JPS62129334A - Methacrylimide-maleimide resin composition - Google Patents

Abstract

PURPOSE:To provide the titled composition of high heat and impact resistances, comprising three kinds of heat-resistant copolymers and one kind of copolymer- grafted rubber. CONSTITUTION:The objective composition comprising (A) 10-70wt% of a copolymer with a viscosity at 25 deg.C in the form of 10wt% methylethyl ketone solution (hereafter referred as 'viscosity') falling between 3 and 20cps constituted by 0.1-50mol% of an acid anhydride unit of formula I and 2-77mol% of an imide unit of formula II (R1 is H, alkyl, etc.), derived from imide-modification of a copolymer from methyl methacrylate, six-membered ring acid anhydride, aromatic vinyl compound and methacrylic acid, (B) 20-80wt% of a maleimide copolymer with a viscosity 3-15cps, (C) 1-60wt% of a third copolymer from aromatic vinyl compound and unsaturated nitrile and (D) 10-70wt% of a graft rubber derived from grafting the copolymer C to a rubber with a glass transition temperature of <=-30 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a methacrylimide-maleimide resin composition. More specifically, the present invention relates to the production of automobile parts by mixing a heat-resistant copolymer and rubber.
The present invention relates to a methacrylimide-maleimide resin composition that has excellent heat resistance and impact resistance and is suitable for use in industrial parts, home appliance parts, and the like.

(Prior art) Thermoplastic resin obtained by graft polymerizing acrylonitrile and styrene to rubber mainly composed of butadiene is known as ABS resin, and has excellent processability, mechanical strength,
Because it has excellent properties such as surface gloss and chemical resistance, it is widely used in many fields today, and as the fields of use are expanding, the demand for it is also increasing.

With the expansion of these five fields of use, the required performance is becoming increasingly strict, and one of them is:
There is a demand for products with even higher heat resistance. ABS
As a method of improving the heat resistance of a resin, it is conventionally known to replace part or all of styrene with α-methylstyrene.

For example, in order to obtain a resin with excellent heat resistance, it has been proposed to replace styrene with methyl methacrylate and α-methylstyrene (Japanese Patent Publication No. 49-37415). However, even though the heat resistance is improved by introducing α-methylstyrene, the polymerization rate decreases significantly as the amount increases, and processability and impact resistance deteriorate, which is the property of ABS resin. In addition to the unavoidable loss of physical properties and balance, there is a limit to the improvement of heat resistance by introducing α-methylstyrene. However, it is not always satisfactory.

Furthermore, in order to obtain a copolymer with excellent impact resistance and heat resistance, it has been proposed to react a -rubber component with maleimide, an olefinically unsaturated nitrile, and an aromatic vinyl compound (US Pat. No. 3,721,724). Specification). However, when a polymerization reaction of maleimide or the like is carried out in the presence of a rubber component, the polymerization rate decreases significantly, and the amount of copolymer that does not participate in bonding with the rubber component increases. If the amount of maleimide is increased in order to avoid this and impart the desired heat resistance, the polymerization time must be lengthened, and the molded product will only have poor impact resistance and surface gloss. There are problems such as not being able to obtain it.

On the other hand, a copolymer obtained by emulsion polymerization of α-methylstyrene, vinyl cyanide monomer, and maleimide or its derivative, and an aromatic vinyl monomer, cyanide in the presence of polybutadiene or butadiene copolymer, A method for producing a composition obtained by blending a vinyl monomer and a graft copolymer obtained by graft copolymerization of maleimide or its derivative (Japanese Patent Application Laid-open No. 135210/1983), α-methylstyrene, A multicomponent copolymer obtained by emulsion polymerization of acrylonitrile, N-phenylmaleimide, and other copolymerizable vinyl monomers, and aromatic vinyl monomers and methacrylic monomers in the presence of a rubbery polymer. A composition obtained by mixing an acid alkyl ester monomer, a vinyl cyanide monomer, N-phenylmaleimide, and a graft copolymer obtained by polymerizing another copolymerizable vinyl monomer. (Unexamined Japanese Patent Publication No. 59-
184243) is disclosed.

However, compositions of copolymers containing maleimide, N-substituted maleimide, etc. as components and rubber exhibit high heat distortion temperatures and good melt fluidity, but resins with no viscosity and low tensile elongation This has the disadvantage of limiting its use.

Furthermore, we have previously discovered a method for obtaining a highly heat-resistant and impact-resistant resin by blending a rubber-like polymer with a six-membered ring structure that has a high heat distortion temperature and high heat decomposition resistance. However, the properties of the resin obtained by this method are that it is sticky and has a mediocre tensile elongation rate, but there are some points that need to be improved, such as insufficient impact resistance against notched parts.

(Problems to be Solved by the Invention) As described above, there is a method of obtaining a highly heat-resistant and impact-resistant resin that has comprehensive strength and impact resistance by an industrially advantageous means. had not been found.

(Means for Solving the Problems) In order to achieve the above object, the present inventors have conducted studies and found that a copolymer containing a five-membered ring structural unit and a copolymer containing a six-membered ring structural unit. We have discovered that copolymers can be blended well with each other and ABS resin, and that an ABS resin composition can be obtained that comprehensively satisfies heat resistance and impact resistance, and based on this knowledge, we have completed the present invention. reached.

That is, the present invention provides 20 to 95 mol% of methyl methacrylate units represented by the general formula (R1 in the formula is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group) A total of 3 to 78 moles of six-membered ring structural units, 0.1 to 50 moles of acid anhydride units of formula (1), 2 to 77 moles of imide units of formula (21), and 1 to 50 moles of aromatic vinyl units. % and 1 to 50 mol% of methacrylic acid units, and the viscosity of a methyl ethyl ketone solution of this copolymer at a concentration of 10% by weight at 25°C is 3 to 20 centipoise (A) 10 to 70% by weight and 30 to 87 mol% of aromatic vinyl units, maleimide or N
-Substituted maleimide 350 Ronitrile 1055 Copolymer (B) whose viscosity at 25° C. of a methyl ethyl ketone solution with a copolymer concentration of 10% by weight is 3 to 15 centipoise 2 0 to 80% by weight, and an aromatic vinyl Units 34-82 mol%, unsaturated nitrile units 18-66
1 to 60% by weight of a copolymer (C) consisting of molti, 34 to 82 mol% of aromatic vinyl units, and 18 unsaturated nitrile units to a rubber having a glass transition temperature of 30°C or less.
The present invention relates to a methacrylimide-maleimide resin composition comprising 10 to 70% by weight of a grafted rubber grafted with a copolymer of 66 to 66 mol.

The resin composition of the present invention is characterized by excellent compatibility between three types of copolymers and one type of copolymer graft rubber, resulting in a resin composition that has excellent overall heat resistance and impact resistance. It's about getting things.

Further showing the characteristics of the resin composition of the present invention, the copolymer (N
is a heat-resistant copolymer containing methyl methacrylate, which is compatible with ABS resin and forms a unique impact-resistant resin. The resulting resin has excellent heat resistance and tensile elongation, which is an indicator of toughness, but on the other hand, it lacks impact resistance in areas with notches. On the other hand, copolymer f
B) is a known maleimide copolymer and contains aromatic vinyl. This material is also compatible with ABS resin,
Although it provides heat resistance and impact resistance, the copolymer (contrary to Al-based compositions) lacks tenacity as expressed by tensile elongation, but has sufficient impact resistance at the notched portion.

The presence of both copolymers together compensates for this phase deficiency problem and also provides good lance properties. Incidentally, the material that develops impact resistance is the graft rubber, and the copolymer (C) having the same composition as this graft copolymer has a higher compatibility between the copolymer (A), (Bl and the rubber part). It became an essential component to improve the quality of the product, and as a result, we were able to complete a composition with properties that had not been seen before in a four-component mixed system.

The copolymer (A) constituting the resin composition of the present invention has excellent heat resistance and has a high heat distortion temperature and a high thermal decomposition temperature, and is mainly composed of methyl methacrylate units, six-membered cyclic acid anhydride, and six-membered cyclic imide units. It also contains necessary amounts of aromatic vinyl units and methacrylic acid units.

The methyl methacrylate unit constituting this copolymer (A) functions to exhibit oil resistance and strength, and is required in an amount of 20 to 95 molty, preferably 25 to 90 molty.

If the amount is less than 20 moles, the strength and oil resistance of the copolymer (A) will be insufficient, and the resin composition will also have insufficient impact resistance, which is not preferable. The six-membered ring structural unit constituting the copolymer (A) consists of the following formulas (1) and (2).

The content is 3 to 78 mol%, preferably 5 to 50 mol%. If the molar ratio is less than 3, there is no effect of improving heat resistance.
If it exceeds 78 mmol, the melt flowability of the resin composition decreases, and the molding processability decreases, which is not preferable. This six-membered ring structural unit has 0.1 to 50 moles of six-membered cyclic acid anhydride units and 2 to 77 moles of six-membered ring imide units, but preferably the six-membered ring imide unit is the main component; The number of cyclic acid anhydride units is 0.1 to 10 molar, and the number of six-membered cyclic imide units is 4.
~50 molti. The six-membered ring imide unit is excellent in terms of heat resistance and water resistance, but it is important to prevent a decrease in melt fluidity and to be compatible with the unsaturated nitrile-containing copolymer, which is another component of the resin composition. A six-membered cyclic acid anhydride unit is necessary to maintain good properties. The aromatic vinyl unit constituting the copolymer has the function of maintaining high melt fluidity and suppressing hygroscopicity, and has a mole content of 1 to 70 moles, preferably 5 to 50 moles. If the molar ratio is less than 1 molar, the melt flow and kinetics will deteriorate, and the hygroscopicity will also decrease, which is undesirable. On the other hand, if it exceeds 70 molti, mechanical strength decreases, which is not preferable. Examples of the aromatic vinyl constituting the copolymer include TE, styrene, α-methylstyrene, p-methylstyrene, chlorostyrene, p-tart butylstyrene, and styrene alone or styrene and α-methylstyrene. It is preferable to use styrene in combination.

The methacrylic acid unit constituting the copolymer (A) plays the role of improving heat resistance together with the six-membered ring structural unit, and is in the range of 1 to 20 molty, preferably 1 to 15 molty. If it is less than 1 mole fraction, it will not be able to improve the heat resistance, and if it exceeds 20 mole fractions, the thermal decomposition will increase, and when the resin composition is molded at 260° C. or higher, gas will be generated, which is not preferable.

This copolymer (A) requires an appropriate molecular weight.

One way to express this molecular weight is at a concentration of 10% by weight.
Using the viscosity of the methyl ethyl ketone solution at a temperature of 25 °C, it is between 3 and 20 centipoise, preferably between 3 and 20 centipoise.
If it is less than 10 centipoise, it is not preferred as a composition. If it is less than 3 cm, the impact resistance of the composition will decrease, which is undesirable. On the other hand, if it exceeds 20 cm, the melt flowability of the composition will decrease, and the moldability will be poor, resulting in a 16 (tai-copolymer). The six-membered ring structural unit of union (A) is obtained by changing most of the six-membered cyclic acid anhydride units into imide units; To this end, ammonia, aliphatic primary amines, aromatic amines, etc. are used.As the ammonia, liquid ammonia, ammonia gas, aqueous ammonia can be used, and as the aliphatic primary amines, for example, Examples of aromatic amines include methylamine, ethylamine, rr-furobylamine, 1so-propylamine, tert-butylamine, pentylamine, hexylamine, cyclohexylamine, and allylamine, which can also be used as an aqueous solution. Examples include aniline, 0-toluidine, p-toluidine, 0-chloroaniline, p-chloroaniline, 2゜4,6-dolichloroaniline, α-su7tylamine, β-su7tylamine, etc. Walnut:/, DL+, D- or L-α-phenethylamine, β-phenethylamine, etc. can also be used.Furthermore, polyamines such as 2-quethylaminoethylamine and hydroxylamines such as inpropaturamine can also be used. Can be used.

Next, various methods can be used to modify the six-membered cyclic acid anhydride unit into the six-membered cyclic imide unit. For example, a copolymer containing six-membered cyclic acid anhydride units is charged as a reaction precursor in an autoclave, then aqueous ammonia is injected in a solution state to react, and the reaction is further carried out at a temperature of 250°C.
After melting the precursor copolymer continuously using a method of imidization by time treatment or using an extruder, aqueous ammonia, cyclohexylamine, aniline, etc. are continuously injected, and then imidization is performed in a vacuum chamber. A method such as cyclization is used.

The copolymer (B) constituting the resin composition of the present invention has excellent heat resistance and has a high heat distortion temperature and a high thermal decomposition temperature, and is mainly composed of aromatic vinyl units and maleimide or N-substituted maleimide units. It has the same type of function as the previous copolymer, but the difference is that copolymer (4) is based on methyl methacrylate, whereas copolymer (B1) is based on aromatic vinyl.

The aromatic vinyl unit constituting this copolymer (B) has the effect of maintaining high melt flowability, imparting moldability due to K and suppressing hygroscopicity, and its amount is 30 to 87 mol%.
, preferably 45 to 75 mol.

If it is less than 30 molar, the melt fluidity will be greatly reduced and the hygroscopicity will also be large, which is not preferable. On the other hand, if it exceeds 87 molt, the other components will be reduced, resulting in a decrease in heat resistance and compatibility with ABS resin, which is not preferable. Examples of the aromatic vinyl unit include styrene, α-methylstyrene, p-methylstyrene, chlorostyrene, p-tert-butylstyrene, and styrene or α-methylstyrene alone or styrene and α-methylstyrene. It is preferable to use them together.

The maleimide or N-substituted maleimide units constituting the copolymer (B) serve to improve the heat resistance of the copolymer (B) and of the composition. The amount ranges from 3 to 50 mole, preferably from 3 to 20 mole. If it is less than 3 molti, the improvement in heat resistance will not be significant, and if it exceeds 50 molti, it is not preferable because of a decrease in melt fluidity.

This maleimide or N-substituted maleimide is synthesized from maleic anhydride, ammonia, and a primary amine by a known method, but commercially available products may also be used. This N-substituent can be selected depending on the type of primary amine, and can be roughly divided into aliphatic primary amines and aromatic primary amines. Examples of aliphatic primary amines include methylamine, ethylamine, n-propylamine, 1SO-propylamine, tert-butylamine, pentylamine,
Examples include hexylamine, cyclohexylamine, and allylamine, which can also be used as an aqueous solution. Examples of aromatic amines include aniline,
Examples include 0-)luidine, p-toluidine, 0-chloroaniline, p-chloroaniline, 2,4.6-)lichloroaniline, α-naphthylabane, β-naphthylamine, and benzylamine, DL -1D- or L-
α-7enethylamine, I-phenethylamine, etc. can also be used. Furthermore, polyamines such as 2-diethylaminoethylamine and hydroxylamines such as isopronominolamine can also be used.

Any maleimide or N-substituted maleimide synthesized in this way can be used in the copolymer used in the resin composition of the present invention, but in particular N-tertbutylmaleimide, N-substituted maleimide
-Cyclohexylmaleimide, N-phenylmaleimide, N-orthomethylmaleimide, and N-orthochloromaleimide are preferred, and N-phenylmaleimide is most preferred.

Next, acrylonitrile constituting the copolymer (B) imparts strength and oil resistance to the composition, and improves the blendability of other components of the copolymer (B).

The amount is from 10 to 55 molt, preferably from 10 to 4 molt.
There are 5 types. If it is less than 10 molar, it is not preferable because imparting oil resistance strength is insufficient and blendability with other copolymers deteriorates. On the other hand, if it exceeds 55 molt, the melt fluidity decreases, which is not preferable.

This copolymer (B) ld requires an appropriate molecular weight.

One way to express this molecular weight is at a concentration of 10
Using the viscosity of a methyl ethyl ketone solution of m at a temperature of 25°C, it is 3 to 15 centimeters/chipoise, preferably 3
It is not preferable as a composition unless it is ~10 cells/cm. If this is less than 3 cm voids, the impact resistance of the composition
On the other hand, if it exceeds 15 centivoise, the meltability of the composition decreases and the moldability is poor, which is not preferable.

The graft copolymers in the copolymers fc) and graft rubber +D) are copolymers of aromatic vinyl and unsaturated dichloromethane. The aromatic vinyl unit is required to be 34 molti or more in order to maintain melt fluidity, and the unsaturated nitrile unit is
It exhibits high strength and impact resistance, and is a copolymer (B) and (B).
In order to have good compatibility with l, a molar ratio of 18 or more is required. Examples of the aromatic vinyl constituting this copolymer include styrene, α-methylstyrene, p-methylstyrene, chlorostyrene, p-tert-butylstyrene, and styrene or α-methylstyrene alone or styrene. A combination of α-methylstyrene and α-methylstyrene is preferred. Examples of unsaturated nitriles include acrylonitrile and methacrylonitrile, with acrylonitrile being preferred.

Graft rubber (Di has the effect of developing impact resistance of the resin composition. Craft rubber is composed of a graft copolymer and rubber, and both of them are 0.2≦graft copolymer/rubber≦ It is made up of a weight ratio of 1.It is impossible to increase impact resistance with kraft rubber outside the above range.Rubber has a glass transition temperature of -30℃ or less; If it exceeds, it becomes impossible to exhibit high impact resistance.This rubber includes polybutadiene, butadiene containing 60% by weight or more and other copolymerizable monomers not more than 40% by weight, Examples include diene copolymers, alkyl acrylate polymers, ethylene-propylene terpolymers, etc., but particularly common are polybutadiene and butadiene copolymers.In the case of this butadiene copolymer, it is possible to copolymerize with butadiene/butadiene. Examples of monomers include aromatic vinyl, unsaturated nitrile, unsaturated carzenic acid, etc. In this case, styrene, α-methylstyrene, and p-methylstyrene are used as the aromatic vinyl, and styrene is particularly popular. It is true.

Examples of unsaturated nitriles include acrylonitrile and methacrylonitrile, with acrylonitrile being preferred. The unsaturated cardanic acid is generally methacrylic acid, but its content is often 5% by weight or less.

Next, the mixing amounts of copolymers (A), (B), (C1 and graft rubber (D) are shown.
The content is in the range of 70% by weight, preferably 10 to 50% by weight. If it is less than 10% by weight, no improvement in heat resistance can be expected;
If it exceeds % by weight, the rigidity becomes high and the impact strength decreases, which is not preferable.

The amount of copolymer (B) is in the range of 20 to 80% by weight, preferably 20 to 60% by weight. If it is less than 20% by weight, the improvement in heat resistance will be insufficient, and if it exceeds 80% by weight, impact strength will decrease.

The copolymer (C1 is in the range of 1 to 60% by weight, preferably 5 to 40% by weight. Less than 1% by weight, the copolymer (A), (B) and graft rubber (D) If it exceeds 60% by weight, the amount of copolymers (A), (B), and rubber (7) will decrease, resulting in a decrease in heat resistance and impact resistance. Undesirable.

Craftsam ■) ranges from 10 to 70% by weight, preferably from io to 50% by weight. If it is less than 10% by weight, the impact resistance will decrease, and if it exceeds 70% by weight, the rigidity of the resin composition will decrease and the practical heat distortion temperature will decrease.

The copolymers (A), (B), (C) and the graft rubber Q)) are usually blended using an extruder, and a twin-screw extruder is particularly preferred.

As for the copolymer (A), first, a terpolymer of methyl methacrylate-aromatic vinyl-methacrylic acid is obtained by copolymerization. In this case, the polymerization method may be bulk polymerization, solution polymerization, or suspension polymerization. This terpolymer is then treated at high temperature and reduced pressure to generate six-membered cyclic acid anhydride units, resulting in methyl methacrylate-aromatic vinyl-
It is a quaternary system of methacrylic acid-6-membered cyclic acid anhydride, and by further acting with ammonia or various primary amines, a part or most of the 6-membered cyclic acid anhydride is modified into a 6-membered cyclic imide. be.

The copolymer FB+ is produced by radical copolymerization of aromatic vinyl and maleimide or N-1t-substituted maleimide and acrylonitrile. In this case, the polymerization method may be bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization.

The copolymer (C) is obtained by dical copolymerization. In this case, the polymerization method may be bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization.

Graft rubber (DJ) is a radical polymerization of aromatic vinyl and unsaturated nitrile in the presence of rubber, and any polymerization method such as bulk polymerization, solution polymerization, bulk/suspension two-stage polymerization, or emulsion polymerization may be used. It can be said that it is more common to use emulsion polymerization.

The composition thus obtained can be used as is for injection molding or extrusion molding, but if necessary, various heat stabilizers and light stabilizers such as benzotriazole type and hindered amine type may be added during blending. may be added, and a nonionic surfactant or anionic surfactant may also be added. In addition, as a lubricant, it can be used as a fluid and ξ
Rough-in, C4-C22 higher fatty acids, metal salts of C4-C22 higher fatty acids (calcium, magnesium, zinc, etc.), ethylene bis fatty acid (C16+ ELs) amides, higher aliphatic alcohols such as stearyl alcohol, adipic acid and Dibutyl or dioctyl ester of cinic acid, mono-, di-, and triglycerides of higher fatty acids (CG to C22), hydrogenated castor oil, hydrogenated middle finger, and cumethylpolysiloxane may be added.

(Effects of the Invention) According to the present invention, an impact-resistant resin composition with excellent heat resistance can be obtained.

The composition is suitably used in various applications such as automobile parts, industrial parts, and home appliance parts.

(Example) Next, the present invention will be explained in more detail with reference to Examples. The measurement method for each physical property is as follows.

(1) Vicat softening temperature: ASTM-D1525
(2) Heating deformation temperature: ASTM-D64B
(IB, 4 Kq/cm”, 1/4 in%, no annealing) (3) Izot impact strength: ASTM-
D256 (174 in%, notched) (4) Tensile strength: ASTM-D638 (5) Tensile strength: ASTM-D638 (6) Solution viscosity; solution of 10% by weight concentration of copolymer in methyl ethyl ketone at 25°C Viscosity: A Cannon-Fenske type viscosity tube (#200) was used.

(:) Production of copolymer (A)-1 28 parts by weight of methyl methacrylate, 13 parts by weight of styrene,
24 parts by weight of methacrylic acid, 35 parts by weight of ethylene glycol monoethyl ether, 0.1 parts by weight of octyl mercaptan, 1.1 parts by weight of 1.1-di-tert-charybutyl-oxy-3°3.5-to-IJ methylcyclohexane, based on a total of 100 parts by weight of ethylene glycol monoethyl ether. A mixed solution was prepared by adding 0.01 part by weight. This mixed solution was continuously supplied to a complete mixing type polymerization vessel at 112° C. for polymerization. A polymerization reaction solution having a solid content of 42% by weight was continuously supplied to a high-temperature vacuum chamber to remove unreacted substances and solvent and to produce a six-membered cyclic acid anhydride. The content of listyrene was determined by ultraviolet absorbance, the amount of methyl methacrylate and six-membered cyclic acid anhydride was determined by infrared spectrophotometry, and the amount of methacrylic oxygen was determined by titration. 28 mol %, 27 mol % of six-membered cyclic acid anhydride units, and 11 mol methacrylic acid units. Before this copolymer (A)-1, the viscosity of a 10% by weight methyl ethyl ketone solution of the skeleton at 25°C was 5.5 centivoise.

Before this, the skeleton and methyl ethyl ketone were placed in an autoclave to form a 20% by weight solution. Next, 2 equivalents of aniline was added to the amount of six-membered cyclic acid anhydride units in this copolymer,
It was treated at 150°C for 2 hours. After taking out the reaction solution, n
-Precipitate the polymer with hexane, and the polymer after purification is 2
The treatment was carried out at 50° C. for 2 hours in a 10 torr volatilization furnace. Measurement of the finally obtained product using an infrared spectrophotometer revealed that the absorption of the six-membered ring acid anhydride was considerably reduced, and at the same time, the formation of a new six-membered ring imide at 1680 ('Fff-') was observed. From the nitrogen content in elemental analysis, the six-membered ring imide unit was 25 mol% and the six-membered ring wrought anhydride unit was 2 mol%, so the imidization rate was 93. The copolymer thus obtained ( The characteristics of N-1 are shown in Table 1.

(n) Copolymer (manufacturing N-2 Methyl methacrylate 45% by weight, styrene 20% by weight,
Octyl mercaptan: 0.13% to 15% by weight of methacrylic acid, 20% by weight of ethylbenzene, 100 parts by weight in total
A mixed solution was prepared by adding parts by weight and o and o o s parts by weight of polymerization initiators. The method for polymerizing this mixed solution with 135c and the post-treatment method used were the same as those for producing copolymer (A)-1. The composition of the obtained copolymer (A-2 precursor is 48 mol% of methyl methacrylate units, 2y mol% of styrene units, 13 mol% of six-membered cyclic acid anhydride units, 9 mol% of methacrylic acid units, and The viscosity of the 10% by weight methyl ethyl ketone solution at 25°C was 6.0 centipoise.The precursor was then imidized with ammonia.

The method is exactly the same except that 2 equivalents of aniline in copolymer (A)-1 is replaced with 2 equivalents of ammonia. The characteristics of copolymerization inner-2 obtained in this way are
Shown in the table.

Production of ft1ll copolymer (Bl-1) The inside of a reactor equipped with a stirrer was replaced with nitrogen, and 200 parts by weight of pure water, 0.9 parts by weight of sodium di-2-ethylhexylsulfosuccinate, and 0 parts by weight of sodium lauryl sulfate were added. .1
parts by weight, 0.03 parts by weight of sodium formaldehyde sulfoxylate, 0.01 parts by weight of ferrous sulfate, and 0.02 parts by weight of disodium ethylenediaminetetraacetate,
The temperature was controlled at 70°C. Next, 20 parts by weight of acrylonitrile,
A mixed solution consisting of 65 parts by weight of α-methylstyrene, 15 parts by weight of N-phenylmaleimide, 0.3 parts by weight of cumene hydroperoxide, and 0.2 parts by weight of t-dodecylmercaptan was continuously supplied to the reactor over a period of 6 hours. did.

After the end of the supply, polymerization was continued at 70° C. for another hour. After the polymerization was completed, the solid content of the latex was measured and the polymerization rate was calculated to be 97%.

This copolymer was designated as (B)-1, and its properties are shown in Table 1.

(1v) Production of copolymer (B)-2 Styrene zsi-t*, 18% by weight of N-phenylmaleimide, 9% by weight of acrylonitrile, 45% by weight of methyl ethyl ketone, based on a total of 100 parts by weight, α-methylstyrene dimer A mixture of 0.03 parts by weight of i,t-bis(tertiarybutylnozo-oxy)-3,3゜5-trimethylcyclohexane and 0.03 parts by weight of The first stage reactor was a complete mixing type with an internal volume of 5λ.The polymerization temperature was 110°C.
The polymerization liquid coming out of the stage reactor contains 48% solids by weight.

This liquid is immediately and continuously fed to the second stage reactor. This second stage reactor is a laminar flow type with an internal volume of 7°C and L/D = 5, and the polymerization temperature is 110°C in the upper stage and 12°C in the middle stage.
The temperature was 0°C, and the lower temperature was 130°C. The polymerization reaction liquid is taken out continuously, and when a part of it is taken out, the solid content is 51.
% by weight. Therefore, the polymerization conversion rate was 93%. The continuously taken out reaction solution was immediately heated to 270°C for 15 t.
After the unreacted monomers and solvent are separated, the product is discharged from the bottom of the devolatilization chamber using a screw type extruder.

The obtained copolymer (B)-2 is a styrene-N-phenylmaleimide-acrylonitrile terpolymer, and
Styrene unit ss mol% N-phenylmaleimide unit 2
It has a composition of 3 mol % and 19 mol of acrylonitrile units. Its characteristics are shown in Table 1.

(Left below) (v) Production of copolymer (C) Styrene, acrylonitrile, and ethyl chloride are continuously fed into a complete mixing reactor. Polymerization temperature is 100-150℃
At a polymerization rate of 30 to 50%, the reactor was led to a high-temperature vacuum chamber, residual monomers and solvent were removed, and an extruder was used to extrude a copolymer of 54 mol% styrene units and 46 mol% acrylonitrile units. Combined product (C) was obtained.

(vl) Production of graft rubber (D) 50 parts by weight of polybutadiene latex in terms of solid content and 150 parts of ion-exchanged water were charged into a reactor, and 35 parts by weight of styrene was heated at 70°C with stirring. , a mixture of 15 parts by weight of acrylonitrile and an aqueous solution of 0.5 parts by weight of potassium persulfate dissolved in 50 parts by weight of ion-exchanged water were polymerized for 5 hours, and after the polymerization reaction was completed, the graft copolymer latex was prepared. A pellet-shaped graft copolymer was obtained by salting out, dehydrating, drying, and granulating. The graft copolymer thus obtained was composed of component (C) and (DJ
It is a mixture of When the insoluble and soluble components were separated using acetone, 75 parts by weight became the insoluble components, ie, the graft copolymer, based on 50 parts by weight of the rubber component.

The grafting rate will be 50cm. On the other hand, the acetone soluble content was 25 parts by weight, a styrene-acrylonitrile copolymer (46 mol % of acrylonitrile units and 54 mol styrene units).
It's C.J. Hereinafter, when mixing each component, the (C1 component and (D+ acid component) in the graft copolymer were separated.

Examples 1 to 4 and Comparative Examples 1 to 4 Copolymers (A)-1, (B)-1, (C) produced with the above (1), (Hi), M and (vl) and the graft rubber ( D) and mixed in the proportions shown in Table 2,
It was granulated using a twin-screw extruder to obtain a pelletized blended resin composition.

Thereafter, this pellet-shaped blended resin composition was sufficiently dried, and molded pieces for physical property tests were injection molded. After this molded piece was left for 48 hours at 23° C. and 50% humidity, its physical properties were measured. The results are shown in Table 2.

Examples 5 to 8 and Comparative Examples 5 to 7 The above (liJ, (lv) 1vl (vl and (vl
) copolymer (Al-2, (B)-2, (c
) and graft rubber (D) were mixed in the proportions shown in Table 3, and granulated using a twin-screw extruder to obtain a pelletized blended resin composition.

Thereafter, this pellet-shaped blended resin composition was sufficiently dried, and molded pieces for physical property tests were injection molded. After this molded piece was left for 48 hours at 23° C. and 50% humidity, its physical properties were measured. The results are shown in Table 3.

(Margin below)

Claims (1)

[Claims] 1. 20 to 95 mol% of methyl methacrylate units, general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) (R_1 in the formula is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group). ~50 mol%, 2 to 77 mol% of imide units of formula (2), 1 to 70 mol% of aromatic vinyl units, and 1 to 20 mol% of methacrylic acid units, and methyl ethyl ketone with a copolymer concentration of 10% by weight. 10 to 70% by weight of copolymer (A) having a viscosity of 3 to 20 centipoise at a solution temperature of 25°C, and 30% by weight of aromatic vinyl units.
~87 mol% maleimide or N-substituted maleimide 3~
50 mol%, acrylonitrile 10-55 mol%, and 20-80% by weight of a copolymer (B), which has a viscosity of 3-15 centipoise at a temperature of 25°C of a methyl ethyl ketone solution with a copolymer concentration of 10% by weight. , aromatic vinyl units 34-82 mol%, unsaturated nitrile units 18
1 to 60% by weight of copolymer (C) consisting of ~66 mol%, a rubber having a glass transition temperature of -30°C or lower, 34 to 82 mol% of aromatic vinyl units, and 1 unsaturated nitrile unit.
A methacrylimide-maleimide resin composition comprising 10 to 70% by weight of a graft rubber (D) grafted with a copolymer comprising 8 to 66 mol%.