JPH0341145A - Thermoplastic maleimide resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in heat resistance, impact resistance and moldability by mixing a maleimide unit component essentially consisting of a polymer having a specified functional group with a component essentially consisting of a soft polymer having a functional group reactive with the functional group of the above polymer in a specified ratio. CONSTITUTION:This composition comprises 95-50wt.% component having 5-70wt.% maleimide units and essentially consisting of a polymer having at least one functional group selected from among aziridine, oxazoline and epoxy groups in the molecule [e.g. styrene/N-phenylmaleimide/2-(1-aziridinyl)ethyl methacrylate copolymer] and 5-50wt.% component essentially consisting of a soft polymer having a functional group reactive with the functional group of the above polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a resin composition having excellent impact resistance, heat resistance and moldability.

[Problems that conventional techniques and inventions attempt to improve]

Although maleimide copolymers have excellent heat resistance and thermal decomposition resistance, they have poor mechanical properties such as impact strength and moldability, and many proposals have been made to improve these drawbacks. There is.

For example, a method in which maleimide and other vinyl monomers are polymerized in the presence of a rubbery polymer (JP-A-59-11322), or a method in which a maleimide copolymer is grafted with a rubbery and vinyl monomer. Method of mixing with polymer (JP-A-61-
No. 73755), but in these methods, if the heat resistance is not improved, mechanical properties such as impact resistance are reduced, and if the impact resistance is improved, the heat resistance is reduced. Due to these problems, it is difficult to obtain a material that has both heat resistance and impact resistance, and the reality is that if you try to satisfy both properties, you can only obtain a material with poor moldability.

[Means and Effects for Solving the Problems 1] In view of these circumstances, the present inventors have developed a method for improving mechanical strength, typified by impact strength, without reducing the excellent heat resistance of maleimide copolymers. As a result of intensive research to improve moldability, a component (A
) and a maleimide-based thermoplastic resin composition consisting of a component (B) which essentially includes a soft polymer (2) having a functional group capable of reacting with the functional group, has been found to be able to achieve the above object, and has completed the present invention. It is something that

That is, the present invention provides polymers having one or more functional groups selected from aziridine groups, oxazoline groups, and epoxy groups in their molecules (
Component (A) 95 to 50% by weight (however,
Component (A) contains 5 to 70% by weight of maleimide units. ) and 5 to 50% by weight of component (B), which essentially includes a soft polymer (2) having a functional group that can react with the functional group in polymer (1).
The present invention relates to a maleimide thermoplastic resin composition comprising the following.

In addition, even if component (A) contains polymer (1) and a soft polymer (4) that does not have compatible functional groups, a compatibilizing agent will be generated due to chemical interaction, and the original Incompatible components (
By forming a microphase-separated state between A) and component (B), a thermoplastic resin composition having both the heat resistance of component (A) and the impact resistance and easy moldability of component (B) can be obtained. It is something that can be done.

In the present invention, the polymer (1) can be used without particular limitation as long as it has one or more functional groups selected from aziridine groups, oxazoline groups, and epoxy groups in its molecule. In order to obtain such a polymer (1), for example, a polymerizable monomer (a) having the functional group in the molecule (hereinafter referred to as monomer (a)) may be copolymerized with these. Possible other polymerizable monomers (b) Below C, monomer (b)
). ).

As the monomer (a), for example, C)I, -CHHO2Co-CH= CHxCHz
-CHI0-Co-C(CH'z')"= CHtCH
m-CH-0-Co-C(CHs)= CHaCHt
= CH-Co-N CH, = C(CH,)-Co-N CH@ = CH-OCO-N<J CHs = C(CHI)-0CO-N off CH, =CH
-5o, -< CHl C(CH,)-NHCO-N2CHz = C(CHx)-Coo-CHaCHt-N
Aziridine group-containing polymerizable monomer represented by HCO-<, etc.; 2-vinyl-2-oxazoline, 2-vinyl-4-
4-Methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-vinyl-4-ethyl-2-
Oxazoline, 2-vinyl-5-ethyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isobro1'/'benyl-2-'oxazoline, 2-isopropenyl-
5-methyl-2-oxazoline, 2-impropenyl-
4-ethyl-2-oxazoline, 2-isopropenyl-
5-ethyl-2-oxazoline, 2-isopropenyl-
Oxazoline group-containing polymerizable monomers such as 4,5-dimethyl-2-oxazoline; (However, R1 in these formulas represents hydrogen or a methyl group, and n is O or an integer from 1 to 20.) Epoxy group-containing polymerizable monomers represented by the following formulas can be mentioned, and one or more types selected from these groups can be used.

The amount of the monomer (a) having these functional groups used is preferably 0.1 to 50% by weight, more preferably 0.5 to 20% by weight, based on the polymer (1).

As the monomer (b), if it does not have a functional group that can react with the functional group contained in the monomer (a) and is copolymerizable with the monomer (a), It can be used without any particular restriction, and examples include maleimide, N-methylmaleimide, N-ethylmaleimide, N-probylmaleimide, N-isopropylmaleimide, methylmaleimide, N-inbutylmaleimide, N-tertiarybutylmaleimide, N- -cyclohexylmaleimide,
N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-naphthylmaleimide, N-laurylmaleimide, N-methoxyphenylmaleimide, N-nitrophenylmaleimide, N-)
Maleimide monomers such as ribromophenylmaleimide;
Styrene, 0-methylstyrene, m-methylstyrene,
Styrenic monomers such as p-methylstyrene, α-methylstyrene, p-methoxystyrene, p-tert-butylstyrene, p-phenylstyrene, 0-chlorostyrene, m-chlorostyrene, p-chlorostyrene, acrylic Methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, stearyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, methacrylate Acrylic acid or methacrylic acid monomers such as isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, vinyl chloride, vinyl acetate, acrylonitrile, acrylamide, methacrylamide, N-vinyl Examples include bilodrin, and one or more of these can be used.

In order to obtain the polymer (1) having a functional group by this method, the monomer (a) and, if necessary, the monomer (b) can be polymerized using conventionally known polymerization methods such as bulk polymerization, suspension polymerization, and emulsion polymerization. Polymerization may be carried out by a polymerization method, a solution polymerization method, or the like. In addition, when component (A) consists only of polymer (1), monomer (b
) must essentially contain the maleimide monomer.

In the present invention, polymer (1) may be replaced with polymer (3) as necessary.
0 polymer (3) used as component (A) with the addition of
is not particularly limited as long as it is compatible with polymer (1) and has no functional groups, but if the polymer obtained by polymerizing monomer (b) is Particularly preferred. The amount of polymer (3) to be used is not particularly limited, but is preferably 500 parts by weight or less per 100 parts by weight of polymer (1).In the present invention, if the maleimide unit in component (A) is It must contain 5-70% by weight.

If it is less than 5% by weight, heat resistance will be insufficient, and if it exceeds 70% by weight, problems will arise in moldability, which is not preferred.

The soft polymer (2) used in the present invention has a functional group that can react with an aziridine group, an oxazoline group, or an epoxy group, and the functional groups include, for example, a carboxyl group and its salt, a carboxylic anhydride group, Examples include hydroxyl group, mercapto group, amino group, etc.
These can also be used together.

The skeleton component of the polymer (2) is soft and has good impact resistance, such as diene polymers such as polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, etc.; polyethylene, chlorinated polyethylene; , olefinic polymers such as ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene copolymer, ethylene-vinyl acetate polymer; polybutyl acrylate,
Examples include acrylic rubbers such as poly-2-ethylhexyl acrylate.

A suitable method for obtaining the soft polymer (2) is to graft an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride onto the soft polymer in an amount of 01 to 50% by weight, more preferably 0.3 to 20% by weight. Examples include a polymerization method and a copolymerization method as a component of a soft polymer.

In the present invention, the amount of the soft polymer (2) is preferably 00 parts by weight or less, if necessary.

In the present invention, the amount of component (A) in the resin composition is 95 to 50% by weight. If it exceeds 95% by weight, impact resistance and moldability will deteriorate, and if it is less than 50% by weight, heat resistance will become insufficient, which is not preferable.

The resin composition according to the present invention may contain conventionally known additives, such as antioxidants, weather resistance modifiers, impact resistance modifiers, and inorganic or organic fillers, as necessary to the extent that the object of the present invention is not impaired. It is also possible to add flame retardants, colorants, antistatic agents, mold release agents, etc. As a blending method for obtaining the resin composition according to the present invention, conventionally known methods such as a Henschel mixer and a ribbon blender can be used. (2) Preliminary mixing using a blender or the like, followed by melt-kneading using a -shaft type kneading extruder, twin-screw type kneading extruder, Banbury mixer, roll mixer, etc.

The resin composition thus obtained can be further made into a desired molded article by extrusion molding, injection molding, or the like.

〔Effect of the invention〕

The resin composition according to the present invention has excellent mechanical properties and moldability while retaining the heat resistance and thermal decomposition resistance inherent to maleimide polymers. Therefore, the resin composition according to the present invention can be effectively used in various applications such as automobile parts, industrial parts, and electrical equipment parts.

[Example] Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

In addition, "parts" in the examples are by weight unless otherwise specified.

Reference Example 1 1260 parts of deionized water and polyvinyl alcohol (PVA-220
E, manufactured by Kuraray) was charged and heated to 80°C under a nitrogen gas atmosphere to dissolve the polyvinyl alcohol, and then cooled to 50°C.

351 parts of styrene, 162 parts of N-phenylmaleimide,
and 2-(1-aziridinyl)ethyl methacrylate [
“Chemitite MZ-11” Manufactured by Nippon Shokubai Chemical Industry ■ 2
After weighing 7 parts into a separate container and heating it to 40°C to dissolve the N-phenylmaleimide, 16.2 parts of benzoyl peroxide was added to obtain a uniform monomer solution. This monomer solution was added to the flask and heated at 300 r under a nitrogen gas atmosphere.
After keeping the monomer solution under stirring for 10 minutes at pm, the monomer solution was made into a suspended state, and then the internal temperature was raised to 80°C to start polymerization.
Thereafter, this temperature was maintained for 7 hours to complete the polymerization. The obtained reaction solution was filtered through a 200-mesh wire mesh, thoroughly washed with deionized water, and then dried in a hot air circulation dryer at 80°C for one day and night to obtain a granular copolymer (a) with a diameter of about 0°2 mm. Approximately 50
I got 0 copies.

Reference Example 2 In Reference Example 1, 2-isopropenyl-2 was used instead of 27 parts of 2-(1-aziridinyl>ethyl methacrylate).
- The same operation as in Reference Example 1 was repeated except that 127 parts of oxazoline (manufactured by Dow Chemical Company) was used, and the diameter was approximately 0.2 parts.
About 500 parts of granular copolymer (b) of No. 1 was obtained.

Reference Example 3 The same operation as in Reference Example 1 was carried out, except that 27 parts of glycidyl methacrylate [“Blenmar〇” manufactured by NOF Chemical Co., Ltd.] was used instead of 27 parts of 2-(1-aziridinyl)ethyl methacrylate. Repeat until the diameter is about 0
．． Approximately 500 parts of a 2 mm granular copolymer (C) was obtained.

Reference Example 4 The same operations as in Reference Example 1 were repeated, except that the monomer composition in the monomer solution was changed to 513 parts of styrene and 27 parts of 2-(1-aziridinyl)ethyl methacrylate. 2 mm granular copolymer (d) approx. 50
I got 0 copies.

Reference Example 5 In Reference Example 4, 2-isopropenyl-2 was used instead of 27 parts of 2-(1-aziridinyl)ethyl methacrylate.
- The same operation as in Reference Example 4 was repeated except that 27 parts of oxazoline was used to obtain a diameter of about 0211II! Approximately 500 parts of granular copolymer (e) were obtained.

Reference Example 6 The same operation as in Reference Example 4 was repeated except that 27 parts of glycidyl methacrylate was used instead of 27 parts of 2mer(1-aziridinyl)ethyl methacrylate to form a granular copolymer with a diameter of about 0.2 mm. Approximately 500 parts of combined (f) was obtained.

Reference Example 7 The same procedure as in Reference Example 1 was repeated except that the monomer composition in the monomer solution was changed to 378 parts of styrene and 162 parts of N-phenylmaleimide to obtain a diameter of approximately 0.2 parts.
Approximately 500 parts of a granular copolymer (g) of 50 mm in diameter was obtained.

Reference Example 8 The same operation as in Reference Example 1 was repeated except that the monomer composition in the monomer solution was changed to only 540 parts of styrene to obtain a granular copolymer (h) having a diameter of 0.2 mm.
I got 00 copies.

Reference Example 9 169.7 parts of deionized water and 15% emal O water dissolved in a 1J2 glass four-bottle flask with a stirrer: ff126
．． 7 parts were charged and heated to 55° C. under a nitrogen gas atmosphere (reaction tank).

In a monomer dropping tank, 162°6 parts of butyl acrylate, 12.6 parts of methyl methacrylate, 12.6 parts of styrene,
7.2 parts of acrylic acid and 5 parts of trimethylolpropane trimethacrylate were charged and stirred to obtain a uniform monomer solution.

The reaction tank was maintained at 55°C, 40 parts of a 2.5% potassium persulfate aqueous solution and 2 parts of a 2% sodium bisulfite aqueous solution were added, and the mixture was kept under stirring for 10 minutes under a nitrogen gas atmosphere.
Next, the monomer solution was added dropwise from the dropping tank over a period of 90 minutes to form a homogeneous solution. During this time, 2 parts of a 2% sodium bisulfite aqueous solution was added nine times at 10 minute intervals after the start of the dropwise addition.

Thereafter, the temperature was kept at this temperature for 3 hours to complete the polymerization.

The resulting reaction solution was added dropwise to a 4% aqueous magnesium sulfate solution for salting out, and the aggregated polymer was thoroughly washed with deionized water and then dried in a hot air circulation dryer at 80°C for one day to determine the reactivity. Approximately iso part of soft copolymer (i) was obtained.

Examples 1 to 10 and Comparative Examples 1 to 5 Each component was melt-kneaded in the proportions shown in Table 1 using a twin-screw kneader, and injection molded to prepare test pieces. At this time, the moldability of the samples other than Comparative Example 4 was good. The performance test results of the obtained test pieces are shown in Table 1, and the heat distortion temperature in the table is A.
STM D-648-56, Izod impact strength is AS
Measured according to TM D-256-56 Method A.

As is clear from this table, the molded articles obtained from the resin compositions of the present invention had excellent heat resistance and impact resistance.

Claims (1)

[Scope of Claims] 1. Component (A) 95 to 50% by weight, which essentially contains a polymer (1) having one or more functional groups selected from aziridine groups, oxazoline groups, and epoxy groups in the molecule. % (However, component (A) contains 5 to 70% by weight of maleimide units.) and a soft polymer (2) having a functional group that can react with the functional group in the polymer (1) is essential. Component (B) 5-50% by weight
A maleimide thermoplastic resin composition comprising: 2. The resin composition according to claim 1, wherein component (A) comprises a polymer (3) which is compatible with polymer (1) and has no functional group. 3. The resin composition according to claim 1, wherein component (B) comprises a soft polymer (4) which is compatible with the soft polymer (2) and has no functional group.