JP2533790B2 - Imide group-containing resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to styrene and / or α-methylstyrene-
Resin consisting of N-substituted maleimide copolymer resin, styrene-acrylonitrile copolymer resin modified with polybutadiene, etc. (hereinafter abbreviated as ABS, hereinafter the same), and styrene-acrylonitrile copolymer resin (hereinafter AS) added as necessary. The composition contains aromatic vinyl-vinyl cyanide-maleic anhydride copolymer [D-1] and aromatic vinyl-N-.
An imide group-containing resin composition excellent in heat resistance / impact resistance and melt fluidity obtained by adding a copolymer mixture consisting of a substituted maleimide-copolymer of a third monomer [D-2] Regarding things.

[Conventional technology]

The composition of styrene or α-methylstyrene-N-substituted maleimide copolymer resin (hereinafter (α) SI) and ABS is known and disclosed in, for example, USP 3,652,726.
Although this composition has high impact resistance because it uses ABS, it cannot be said that the heat resistance is sufficient because (α) SI and ABS have poor compatibility.

Further, a ternary resin composition of (α) SI, ABS and AS is also known, and examples thereof include JP-A-59-93,746. In this example, by using an appropriate amount of AS as a modifier in the composition of (α) SI and ABS, it is possible to obtain a composition having higher heat resistance than a simple composition of (α) SI and ABS. Disclosure.
However, also in this composition, the matrix resin is essentially incompatible, and although the heat resistance is high, the impact resistance and the melt fluidity are not sufficient.

For the purpose of improving the performance of the composite resin composition, attempts have been made to add a solid compatibilizer having a high affinity to both resins, for example, JP-A-61-179,212 discloses that AS in the presence of a radical initiator. A modified polymer obtained by kneading a polymer mixture of MS (methyl methacrylate-styrene copolymer resin) was added to an AS / MS blend system to develop physical properties that cannot be obtained by a simple blend. But with (α) SI
For a composition consisting of ABS or (α) SI and ABS and AS, there is no effective compatibilizer (complex type modifier) and the composition must be blended while remaining incompatible. It didn't have enough performance.

[Problems to be Solved by the Invention]

In order to improve the compatibility and improve the physical properties of the blend composition of ABS and AS used as necessary with (α) SI as an essential component, the present invention uses a polymer component of (α) SI and AS. By synthesizing a solid compatibilizer in the same molecule and adding it to a blend composition of (α) SI and ABS or (α) SI and ABS and AS, a simple blend composition can be obtained. The purpose is to obtain a composite resin composition having high heat resistance, impact resistance and melt flowability.

[Means for solving the problem]

The present invention relates to a copolymer [D-1] composed of an aromatic vinyl compound, a vinyl cyan compound and maleic anhydride, an aromatic vinyl compound, an N-substituted maleimide compound and 2
-A copolymer comprising a functional group-containing monomer selected from at least one of hydroxyethyl methacrylate, glycidyl methacrylate and p-aminostyrene [D-
2] in the presence of a small amount of water, the temperature of 180 ~ 300 ℃
By adding a small amount of the copolymer composition [D] obtained by melt-kneading at 5 to 30 minutes to a blend of (α) SI and ABS or AS used as necessary, heat resistance and resistance can be improved. It is an object of the present invention to provide a high-performance resin composition having excellent impact properties and melt flowability.

That is, the present invention includes (1) a) 40 to 70% by weight of an aromatic vinyl compound, 30 to 60% by weight of an N-substituted maleimide compound, and 40 to 80 parts by weight of a copolymer resin [A], and b) a rubber. In the presence of 30 to 70% by weight of the polymer, 25 to 50% by weight of an aromatic vinyl compound and 5 to 20% of a vinyl cyanide compound.
% By weight, and 0 to 50% by weight of another copolymerizable vinyl compound, which is a graft copolymer resin [B].
20-60 parts by weight, c) A copolymer resin [C] comprising 60-82% by weight of an aromatic vinyl compound, 18-40% by weight of a vinyl cyanide compound and 0-50% by weight of another copolymerizable vinyl compound. 0 to 20 parts by weight, based on 100 parts by weight of a resin composition consisting of: d) 50 to 84% by weight of aromatic vinyl compound, 15 to 49% by weight of vinyl cyanide compound and 1 to 10% by weight of maleic anhydride.
30 to 70 parts by weight of a copolymer [D-1] composed of 40 to 74% by weight of an aromatic vinyl compound and an N-substituted maleimide compound 25
To 59% by weight and a functional group-containing monomer 1 to 10 selected from at least one of 2-hydroxyethyl methacrylate, glycidyl methacrylate and p-aminostyrene.
Copolymer composition [D] 5 obtained by melt-kneading a copolymer mixture consisting of 30 to 70 parts by weight of copolymer [D-2] at a temperature of 180 to 300 ° C. An imide group-containing resin composition having excellent heat resistance, impact resistance, and melt flowability, which is formed by adding 30 parts by weight.

(2) N-substituted maleimide compounds are N-phenylmaleimide, N-cyclohexylmaleimide, N- (2,4,
The resin composition according to claim 1, which is at least one selected from 6-tribromo) phenylmaleimide.

The copolymer resin [A] used in the present invention comprises an aromatic vinyl compound 40 to 70% by weight and an N-substituted maleimide compound 30 to 60%.
It is a copolymer consisting of wt%, solution polymerization, suspension polymerization,
It may be produced by any method such as emulsion polymerization, but the method by emulsion polymerization is preferred. Copolymer of the present invention [A]
As the aromatic vinyl compound used in, styrene,
Examples include α-methylstyrene and p-methylstyrene. Of these, α-methylstyrene is particularly preferable. The amount of the aromatic vinyl compound used is 40 to 70% by weight. If it is less than 40% by weight, the fluidity is lowered, which is not preferable, and if it exceeds 70% by weight, the heat resistance is lowered. Examples of the N-substituted maleimide used in the copolymer [A] of the present invention include N-
Phenylmaleimide, N-cyclohexylmaleimide,
N- (2,4,6-tribromo) phenylmaleimide is preferred. If N-substituted maleimide other than these is used, the heat resistance is lowered. The amount of N-substituted maleimide used is
30 to 60% by weight. If this amount is less than 30% by weight,
It is not preferable because it is inferior in heat resistance, and when it exceeds 60% by weight, fluidity is lowered, which is not preferable.

The graft copolymer resin [B] used in the present invention is an aromatic vinyl compound in the presence of 30 to 70% by weight of a rubbery polymer.
It is obtained by graft copolymerizing 25 to 60% by weight, vinyl cyanide compound 5 to 20% by weight and other copolymerizable vinyl compound 0 to 50% by weight, preferably 0 to 20% by weight. The graft copolymer resin [B] is produced by an emulsion polymerization method in which a latex of a rubber-like polymer is grafted with the above-mentioned monomer mixture, or a solution of graft-polymerizing the monomer mixture in a solution of the rubber-like polymer. Any method such as a polymerization method may be used. As the rubber-like polymer, butadiene rubber, styrene-butadiene copolymer rubber, ethylene-propylene copolymer rubber, acrylic rubber or the like is used. When the amount of the rubbery polymer used is less than 30% by weight, the impact resistance of the resin [B] is low, and when it exceeds 70% by weight, the heat resistance of the final composition is lowered. As the aromatic vinyl compound in the graft copolymer resin [B], the same compounds as those used in the above [A] are used, but styrene is particularly preferable.
The amount of aromatic vinyl compound in [B] is in the range of 25 to 60% by weight. If it is less than 25% by weight, the melt fluidity of [B] is low, and if it exceeds 60% by weight, the heat resistance of [B] is lowered. When styrene and α-methylstyrene are used together, the proportion of α-methylstyrene is 50% by weight in the wholly aromatic vinyl compound.
The following is desirable. If it is used more than that, the impact resistance of the final composition is lowered. Acrylonitrile is most suitable as the vinyl cyanide in [B]. The amount of vinyl cyanide used is 5 to 20% by weight. Below 5% by weight,
If the solvent resistance of [B] or the final composition is low and exceeds 20% by weight, the melt fluidity of [B] is low. Examples of the polymerizable vinyl compound used in [B] as required include acrylic acid esters such as methyl acrylate, ethyl methacrylate and butyl acrylate, and unsaturated acids such as acrylic acid and methacrylic acid. Of these, methyl methacrylate is preferable for improving the heat shrinkage ratio of the final composition. The usage rate of this thing is less than 50% by weight,
It is preferably less than 20% by weight. It is not preferable to use more than that, because the heat resistance will decrease.

The copolymer resin [C] used in the present invention may be produced by any method such as solution polymerization, suspension polymerization and emulsion polymerization, but it means that it can be easily blended with [A] or [B]. The emulsion polymerization method is preferred. As the aromatic vinyl compound used in [C], the same kind as in [A] or [B] can be used. Particularly, styrene alone or styrene and α-
The combined use of methylstyrene is preferred. When styrene and α-methylstyrene are used in combination, the ratio of α-methylstyrene in the aromatic vinyl compound is preferably less than 50% by weight. If it is 50% by weight or more, the impact resistance of the final composition becomes low. The amount of aromatic vinyl compound in [C] is 60
If it is less than 60% by weight, the fluidity is lowered, and if it exceeds 82% by weight, the compatibility of the copolymer resins [A], [B] and [C] is lowered. Is not preferred. Examples of vinyl cyanide in [C] include [B]
Acrylonitrile is used as in. The amount of this substance used is from 18 to 40% by weight. If it is less than 18% by weight, the compatibility with [A] and [B] is poor, while if it exceeds 40% by weight, the resin is colored, which is not preferable. As the other monomer copolymerizable with the aromatic vinyl compound or the vinyl cyanide compound, the same acrylic acid ester or unsaturated acid as in [B] can be used, and methyl methacrylate is particularly preferable. The amount used of this is less than 50% by weight, and more preferably less than 20% by weight. If it is 50% by weight or more, the physical properties of the final composition, particularly the heat resistance, deteriorate.

The copolymer [D-1] used in the present invention can be produced by any known method. For example, when adopting the solution polymerization method, an aromatic vinyl compound, a vinyl cyanide compound and a small amount of maleic anhydride are dissolved in a solvent such as methyl ethyl ketone, and a radical initiator is added and charged into a reaction vessel under an inert gas atmosphere. Polymerize with. In order to keep the composition of the polymer constant, it is desirable to add the remaining maleic anhydride in portions during the polymerization. Polymerization temperature is 70-120
The temperature can be arbitrarily selected within the range of 0 ° C, but a relatively low temperature of around 80 ° C is preferable in order to increase the molecular weight of the polymer. It is convenient for the subsequent blending operation that the dope after completion of the polymerization is devolatilized with a vacuum dryer, and the finally obtained lump product is pulverized into a fine powder.

The aromatic vinyl compound used in [D-1] is particularly preferably styrene and α-methylstyrene alone or in combination. Examples of the vinyl cyan compound used at the same time include acrylonitrile and methacrylonitrile, with acrylonitrile being preferred. [D-1]
The composition ratio of the aromatic vinyl compound (a), the vinyl cyan compound (b) and the maleic anhydride (c) in the
50-84 wt%, (b) 15-49 wt% and (c) 1-
It must be in the range of 10% by weight. When the content of (a) is less than 50% by weight, the [D-1] tends to be colored during heating and kneading. When the content of (a) exceeds 84% by weight, the heat resistance of [D-1] decreases. Vinyl cyanide compound (B) in [D-1]
If it is less than 15% by weight, the affinity for blending with (α) SI or the like is poor, and if it exceeds 40% by weight, color deterioration is likely to occur. When the amount of maleic anhydride (C) in [D-1] is less than 1% by weight, the effect as a compatibilizing agent of the copolymer composition [D] is poor, while when it is 10% by weight or more, D-1]
Composition [D] obtained by kneading and [D-2] is not preferable because it gels. The solution viscosity [η] as an index of the degree of polymerization of the polymer [D-1] is preferably 0.3 to 1.0 when measured in tetrahydrofuran at 30 ° C. When it is less than 0.3, the strength as a resin is poor, and when it is 1.0 or more, the molecular weight is too high and the fluidity is poor.

The production method of the copolymer [D-2] used in the present invention can be arbitrarily selected, but for example, the suspension polymerization method is preferable. Specifically, a functional group-containing monomer (e) selected from at least one kind of aromatic vinyl compound (a), N-substituted maleimide (d) and 2-hydroxyethyl methacrylate, glycidyl methacrylate and p-aminostyrene. The monomer mixture consisting of the above three components is put into an aqueous solution containing a calcium phosphate-based dispersant to form a suspension, and a radical initiator such as benzoyl peroxide is used in a nitrogen atmosphere.
Polymerize at ~ 80 ° C for about 10 hours. The resulting 100μ
A bead-shaped polymer having a particle size of about 3 is filtered and dried.
The fact that the polymer shape is beaded means that the following [D-1]
And [D-2] have an advantage that they are easily mixed in the kneading process. Aromatic vinyl compound (a) which is a component of [D-2]
The same monomer as [D-1] can be used. Further, as the N-substituted maleimide (d), N-phenylmaleimide, N-cyclohexylmaleimide, N-
(2,4,6-Tribromo) phenylmaleimide and the like are preferable, and N-phenylmaleimide is particularly preferable. The functional group-containing monomer (e) means a monomer having a so-called reactive functional group such as a hydroxyl group, an epoxy group, an amino group, and specifically, 2-hydroxyethyl methacrylate, glycidyl methacrylate, p -Aminostyrene and the like. The amount of the aromatic vinyl monomer used in [D-2] is preferably 40 to 74% by weight. If it is less than 40% by weight, the copolymer [D-2] has poor thermal stability and low fluidity. When it is 74% by weight or more, the heat resistance of [D-2] is low,
The effect of the composition comprising [-1] and [D-2] as a compatibilizer or a composite resin modifier is also low. N- in [D-2]
The composition ratio of the substituted maleimide compound needs to be 25 to 59% by weight. When the N-substituted maleimide compound is less than 25% by weight, the heat resistance of [D-2] becomes poor. [D-
The ratio of the third component monomer (e) in 2) is preferably 1 to 10% by weight. If it is less than 1% by weight, the effect of the composition of [D-1] and [D-2] as a compatibilizer is not exhibited. [D-
[Η] (measurement conditions are the same as those of [a]) as a polymerization index of 2] is preferably 0.3 to 1.0. When it is less than 0.3, the strength as a polymer is low, and when it is 1.0 or more, the fluidity of the final composition is poor.

The copolymer composition [D] in the present invention is a copolymer [D
-1] and [D-2] are melt-kneaded and obtained. As the melt-kneading method, a method used for ordinary plastics kneading can be arbitrarily selected. Specifically, a melt mixing device such as a roll, a kneader, or a kneading extruder can be used, but it is particularly effective to use a kneading extruder with a biaxial vent.
The melt-kneading temperature is preferably 180 to 300 ° C. If it is less than 180 ° C., the kneading is insufficient and the reaction does not proceed, and if it is 300 ° C. or more, the resin is decomposed, which is not preferable. The melt kneading time is preferably about 5 to 30 minutes. Copolymer at the time of kneading [D-
The weight composition ratio of 1] and [D-2] is [D-1] / [D-
2] = (30 to 70) / (70 to 30), but the more preferable range is determined by the following method.
That is, the weight% of the maleic anhydride unit in [D-1]
N, its molecular weight is 98, the amount (composition ratio) of [D-1] in the composition is X part, and the weight% of the third monomer (e) in [D-2] is m, When the use amount of M and [D-2] of the molecular weight is Y part, X + Y = 100 (parts by weight) (1), and the maleic anhydride unit in [A] and [B]
When the molar ratio of the functional groups of is Q, 0.5 ≦ Q = (M × n × X) / (98 × m × Y) <1.5
(2) However, X and Y are calculated and blended so as to satisfy n, m ≠ 0 (3).
When Q represented by the formula (2) is less than 0.5 or 1.5 or more, the composition does not exhibit a sufficient effect as a compatibilizer. The more preferable range of Q is 0.8 ≦ Q <1.2.

As a method for obtaining the final composition of the present invention, resins [A] and [B] and optionally a resin [C]
A predetermined amount of pellets of the copolymer composition [D], which is the solid compatibilizing agent of the present invention, is weighed in the powder of 1. and a small amount of a heat stabilizer is added, and then thoroughly mixed with a tumbler mixer or the like. The mixed sample may be kneaded and extruded using a biaxial kneading extruder or the like to form pellets.

When the final composition of the present invention is obtained, the proportion of the resin [A] used is preferably 40 to 80 parts by weight, and when it is less than 40 parts by weight, the heat resistance of the final composition is low. If it exceeds 80 parts by weight, the impact resistance and melt fluidity of the final composition will decrease. The proportion of the graft copolymer resin [B] in the final composition is preferably 20 to 60 parts by weight. If it is less than 20 parts by weight, the impact resistance of the final composition is low, and if it exceeds 60 parts by weight, the heat resistance is lowered. Next, the amount of the copolymer resin [C] used as required needs to be less than 20 parts by weight. If it exceeds 20 parts by weight, the heat resistance and impact resistance of the final composition will deteriorate.

Next, the proportion of the solid compatibilizer [D] used in the final composition is preferably 5 to 30 parts by weight. If it is less than 5 parts by weight, the impact resistance of the final composition will be low, and if it exceeds 30 parts by weight, the heat resistance of the final composition will be low.

〔Example〕

The present invention will be described below with reference to specific examples. Parts and percentages are by weight unless otherwise specified.

[Production Example of Copolymer [A]] The inside of a reactor equipped with a stirrer was replaced with nitrogen, and 150 parts of ion-exchanged water, α-methylstyrene (αS), 70 parts, and N-phenylmaleimide ( pMI) ・ 30 parts, and then the internal temperature was raised to 60 ℃, sodium pyrophosphate.
Add 2 parts, ferrous sulfate hydrate 0.01 part, glucose 0.4 parts dissolved in ion-exchanged water 20 parts, add cumene hydroperoxide (CPO) 0.05 parts to start polymerization, It was polymerized for 4 hours. The obtained copolymer was coagulated with calcium chloride, washed with water and dried. Composition analysis of this copolymer (αSI) revealed that αS = 72% and pMI = 28%. Moreover, [η] = 0.
It was 52. The analytical data are shown in Table 1 together with an example in which N-cyclohexylmaleimide was used as the N-substituted maleimide.

[Copolymer resin [B] and [C]] As the copolymer resins [B] and [C] used in the present invention, commercially available products shown in Table 2 were used.

[Production of Copolymer [D-1] _X ] By replacing the inside of a reactor equipped with a stirrer with nitrogen,
Methyl ethyl ketone (MEK) · 30 parts, styrene (ST) · 7
0 parts, acrylonitrile (AN), 27 parts and maleic anhydride (MAH), 3 parts, and a polymerization initiator, lauroyl peroxide (LPO), 0.2 parts were added all at once, and the mixture was heated at 75 ° C under a nitrogen atmosphere at 3.
Polymerization was carried out for 5 hours. During the polymerization, MAH (5 parts) was dissolved in MEK (10 parts) and added every 10 minutes. After the completion of the polymerization, the inside was rapidly cooled, the dope was transferred to a vacuum dryer, and volatilized and dried. The devolatilized block-like sample was pulverized into a fine powder. Analysis of powder sample by IR spectrum shows ST = 66%,
AN = 26% and MAH = 8%, and [η] was 0.80. Table 3 shows the results of the production of four kinds of [D-1] _{x (x = a, b, c, d) in} which the kind and composition of the monomer and the amount of the molecular weight modifier were changed. However, [D-1] _d is an example in which maleic anhydride was not used.

[Production of Copolymer [D-2] _x ] By replacing the inside of a reactor equipped with a stirrer with nitrogen,
70 parts α-methylstyrene (αS), 10 parts N-phenylmaleimide (pMI) and glycidyl methacrylate (GMA)
-A monomer mixture containing 5 parts, benzoyl peroxide (BPO) as a polymerization initiator-0.35 parts, and a tertiary weight decyl mercaptan (TDM) -0.18 as a molecular weight regulator
Part of the mixture was charged and mixed well. Next, 100 parts of an aqueous dispersion containing 0.2 part of a calcium phosphate dispersant and 0.01 part of sodium dodecyl sulfate as a dispersion stabilizing aid was added to the above-mentioned monomer mixture and stirred at a high speed to obtain a suspension state. The internal temperature was raised to 75 ° C to polymerize, and the state was maintained for 6 hours. During this polymerization, αS ・ 5 parts and pMI ・
A 2 part solution was post-added over 5 hours. afterwards,
The internal temperature was raised to 85 ° C and the polymerization was continued for 2 hours.

After the polymerization was completed, the dispersant was decomposed with hydrochloric acid, filtered, washed with water and separated by filtration. After drying, a bead-like copolymer having a particle size of about 100 μm was obtained, and the yield based on the charged amount of the monomer was 98%. Table 4 shows the results ([D-2] _x ) of polymerization by changing the kinds and composition ratios of the monomers.

[Production of Copolymer Composition [D] of Copolymer [D-1] _{x as} Solid Compatibilizer and Copolymer [D-2] _x ] [D-1] _x and [D-2 The following method was adopted to obtain the blend composition from _x . That is, [D-1] _a = 41
Parts, [D-2] _a = 59 parts and 0.6 parts of deionized water were mixed and then fed to a 30 mmφ vented twin-screw extruder. The extrusion conditions are: screw temperature: 240 ° C, screw speed: 8
It was 0 rpm and the degree of vacuum of the vent was 30 Torr. IR analysis of the pellets after extrusion revealed that [D-1] _a [D-2] _a
The absorption of the acid anhydride and the absorption of the epoxy group became much weaker than the case of each alone, while the absorption of the free carboxyl group and the hydroxyl group was observed, so that the copolymer [D-1]
_It is considered that a chemical bond occurred between _a and [D-2] _a . Table 5 shows the contents of the same experiment with different kinds and amounts of [D-1] and [D-2].

(Resin property evaluation method) a. Heat distortion temperature (HDT) conforming to ASTM D-648, FS = 18.56kgf / cm ² : 1/4 ″, no annealing b. Izod impact strength (IS) conforming to ASTM D-256, 1/4 ″, cutting notch c. Melt index (MI) according to ASTM D-1238, 230 ℃ x 5KgL d. Tensile breaking strength (TS _b ) and tensile breaking elongation (T
E _b ) ASTM D-638 compliant, pulling speed: 5 mm / min [Example-1] αSI-1 = 2,400 (g), ABS = 1,600 (g) in Table-1
The compatibilizer [D] _aa = 400 (g) was weighed, and Sumitomo Chemical's Sumilizer WXR = 8.0 (g) was added as a heat stabilizer and mixed for 10 minutes in a mixing stirrer. The resin blending ratio at this time is [A]: [B] = 60: 40, and the addition amount of [D] _aa is [D] / ([A] + [B]) = 10/100. .
This dry blend was kneaded and extruded into pellets using a 300 mmφ twin-screw extruder at a cylinder temperature of 260 ° C. and a screw rotation speed of 80 rpm.

The extruded pellets were measured for MI and then injection molded to form 1/4 "test pieces and tensile test pieces, and the heat distortion temperature (HDT), Izod impact strength (IS), tensile rupture strength and elongation were measured. (TS _b , TE _b ), HDT = 12 in this example
3 ℃, IS = 13Kg · cm / cm, TS b = 423Kg / cm 2, TE b = 18% And MI was 1.2 g / 10 minutes. These physical properties, while maintaining the high heat resistance that is a characteristic of the imide resin,
In addition, impact resistance and melt flowability have also been greatly improved over the past. The results are summarized in Table-6.

[Example-2] αSI-1 = 2,400 (g), AS = 440 (g), ABS = 1,160
(G) and [D] _bb = 400 (g) as a compatibilizer were weighed, and Sumilizer WXR (Sumitomo Chemical Co., Ltd.) = 8.0 (g) was added and mixed for 10 minutes with a mixing stirrer. The resin blend ratio at this time is [A]: [B]: [C] = 60: 11: 29 and [D] / ([A] + [B] + [C]) = 10/100. .
This resin blend was kneaded and pelletized by an extruder in the same manner as in [Example-1], and after measuring MI, 1 / was measured by an injection molding machine.
A 4 ″ bar and a tensile dumbbell were molded. The physical property evaluation results of this test piece are shown in Table 6 and HDF = 1, respectively.
25 (℃, the following units are omitted), IS = 11, TS _b = 435, TE _b = 1
5, MI = 1.5, and this composition had an excellent balance of physical properties.

Example-3 This example is an example using αSI-2. αSI-2 = 2,80
0 (g), ABS = 1,200 (g) as compatibilizer [D] _ac
= 400 (g), the heat stabilizer = 8 (g) was added, and the mixture was mixed for 10 minutes with a mixing stirrer. The weight ratio at this time is [A]:
[B] = 70: 30 and [D] / ([A] + [B]) = 10 /
It was 100. After pelletizing with an extruder in the same manner as in [Example-1], MI was measured. The obtained pellets were molded into a sample for physical property evaluation with an injection molding machine. This result, as shown in Table -6 HDT = 127, IS = 11 , TS b = 415, TE
_{While b} = 15 and MI = 1.0, which had considerable impact resistance, the heat resistance was very high.

[Example-4] This is an example in which a part of ABS was replaced with AS in [Example-3]. Specifically, αSI-2 = 2,800 (g), ABS
= 760 (g), AS = 440 (g) and compatibilizer [D] _ab = 40
0 (g) was weighed, WXR was added, and then mixed. The weight composition ratio at this time is [A]: [B]: [C] = 70: 11: 19 and [D] / ([A] + [B] + [C]) = 10/100. .
This mixture was pelletized with an extruder and then injection-molded to obtain an evaluation sample. The results of evaluation of the physical properties the composition as shown in Table -6 HDT = 129, IS = 10 , TS b = 420, TE b = 1
3, MI = 1.1, the heat resistance was very high.

[Comparative Example-1] This example shows the result when [D] _ad was used as a compatibilizing agent. [D] _ad is the case where [D-2] does not contain a reactive functional group. ΑSI-1 = 2,400 as [A]
(G), [B] = 1,600 (g) and [D] _ad = 400 (g)
And 0.2 parts of WXR were weighed and mixed, and then pelletized by an extruder. After measuring MI, a test piece for evaluation was molded by an injection molding machine.
The results of evaluation of physical properties of this composition are shown in Table-6, where MI = 1.0.
When fairly high but non HDT = 121, IS = 5 and TS _b = 385 and MI physical properties, the effect of adding a very low compatibilizer hardly observed.

[Comparative Example-2] This example is an example using [D] _da obtained by using [D-1] that does not contain a maleic anhydride as a functional group as a compatibilizing agent. The blend composition ratio in this case is [A];
[B] = 70: 30 and [D] / ([A] + [B]) = 10/10
It is 0. The results of evaluation of physical properties of this product are shown in Table-6. The results were high with HDT = 123, but low with IS = 4 and MI = 0.8, and the performance was not sufficient.

[Comparative Example-3] This example is an example using [D] _ce , which is outside the scope of the present invention, as a compatibilizing agent. Since [D] _ce has a high content of functional groups in the component copolymers [D-1] and [D-2] and an intermolecular reaction occurs too much, [D] _ce itself is difficult to dissolve in a solvent. The melt flowability of the simple substance was also low. Table 6 shows the composition ratio and the physical property evaluation results in this case. However, [A]; [B] = 60: 40 and [D] / ([A] +
[B]) = 10/100. This composition has a low MI = 0.6 and a low IS = 3.

[Comparative Example-4] In this example, a compatibilizing agent [D] _dd containing no functional group was used. This composition has [A]; [B] = 70: 30 and [D] / ([A] + [B]) = 10/100. Table-6
As shown in, the composition has a very high MI = 1.2, but IS
It was as low as = 4.

[Comparative Example-5] In this Example, the compatibilizing agent [D] was not used. αSI-1 = 2,400 (g), ABS = 1,600 (g)
WXR = 8.0 (g) was added to ([A]: [B] = 60: 40) and mixed. After pelletizing with an extruder, MI was measured. An evaluation test piece was prepared with an injection molding machine and its physical properties were measured. Table-6 shows the results. HDT = 124 was high, but IS = 4 and MI = 0.2 were low.

Example-5 In this example, as shown in Table-7, αSI-1 = 2,400
(G), ABS = 1,600 (g) and [D] _aa = 800 (g) were weighed, and the heat stabilizer WXR = 8.0 (g) was added and mixed.
[A]: [B] = 60: 40 and [D] / ([A] +
[B]) = 20/100. After pelletizing with an extruder and measuring MI, a test piece was prepared with an injection molding machine. The results of measuring physical properties are shown in Table 7. HDT = 119, not so high,
The IS was very high at 16 and the MI was also high at 2.3.

[Example-6] In this example, αSI-2 = 3,200 (g), ABS = 800 (g)
And a compatibilizer [D] _bb = 400 (g), [A]: [B]
= 80: 20 and [D] / ([A] + [B]) = 10/100. After adding 0.2 parts of the heat stabilizer, they were mixed and kneaded into pellets. After measuring the MI of the pellets, the physical properties were evaluated by injection molding test pieces. The results are shown in Table-7, which was as low as IS = 8. However, HDT = 132, which is high, and MI = 1.0, indicating a fairly high fluidity as a heat-resistant resin.

[Comparative Examples-6 and 7] These two examples are examples in which the performance is low even if the compatibilizing agent is within the range of the invention if the composition ratio of [A] and [B] is out of the range. . In [Comparative Example-6], [A]: [B] = 9
In this example, 5: 5 [D] / ([A] + [B]) = 10/100. On the contrary, in [Comparative Example-7], the amount of [D] added was 10 parts by weight, but [A]: [B] = 10: 90. Table 7 shows the evaluation results of physical properties of these compositions. The former is HDT = 1.
The highest value was 34, but the effect of adding IS = 2 and ABS was not seen, and MI was as low as 0.2. On the contrary, the latter had the highest IS = 20, but was low as HDT = 109 and was unsuitable as a heat resistant resin.

[Comparative Examples-8, 9] These two examples are [A]: [B] = 60: 40 and [D] / ([A] + [B]) = 10/100. -8] is an example in which [D] ' _aa is used as [D].
-2] Since the amount of _a was large, the fluidity of [D] ' _aa was good and the plasticizer effect was exhibited. Therefore, as shown in the results in Table 7, the composition had a high MI = 2.0, but an IS = 8. Low.

On the other hand, in [Comparative Example-9], the amount of [D-1] _{a in} [D] was large, so that the heat resistance did not decrease so much, but the effect of adding the compatibilizer was poor, and this was not produced during molding. Coloring and foaming were observed due to the deterioration of retention.

[Comparative Example-10] This example is an example in which even if the type of the compatibilizer is within the range of the invention, if the addition amount is too large, the physical properties deteriorate. [A]:
[B] = 60: 40, [D] / ([A] + [B]) = 50/10
In the case of 0, as shown in Table-7, IS = 18 is high, but HDT = 10
It decreased to 9.

[Comparative Example-11] In this example, [A]: [B] = 70.4: 29.6,
[D] / ([A] + [B]) = 2/100, which is the case where the amount of the compatibilizer is small. The evaluation results are shown in Table-7. HDT = 126
Although it was high, it was low with IS = 5 and low with MI = 0.3.

(Effects of the Invention) When an imide-modified resin composition having high heat resistance and high impact is to be obtained by blending an imide group-containing resin and ABS, the blended composition of the prior art is certainly high in heat resistance, Due to insufficient impact resistance and melt flowability, it was difficult to apply it as a molding resin material for large equipment such as automobile front grills and OA equipment housings. As a result of the present invention, although the cost for separately preparing the compatibilizing agent is added, the imide-modified resin composition, which has hitherto been impossible, can be used as a large-sized molding resin material instead of engineering plastics.

Claims (2)

(57) [Claims] 1. A) 40 to 70% by weight of an aromatic vinyl compound, N
40-80 parts by weight of a copolymer resin [A] consisting of 30-60% by weight of a substituted maleimide compound, and b) 25-50% by weight of an aromatic vinyl compound in the presence of 30-70% by weight of a rubber-like polymer. , Vinyl cyanide compound 5 to 20% by weight, and other copolymerizable vinyl compound 0 to 50% by weight
20% of the graft copolymer resin [B] obtained by graft copolymerizing
To 60 parts by weight, c) a copolymer resin [C] comprising 60 to 82% by weight of an aromatic vinyl compound, 18 to 40% by weight of a vinyl cyanide compound, and 0 to 50% by weight of another copolymerizable vinyl compound. 0 to 20 parts by weight, based on 100 parts by weight of a resin composition consisting of: d) 50 to 84% by weight of aromatic vinyl compound, 15 to 49% by weight of vinyl cyanide compound, and 1 to 10% by weight of maleic anhydride.
30 to 70 parts by weight of a copolymer [D-1], 40 to 74% by weight of an aromatic vinyl compound, and an N-substituted maleimide compound 25
To 59% by weight, and a functional group-containing monomer 1 to 10 selected from at least one of 2-hydroxyethyl methacrylate, glycidyl methacrylate and p-aminostyrene.
5 to 30 parts by weight of a copolymer composition [D] obtained by melt-kneading a mixture of 30 to 70 parts by weight of a copolymer [D-2] composed of 1% by weight at a temperature of 180 to 300 ° C. An imide group-containing resin composition which is excellent in heat resistance, impact resistance, and melt fluidity. 2. An N-substituted maleimide compound is N-phenylmaleimide, N-cyclohexylmaleimide or N-phenylmaleimide.
The resin composition according to claim 1, which is at least one selected from (2,4,6-tribromo) phenylmaleimide.