JP3188917B2 - Heat resistant 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 comprising an N-alkyl-substituted maleimide-olefin copolymer and a polyester resin and having excellent heat resistance, rigidity and impact resistance.

[0002]

2. Description of the Related Art In recent years, the development of various high-performance resins due to the progress of polymer alloying technology has been activated. As a result, plasticization for applications that have not been used so far is rapidly progressing.

[0003] Particularly, in the fields of automobiles, electric and electronic devices and the like, studies are being actively conducted. For example, the use of steel plates for automobile outer panels has been studied. Although there has been a track record of using polycarbonate and ABS alloys as this material, they were coated off-line due to insufficient heat resistance, and had problems in productivity, color tone, and the like.

An alloy of polyamide and polyphenylene oxide has been developed by GE and the like as a material that can be coated on-line. Although this material has improved heat resistance, water absorption and accompanying dimensional change, change in physical properties, etc. as compared to polyamide, it suffers from the disadvantages of polyamide, and it is difficult to say that it has sufficient properties. There are problems such as insufficient rigidity.

Polyesters such as polybutylene terephthalate have low water absorption and good properties, and blends with various resins such as polyphenylene oxide, polycarbonate, and elastomer are being studied. . However, even such a blend has not yet reached a satisfactory state in terms of balance of heat resistance, rigidity, impact resistance and the like.

[0006] On the other hand, various studies have been made on maleimide copolymers because of their high heat resistance. For example, a method of copolymerizing N-aromatic substituted maleimide with methyl methacrylate is disclosed in JP-B-43-9753, JP-A-61-1.
JP-A-41715, JP-A-61-171708 and JP-A-62-109811 disclose a method of copolymerizing a styrene resin with an N-aromatic substituted maleimide in JP-A-47-6891. It is disclosed in JP-A-61-76512 and JP-A-61-276807. However, the resins obtained by these methods have better heat resistance as the N-aromatic substituted maleimide content increases, but have problems such as very brittleness, poor workability, and coloring.

[0007] N-alkyl-substituted maleimide-olefin copolymers are interesting polymers having properties such as excellent heat resistance, weather resistance, high rigidity and practical mechanical strength, but further improvements in properties are desired. ing.

[0008]

An object of the present invention is to provide a resin composition having excellent heat resistance, rigidity, impact resistance and the like.

[0009]

The present inventors have conducted intensive studies in view of this problem, and as a result, have found that a resin composition comprising an N-alkyl-substituted maleimide-olefin copolymer, a polyester resin and an elastomer according to the present invention is obtained. The inventors have found that the above objects are satisfied, and have completed the present invention.

That is, according to the present invention, a) the following component (I) is 30 to 98 mol% of the whole polymer, and component (II) is 70 to 2 mol% of the whole polymer. Weight average molecular weight is 1 × 10 ³ or more and 5 × 1
0 ⁶ 1-99 weight% resin or less, b) relates to heat-resistant resin composition characterized by comprising a 1-99 wt% polyester resin and c) an elastomeric -0～40 wt%.

[0011]

Embedded image (Where R ¹ represents an alkyl group having 1 to 18 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms)

[0012]

Embedded image (Where R ² , R ³ and R ⁴ are hydrogen or carbon 1
The resin composition of the present invention has excellent heat resistance, rigidity and impact resistance. Hereinafter, the present invention will be described in detail.

The resin constituting the resin composition of the present invention a)
Can be obtained, for example, by a radical copolymerization reaction between an N-alkyl-substituted maleimide that gives the component (I) and an olefin that gives the component (II).

Here, the N-alkyl-substituted maleimides providing the component (I) include N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, Ni-propylmaleimide, and Nn-maleimide. Butylmaleimide, Ni-butylmaleimide, Ns-butylmaleimide, Nt-butylmaleimide, Nn-pentylmaleimide, Nn-hexylmaleimide, Nn-
Heptylmaleimide, Nn-octylmaleimide, N
Lauryl maleimide, N-stearyl maleimide, N
Specific examples include -cyclopropylmaleimide, N-cyclobutylmaleimide, N-cyclohexylmaleimide, and particularly preferred are N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide and N-cyclohexylmaleimide. In addition, these are 1
They can be used alone or in combination of two or more.

The olefins which provide the component (II) include ethylene, isobutene, 2-methyl-1
-Butene, 2-methyl-1-pentene, 2-methyl-1
-Hexene, 1-methyl-1-heptene, 1-isooctene, 2-methyl-1-octene, 2-ethyl-1-pentene, 2-methyl-2-butene, 2-methyl-2-pentene, 2-methyl Olefins such as -2-hexene; and isobutene is preferably used in terms of heat resistance and mechanical strength. These can be used alone or in combination of two or more.

The content of the component (I) is 30 to 98 mol% of the whole polymer, 40 to 85 mol%, especially 4
5-75 mol% is preferred. If the amount of the component (I) exceeds 98 mol%, the formed polymer becomes brittle, and
If the amount is less than mol%, the heat resistance of the polymer is undesirably reduced. In addition, the content of these constituent components can be determined as appropriate by adjusting the amounts used, for example, when reacting the above-mentioned compounds.

The above-mentioned resin a) may be further modified with a reactive group, such as a carboxylic acid or a derivative thereof, an acid anhydride, an epoxy group, an amino group, a hydroxyl group, a thiol group. , An alkoxysilyl group and an isocyanate group. In this case, the content of the reactive group is 0 to 25 mol%, preferably 0.01 to 25 mol%.
It is 20 mol%, particularly preferably 0.02 to 5 mol%. If the content of the reactive group is more than 25 mol%, the thermal stability or mechanical strength of the resulting resin tends to decrease, which is not preferable.

Such modified resins include, for example, maleic anhydride, citraconic anhydride, itaconic anhydride, (meth) acrylic acid, itaconic acid, glycidyl (meth) acrylate, aminoethyl (meth) acrylate. And hydroxyethyl (meth) acrylate, triethoxysilylpropyl (meth) acrylate, aminostyrene, allylamine and the like by copolymerization or graft polymerization.

Further, 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-cyanopropano-
), An initiator having a reactive group such as 2,2'-azobisisobutylamide or a chain transfer agent having a reactive group such as mercaptoacetic acid or mercaptopropionic acid reacts with the polymer terminal. It is also possible to introduce a sex group.

When the resin a) is obtained by post-imidization of a maleic anhydride and an olefin copolymer as described later, an acid anhydride unit can be left by adjusting the amount of imidization.

If necessary, other vinyl monomers can be copolymerized within a range not to impair the object of the present invention. Other vinyl monomers include styrene, α
-Methylstyrene, vinyltoluene, 1,3-butadiene, isoprene and halogen-substituted derivatives thereof,
Methacrylates such as methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, etc. Acrylates, vinyl esters such as vinyl acetate and vinyl benzoate, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether,
One or more compounds selected from vinyl ethers such as butyl vinyl ether, vinyl chloride, vinylidene chloride, maleic anhydride, N-phenylmaleimide, N-carboxyphenylmaleimide, and acrylonitrile.

For the polymerization of these monomers, any of known polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization can be employed.

Examples of the polymerization initiator include benzoyl peroxide, lauryl peroxide, octanoyl peroxide, acetyl peroxide, di-tert-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, and t-butyl peroxyacetate.
Or an organic peroxide such as t-butylperoxybenzoate, or 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-butyronitrile), 2,2 ′ -Azobisisobutyronitrile, dimethyl-2,2'-azobisisobutyrate, 1,1'-
An azo initiator such as azobis (cyclohexane-1-carbonitrile) is exemplified.

Solvents usable in the solution polymerization method include benzene, toluene, xylene, ethylbenzene,
Cyclohexane, dioxane, tetrahydrofuran, acetone, methyl ethyl ketone, dimethylformamide,
Isopropyl alcohol, butyl alcohol and the like can be mentioned.

The polymerization temperature can be appropriately set in accordance with the decomposition temperature of the initiator, but is generally preferably in the range of 40 to 300 ° C.

The above resin can also be obtained by post-imidizing a resin obtained by copolymerizing maleic anhydride and an olefin with an alkylamine or the like.

Such a post-imidization reaction is carried out, for example, by subjecting the maleic anhydride-isobutene copolymer to a molten state or an alcohol such as methanol, ethanol or propanol.
Dissolved or dispersed in an aromatic solvent such as benzene, toluene, etc.
The reaction is performed at a temperature of 00 to 350 ° C.

Here, the weight average molecular weight (Mw) of the produced resin is determined by gel permeation chromatography.
(GPC). The molecular weight of the maleimide copolymer is 1 × 10 ³ or more and 5 × 10 ⁶ or less, especially 1
Those having a size of × 10 ⁵ or more and 1 × 10 ⁶ or less are preferable. When the molecular weight exceeds 5 × 10 ⁶ , the moldability deteriorates and 1 ×
Tends to the resulting resin becomes brittle in the case of less than 10 ^3.

The maleimide copolymer thus obtained is excellent in heat resistance and particularly high in rigidity, so that the heat resistance and rigidity of the resin composition of the present invention are remarkably improved.

Examples of the polyester resin used in the resin composition of the present invention include polybutylene terephthalate, polyethylene terephthalate, polyarylate and liquid crystalline polyester.

The elastomer used in the resin composition of the present invention includes polybutadiene, styrene / butadiene copolymer, acrylonitrile / butadiene copolymer,
Acrylonitrile / styrene / butadiene copolymer, methyl methacrylate / thrylene / butadiene copolymer, diene elastomers such as polyisoprene and polychloroprene and hydrogenated products thereof, ethylene / propylene (ethylidene norbornene) rubber, butyl rubber, ethylene / Olefin-based elastomers such as vinyl acetate rubber, ethylene / methyl acrylate, etc., acrylic rubbers mainly composed of acrylates, silicone-based elastomers, fluorine-based elastomers, urethane-based elastomers, ester-based elastomers, amide-based elastomers, etc. Is mentioned.

The above-mentioned elastomer is preferably modified with a reactive group such as an acid anhydride, a carboxylic acid, an epoxy group, a hydroxyl group, an amino group, an alkoxysilyl group, an isocyanate group.

The content of the reactive group is 0.001 to 30 mol%, preferably 0.01 to 20 mol%, particularly preferably 0.05 to 5 mol% of the whole elastomer.

Further, various catalysts can be added to the system for the purpose of accelerating the reaction between the maleimide copolymer, the polyester resin and the elastomer.

Also, a component capable of reacting with a polyamino compound such as diaminodiphenyl ether, resorcin diglycidyl ether, diglycidyl ether phthalate, a maleimide copolymer such as a polyepoxy compound, a polyester resin, an elastomer or the like. Is added, the dispersibility and compatibility of each component can be improved.

In the present invention, the alkylmaleimide-olefin copolymer, polyester resin and elastomer are used.
Is from 1 to 99:99 to 1: 0 to 40, preferably from 5 to 95:95 to 5: 5 to 40, particularly from 10 to 75:90 to 25:10 to 30. Is preferred.

When the amount of the alkylmaleimide-olefin copolymer is less than 1% by weight, the heat resistance and rigidity of the obtained resin composition are reduced. When the amount of the elastomer component is more than 40% by weight, the obtained resin composition is obtained. This is not preferable because the rigidity of the object tends to decrease.

The resin composition of the present invention further comprises other resins such as acrylic resin, polystyrene, vinyl chloride resin, polyphenylene ether, polyacetal, polyamide, polyester, polyphenylene sulfide, polyimide, polycarbonate, and the like. , Polysulfone, fluororesin, and random, block, and graft polymers thereof can also be mixed.

The above-mentioned maleimide compound and olefin can be polymerized in the presence of an elastomer to be used as a graft polymer.

In the resin of the present invention, various dyes, glass fiber, carbon fiber, potassium titanate, asbestos, silicon carbide, ceramic fiber, metal fiber, silicon nitride, silicon fiber, which may be surface-treated, may be used at the time of use. Barium sulfate, calcium sulfate, kaolin, clay, pyroferrite,
Inorganic and organic fillers such as zeolite, mica, mica, talc, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, antimony trioxide, zinc oxide, titanium oxide, iron oxide, glass balloon, aramid fiber, etc .; And heat stabilizers such as organic phosphoric acid esters, benzotriazole-based or hindered amine-based ultraviolet stabilizers, flame retardants, foaming agents, antistatic agents, and various lubricants.

Further, the method for producing the resin composition of the present invention is not particularly limited.
A method in which an alkyl-substituted maleimide-olefin copolymer, a polyester resin, an elastomer and other additives are mixed, or supplied to an extruder without mixing, and melt-kneaded.

[0042]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the examples.

The molecular weight of the produced polymer was determined by GPC (Toso
It was determined in terms of polystyrene using HLC-802A manufactured by Co., Ltd.).

The composition of the produced polymer was determined mainly by elemental analysis and 1N-NMR measurement.

The heat distortion temperature was measured in accordance with ASTM D648, the flexural strength and the flexural modulus were measured in accordance with ASTM D790, and the impact strength was measured in accordance with ASTM D256.

REFERENCE EXAMPLE Synthesis of N-alkyl-substituted maleimide-olefin copolymer A-1 N-methylmaleimide was added to a 30-liter autoclave equipped with a stirrer, nitrogen inlet tube, isobutene inlet tube, thermometer and degassing tube. 1180 g, 2-hydroxyethyl methacrylate
153 g, 8 g of perbutyl neodecaneate and 15 l of a toluene / methanol mixed solvent (1/1 weight ratio) were charged, purged several times with nitrogen, and then liquefied isobutene 8.5.
and then reacted at 60 ° C. for 12 hours.

The particulate polymer obtained by the reaction was separated by centrifugation and dried at 60 ° C. under reduced pressure for 24 hours. The yield was 1770 g.

The obtained polymer was purified by reprecipitation with chloroform / methanol solvent, elemental analysis and ¹ H-NMR.
As a result of analysis by the following method, maleimide units in the resulting polymer were 49.5 mol%, and 2-hydroxyethyl methacrylate
(G) unit was 1.0 mol% and isobutene unit was 49.5 mol%. The obtained polymer had a molecular weight (Mw) of 26500.
It was 0.

A-2 N-methylmaleimide 1 was prepared using the same reactor as A-1.
180, 23 g of maleic anhydride, 8 g of perbutyl neodecaneate and a mixed solvent of toluene / methanol (1/1).
(15% by weight), purged several times with nitrogen, 8.5 l of liquefied isobutene, and reacted at 60 ° C. for 12 hours.

The particulate polymer obtained by the reaction was separated by centrifugation and dried under reduced pressure at 60 ° C. for 24 hours. The yield was 1750 g.

From the results of elemental analysis of the obtained polymer and the results of elemental analysis and ¹ H-NMR analysis of a sample obtained by subjecting the maleic anhydride portion of the obtained polymer to methyl esterification, the maleimide unit in the produced polymer was 49 mol%,
It was 1 mol% of maleic anhydride units and 50 mol% of isobutene units. The obtained polymer has a molecular weight (Mw) of 270.
000.

Polyester resin B-1 polybutylene terephthalate (NO.
VADUR).

Elastomer C-1 A copolymer comprising 97.20 mol% of ethylene units and 2.80 mol% of glycidyl methacrylate units.

C-2 An ethylene / propylene elastomer comprising 73% by weight of ethylene units and 27% by weight of propylene units modified with 0.5% by weight of maleic anhydride.

Examples 1 to 4 and Comparative Example 1 The maleimide-isobutene copolymer, polybutylene terephthalate resin and elastomer shown in Reference Example were powdered or pelleted with the resin composition (weight ratio) shown in Table 1. And kneaded and extruded twice at 260 to 320 ° C. using a twin-screw extruder (Laboplast Mill (manufactured by Toyo Seiki Co., Ltd.)) to obtain pellets. Using an injection molding machine (Panajection (manufactured by Matsushita Electric Industrial Co., Ltd.)), the obtained pellets were heated at a cylinder temperature of 260 to 350 ° C. and a mold temperature of 100.
Injection molding was performed at ~ 140 ° C to prepare a sample, which was used as a physical property measurement sample. Table 2 shows the obtained results.

[0056]

[Table 1]

[0057]

[Table 2]

[0058]

As is clear from the examples, the resin composition of the present invention is excellent in heat resistance, rigidity and impact resistance and has good mechanical properties.
It is extremely useful in a wide range of applications such as the aviation / ship field, the housing field, the medical field, and the food field.

Claims (1)

(57) [Claims] (A) A component (I) shown below is a polymer
30-98 mol% of the whole, the component (II) is a polymer
1 to 99% by weight of a resin having a weight average molecular weight in terms of polystyrene of 1 × 10 ³ or more and 5 × 10 ³ or less, and b) 1 to 99% by weight of a polyester resin.
And c) a heat-resistant resin composition comprising from 0 to 40% by weight of an elastomer. Embedded image (Where R ¹ represents an alkyl group having 1 to 18 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms) (Where R ² , R ³ and R ⁴ are hydrogen or carbon 1
~ 8 alkyl groups)