JPH072873B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention has a balance of impact resistance represented by impact strength, rigidity represented by flexural modulus, heat resistance represented by heat distortion temperature, and weather resistance. And an excellent thermoplastic resin composition.

<Prior art> Acrylonitrile-butadiene-styrene terpolymer resin (ABS resin) and methyl methacrylate-butadiene-styrene terpolymer resin (MBS resin) are widely used as typical impact-resistant resins. Used in the field. As a resin having improved weather resistance of these resins, an acrylonitrile-styrene graft copolymer resin (AES resin and AAS resin) using ethylene-propylene rubber or acrylic rubber as a base rubber is also used.

On the other hand, a resin composition in which a carboxylic acid-containing olefin polymer is blended with polyamide has also been proposed for the purpose of increasing the impact of polyamide. (Japanese Patent Publication No. 42-12546, Japanese Patent Publication No. 55-4
4018 bulletin etc. ) <Problems to be solved by the invention> However, the impact-resistant resin represented by ABS resin has poor weather resistance, and when the impact strength is increased, the flexural modulus decreases, resulting in high impact resistance. However, it is not possible to obtain a highly rigid resin. Although AES resin and AAS resin have improved weather resistance, they cannot achieve high impact resistance and high rigidity like ABS resin.

A resin composition comprising a polyamide and a carboxylic acid-containing olefin polymer can obtain high impact strength, but cannot obtain a sufficient flexural modulus. In addition, the resin composition has a drawback that the flexural modulus is further significantly reduced due to moisture absorption. A resin composition comprising an imidized acrylic resin and a polyamide has also been proposed for the purpose of obtaining a good flexural modulus (Japanese Patent Laid-Open No. 58-208348), but the resin composition has a sufficiently high impact. You cannot get strength.

That is, a resin having high impact resistance, high rigidity, high heat resistance, and excellent weather resistance has not yet been obtained, and under the present circumstances, the development of a resin having these properties is desired.

The present inventors have conducted intensive studies for the purpose of developing a resin having a high impact strength and a high flexural modulus, and having excellent heat resistance and weather resistance. As a result, polyglutarimide, polyamide, and a specific modified polyolefin have been identified. The inventors have found that the above objects can be achieved by blending in a ratio, and have reached the present invention.

<Means for Solving Problems> That is, the present invention provides at least one functional group selected from the group consisting of (A) polyglutarimide, (B) polyamide and (C) carboxylic acid group and acid anhydride group. (A) is 5 to 90% by weight, and (B) is 5 to 5% by weight.
The present invention provides a thermoplastic resin composition obtained by mixing 90% by weight and (C) in a ratio of 5 to 60% by weight.

The thermoplastic resin composition of the present invention is obtained by mixing polyglutarimide (A), polyamide (B) and modified polyolefin (C).

The polyglutarimide (A) used in the present invention is a polymer or copolymer containing a cyclic imide unit represented by the following formula (I).

(However, each of R ₁ , R ₂ and R ₃ in the formula represents hydrogen or a substituted or unsubstituted alkyl group or aryl group having 1 to 20 carbon atoms.) Any chemical structure can be used as long as it contains the above cyclic imide unit. Although it can be applied to the present invention even a polyglutarimide, usually R ₁ and R ₂ in the cyclic imide unit is hydrogen or a methyl group, R ₃ is hydrogen, a methyl group, an ethyl group, Those which are propyl, butyl or phenyl groups are commonly used. Further, the production method of polyglutarimide is not particularly limited, for example, polymethyl methacrylate described in JP-A-52-63989 and ammonia or primary amines such as methylamine and ethylamine are reacted in an extruder, A method of forming a glutarimide ring is useful.

The polyamide (B) used in the present invention is a polyamide obtained by ring-opening polymerization of lactams such as ε-caprolactam and ω-dodecalactam, 6-aminocaproic acid,
Polyamides derived from amino acids such as 11-aminoundecanoic acid and 12-aminododecanoic acid, ethylenediamine,
Tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,
2,4- / 2,4,4-trimethylhexamethylenediamine, 1,3
-And 1,4-bis (aminomethyl) cyclohexane,
Aliphatic, alicyclic and aromatic diamines such as bis (4,4′-aminocyclohexyl) methane, meta and paraxylylenediamine and adipic acid, speric acid, sebacic acid,
Dodecanedioic acid, 1,3- and 1,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, polyamides derived from aliphatic, alicyclic, aromatic dicarboxylic acids such as dimer acid and copolyamides thereof, It is a mixed polyamide. Of these, polycaproamide (nylon 6) and polyundecane amide (nylon 1) are usually used.
1), polydodecanamide (nylon 12), polyhexamethylene adipamide (nylon 66) and copolyamides containing these as the main components are useful. As a method for polymerizing the polyamide, generally known melt polymerization, solid phase polymerization and a combination of these methods can be adopted. The polymerization degree of polyamide is not particularly limited, and the relative viscosity (polymer 1 g is 98%
A polyamide dissolved in 100 ml of concentrated sulfuric acid and measured at 25 ° C) within the range of 2.0 to 5.0 can be arbitrarily selected according to the purpose.

The modified polyolefin (C) used in the present invention 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 olefinic monomers such as ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer, ethylene / fumaric acid copolymer, ethylene / ethyl acrylate / acrylic acid copolymer, ethylene / anhydrous. Copolymers of olefinic monomers represented by maleic acid copolymers, ethylene / propylene / maleic anhydride copolymers and the like, and vinylic monomers having a carboxylic acid group or an acid anhydride group, and ethylene- g-maleic anhydride copolymer (“g” represents a graft; the same applies hereinafter), ethylene / propylene-g-maleic anhydride copolymer, ethylene / propylene-g-acrylic acid copolymer, ethylene / 1 -Butene-g
-Maleic anhydride copolymer, ethylene / 1-butene-g-
Fumaric acid copolymer, ethylene / 1-hexene-g-itaconic acid copolymer, ethylene / propylene / 1,4-hexadiene-g-maleic anhydride copolymer, ethylene / propylene / dicyclopentadiene-g-anhydrous Maleic acid copolymer, ethylene / propylene / dicyclopentadiene-g
-Fumaric acid copolymer, ethylene / propylene / 5-ethylidene-2-norbornene-g-maleic anhydride copolymer, ethylene / propylene / 5-ethylidene-2-norbornene-g-maleic acid copolymer, ethylene / Examples thereof include polyolefin, which is graft-modified with a vinyl-based monomer having a carboxylic acid group or an acid anhydride group, such as a vinyl acetate-g-acrylic acid copolymer. Among these, polyolefin which is graft-modified with a vinyl monomer having a carboxylic acid group or an acid anhydride group is particularly preferable. It is also possible to use two or more types of the above modified polyolefins in combination.

The modified polyolefin (C) can be usually produced by a known method. For example, Japanese Patent Publication No. 59-8299, Japanese Patent Publication No. 5
It can be produced by the method shown in Japanese Patent Publication No. 6-9925.

In the thermoplastic resin composition of the present invention, the compounding ratio of polyglutarimide (A), polyamide (B) and modified polyolefin (C) is (A) 5 to 90% by weight, preferably 15
To 80% by weight, particularly preferably 20 to 70% by weight, (B) is 5
~ 90% by weight, preferably 10-80% by weight, particularly preferably
15 to 70% by weight and (C) are 5 to 60% by weight, preferably 8 to 50% by weight, particularly preferably 10 to 40% by weight.
If (A) is less than 5% by weight, heat resistance and rigidity are poor, and (A)
Is more than 90% by weight, the impact resistance is poor, which is not preferable. If (B) is less than 5% by weight or (C) is less than 5% by weight, impact resistance is poor, and if (B) exceeds 90% by weight or (C) exceeds 60% by weight, rigidity is high. Is inferior, which is not preferable.

The method for producing the thermoplastic resin composition of the present invention is not particularly limited, and a generally known method can be adopted.
That is, polyglutarimide (A), polyamide (B)
And the modified polyolefin (C) are uniformly mixed in pellets, powders, pieces, etc. using a high-speed stirrer, and then melt-kneaded with a uniaxial or multiaxial extruding group having sufficient kneading ability, and a Banbury mixer or Various methods such as a method of melt kneading using a rubber roll machine can be adopted. Further, the polyglutarimide (A) and the polyamide (B), the polyamide (B) and the modified polyolefin (C), the polyglutarimide and the modified polyolefin (C), and the like are pre-kneaded in advance and adjusted to a predetermined compounding ratio later. A method of kneading is also possible.

The thermoplastic resin composition of the present invention comprises, in addition to polyglutarimide (A), polyamide (B) and modified polyolefin (C), polystyrene (PS), styrene / acrylonitrile copolymer (SAN), poly Methyl methacrylate (PMMA), styrene / methyl methacrylate / acrylonitrile copolymer, α-methylstyrene / acrylonitrile copolymer, α-methylstyrene / styrene / acrylonitrile copolymer, α-methylstyrene /
Methyl methacrylate / acrylonitrile copolymer, p-
Methylstyrene / acrylonitrile copolymer, styrene
/ N-phenylmaleimide copolymer, vinyl-based polymer such as styrene / maleic anhydride copolymer, acrylonitrile-butadiene-styrene terpolymer (ABS) resin,
Methacrylic acid resin-butadiene-styrene terpolymer (MBS) resin, AES resin, AAS resin, polycarbonate,
Thermoplastic resins such as polybutylene terephthalate and polyethylene terephthalate are appropriately mixed, polyethylene, polypropylene, ethylene / propylene copolymers,
Ethylene / butene-1 copolymer, ethylene / propylene / dicyclopentadiene copolymer, ethylene / propylene / 5-ethylidene-2-norbornene copolymer, ethylene / propylene / 1,4-hexadiene copolymer, ethylene /
It is also possible to adjust to more desirable physical properties and characteristics by appropriately mixing a polyolefin rubber such as a vinyl acetate copolymer and an ethylene / butyl acrylate copolymer. Depending on the purpose, reinforcing materials and fillers such as pigments and dyes, glass fibers, metal fibers, metal flakes, carbon fibers, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, lubricants, plasticizers, electrification Inhibitors and flame retardants can be added.

<Example> Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. Izod impact strength is ASTM D256-56, Meth
od A, heat distortion temperature is ASTM D648-56, flexural modulus is ASTM D
Measured according to 790-61. The weather resistance was evaluated by irradiating a notched Izod impact test piece for 40 hours with a Sanshear weatherometer and measuring the change in Izod impact strength. The Izod impact strength was measured in an absolutely dry state. The flexural modulus was measured in an absolutely dry state and in a state where the test piece was immersed in water at 23 ° C. for 48 hours to absorb water.

Reference Example 1 (Production of Polyglutarimide (A)) A-1: A pellet of polymethylmethacrylate was charged into an extruder together with ammonia, and a resin was generated while degassing the generated gas from an exhaust port attached to the extruder. Extrusion was carried out at a temperature of 270 ° C. to produce polyglutarimide (A-1).

A-2: Polyglutarimide (A-2) was produced by the same method as (A-1) except that methylamine was used instead of ammonia as the imidizing agent.

A-3: Polyglutarimide (A-3) was produced by the same method as (A-1) except that aniline was used instead of ammonia as the imidizing agent.

Reference Example 2 (Production of Polyamide (B)) The following nylon 6, nylon 66, and nylon 12 were produced by the melt polymerization method.

Nylon 6: ε-caprolactam to concentrated sulfuric acid relative viscosity 2.75
Nylon 6 was polymerized.

Nylon 66: Nylon 66 having a relative viscosity of 2.60 in concentrated sulfuric acid was polymerized from a molar salt such as hexamethylenediamine and adipic acid.

Nylon 12: 12-aminododecanoic acid to concentrated sulfuric acid relative viscosity
2.35 nylon 12 was polymerized.

Reference Example 3 (Production of Modified Polyolefin (C)) C-1: To 100 parts by weight of an ethylene / propylene copolymer consisting of 70 mol% of ethylene and 30 mol% of propylene,
After adding 0.03 parts by weight of α, α'-bis-t-butylperoxy-p-diisopropylbenzene and 1.0 part by weight of maleic anhydride dissolved in a small amount of acetone, kneading at 230 ° C using an extruder with a diameter of 40 mm. Then, ethylene / propylene-g-maleic anhydride copolymer ("g" represents graft) C-1 was produced by pelletizing.

C-2: to 100 parts by weight of an ethylene / propylene copolymer consisting of 80 mol% of ethylene and 20 mol% of propylene,
Di-t-butyl peroxide dissolved in a small amount of acetone
After adding 0.1 part by weight and 1.0 part by weight of acrylic acid, C
In the same manner as in -3, ethylene / propylene-was kneaded at 200 ° C using an extruder with a diameter of 40 mm and pelletized.
A g-acrylic acid copolymer C-2 was produced.

C-3: 100 parts by weight of ethylene-propylene-5-ethylidene-2-norbornene (EPDM) terpolymer (ethylene / propylene = 68.5 / 31.5 (molar ratio)) having a Mooney viscosity of 60 and an iodine value of 12 After adding 0.1 part by weight of di-t-butyl peroxide dissolved in a small amount of acetone and 0.5 part by weight of maleic anhydride, the same as C-3, 40 mmφ
EPDM-g-maleic anhydride copolymer (C- was prepared by kneading and pelletizing at 230 ° C using an extruder having a caliber.
3) was produced.

Example 1 Polyglutarimide (A), polyamide (B) and modified polyolefin (C) produced in Reference Example were mixed at the compounding ratio shown in Table 1 and melt-kneaded using an extruder having a diameter of 40 mmφ, Pelletized. The extrusion temperature is 26 when nylon 6 or nylon 12 is used as polyamide (B).
The test was carried out at 0 ° C and 290 ° C when nylon 66 was used. Then, this pellet was vacuum dried, and then a test piece for measuring physical properties was molded by injection molding. Cylinder temperature during injection molding is nylon 6 and nylon 12 as polyamide (B).
260 ℃ when using, 290 ℃ when using nylon 66
Set to. The mold temperature was set to 80 ° C.

The measurement results are shown in Table 1.

Comparative Example Polyglutarimide (A), polyamide (B) and modified polyolefin (C) produced in Reference Example, polymethylmethacrylate (hereinafter abbreviated as PMMA) used as a raw material polymer in Reference Example 1 and the following. Polyolefin was mixed at the compounding ratio shown in Table 1 and the physical properties were measured by the same methods as in Example 1. The measurement results are shown in Table 1.

Polyolefin C-4: Ethylene / propylene copolymer consisting of 70 mol% ethylene and 30 mol% propylene C-5: Ethylene-propylene-5-ethylidene-2-norbornene (EPDM) ternary with Mooney viscosity 60 and iodine value 12 Copolymer (ethylene / propylene = 68.5 / 31.5 (molar ratio)) From the results of Example 1 and Comparative Example, the following is clear. The resin compositions (Nos. 1 to 13) of the present invention are all high in Izod impact strength, heat deformation temperature and flexural modulus. Izod impact strength does not decrease even after 400 hours irradiation with a Sanshear weatherometer, and the weather resistance is excellent. The flexural modulus retains a relatively high level even after water absorption treatment.

That is, the resin composition of the present invention is a resin composition having high impact resistance, high rigidity, high heat resistance, and excellent weather resistance. On the other hand, a resin composition comprising only polyglutarimide (A) containing no polyamide and modified polyolefin (C) (No. 14
~ 16) has low impact strength. The resin composition (Nos. 17 and 18) consisting only of polyamide (B) containing no polyburtarimide and modified polyolefin (C) has a poor balance of flexural modulus and impact strength, and flexural modulus is also water-absorbing. Significantly decreases. Further, it is not preferable because it has drawbacks such as a low heat deformation temperature under a high load (18.56 kg / cm ² ).
The resin composition (Nos. 19 to 21) containing no modified polyolefin (C) and composed only of polyglutarimide (A) and polyamide (B) has low impact strength. The composition containing the modified polyolefin (C) in an amount of more than 60% by weight (No. 22) has a low flexural modulus. When polymethylmethacrylate was used instead of polyglutarimide (A) (No. 23), the impact strength and heat distortion temperature were low. When the modified polyolefin (C) has no carboxylic acid group or acid anhydride group (No. 2
4 and 25) have extremely low impact strength.

Example 2 The polyglutarimide (A) polyamide (B) produced in the reference example, the modified polyolefin (C) and the polyolefin rubbers (C-4 and C-5) shown in the comparative examples were mixed at the compounding ratios shown in Table 1. After mixing, the physical properties were measured in the same manner as in Example 1.

The measurement results are shown in Table 1. Polyglutarimide (A),
In addition to polyamide (B) and modified polyolefin (C), ethylene / propylene copolymer rubber (EPR) and ethylene / propylene / non-conjugated diene copolymer rubber (EP
A desirable resin composition having excellent impact strength, flexural modulus, heat resistance and weather resistance can be obtained even by mixing a polyolefin rubber such as DM).

<Effects of the Invention> As described above, the resin composition of the present invention has a good balance of impact resistance represented by impact strength, rigidity represented by flexural modulus, heat resistance represented by heat deformation temperature, and weather resistance. It is expected that it will be applied to various fields by utilizing these characteristics.

Claims (1)

[Claims] 1. (A) is a polyglutarimide, (B) polyamide, and (C) a polyolefin having at least one functional group selected from the group consisting of carboxylic acid groups and acid anhydride groups. A thermoplastic resin composition obtained by mixing in an amount of from 90 to 90% by weight, (B) from 5 to 90% by weight, and (C) from 5 to 60% by weight.