyamides derived from aromatic dicarboxylic acids, copolyamides thereof, and mixed polyamides. Among these, polycaproamide (nylon 6), polyundecaneamide (nylon ll), polydodecanamide (nylon 12), polyhexamethylene adipamide (
Nylon 66) and copolyamides containing these as main components are useful. As a method for polymerizing polyamide, generally known methods such as melt polymerization, in-phase polymerization, and a combination thereof can be employed. Moreover, the degree of polymerization of polyamide is not particularly limited, and the relative viscosity (polymer 1f is mixed with 98% concentrated sulfuric acid 100%
A polyamide having a value (dissolved in *1 and measured at 25°C) of 2.0 to 5.0 can be arbitrarily selected depending on the purpose.

The modified polyolefin used in the present invention (0 is a polyolefin having at least one functional group selected from the group consisting of a carboxylic acid group and an acid anhydride group. Specific examples include ethylene/acrylic acid copolymer, ethylene/
Olefin monomers such as methacrylic acid copolymers, ethylene/fumaric acid copolymers, ethylene/ethyl acrylate/acrylic acid copolymers, ethylene/maleic anhydride copolymers, ethylene/propylene/maleic anhydride copolymers Copolymers of olefin monomers such as polymers and vinyl monomers having carboxylic acid groups or acid anhydride groups, and ethylene-g-maleic anhydride copolymers (IIgI
+ represents graft. same as below. ), ethylene/propylene-g-maleic anhydride copolymer, ethylene/propylene-g-acrylic acid copolymer, ethylene/l-butene-g-maleic anhydride copolymer, ethylene/l-butene-g-fumar e CoM combination, ethylene/I-hexene-g-itaconic acid copolymer, ethylene/propylene/
1,4-hexadiene-g-maleic anhydride copolymer,
Ethylene/propylene/dicyclopentadiene-g-maleic anhydride copolymer, ethylene/propylene/dicyclopentadiene-g-fumaric acid copolymer, ethylene/propylene 15-ethylidene-2-norbornene-g-
Representative examples include fl water'-r leic acid copolymer, ethylene/propylene 15-2f IJ f no-2-norbornene-g-maleic acid copolymer, and ethylene/vinyl acetate to g-acrylic acid copolymer. Examples include polyolefins graft-modified with vinyl monomers having carboxylic acid groups or acid anhydride groups. Among these, polyolefins graft-modified with vinyl monomers having carboxylic acid groups or acid anhydride groups are particularly preferred. It is also possible to use two or more modified polyolefins in combination.

Modified polyolefin (C) can usually be produced by a known method. For example, Japanese Patent Publication No. 59-8299,
It can be manufactured by the method disclosed in Japanese Patent Publication No. 56-9925.

In the thermoplastic resin composition of the present invention, the blending ratio of the polyphenylene ether resin, polyamide (B) and modified polyolefin (C) is such that (A) is 5 to 90% by weight, preferably 15 to 80% by weight, particularly preferably is 20-70
tl'Eri%, (B) is 5 to 90% by weight, preferably 10 to 80% by weight, particularly preferably 15 to 70% by weight and single teeth, and C) is 5 to 60% by weight, preferably 8-50
% by weight, particularly preferably from 10 to 40% by weight and 11%. (
If ~ is less than 5% by weight, the heat resistance and weather resistance will be poor, and the concentration will be 90%.
If it exceeds 1% by weight, the impact resistance and W properties will be poor, and furthermore, the moldability will be lowered, which is not preferable. If (8) is less than 5% by weight or C) is less than 5% by weight, the impact resistance and chemical resistance will be poor, and if (I3) is more than 90% by weight or (C) is less than 60% by weight. If it exceeds it, it is not preferable because the heat resistance will be poor.

There are no particular restrictions on the method for producing the thermoplastic resin composition of the present invention, and generally known methods can be employed. That is, after uniformly mixing polyphenylene ether resin (A), polyamide (B), and modified polyolefin (C) in the form of pellets, powder, or small pieces using a high-speed stirrer or the like, a uniaxial or multiaxial mixer with sufficient cross-talk ability is used. Any method can be employed, such as melt-kneading using an extruder, or melt-kneading using a Banbury mixer or a rubber roll machine. In addition, polyphenylene ether resin (A) and polyamide (B), polyamide (]3) and modified polyolefin C), polyphenylene ether resin (A) and modified polyolefin (0, etc.) are pre-kneaded in advance, and then a predetermined mixture is prepared. A method of adjusting the blending ratio and kneading is also possible.

The thermoplastic resin composition of the present invention optionally contains polystyrene (PS), styrene/acrylonitrile copolymer (SA), polyphenylene ether resin IA), polyamide tB) and modified polyolefin (C).
N), polymethacrylic methyl (PMMA), styrene/methyl methacrylate/acrylonitrile copolymer,
α-methylstyrene/acrylonitrile copolymer,
-11--α-methylstyrene/styrene/acrylonitrile copolymer, α-methylstyrene/methyl methacrylate/acryloni) IJ copolymer, p-methylstyrene/acrylonitrile copolymer, styrene/N-phenylmaleimide copolymers, vinyl polymers such as styrene/maleic anhydride copolymers, acrylonitrile-butadiene-styrene terpolymers (
ABS) resin, methacrylic acid resin-butadiene-styrene terpolymer (MBS) resin, AES resin, AASg
fat, polycarbonate, polybutylene terephthalate,
Thermoplastic resins such as polyethylene terephthalate may be appropriately mixed, or polyethylene 12-ethylene, polypropylene, ethylene/propylene copolymer, ethylene/butene-1 copolymer, ethylene/propylene/dicyclopentadiene copolymer, ethylene/ Propylene 15-ethylidene 2-norbornene copolymer, ethylene/propylene/1,4-hexadiene copolymer,
By appropriately mixing polyolefin rubbers such as ethylene/vinyl acetate copolymer and ethylene/butyl acrylate copolymer, it is also possible to adjust the physical properties and characteristics to more desirable ones.

Depending on the purpose, pigments, dyes, glass fibers, metal fibers,
Reinforcing materials and fillers such as metal flakes and carbon fibers, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, lubricants, plasticizers, antistatic agents, and flame retardants can be added.

<Examples> Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparison Examples. Izotsu impact strength is ASTM D25
6-56, Method A, heat distortion temperature is AST
M D648-56, flexural modulus is ASTfViD79
Measured according to 0-61. The weather resistance was measured using a Sanyain Weatherometer using an Izotsu plate with a notch and a test piece.
It was irradiated for 0 hours and evaluated by measuring the change in Izod impact strength.

Izot strength was measured in an absolutely dry state. The flexural modulus was measured in an absolutely dry state and in a state in which the test piece was immersed in water at 23° C. for 48 hours to absorb water.

Reference 8 Example 1 <Manufacture of polyphenylene ether) 555 parts by weight of 500 parts of a toluene solution containing 3.81 parts of anhydrous (+) copper chloride and 54.5 parts of di-n-butylamine were added to polymerization ↑・h. Toluene solution of xylenol 24
was added and stirred while blowing oxygen into this mixed solution kept at 30° C., thereby carrying out oxidative polymerization of 2,6-quinletool. After polymerization, an acetic acid aqueous solution was added to deactivate the catalyst and stop the reaction. This reaction solution was diluted and methanol was added to precipitate the polymer.

The precipitated polymer was filtered, washed, and dried to produce polyphenylene ether.

Reference υ12 (manufacture of polyamide (B)) The following nylon 6, nylon 66 and nylon 1 were produced by the melt polymerization method.
2 was manufactured.

Nylon 6: ε-caprolactam to concentrated sulfuric acid Relative viscosity 2
．． 75 of nylon 6 was polymerized.

Nylon 66: Nylon 66 having a relative viscosity of 2.60 was polymerized from an equimolar salt of hexamethylene diamine and adipic acid in concentrated sulfuric acid.

Nylon 12: Nylon 12 having a relative viscosity of 235 was polymerized from 12-aminododecanoic acid using concentrated sulfuric acid.

Reference Example 3 (Production of modified polyolefin) C-1:
For 100 parts by weight of an ethylene/furopylene copolymer consisting of 70 mol% ethylene and 30 mol% hyfropylene,
α,α′-bisubf dissolved in a small amount of acetone
/l/ /Z-oxy-p-diisopropylbenzene 0
．． After adding 3 parts by weight of 0.03 parts by weight and 1.0 parts by weight of maleic anhydride, an ethylene/propylene-g-m water mash was prepared by kneading and pelletizing at 230°C using an extruder with a diameter of 40 mm. , leic acid copolymer ("g" represents graft) C-1 was prepared.

C-2: 80 mol% ethylene and 20 mol% propylene To 100 parts by weight of the above ethylene/propylene copolymer, 0.1 part by weight of di-t-butyl peroxide dissolved in a small amount of acetone and 1.0 parts by weight of acrylic acid. After adding 0 parts by weight, ethylene/propylene-g-acrylic acid copolymer C-2 was obtained by kneading and pelletizing at 200°C using an extruder with a diameter of 40 mm in the same manner as C-1. Manufactured.

C-3: Ethylene-propylene-5-ethylidene-2-norbornene (EPD) with a Mooney viscosity of 60 and an iodine value of 12.
IVf) Terpolymer (ethylene/propylene-68,
5/31.5 (molar ratio)) After adding 0.1 part by weight of di-t-butyl peroxide and 0.5 parts by weight of maleic anhydride dissolved in a small amount of acetone to 100 parts by weight, Similar to C-1, EP was produced by kneading and pelletizing at 230°C using an extruder with a diameter of 40flφ.
DM-g-maleic anhydride copolymer C-3 was produced.

Example 1 Polyphenylene ether (5), polyamide (B), and modified polyolefin (0) produced on the reference side were mixed at the compounding ratio shown in Table 1, melt-kneaded using an extruder with a diameter of 40 MMφ, and then pelletized. did.

The extrusion temperature was 280°C. Next, the pellets were dried in vacuum, and then injection molded to form test pieces for measuring physical properties. During injection molding, the cylinder temperature was set at 280°C. The mold temperature was set at 80°C.

The measurement results are shown in Table 1.

Comparative Example Polyphenylene ether (A), polyamide (T)) produced in Reference Example and modified bodyolefin (0) and the following polyolefins were mixed at the blending ratio shown in Table 1, and the physical properties were measured in the same manner as in Example 1. did.

The measurement results are shown in Table 1.

Polyolefin C-4: Ethylene/propylene copolymer consisting of 70 mol% ethylene and 30 mol% yohypropylene C-5: Ethylene-propylene-5-ethylidene-2-norbornene (EPD) having a Mooney viscosity of 60 and an iodine value of 12.
IVI) Terpolymer (ethylene/propylene = 68
．． 5/31.5 (molar ratio)) The following is clear from the results of Example I and Comparative Example.

The resin composition (Al-13) of the present invention has high isot impact strength, high heat distortion temperature, and high flexural modulus, and has improved moldability. Further, the Izot impact strength hardly decreases even after 400 hours of irradiation with a sunshine weatherometer, and the weather resistance is also excellent. Furthermore, the flexural modulus maintains a relatively high value even after water absorption treatment.

That is, the resin composition of the present invention is a right-eye sebum composition that has high impact strength, high rigidity, high heat resistance, and excellent weather resistance. On the other hand, as is clear from the comparative example, polyphenylene ether (A) containing no polyamide and modified polyolefin (C
) The four-fat composition (cup 14) consisting only of the following has high impact strength and heat deformation temperature, but high melting viscosity and poor moldability.

In addition, resin compositions (!15, 16) consisting only of polyamide (B) that does not contain polyphenylene ether (A) and modified polyolefin (!15, 16) have a good balance between flexural modulus and impact strength. The flexural modulus decreases significantly due to water absorption. Furthermore, it has drawbacks such as low heat distortion temperature under high loads (18,5619/cI).
A resin composition consisting only of polyphenylene ether and polyamide CB) without V polyolefin
17) has extremely low surface impact strength. The composition containing more than 60% by weight of modified polyolefin (cup 18) has a low flexural modulus. When the modified polyolefin does not have a carboxylic acid group or an acid anhydride group (A19°20), the impact strength is extremely low.

Example 2 The polyphenylene ether powder, polyamide (B), modified polyolefin C) produced in the bag example and the polyolefin rubbers (C-4 and C-5) shown in the comparative example were mixed at the compounding ratio shown in Table 1. , Product 1 was measured in the same manner as in Example 1.

The measurement results are shown in Table 1.

Polyphenylene ether (A), polyamide (J3) and modified polyolefin (in addition to 0, Ethyre-21
= Propylene copolymer rubber (EPR), ethylene/propylene copolymer rubber (EPR),
Even if a polyolefin rubber such as propylene/non-conjugated diene copolymer comb (EPDM) is mixed, a desirable resin composition with improved impact strength, flexural modulus, heat resistance and weather resistance can be obtained.

<Effects of the Invention> The resin composition of the present invention has excellent impact resistance, rigidity, heat resistance, weather resistance, and moldability.

Claims (1)

[Claims] (A) polyphenylene ether resin 5 to 90% by weight, (
B) Thermoplastic consisting of 5-90% by weight of polyamide and (C) 5-60% by weight of modified polyolefin having at least one functional group selected from the group consisting of carboxylic acid groups, carboxylic acid metal bases and acid anhydrides. Resin composition.