JP2003041080A - Maleimide heat resistance-imparting material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a maleimide heat resistance-imparting material for heat- resistant ABS resins, excellent in balance of physical properties of impact resistance, heat resistance and fluidity, having good hue and excellent in appearance of the molded articles, and the heat-resistant ABS resins containing the heat resistance-imparting material and to provide a method for producing the heat- resistant ABS resin. SOLUTION: This maleimide heat resistance-imparting material is obtained by compounding (A) a maleimide copolymer composed of an aromatic vinyl monomer, an unsaturated dicarboxylic imide derivative, unsaturated dicarboxylic anhydride monomer and a vinyl monomer copolymerizable with these monomers and (B) a vinyl copolymer composed of an aromatic vinyl monomer, a vinyl cyanide monomer and a vinyl monomer copolymerizable therewith with one or more kinds of specific organophosphorus compounds in an amount of 0.1-5.0 pts.wt. based on the total amount of the components (A) and (B). This heat- resistant ABS resin comprises the heat-resistance-imparting material. This method for producing the heat-resistant ABS resin is further provided.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a maleimide heat resistance imparting material having a heat resistance imparting effect on ABS resin.
When a heat-resistant ABS resin is produced by kneading and mixing with an S resin and, if necessary, an AS-based copolymer, the heat-resistant ABS resin obtained by an extremely general kneader such as a single-screw extruder has a high impact resistance, The present invention relates to a maleimide heat resistance-imparting material having an excellent balance of physical properties such as heat resistance and fluidity, a good hue, and a beautiful appearance of the molded product. Further, since an extremely general kneading machine such as a single screw extruder can be used, it is excellent in economic efficiency.

[0002]

2. Description of the Related Art Conventionally, a maleimide copolymer has been added for the purpose of improving the heat resistance of ABS resin (US Pat. No. 3,642,949, US Pat. No. 36).
52726, JP-A-57-98536, JP-A-57-125241). However, since these maleimide-based copolymers have high heat resistance, the processing temperature is high, the hue of the resulting heat-resistant ABS resin is yellowish, and the appearance of natural colors is poor and the colorability is poor. occured. Further, these maleimide-based copolymers have a high melt viscosity, and when they are kneaded and mixed with an ABS resin and, if necessary, an AS-based copolymer, there is a large difference in melt viscosity and it is expensive and operability for uniform kneading. Unless a special kneading machine such as a crowded twin-screw extruder is used, the resulting heat-resistant ABS resin has poor physical properties and the molded product has a defective phenomenon such as silver.

[0003]

SUMMARY OF THE INVENTION According to the present invention, a heat-resistant A resin is prepared by kneading and mixing with an ABS resin and, if necessary, an AS-based copolymer.
When manufacturing a BS resin, even a very general kneader such as a single-screw extruder which is inexpensive and easy to operate can be uniformly kneaded, and the heat-resistant ABS resin obtained has impact resistance, heat resistance, It is an object of the present invention to provide a maleimide heat resistance imparting material which has an excellent balance of fluidity, a good hue, and a beautiful appearance of the molded product, a heat resistant ABS resin containing the same, and a method for producing the same.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that an ABS resin and, if necessary, A
When kneaded and mixed with the S-based copolymer, the heat-resistant ABS resin obtained by an extremely general kneading machine such as a single-screw extruder has an excellent balance of physical properties such as impact resistance, heat resistance and fluidity, and a hue And the appearance of the molded product was beautiful.

Specifically, the present invention will be outlined. (A) Aromatic vinyl monomer 15 to 70% by mass, unsaturated dicarboxylic acid imide derivative 25 to 65% by mass, unsaturated dicarboxylic acid anhydride monomer 0 to 25% by mass, and 35 to 91% by mass of a maleimide copolymer composed of 0 to 40% by mass of a vinyl monomer copolymerizable with these monomers, (B) 40 to 80% by mass of an aromatic vinyl monomer. A vinyl copolymer 9 to 65% by mass, which comprises 15 to 40% by mass of a vinyl cyanide monomer and 0 to 40% by mass of a vinyl monomer copolymerizable therewith, and (A) and (B) A maleimide heat resistance-imparting material obtained by blending 0.1 to 5.0 parts by mass of one or more of the organophosphorus compounds represented by the chemical formula (C) (C) with respect to 100 parts by mass in total. A heat-resistant ABS resin containing the same and a method for producing the same. That.

[Chemical 2] (In the formula, R1 and R2 are each independently a halogen atom,
An alkyl group, an alkyl group substituted with a halogen atom, an aryl group or an aralkyl group, R3 is an OH group, SH
A group, an NH2 group, a halogen atom, an alkyl group, an alkyl group substituted with a halogen atom, an aryl group or an aralkyl group, and x and y each represent an integer of 1 to 3. )

The (A) maleimide-based copolymer in the maleimide-based heat resistance imparting material of the present invention is the aromatic vinyl monomer 1
5 to 70% by mass, unsaturated dicarboxylic acid imide derivative 25
~ 65% by mass, unsaturated dicarboxylic acid anhydride monomer 0-2
5% by mass and 0 to 40% by mass of a vinyl monomer copolymerizable with these monomers. Preferably, the aromatic vinyl monomer is 25 to 65% by mass, the unsaturated dicarboxylic acid imide derivative is 30 to 60% by mass, the unsaturated dicarboxylic acid anhydride monomer is 0 to 10% by mass, and copolymerization with these monomers. It is composed of 0 to 30 mass% of possible vinyl monomers, more preferably 35 to 60 mass% of aromatic vinyl monomer, 35 to 55 mass% of unsaturated dicarboxylic acid imide derivative, and unsaturated dicarboxylic acid anhydride. It is composed of 0 to 5 mass% of a monomer and 0 to 20 mass% of a vinyl monomer copolymerizable with these monomers. If the amount of the aromatic vinyl monomer is less than 15% by mass or the amount of the unsaturated dicarboxylic acid imide derivative exceeds 65% by mass, the melt viscosity difference with the (B) vinyl copolymer becomes large, and the extrusion stability during melt mixing is high. Will be lower. If the amount of the aromatic vinyl monomer exceeds 70% by mass or the amount of the unsaturated dicarboxylic acid imide derivative is less than 25% by mass, the heat resistance imparting effect becomes poor. Furthermore, when the unsaturated dicarboxylic acid anhydride monomer exceeds 25% by mass, heat resistance AB
When the S resin is produced, the heat stability of the resulting heat resistant ABS resin is low.

Examples of the aromatic vinyl monomer in the maleimide type copolymer include styrene monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene and chlorostyrene and their substitution products. Of these, styrene is particularly preferable.

Examples of unsaturated dicarboxylic acid imide derivatives include maleimide monomers such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide and N-naphthylmaleimide. Among them, N-phenylmaleimide is particularly preferable. Examples of the unsaturated dicarboxylic acid anhydride monomer include anhydrides such as maleic acid, itaconic acid, citraconic acid and aconitic acid, with maleic acid being particularly preferred.

Vinyl monomers copolymerizable with the above monomers include acrylonitrile, methacrylonitrile, α
-Vinyl cyanide monomer such as chloroacrylonitrile,
Acrylic acid ester monomers such as methyl acrylic acid ester, ethyl acrylic acid ester, butyl acrylic acid ester, methacrylic acid ester monomers such as methyl methacrylic acid ester and ethyl methacrylic acid ester, vinyl carboxylic acid such as acrylic acid and methacrylic acid. Examples thereof include acid monomers, acrylic acid amides, and methacrylic acid amides.

As the method for producing the maleimide-based copolymer of the present invention, an aromatic vinyl monomer, an unsaturated dicarboxylic acid imide derivative, and an unsaturated dicarboxylic acid anhydride monomer used as necessary, and a single amount thereof are used. May be directly copolymerized with a known method, or an unsaturated dicarboxylic acid anhydride monomer may be copolymerized with an aromatic vinyl monomer and these monomers. After being copolymerized with another vinyl monomer, it may be reacted with ammonia and / or a primary amine to form an unsaturated dicarboxylic acid imide derivative. However, as a method for producing these copolymers, the latter, that is, an unsaturated dicarboxylic acid anhydride monomer is copolymerized with an aromatic vinyl monomer and a vinyl monomer copolymerizable with these monomers. The method of imidization later is more preferable in terms of copolymerizability and economy. The primary amines used in the imidization reaction include methylamine, ethylamine, propylamine, butylamine, hexylamine, cyclohexylamine, decylamine, aniline, toluidine, naphthylamine, chlorophenylamine, dichlorophenylamine, bromophenylamine, dibromophenyl. Examples include amines.

The imidization reaction can be carried out in a solution state, a lump state or a suspension state using an autoclave. It is also possible to carry out the reaction in a molten state by using a melt-kneading device such as a screw extruder. The solvent used for the solution reaction in imidization is arbitrary,
For example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethers such as tetrahydrofuran and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethyl sulfoxide, N-methyl-2- Pyrrolidone and the like are exemplified.

The reaction temperature for imidization is preferably in the range of 50 to 350 ° C, particularly preferably in the range of 100 to 300 ° C. The imidization reaction does not necessarily require the presence of a catalyst, but if used, trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline,
Tertiary amines such as N, N-diethylaniline are preferred. The maleimide-based copolymer of the present invention may be one obtained by any one of the conventionally known emulsion polymerization method, suspension polymerization method, bulk polymerization method, and solution polymerization method. Although it may be a composite method of the above-mentioned polymerization methods, a solution polymerization method is preferable. Further, either batchwise polymerization or continuous polymerization may be used.

The vinyl copolymer (B) of the present invention comprises 40 to 80% by mass of an aromatic vinyl monomer, 15 to 40% by mass of a vinyl cyanide monomer, and 0 to 40% by mass of a vinyl monomer copolymerizable therewith. .About.40% by mass. Preferably, the aromatic vinyl monomer is 45 to 80% by mass and the vinyl cyanide monomer is 20.
~ 35% by mass and vinyl monomer copolymerizable with these 0
To 30% by mass, and more preferably,
It is composed of 50 to 75% by mass of an aromatic vinyl monomer, 20 to 30% by mass of a vinyl cyanide monomer, and 0 to 20% by mass of a vinyl monomer copolymerizable therewith. When the aromatic vinyl monomer is less than 40% by mass or more than 80% by mass, or when the vinyl cyanide monomer is less than 15% by mass or more than 40% by mass, (A) the maleimide-based copolymer The compatibility with the union becomes poor, and the extrusion stability becomes low when melt mixing.

Examples of the aromatic vinyl monomer in the vinyl copolymer include styrene monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene and the like as described above and their substitution products. Of these, styrene is particularly preferred. Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and of these, acrylonitrile is particularly preferable.

As the vinyl monomer copolymerizable with the above-mentioned monomers, the same methyl (meth) acrylate as described above,
Ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, decyl (meth) acrylate,
There are octadecyl (meth) acrylate, hydroxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, glycidyl (meth) acrylate and the like, and these can be used alone or in combination.

The method for producing the (B) vinyl copolymer used in the present invention is not particularly limited. For example, an emulsion polymerization method,
Polymerization methods such as suspension polymerization method, bulk polymerization method and solution polymerization method can be adopted.

The maleimide heat resistance imparting material of the present invention is
(A) Maleimide-based copolymer 35 to 91% by mass, (B)
It had a specific structure with respect to 9 to 65% by mass of the vinyl copolymer and 100 parts by mass of the total amount of (A) and (B) (C).
0.1 to 5.0 parts by mass of one or more organic phosphorus compounds are blended. Preferably, the organophosphorus compound (C) is added to 0.1 parts by weight per 100 parts by mass of the total amount of (A) and (B).
To 2.0 parts by mass, more preferably 0.1 to 1.0 parts by mass of the (C) organophosphorus compound with respect to 100 parts by mass of the total amount of (A) and (B). It is to be blended. (A) maleimide-based copolymer and (B)
Less than 35% by mass of the (A) maleimide-based copolymer in the total amount of the vinyl copolymer, that is, 6 (B) of the vinyl copolymer.
If it exceeds 5% by mass, the effect of imparting heat resistance becomes low. Also,
When the amount of (A) maleimide copolymer in the total amount of (A) maleimide copolymer and (B) vinyl copolymer exceeds 91% by mass, that is, when (B) vinyl copolymer is less than 9% by mass. In that case, when a heat resistant ABS resin is produced, the resulting heat resistant ABS resin has a low impact strength, and a defective phenomenon such as silver occurs in a molded product. Further, the organophosphorus compound (C) is less than 100 parts by mass of the total amount of (A) and (B).
When the amount is less than 1% by mass, when the heat-resistant ABS resin is produced, the hue of the resulting heat-resistant ABS resin becomes yellowish, and when it exceeds 5.0 parts by mass, the heat-resistant ABS resin is obtained.
A defective phenomenon such as silver occurs in the S resin molded product. The (C) organophosphorus compound is limited to those having a specific structure represented by the chemical formula (Formula 1). For example, TN, which has been conventionally used in a wide range of fields as a phosphorus-based antioxidant
Even with P (trisnonylphenylphosphite),
The effect of preventing the phenomenon that the hue becomes yellowish is low.

[0018]

The present invention will be described in more detail with reference to the following examples. These are merely examples and do not limit the content of the present invention. The extrusion stability at the time of preparing the maleimide heat resistance imparting material and various evaluation methods after kneading with ABS are as follows.

(1) Evaluation of Extrusion Stability during Preparation of Maleimide Heat Resistant Material: Stability during extrusion kneading was measured by TEM35B.
The following evaluation was performed in the state of being extruded into pellets by an extruder. ◯: Almost no surging and good extrudability. X: Surging is severe and extrusion is difficult. (2) Heat resistance: According to ASTM D-1525, a Vicat softening point (49 N load) was measured using an injection-molded product having a thickness of 3.2 mm and molded at a molding temperature of 250 ° C.

(3) Impact strength: According to ASTM D-256, a notched IZOD impact strength was measured at a relative humidity of 50% and an ambient temperature of 23 ° C. by using an injection molded product having a thickness of 6.4 mm molded at a molding temperature of 250 ° C. It was measured. (4) Appearance of molded product: injection molding machine (Kawaguchi Tekko, K-125
-I) was used to form a plate (9 cm × 5 cm) at a forming temperature of 250 ° C., and the appearance was evaluated as follows. ◯: No defective molding is observed. X: Molding defects such as silver are observed. (5) Hue evaluation: injection molding machine (Kawaguchi Tekko, K-125-
I) the plate (9 cm x 5 cm) at a molding temperature of 2
It was molded at 50 ° C., and the yellowness YI was measured by a color difference meter (Suga Tester, SM-5).

[0021]

The present invention will be described in more detail with reference to the following examples. These are merely examples and do not limit the content of the present invention.

[0022]

Reference Example 1 (A) Production of Maleimide Copolymer Into an autoclave equipped with a stirrer, 15.0 kg of methyl ethyl ketone, 10.0 kg of styrene and 14 g of α-methylstyrene dimer were charged, and the inside of the system was replaced with nitrogen gas. Then, it heated at the temperature of 80 degreeC. A solution prepared by dissolving 6.2 kg of maleic anhydride and 40 g of benzoyl peroxide in 9.0 kg of methyl ethyl ketone was added thereto over 10 hours. After the addition, the temperature was kept at 80 ° C. for another 2 hours. 20.0 kg of methyl ethyl ketone was added to this reaction liquid, and it cooled to room temperature. Methanol 1 with vigorous stirring
The mixture was poured into 20.0 kg, filtered and dried to obtain a white powdery polymer. 10.0 kg of this polymer, 1 triethylamine
Methyl ethyl ketone 23.00 g in an autoclave.
Dissolve in 0 kg, add 3.6 kg of aniline to this, and
The imidization reaction was performed at 30 ° C. for 7 hours. The reaction solution was cooled to room temperature and stirred vigorously with 100.0 kg of methanol.
, Filtered and dried to obtain maleimide copolymer (a-1)
Got Other maleimide-based copolymers (a-2 to 4) are also
The composition was prepared under substantially the same conditions except that the composition was changed as shown in Table 1. The final polymer composition is also shown in Table 1.

[0023]

[Table 1]

[0024]

Reference Example 2 (B) Production of Vinyl Copolymer Reference Example 2-1: Vinyl Copolymer b-1 Styrene 6.98 kg, Acrylonitrile 3.02 k
g, 250 g of tricalcium phosphate, 50 g of t-dodecyl mercaptan, 20 g of benzoyl peroxide and 25 kg of water were heated to 70 ° C. to initiate polymerization. Seven hours after the initiation of polymerization, the temperature was raised to 75 ° C. and maintained for 3 hours to complete the polymerization (polymerization rate 97%). The obtained reaction solution was neutralized with hydrochloric acid, dehydrated and dried to obtain white bead-shaped vinyl copolymer (b-1) (final polymer composition ratio: styrene 7
0.3% by mass, acrylonitrile 29.7% by mass).

Reference Example 2-2: Vinyl Copolymer b-2 Similar to Vinyl Copolymer b-1 except that in Reference Example 2-1, styrene 7.77 kg and acrylonitrile 2.23 kg were used. A white bead-shaped vinyl copolymer (b-2) was produced (final polymer composition ratio: styrene 77.4% by mass, acrylonitrile 22.6% by mass).

Reference Example 2-3: Vinyl Copolymer b-3 Produced in the same manner as Vinyl Copolymer b-1 except that in Reference Example 2-1, styrene 88.6 kg and acrylonitrile 11.4 kg were used. Then, a white bead-shaped vinyl copolymer (b-3) was obtained (final polymer composition ratio: styrene 88.2% by mass, acrylonitrile 11.8% by mass).

[0027]

Reference Example 3 (C) Organophosphorus compound c-1: Commercially available organophosphorus compound, HCA (9,
10-dihydro-9-oxa-phosphaphenanthrene-10-oxide or 3,4,5,6-dibenzo-1,
2-oxaphosphane-2-oxide, Sanko Kagaku) was used. c-2: Phosphorus antioxidant tris (2,4-di-
t-Butylphenyl) phosphite was used.

[0028]

Reference Example 4 (D) Production of ABS Graft Copolymer 143 parts of polybutadiene latex (solid content 35 mass%, average particle size 0.25 μm, gel content 90%), sodium stearate 1 part, sodium formaldehyde Sulfoxylate 0.1 part, tetrasodium ethylenediamine tetraacetic acid 0.03 part, ferrous sulfate 0.0
03 parts and 150 parts of pure water were heated to 50 ° C., and 50 parts of a monomer mixture consisting of 70% styrene and 30% acrylonitrile, 0.2 part of t-dodecyl mercaptan, 0.15 of cumene hydroperoxide. Parts were continuously added for 6 hours, and after the addition was completed, polymerization was carried out at 65 ° C. for 2 hours (polymerization rate 97%). An antioxidant was added to the obtained latex, coagulated with calcium chloride, washed with water, and dried to obtain a white powdery copolymer (d-1). After swelling the copolymer (d-1) in a methyl ethyl ketone solution and stirring for 24 hours,
It was separated into soluble and insoluble components by centrifugation. As a result of pyrolysis gas chromatography (PGC) analysis, the soluble content was substantially styrene-acrylonitrile copolymer and the insoluble content was substantially butadiene-styrene-acrylonitrile graft copolymer. The composition of insoluble matter (graft copolymer and polybutadiene rubber) was analyzed by Kjeldahl nitrogen quantitative analysis and pyrolysis gas chromatography, and the mass of the graft copolymer was measured from the amounts of styrene and acrylonitrile. The polybutadiene rubber was analyzed by the bromine addition method to determine the mass of the polybutadiene rubber. From the mass of the graft copolymer and the mass of polybutadiene thus obtained, the graft ratio was calculated from the following formula (1), and the graft ratio was 33%. Grafting rate = (mass of graft copolymer / mass of polybutadiene rubber) × 100 (%) (1)

[0029]

Examples-1 to 6 and Comparative Examples 1 to 9/11 Tables 2 to 4
In the blending ratio shown in (A), the maleimide-based copolymer (A),
(B) vinyl copolymer, and (C) organophosphorus compound,
Add to 20 liter Henschel and blend, then TEM3
A maleimide heat resistance imparting material was obtained by extruding at a temperature of 280 ° C. with a 5B extruder (Toshiba, biaxial same direction). This maleimide-based heat resistance imparting material and ABS (GR-3
000, manufactured by Denki Kagaku Kogyo Co., Ltd.) was added to a 20 liter Henschel at a blending ratio shown in Tables 2 to 4 and blended.
An S40 m / m extruder (manufactured by Tanabe Plastic Machinery Co., Ltd., single-screw extruder) was used to extrude and pelletize at a temperature of 260 ° C. Using this pellet, a test piece was prepared by an injection molding machine, and IZOD impact strength, Vicat softening point, yellowness YI
And the appearance of the molded product was evaluated. The results are shown in Tables 2 to 4.

[0030]

Comparative Example 10 (A) maleimide-based copolymer, (B) vinyl copolymer, and (C) organophosphorus compound in the compounding ratios shown in Table 4 were put into a 20-liter Henschel and blended, and then TEM35B was used. Extrusion machine (Toshiba, biaxial same direction) was extruded at a temperature of 280 ° C. to obtain a maleimide heat resistance imparting material. This maleimide heat resistance-imparting material and generally commercially available ABS (GR-3000, manufactured by Denki Kagaku Kogyo) were added to 20 liter Henschel at the compounding ratio shown in Table 4 and blended, followed by TEM35B extruder (Toshiba, twin screw). In the same direction), the mixture was extruded and pelletized at a temperature of 250 ° C. Using this pellet, a test piece was prepared with an injection molding machine, and IZO
D impact strength, Vicat softening point, and yellowness YI were measured, and the appearance of the molded product was evaluated. The results are shown in Table 4.

[0031]

[Table 2]

[0032]

[Table 3]

[0033]

[Table 4]

[0034]

Examples-7 to 12 and Comparative Examples 12 to 16 Tables 5 to 6
In the blending ratio shown in (A), the maleimide-based copolymer (A),
(B) vinyl copolymer, and (C) organophosphorus compound,
Add to 20 liter Henschel and blend, then TEM3
A maleimide heat resistance imparting material was obtained by extruding at a temperature of 280 ° C. with a 5B extruder (Toshiba, biaxial same direction). This maleimide heat resistance imparting material, (B) vinyl copolymer, and (D) A
The BS-based graft copolymer was added at a blending ratio shown in Tables 5 to 6 to 20 liters of Henschel and blended.
A 40 m / m extruder (manufactured by Tanabe Plastic Machine Co., Ltd., single-screw extruder) was extruded and pelletized at a temperature of 260 ° C. Using this pellet, create a test piece with an injection molding machine,
The IZOD impact strength, the Vicat softening point, and the yellowness YI were measured, and the appearance of the molded product was evaluated. The results are shown in Table 5
It shows in Table 6.

[0035]

[Comparative Example 17] (A) a maleimide-based copolymer, (B) a vinyl copolymer, and (C) an organophosphorus compound in the compounding ratios shown in Table 6 were charged into 20 liters of Henschel, and blended, followed by TEM35B. Extrusion machine (Toshiba, biaxial same direction) was extruded at a temperature of 280 ° C. to obtain a maleimide heat resistance imparting material. The maleimide heat resistance-imparting material, the (B) vinyl copolymer, and the (D) ABS graft copolymer were added to a 20 liter Henschel at a blending ratio shown in Table 6 and blended, followed by TEM35B extruder (Toshiba, Extruded into pellets at a temperature of 250 ° C. in the same direction of two axes. Using this pellet, a test piece was prepared with an injection molding machine, and IZO
D impact strength, Vicat softening point, and yellowness YI were measured, and the appearance of the molded product was evaluated. The results are shown in Table 6.

[0036]

[Table 5]

[0037]

[Table 6]

From the results of Examples and Comparative Examples, the amount of the aromatic vinyl monomer of the maleimide copolymer (A) in the maleimide heat resistance-imparting material of the present invention was less than 15% by mass or the unsaturated dicarboxylic acid imide derivative was If it exceeds 65% by mass,
(B) The difference in melt viscosity from the vinyl copolymer becomes large, and extrusion stability becomes low when melt-mixing. If the amount of the aromatic vinyl monomer exceeds 70% by mass or the amount of the unsaturated dicarboxylic acid imide derivative is less than 25% by mass, the heat resistance imparting effect becomes low. Further, when the unsaturated dicarboxylic acid anhydride monomer exceeds 25% by mass, when the heat-resistant ABS resin is produced, the heat stability of the obtained heat-resistant ABS resin becomes low, resulting in a defective phenomenon such as silver in a molded product. Occurs.
(B) When the aromatic vinyl monomer of the vinyl copolymer is less than 40% by mass or more than 80% by mass, or when the vinyl cyanide monomer is less than 15% by mass or more than 40% by mass. , (A) the compatibility with the maleimide-based copolymer becomes poor, and the extrusion stability becomes low during melt mixing. If the amount of (A) maleimide copolymer in the total amount of (A) maleimide copolymer and (B) vinyl copolymer is less than 35% by mass, that is, (B) vinyl copolymer exceeds 65% by mass, The heat resistance imparting effect becomes low. Further, when the amount of the (A) maleimide-based copolymer in the total amount of the (A) maleimide-based copolymer and the (B) vinyl copolymer exceeds 91% by mass, that is, (B) the vinyl copolymer is 9% by mass. If the amount is less than the above, when the heat-resistant ABS resin is produced, the heat-resistant ABS resin obtained has a low impact strength and a defective phenomenon such as silver occurs in a molded product. Furthermore, the total amount of (A) and (B) is 10
When the (C) organophosphorus compound having a specific structure is less than 0.1% by mass with respect to 0 parts by mass, when the heat resistant ABS resin is produced, the hue of the resulting heat resistant ABS resin becomes yellowish. It can be seen that when it exceeds 5.0 parts by mass, a defective product such as silver occurs in the obtained heat-resistant ABS resin molded product.

[0039]

The maleimide heat resistance imparting material of the present invention is A
When a heat-resistant ABS resin is manufactured by kneading and mixing with a BS resin and, if necessary, an AS-based copolymer, the heat-resistant ABS resin obtained by an extremely general kneader such as a single-screw extruder has a high impact resistance. It has an excellent balance of physical properties such as heat resistance, heat resistance and fluidity.
The hue is good, and the appearance of the molded product is beautiful,
Extremely useful.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 33/24 C08L 33/24 55/00 55/00 (72) Inventor Masamichi Endo Goi Minami, Ichihara City, Chiba Prefecture Kaigan 6 Electric Chemical Industry Co., Ltd. Chiba factory F term (reference) 4F070 AA17 AA33 AA38 AB08 FA01 FA03 FA17 FC05 4J002 BC04W BC06X BC07W BG10X BG12W EW106 EW126 EW156 EW166 4J100 AB02P AB03P AB04P AB08P AJ02R AJ15SQAMQR AM47Q AM48Q BB01Q BC04Q BC49Q CA04 CA05 CA06 FA18 FA19 FA20 FA21

Claims (7)

[Claims] 1. (A) Aromatic vinyl monomer 15 to 70% by mass, unsaturated dicarboxylic acid imide derivative 25 to 65% by mass, unsaturated dicarboxylic acid anhydride monomer 0 to 25% by mass,
And vinyl monomers 0 to 40 copolymerizable with these monomers
35 to 91% by mass of a maleimide-based copolymer comprising 40% by mass, (B) 40 to 80% by mass of an aromatic vinyl monomer, 15 to 40% by mass of a vinyl cyanide monomer, and a vinyl monomer copolymerizable therewith. 9-65% by mass of vinyl copolymer consisting of 0-40% by mass, and the total amount of (A) and (B) 1
A maleimide heat resistance-imparting material obtained by blending 0.1 to 5.0 parts by mass of one or two or more of the organophosphorus compounds represented by the chemical formula (C) (C) with respect to 00 parts by mass. [Chemical 1] (In the formula, R1 and R2 are each independently a halogen atom,
An alkyl group, an alkyl group substituted with a halogen atom, an aryl group or an aralkyl group, R3 is an OH group, SH
Group, NH2 group, alkyl group, alkyl group substituted with a halogen atom, aryl group or aralkyl group, and x and y each represent an integer of 1 to 3. ) 2. The aromatic vinyl monomer (A) of the maleimide copolymer is styrene, the unsaturated dicarboxylic acid imide derivative is N-phenylmaleimide, and the unsaturated dicarboxylic acid anhydride monomer is maleic anhydride. The maleimide-based heat resistance imparting material according to claim 1, wherein 3. The maleimide system according to claim 1, wherein the aromatic vinyl monomer of the vinyl copolymer (B) is styrene and the vinyl cyanide monomer is acrylonitrile. Heat resistance imparting material. 4. The maleimide heat-resistant material according to any one of claims 1 to 3, wherein the organophosphorus compound (C) is 9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide. Grant material. (A) 15-70% by mass of an aromatic vinyl monomer, 25-65% by mass of an unsaturated dicarboxylic acid imide derivative, 0-25% by mass of an unsaturated dicarboxylic acid anhydride monomer,
And vinyl monomers 0 to 40 copolymerizable with these monomers
35 to 91% by mass of a maleimide-based copolymer comprising 40% by mass, (B) 40 to 80% by mass of an aromatic vinyl monomer, 15 to 40% by mass of a vinyl cyanide monomer, and a vinyl monomer copolymerizable therewith. 9-65% by mass of vinyl copolymer consisting of 0-40% by mass, and the total amount of (A) and (B) 1
0.1 to 5.0 parts by weight of (C) one or more of the organophosphorus compounds represented by the above chemical formula (Formula 1) per 100 parts by mass.
A heat-resistant ABS resin obtained by kneading and mixing a maleimide-based heat resistance-imparting material mixed in parts by mass with an ABS resin. 6. (A) 15 to 70% by mass of an aromatic vinyl monomer, 25 to 65% by mass of an unsaturated dicarboxylic acid imide derivative, 0 to 25% by mass of an unsaturated dicarboxylic acid anhydride monomer,
And vinyl monomers 0 to 40 copolymerizable with these monomers
35 to 91% by mass of a maleimide-based copolymer comprising 40% by mass, (B) 40 to 80% by mass of an aromatic vinyl monomer, 15 to 40% by mass of a vinyl cyanide monomer, and a vinyl monomer copolymerizable therewith. Vinyl copolymer 9-65% by weight, which is obtained by copolymerizing a monomer mixture consisting of 0-40% by weight
0.1 to 5.0 parts by mass of (C) one or more of the organophosphorus compounds represented by the chemical formula (Formula 1) per 100 parts by mass of the total amount of (A) and (B). The maleimide heat resistance-imparting material formed by blending (D) rubber-like polymer 5 to 80
ABS-based graft copolymerization consisting of 40 to 80 mass% of aromatic vinyl monomer, 15 to 40 mass% of vinyl cyanide monomer, and 0 to 40 mass% of vinyl monomer copolymerizable therewith. A heat-resistant ABS resin obtained by kneading and mixing with 5 to 100 parts by mass of the coalesced product. (A) 15-70% by mass of an aromatic vinyl monomer, 25-65% by mass of an unsaturated dicarboxylic acid imide derivative, 0-25% by mass of an unsaturated dicarboxylic acid anhydride monomer,
And vinyl monomers 0 to 40 copolymerizable with these monomers
35 to 91% by mass of a maleimide-based copolymer comprising 40% by mass, (B) 40 to 80% by mass of an aromatic vinyl monomer, 15 to 40% by mass of a vinyl cyanide monomer, and a vinyl monomer copolymerizable therewith. 9-65% by mass of vinyl copolymer consisting of 0-40% by mass, and the total amount of (A) and (B) 1
0.1 to 5.0 parts by weight of (C) one or more of the organophosphorus compounds represented by the above chemical formula (Formula 1) per 100 parts by mass.
A method for producing a heat-resistant ABS resin, which is obtained by kneading and mixing a maleimide heat resistance-imparting material blended in an amount of part by mass with an ABS resin.