JP3331602B2 - 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 an olefin resin and having excellent heat resistance, rigidity, impact resistance, weather resistance and dimensional stability. Things.

[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 as an online coatable material. Although this material has improved water absorption and accompanying dimensional change and physical property change as compared with polyamide, it suffers from the drawbacks of polyamide, and it is difficult to say that it has sufficient properties, and furthermore, rigidity is increased. Insufficient, there are problems such as poor weather resistance.

[0005] 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-61-975.
No. 141715, JP-A-61-171708 and JP-A-62-109811 disclose a method of copolymerizing a styrene resin with an N-aromatic substituted maleimide.
JP-A-47-6891 and JP-A-61-76512.
And Japanese Patent Application Laid-Open No. 61-276807. However, the resins obtained by these methods are N-
As the content of the aromatic-substituted maleimide increases, the heat resistance becomes better, but there are problems such as very brittleness, poor workability, and coloring.

[0006] 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 improvement in impact strength is desired. Rareness is also desired, and improvements in terms of changes in physical properties and dimensional changes due to water absorption are also desired.

[0007]

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

[0008]

Means for Solving the Problems The present inventors have made intensive studies in view of this problem, and as a result, the resin composition comprising an N-alkyl-substituted maleimide-olefin copolymer and a polyolefin of the present invention satisfies the above objects. Heading that
The present invention has been completed.

That is, in 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; Molecular weight of 1 × 10 ³ or more and 5 × 1
0 ⁶ or less is a resin or further carboxylic acids and their derivatives, acid anhydride, epoxy group, an amino group, a hydroxyl group, a thiol group, an alkoxysilyl group, a monomer having a reactive group selected from an isocyanate group 0-2
5 mol% copolymerized or graft polymerized resin and b)
It consists of a resin obtained by copolymerizing or graft-polymerizing a monomer selected from ethylene, propylene, and 4-methyl-1-pentene with another copolymerizable unsaturated monomer, and the content is a ) / B) = 5/95 to 99/1.

[0010]

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)

[0011]

Embedded image (Where R ₂ represents hydrogen or an alkyl group having 1 to 8 carbon atoms, and R ₃ and R ₄ represent an alkyl group having 1 to 8 carbon atoms). The resin composition of the present invention has excellent heat resistance and rigidity. , Impact resistance, weather resistance and dimensional stability. Hereinafter, the present invention will be described in detail.

Resin (a) constituting the resin composition of the present invention
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 that provide the component (II) include 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,
Examples include olefins such as 2-methyl-2-hexene, and among them, isobutene is preferably used. These can be used alone or in combination of two or more.

The content of the component (I) is 30 to 98 mol%, preferably 40 to 85 mol%, particularly 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, and allylamine.

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.

These reactive groups are the same as the modified elastomers described below.
Can be selected depending on the reactive group.

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,
Vinyl ethers such as butyl vinyl ether, vinyl chloride, vinylidene chloride, maleic anhydride, N-phenylmaleimide, N-carboxyphenylmaleimide, acrylonitrile, ethylene, propylene, 1-butene, 2-
One or more compounds selected from butene and 1-hexene are exemplified.

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 150 ° 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 olefin resin used in the resin composition of the present invention includes polyethylene, polypropylene,
Examples thereof include poly-4-methyl-1-pentene and modified products thereof.

Here, polyethylene used in the composition of the present invention is a resin mainly composed of ethylene units, and the ethylene units are at least 60 mol%, preferably at least 80 mol%, particularly preferably at least 90 mol% of the whole resin. Is referred to as a polymer.

The polyethylene which can be used as the olefin resin of the present invention includes other copolymerizable unsaturated monomers, for example, propylene, 1-butene, 1-
Α-olefins such as hexene, vinyl ethers, vinyl esters such as vinyl acetate and vinyl propionate,
Acrylic esters, methacrylic esters, acrylonitrile, and the like may be copolymerized or graft-polymerized, and the amount thereof is 0 to 40 mol%, preferably 0 to 40 mol%.
It is in the range of 25 mol%, particularly preferably 0 to 15 mol%.

Further, these polyethylenes may be modified with various reactive groups. In this case, the reactive groups include acid anhydrides, carboxylic acids and derivatives thereof, hydroxyl groups, thiol groups and amino groups. , An epoxy group, an alkoxysilyl group, an isocyanate group and the like. These modifications are, for example, maleic anhydride, citraconic anhydride, itaconic anhydride, acrylic acid, methacrylic acid, hydroxyethyl methacrylate, aminoethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, etc., using known copolymerization or It is performed by graft polymerization or the like.

The amount of modification by these reactive groups is 0 to 25 mol%, preferably 0.01 to 15 mol%, particularly preferably 0.02 to 5 mol%.

The polypropylene which can be used as the olefin resin of the present invention has a polypropylene unit content of not less than 80% by mole of the whole resin, and other copolymerizable unsaturated monomer such as ethylene, -Butene,
Α-olefins such as 1-hexene, vinyl ethers, vinyl esters such as vinyl acetate and vinyl propionate, acrylic esters, methacrylic esters, and acrylonitrile may be copolymerized or graft-polymerized. , Its amount ranges from 0 to 20%.

Further, these polypropylenes may be modified with various reactive groups. In this case, the reactive groups include acid anhydrides, carboxylic acids and derivatives thereof,
And a hydroxyl group, an amino group, an epoxy group, an alkoxysilyl group, and the like.These modifications are carried out using known maleic anhydride, acrylic acid, methacrylic acid, hydroxyethyl methacrylate, aminoethyl methacrylate, or glycidyl methacrylate. It is performed by polymerization, graft polymerization or the like. Among them, modified polypropylene grafted with maleic anhydride or acrylic acid is preferred. The amount of modification with these reactive groups is 0 to 20 mol%, preferably 0.01 to 5 mol%.

Further, poly-4-methyl-1-pentene which can be used as the olefin resin of the present invention is:
It is a polymer mainly composed of 4-methyl-1-pentene units, and may be similarly modified with various reactive groups.

[0037]

[0038]

[0039]

It is also possible to carry out the polymerization of maleimide and olefins in the presence of a rubbery polymer and use it as a graft polymer.

The resin composition of the present invention comprises the above resin a) N
The content (weight ratio) of the alkyl-substituted maleimide-olefin copolymer and the resin b) polyolefin is 5 to 99:
95-1, especially 50-99; 50-1, even 7
The range of 0 to 98:30 to 2 is preferred.

In the resin of the present invention, various dyes, glass fibers, carbon fibers, potassium titanate, asbestos, silicon carbide, ceramic fibers, metal fibers, silicon nitride, silicon nitride, 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, and aramid fiber; 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 is mixed with a polyolefin and other additives, or supplied to an extruder without being mixed and melt-kneaded.

[0044]

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 ¹ N-NMR measurement.

The weather resistance was evaluated using a weather meter (manufactured by Suga Test Instruments Co., Ltd.) based on changes in physical properties and appearance after irradiation for 200 hours.

The heat distortion temperature was measured in accordance with ASTM D648, the flexural strength and 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 50 equipped with a stirrer, nitrogen inlet tube, thermometer and degassing tube
In an autoclave, 2780 g of N-methylmaleimide
(25 mol), 71 g of glycidyl methacrylate (0.
5 mol), 2,2'-azobisisobutyronitrile (A
IBN) 3.2 g (0.02 mol) and dioxane 3
After charging 5 l and purging several times with nitrogen, isobutene 56 was added.
10 g (100 mol) was charged and reacted at 60 ° C. for 12 hours.

The reaction content was poured into ethanol and the polymer
Was precipitated. It dried at 60 degreeC under reduced pressure for 24 hours. The yield was 4175 g.

Elemental analysis of the obtained polymer and ¹ H-
From NMR, the number of maleimide units in the resulting polymer was 49.
5 mol% and glycidyl methacrylate units were 0.8 mol%. The obtained polymer had a molecular weight (Mw) of 213.
000.

A-2 Using the same reactor as in A-1, 2780 g (25 mol) of N-methylmaleimide and 48 g of 4-aminostyrene
(0.4 mol), 3.2 g (0.02 mol) of 2,2'-azobisisobutyronitrile (AIBN) and 35 l of dioxane were charged, purged several times with nitrogen, and 5610 g (50 mol) of isobutene. ) And reacted at 60 ° C. for 12 hours.

The reaction contents were poured into ethanol, and the polymer was
Was precipitated. It dried at 60 degreeC under reduced pressure for 24 hours. The yield was 4182 g.

Elemental analysis of the obtained polymer and ¹ H-
From NMR, the number of maleimide units in the resulting polymer was 50.
0 mol% and the amount of 4-aminostyrene unit were 1.0 mol%. The obtained polymer had a molecular weight (Mw) of 250,000.
Met.

A-3 N-cyclohexylmaleimide was used in place of N-methylmaleimide, except that N-cyclohexylmaleimide was used.
A cyclohexylmaleimide / glycidyl methacrylate / isobutene copolymer was synthesized.

From the results of elemental analysis of the obtained polymer, the amount of maleimide units in the produced polymer was 51 mol%, and that of glycidyl methacrylate units was 0.6 mol%. The obtained polymer had a molecular weight (Mw) of 277,000.

A-4 In the same manner as in A-1, N-methylmaleimide / isobutene copolymer was synthesized without using glycidyl methacrylate. The obtained polymer had a maleimide unit of 50 mol% and a molecular weight of 240,000.

B-1 91.86 mol% of ethylene units, 7.93 mol% of ethyl acrylate units, 0.21 mol% of maleic anhydride units
A copolymer comprising

B-2 A copolymer comprising 97.20 mol% of ethylene units and 2.80 mol% of glycidyl methacrylate units.

B-3 A polypropylene modified by a reactive extrusion method using maleic anhydride, wherein the maleic anhydride unit is 0.4 mol%
Grafted modified polypropylene.

Examples 1 to 6 and Comparative Example 1 The maleimide / isobutene copolymer synthesized in the reference example and the olefin resin were shaken in advance in the form of powder or pellets with the resin composition shown in Table 1, and a twin screw extruder (lab 2 at 260-320 ° C by plastmill (Toyo Seiki Co., Ltd.)
The mixture was kneaded and extruded to obtain pellets. The obtained pellets were subjected to injection molding using an injection molding machine (Panajection (manufactured by Matsushita Electric Industrial Co., Ltd.)) at a cylinder temperature of 260 to 350 ° C. and a mold temperature of 100 to 140 ° C. to prepare a sample and to measure physical properties. A sample was used. Tables 2 and 3 show the obtained results.
And Table 4.

[0062]

[Table 1]

[0063]

[Table 2]

[0064]

[Table 3]

[0065]

[Table 4]

[0066]

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

──────────────────────────────────────────────────続 き Continuation of front page (51) Int.Cl. ⁷ Identification code FI (C08L 23/18 C08L 23:02 23:02) (C08L 35/00 23:02) (56) References JP-A-51- 125126 (JP, A) JP-A-52-102389 (JP, A) JP-A-2-300262 (JP, A) JP-A-61-162543 (JP, A) JP-A-5-117484 (JP, A) JP-A-5-117461 (JP, A) JP-A-5-59193 (JP, A) JP-A-5-196801 (JP, A) JP-A-4-50214 (JP, A) JP-A-4-50213 (JP, A) JP-A-4-50210 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 35/00-35/08 C08L 23/00-23/36 C08F 210 / 00-210/18 C08F 222/00-222/40 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. a) Component (I) shown below is 30 to 98 mol% of the whole polymer, component (II) is 70 to 2 mol% of the whole polymer, and the weight average molecular weight in terms of polystyrene is 1 A resin of not less than × 10 ^{3 and not} more than 5 × 10 ⁶ ,
Or further carboxylic acids and derivatives thereof, acid anhydrides,
Epoxy group, amino group, hydroxyl group, thiol group,
A resin obtained by copolymerizing or graft-polymerizing a monomer having a reactive group selected from an alkoxysilyl group and an isocyanate group, and b) a monomer selected from ethylene, propylene, and 4-methyl-1-pentene;
It consists of a resin copolymerized or graft-polymerized with another copolymerizable unsaturated monomer, and its content is a) / b) = 5/95 to 99/1 by weight. Heat resistant resin composition. 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 is hydrogen or an alkyl group having 1 to 8 carbon atoms, and R ₃ and R ₄ are an alkyl group having 1 to 8 carbon atoms)