JPS63178154A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition excellent in hue, chemical resistance, heat resistance and impact resistance, by mixing three specified copolymers with each other. CONSTITUTION:A copolymer (A) of a copolymer (a) containing 80wt.% (poly) butadiene with acrylonitrile (b) and an aromatic vinyl compound (c) is mixed with a copolymer (B) of component (B) with component (C) and a mixture (C) of a copolymer of component (b) with N-phenylmaleimide (d) and component (c) with, optionally, a copolymer of component (d) with component (c) to obtain a resin composition comprising 15-40wt.% portion insoluble in a mixed solvent comprising acetone and methylene chloride at a weight ratio of 80:20 and 85-60wt.% portion soluble in it, wherein said soluble portion comprises 95-20wt.% portion soluble in methyl isobutyl ketone and 95-20wt.% insoluble portion of a composition of 20-40mol.% component (b) units, wherein said insoluble portion comprises 60-99% portion soluble in acetone, 40-1wt.% insoluble portion of a composition of 1-15mol.% component (b) units, 30-50mol.% component (d) units and 45-60mol.% component (c) units in an amount to give a molar ratio to component (b) units >=4 and containing at least 35mol.% styrene units.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel ABS resin composition. More specifically, the present invention is an AB material that has good color tone and chemical resistance, and has excellent heat resistance and impact strength, which is particularly suitable for applications that require heat resistance such as automobile parts.
This invention relates to an S-based resin composition.

Conventional technology Conventionally, rubber containing butadiene as the main component, acrylonitrile)
A thermoplastic resin made by graft polymerizing IJ and styrene is known as ABS resin.

It is widely used in many fields because of its excellent physical properties such as processability, mechanical strength, and chemical resistance. but,
In recent years, as the field of use has expanded, even higher performance has been required, one of which is improved heat resistance.

It is known to improve the heat resistance of AES resin by replacing part or all of the stereo with α-methylstyrene, but there is a limit to the improvement in heat resistance due to the introduction of α-methylstyrene. shi, recent automobile parts, etc.
The reality is that we still cannot meet the needs of applications that require high heat resistance.

On the other hand, as a resin composition with excellent heat resistance, for example, ABS
A composition containing a copolymer of an aromatic vinyl compound and N-arylmaleimide has been proposed (U.S. Pat. No. 3,652,726), and the present inventors also previously We developed a composition consisting of a copolymer of N-arylmaleimide and a vinyl monomer, and a graft copolymer of a butadiene rubber and a vinyl monomer (Japanese Patent Laid-Open No. 167341/1989). Public bulletin).

However, the N-arylmaleimide.

Heat resistance of resin? Regarding the purpose of improvement, there are definitely 7 α
-Methylstyrene is also an excellent monomer, but on the other hand, an alternating copolymer with a 1:1 molar ratio with an aromatic vinyl compound preferentially produces 4C ["Macromolecular Cumistry"] Makromol, Chem
, ) J Volume 53, Page 33 (1962)]
, it is difficult to obtain a copolymer of any composition, and since the superimposed N-arylmaleimide is usually solid at room temperature, the copolymer and unreacted N-aryl maleimide must be completely consumed in the polymerization. Because it is difficult to separate maleimide by industrial means, the heat resistance and impact strength of the resulting copolymer itself or the composition of this copolymer and other resins cannot be sufficiently improved. It is not a fool's errand, but it often suffers from deterioration of color tone, which significantly lowers the commercial value.

Furthermore, a terpolymer of acrylonitrile, styrene, and N-0-chlorophenylmaleimide, and a composition comprising this terpolymer and an ABS resin are also known (U.S. Pat. No. 3,652,726). issue specification), WN-O
- The amount of chlorophenylmaleimide used is as low as 9.9% by weight (4.1 mol) based on the total monomers, and the heat resistance and properties of the resulting terpolymer and the composition containing it are low. Not enough.

In addition, there is one technique previously proposed by the present inventors (Japanese Patent Laid-Open No.
167341), it is possible to obtain a composition with excellent heat resistance; It is necessary to use a large amount of arylmaleimide, and as a result, there arises the problem that not only the impact strength is inevitably reduced, but also the color tone is likely to deteriorate.

Problems to be Solved by the Invention As described above, an ABS resin composition that has good color tone and chemical resistance, and also satisfies heat resistance and impact strength at the same time has not been known so far.

Under these circumstances, the present invention not only provides good color tone and chemical resistance, but also has excellent heat resistance and impact strength.

The entire purpose of this invention is to provide an ABS resin composition.

Means for Solving the Problems As a result of extensive research by the present inventors in order to develop a resin composition having the above-mentioned excellent properties, we found that ABS resin and
A resin composition containing a copolymer having a specific composition of N-phenylmaleimide units as a constituent component and prepared to exhibit predetermined solubility characteristics in a specific solvent is suitable for its purpose. Based on this finding, the present invention was completed.

That is, 1 the present invention provides (A) a graft copolymer obtained by grafting polybutadiene or a copolymer containing 80 or more butadiene units with acrylonitrile and an aromatic vinyl compound; 03) a copolymer of acrylonitrile and an aromatic vinyl compound; A copolymer of at least one type of acrylonitrile, N-phenylmaleimide, and an aromatic vinyl compound, or a copolymer of N-phenylmaleimide and an aromatic vinyl compound mixed with this copolymer. (a) The insoluble part in a mixed solvent of acetone and methylene chloride in a weight ratio of 80:20 is 15 to 40% by weight, and the insoluble part is 85 to 60% by weight. b) It is regrettable that the soluble portion is 5 to 80% by weight for methyl isobutyl ketone and the 95 to 20% by weight portion is regrettable, and this insoluble portion is 20 to 40 mol% of acrylonitrile units and N-phenylmaleimide. having an average composition of 10 to 25 moles of units and 45 to 60 moles of aromatic vinyl compound units;
And the insoluble portion of H←) is further soluble in acetone 6
0 to 99% by weight and 40 to 1% by weight, and this acetone insoluble part contains 1 to 15 acrylonitrile units.
mol % + average composition of 30 to 50 moles of N-phenylmaleimide units and 45 to 60 moles of aromatic vinyl compound units, 35 moles or more of the aromatic vinyl compound units are styrene units, and aromatic The present invention provides a resin composition characterized in that the molar ratio of vinyl compound units to acrylonitrile units is greater than 4.

In the composition of the present invention, a graft copolymer obtained by grafting polybutadiene or a copolymer containing 80 heavy European a4 or more butadiene units with acrylonitrile and an aromatic vinyl compound is used as the component (4). The coalescence is preferably carried out by adding acrylonitrile and an aromatic vinyl compound in the presence of polybutadiene or a copolymer containing 80 or more butadiene units, respectively.
It can be produced by emulsion polymerization using a known method at a ratio of 55 molti and 65 to 45 molti. The aromatic vinyl compounds used for this removal include fll,
t is styrene, α-methylstyrene, or styrene and α-
There is a mixture with methylstyrene.

Next, the copolymer of acrylonitrile and aromatic vinyl compound used as component (B) is produced as a by-product during the production of component (A), so it can be used in its entirety, or it can be used separately. May be blended.

This copolymer is produced by, for example, solution polymerizing a monomer mixture of 35 to 55 moles of acrylonitrile and 65 to 45 moles of an aromatic vinyl compound according to a conventional method.

It can be produced by emulsion polymerization or suspension polymerization.

As the aromatic vinyl compound at this time, the same compound as that used in the production of components (-) described above can be used.

In addition, the copolymer of N-phenylmaleimide and an aromatic vinyl compound or the copolymer of acrylonitrile, N-phenylmaleimide, and an aromatic vinyl compound used as component (C) is a copolymer of N-phenylmaleimide and an aromatic vinyl compound. Alternatively, it can be produced by radical copolymerizing a monomer mixture in which acrylonitrile is further added in a batch operation. In this case, it is necessary to use a radical copolymerized product in a batch operation, and it can be obtained by radical copolymerization in other methods, such as a semi-batch operation or a continuous operation. A copolymer consisting of IJronitrile units, N-phenylmaleimide units and aromatic vinyl compound units having a relatively uniform composition, and a copolymer consisting of acrylonitrile units, N-phenylmaleimide units and aromatic vinyl compound units having a relatively uniform composition. A mixture of a copolymer consisting of N-phenylmaleimide units and an aromatic vinyl compound unit having a composition 'fc with a molar ratio of around 1:1 has good color tone and chemical resistance, and A product with excellent impact resistance cannot be obtained.

Copolymer of acrylonitrile and N-phenylmaleimide and aromatic vinyl compound used as component (C) in the composition of the present invention, or copolymer of N-phenylmaleimide and aromatic vinyl compound in this copolymer 1 -1 The combined product itself is transparent to visible light, and although each component in the composition is uniformly dispersed with a size of 500X or less, it has a high solubility in solvents. They can be classified based on the difference in

This separable portion can be roughly divided into a methyl isobutyl ketone soluble portion, a methyl isobutyl ketone insoluble but acetone soluble portion, and a methyl isobutyl ketone insoluble but acetone insoluble portion.

The methyl in butyl ketone soluble portion is a copolymer of acrylonitrile and an aromatic vinyl compound, or a copolymer of a relatively small amount of N-phenylmaleimide, acrylonitrile and an aromatic vinyl compound, or methyl in butyl ketone. The part that is insoluble in acetone and is insoluble in acetone is a copolymer of a relatively large amount of N-phenylmaleimide, acrylonitrile, and an aromatic vinyl compound, and the part that is insoluble in methyl isobutyl ketone and insoluble in acetone has a molar ratio close to 1.1. It corresponds to a copolymer of N-phenylmaleimide and an aromatic vinyl compound having a composition of 7.

Furthermore, the copolymer of acrylonitrile, N-phenylmaleimide, and an aromatic vinyl compound used in the present invention, or a mixture of this copolymer with a copolymer of N-7 alemaleimide and an aromatic vinyl compound, is ( In order to improve the compatibility with component B), for example, a copolymer consisting of 35 to 57 moles of acrylonitrile units and 65 to 43 moles of aromatic vinyl compound units, the composition is insoluble in a mixed solvent of acetone and methylene chloride. The polymer is transparent to visible light, and each constituent component is uniformly dispersed with a diameter of 500 mm or less.

In the composition of the present invention, the insoluble portion in a mixed solvent of acetone and methylene chloride in a weight ratio of 80:20 is 15 to 4.
0% by weight, and the soluble portion is required to be in the range of 85 to 60% by weight. This insoluble portion mainly consists of a graft copolymer of component (A).

If the insoluble portion is less than 15% by weight, the impact strength of the composition will be low, while if it exceeds 40% by weight, the heat resistance of the composition will be reduced.

Further, the soluble portion in the mixed solvent of acetone and methylene chloride must be in the range of 5 to 80 weight percent for methyl isobutyl ketone, and 95 to 20 weight percent for the soluble portion in methyl isobutyl ketone. If the methyl in butyl ketone soluble portion has a 10% content of less than 5%, the graft copolymer of the component (F) CB> The copolymer of the component (C) and the copolymer of the component (C) should be uniformly mixed. It is difficult to mold the entire composition, and the surface of the molded product obtained by molding the composition is often uneven. On the other hand, if it exceeds 80% by weight, the heat resistance of the composition deteriorates.

The composition and amount of the polymer that is soluble in the mixed solvent of acetone and methylene chloride and insoluble in methyl isobutyl ketone depends on the properties of the composition.

In particular, it has a dominant effect on heat resistance and color tone. therefore,
In the present invention, the acrylonitrile unit is 20 to 40
It is necessary to have an average composition in the range of 10 to 25 moles of N-phenylmaleimide units and 45 to 60 moles of aromatic vinyl compound units. If the acrylonitrile unit content is less than 20 mol%, it will be difficult to dissolve N-phenylmaleimide during the preparation of the monomer mixture, and the composition will have low impact strength and poor chemical resistance; Exceeding this is not preferable because the heat resistance of the composition decreases and thermal discoloration becomes noticeable. -! Ta. N
- If the phenylmaleimide unit is less than 10 mol, the heat resistance will be low, while if it exceeds 25 mol, it will be difficult to dissolve when preparing a monomer mixture, and the monomer will be difficult to consume during polymerization. The color tone and impact strength of the product decrease. Furthermore, if the aromatic vinyl compound unit is less than 45 molar units, N-phenylmaleimide is difficult to consume during polymerization.
On the other hand, if it exceeds 60 mol%, chemical resistance and heat resistance will deteriorate and impact strength will decrease.

When a mixture of styrene and α-methylstyrene is used as the aromatic vinyl compound, the polymerization rate decreases as the proportion of α-methylstyrene increases, so in order to obtain an appropriate polymerization rate.

It is necessary to select the aromatic vinyl compound in such a proportion that the content of stereo units in the total amount of aromatic vinyl compound units is 35 molar or more.

Further, in the composition of the present invention, the methyl isobutyl ketone insoluble portion has a soluble portion in acetone of 60 to 99.
It is necessary that the insoluble portion be in the range of 40 to 1% by weight. If this acetone-insoluble portion is less than 1% by weight, heat resistance and chemical resistance will be low, while if it exceeds 40M@%, compatibility with graft copolymers and other copolymers will be poor. The impact strength of the composition is reduced. The acetone-insoluble part is mainly a copolymer of N-phenylmaleimide units and aromatic vinyl compound units with a molar ratio close to 1:1, and its average composition is 10 mols or less of acrylonitrile units and 40 to 40 mols of N-phenylmaleimide units. 50 molti and 40 to 50 molti aromatic vinyl compound units. Also,
This insoluble portion has a glass transition temperature of 200° C. or higher and has specific solvent resistance.

In this insoluble portion, 35 moles or less of aromatic vinyl compound units must be styrene units, and the remainder must be α-methylstyrene units and other aromatic vinyl compound units. If the proportion of styrene units exceeds 35 molty, the heat resistance will not be sufficiently improved. Further, the molar ratio of aromatic vinyl compound units to acrylonitrile units in this insoluble part is larger than 4, preferably 5.
It is necessary to do more than that. If this molar ratio is less than 4, the improvement in yellowness will be insufficient.

The copolymer of component (C) used in the composition of the present invention is usually produced by radical copolymerization, and in this radical copolymerization, N-phenylmaleimide and α-methylstyrene are used as the aromatic vinyl compound. In this case, it is important to consume this α-methylstyrene.
The presence of unreacted N-phenylmaleimide causes a decrease in color tone and impact strength, and the presence of unreacted α-methylstyrene causes a decrease in heat resistance, so choose an appropriate monomer composition and polymerization conditions. is necessary.

Examples of polymerization methods include suspension polymerization, bulk-suspension polymerization,
Although methods such as cast polymerization may be used, suspension polymerization and bulk-suspension polymerization are particularly preferred when productivity on an industrial scale is considered.

Next, as an example of the copolymer used as component (C) of the composition of the present invention, a quaternary copolymer consisting of acrylonitrile, N-phenylmaleimide, styrene and α-methylstyrene was prepared by suspension polymerization. To explain a preferable method for producing a monomer, first, acrylonitrile, N-phenylmaleimide, styrene and α-methylstyrene are mixed in a desired ratio to prepare a monomer mixture, and a radical 1 initiator and a molecular weight Add a predetermined amount of each modifier and dissolve uniformly. Next, the entire monomer mixture was added and dispersed in polymerization water prepared using a suspending agent and a suspension aid.

For example, the desired component t is copolymerized at a temperature of 50 to 90°C.
A resin is obtained. As a polymerization initiator, for example, azobisisobutyronitrile, benzoyl peroxide, octanoyl peroxide, lauroyl peroxide, butyl peroxyisobutyrate, butyl peroxy-
Examples of molecular weight regulators include butyl mercaptan, octyl mercaptan, dodecyl mercaptan, ethylhexyl thioglycolate, and α-methylstyrene dimer. On the other hand, examples of suspending agents include barium sulfate, barium carbonate, calcium phosphate, aluminum hydroxide, partially saponified polyvinyl alcohol, methyl cellulose, alkali metal salts of polyacrylic acid, polyacrylamide, copolymers of acrylamide and acrylic acid, etc. Examples of suspension aids include sodium chloride.

Sodium sulfate, disodium hydrogen phosphate, anionic, cationic, nonionic surfactants, etc. can be used. The amount of the polymerization initiator used is usually 0.1 to 1%, preferably about 0.1%, based on the total amount of monomers (1c).
5%. The polymer obtained by this suspension polymerization has the shape of beads, and the size of the beads can be adjusted within the range of 01 to 5 as required.

The resin composition of the present invention contains the component (A), component (B), and component (C) in the form of powder, beads, or pellets.

For example, roll, screw, pan puri mixer.

υ can be obtained by kneading using a kneader or the like.

During this kneading, additives commonly used in ABS resins may be used within the range that does not impair the purpose of the present invention.

For example, antioxidants, ultraviolet absorbers, pigments, dyes, fillers, 1liT plasticizers, mold release agents, etc. can be added.

Effect of the invention The resin composition of the present invention is an ABS resin composition,
Besides having extremely good color tone and chemical resistance.

It also has excellent heat resistance and impact resistance, and is suitable for use in, for example, automobile parts, industrial parts, and home appliance parts.

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.

The heat deformation temperature, yellowness, and chemical resistance in Examples were measured as follows.

(1) Heating deformation temperature; Measurement was performed without annealing according to JIS K6871.

(2) Yellowness (Y): Measured according to JIS K7103 and evaluated according to the following criteria.

〇--- Less than 25 Δ--- 25-50 Greater than X-1-50 (3) Chemical resistance; Dip a dumbbell test piece in gasoline (regular) at 23°C.
Changes in appearance after soaking for a period of time were visually judged according to the following criteria.

○--- No change at all Δ--- Slight decrease in surface gloss, but no cracking ×-m-Surface swelling or cracking Reference example 1 Graft copolymer of polybutadiene, acrylonitrile, and styrene (A ) Manufacturing the inside of a polymerization vessel equipped with a stirrer, reflux condenser, and thermometer was replaced with nitrogen, and 150 parts by weight of pure water and polybutadiene latex (weighted average particle size 0.3μ) were added in terms of solid content. 50 parts by weight was added, and the temperature was raised to 65°C. Next, a mixed solution consisting of 17 parts by weight of acrylonitrile, 33 parts by weight of styrene, 3 parts by weight of cumene hydroperoxide, and 0.3 parts by weight of n-octyl mercaptan and 30 parts by weight of pure water were added. rate 0
．． Water-soluble tTi, f consisting of 03 parts by weight, ferrous sulfate o, otzB parts, and 0.02 parts by weight of disodium ethylenediaminetetraacetate were each continuously supplied to the polymerization vessel over a period of 5 hours. During this time, the temperature inside the polymerization vessel was adjusted to 65°C. After supplying the mixed liquid and aqueous solution, continue for 1 hour at 65°C.
Polymerization was continued at ℃. After the polymerization was completed, the solid content of the latex was measured and the polymerization rate for acrylonitrile and styrene was calculated to be 97%. The obtained latex was added to a 2% aluminum sulfate aqueous solution at 70° C. for salting out, dehydrated and dried to obtain a graft copolymer (A).

Reference Example 2 7 - IJ Ronitrile, N-phenylmaleimide, styrene and α-methylstyrene The inside of a polymerization vessel equipped with a stirrer, reflux condenser, and thermometer was replaced with nitrogen, and 200 parts by weight of pure water, aluminum sulfate, 14H201,41 Akibu was charged and heated to 70°C. Next, 0.6 parts of sodium hydroxide dissolved in 6M parts of pure water was added to this to produce aluminum hydroxide which acts as a dispersant, and then CI
4-16 Sodium salt of alkyl sulfonic acid 1024
Part by weight and polyethylene oxide (molecular weight 5000-6
000) 0.009 heavy weight 1i was added in the form of a 10% aqueous solution. Next, add acrylonitrile to this aqueous phase.
20-layer N-phenylmaleimide 25
〃Styrene 35 #α-
A monomer mixture consisting of methylstyrene 201F lauroyl peroxide 0.57 ethylhexylthioglycolate 0.3# was added while stirring vigorously, and polymerization was carried out at a bath temperature of about 70° C. for 3 hours.

Next, after stirring for another hour at 85°C, the inorganic suspending agent was cooled to room temperature and decomposed by adding 2 parts by weight of about 50% sulfuric acid, followed by suction filtration, and 100 parts by weight of each of the 3 sulfuric acids were added to decompose the inorganic suspending agent. Cleaned with gold. Completely dry the beads at 100°C to form a copolymer (
C-1) was obtained.

25.0 parts by weight of acrylonitrile, 25.0 parts by weight of N-phenylmaleimide, 30.0 parts by weight of styrene, and α-
Reference Example 2 except that 20.0 parts by weight of methylstyrene was used.
By repeating the same operation.

A copolymer (C-2) was obtained.

Reference Example 1 Production of copolymer (C-3) Acrylonitrile 30-ON all, N-phenylmaleimide 15.
A copolymer (c-3) was obtained by repeating the same operation as in Reference Example 2 except for using 0 parts of superposition, 35.01 parts of styrene, 20.0 parts of α-methylstyrene, and 1 part of Mg.

Reference Example 5 Production of copolymer (C-4) 25.0 parts by weight of acrylonitrile, 30.0 parts by weight of N-phenylmaleimide, 25.0 parts by weight of styrene, and α~
Reference Example 2 except that 2060 parts by weight of methylstyrene was used
By repeating the same operation.

A copolymer (0-4) was obtained.

15.0 parts by weight of acrylonitrile, 25.0 parts by weight of N-phenylmaleimide, 40.0 parts by weight of styrene, and α
- Copolymer (C-
5) was obtained.

Reference Example 7 Production of copolymer (C-6) All amounts of acrylonitrile 20-Oit except for use with 30.0 parts by weight of N-phenylmaleimide, 30.0 parts by weight of styrene, and 20.0 parts by weight of α-methylstyrene By repeating the same procedure as in Reference Example 2 nine times, the copolymer (
C-6) was obtained.

Reference Example 8 Production of copolymer (C!-7) Acrylonitrile 22.0 parts by weight, N-phenylmaleimide 18.0 parts by weight, styrene 40.03 parts! By repeating the same operation as in Reference Example 2 except for using part i and 20.0 parts by weight of α-methylstyrene.

A copolymer (C!-7) was obtained.

The inside of a polymerization vessel equipped with a stirrer, a reflux condenser, and a thermometer was replaced with nitrogen, and 200 parts by weight of pure water was added.

Sodium di2-ethylhexyl sulfosuccinate 0.9
1 part by weight, 0.1 part by weight of sodium lauryl sulfate, 0.03 part by weight of sodium formaldehyde sulfoxylate, 0.01 part by weight of ferrous sulfate, and 102 parts by weight of disodium ethylenediaminetetraacetate, and heated to 70°C. I tuned it. Next, 20 parts by weight of acrylonitrile, 15 parts by weight of N-phenylmaleimide, 65 parts by weight of α-methylstyrene,
A mixed solution consisting of 0.3 parts by weight of cumene hydroperoxide and 2 parts by weight of dodecyl mercaptan was continuously fed into the polymerization vessel over a period of 6 hours. 1 more after supply ends
Polymerization was continued at 70° C. for hours to obtain a copolymer (C-8).

A pressure-resistant polymerization vessel equipped with a stirrer and a thermometer was purged with nitrogen, and 18 parts by weight of styrene and 22 parts by weight of N-phenylmaleimide were added.
parts by weight, 60 Mrft parts of methyl ethyl ketone, 0.15 parts by weight of n-octyl mercaptan, and 0.075 parts by weight of hypenzoyl peroxide were charged and uniformly dissolved. Thereafter, the temperature was raised to 70°C and polymerization was continued for 5 hours. After cooling, the obtained polymer was washed with methanol and sufficiently dried in a vacuum dryer to obtain a copolymer (C'). When the composition was investigated by nitrogen content analysis, the styrene unit was 53.0 molti,
47.0 mol of N-phenylmaleimide units.

Example 1, Comparative Example 1.2 33.5 parts by weight of the graft copolymer (A) obtained in Reference Example 1 and 66.5 parts by weight of the copolymer (C-1) obtained in Reference Example 2,
0.3 parts by weight of 4,4'-butylidenebis (3-methyl-6-butylphenol) was added as an antioxidant, and the mixture was melt-mixed in a vented twin-screw extruder and pelletized. The amount of insoluble parts in acetone and methylene chloride mixture (weight ratio 80:20) measured using this pellet was 26.3% by weight, and the soluble part insoluble in methyl isobutyl ketone in acetone and methylene chloride mixture. The poison of the part is 76
．． It was deeply regrettable. The composition of the polymer, which is soluble in acetone and methylene chloride mixture and insoluble in methyl isobutyl ketone, was determined by nitrogen content analysis and 130-N
When examined by MR (JEOL ■, TNM-GX-270), it was found that 29.2 mol% of acrylonitrile units, N
-phenylmaleimi) J1 position was 16.7 mol%, and the aromatic vinyl compound unit was 54.1 mol%. Further, the amount of the acetone insoluble part in the methyl isobutyl ketone insoluble part is 9.4% by weight, and its composition is 10.1 mol% of acrylonitrile units, 37.3 mol% of N-phenylmaleimide units.
mole%.

The aromatic vinyl compound unit was 52.6 mol%.

Separation using a mixture of acetone and methylene chloride.

Fractionation using methyl isobutyl ketone and fractionation using acetone were each carried out by the methods described below.

Approximately 19% of the resin that was separated and dried with a mixture of acetone and methylene chloride was accurately weighed, and the mixture of acetone and methylene chloride (
Add 209 (weight ratio: 80:20) and shake at 30°C for 5 hours. Thereafter, all the insoluble and soluble parts are separated by centrifugation at 20,000 rpm, and the soluble part is separated into another container by decantation. Add 20 fi of acetone and methylene chloride mixture to the insoluble part again, and separate into insoluble part and soluble part by the same operation. The soluble portion is combined with the soluble portion, dropped into excess methanol, and the coagulated material is taken out, dried, and weighed (a2). Also dry and weigh the insoluble part (b?)
. The weight ratio of the insoluble part to the soluble part for the acetone and methylene chloride mixture is calculated using the following formula.

Using the same method as the fractionation using a mixture of acetone and methylene chloride, but using methyl isobutyl ketone instead of the mixture of acetone and methylene chloride, and the soluble portion of the above mixture of acetone and methylene chloride instead of the resin. Separate.

Fractionation using acetone In the same manner as the fractionation using a mixture of acetone and methylene chloride, acetone is used instead of the mixture of acetone and methylene chloride, and the methyl isobutyl ketone insoluble portion is used instead of the resin.

On the other hand, a predetermined test piece was prepared from the pellet by injection molding, and physical properties were measured, and the results shown in Table 1 were obtained. Note that Table 1 shows Comparative Example 1 as Stylac (registered trademark), a heat-resistant ABS resin manufactured by Asahi Kasei Corporation.
ABS 1851&:, and as Comparative Example 2, Zylon (registered trademark)-500H, which is a modified polyphenylene ether, was also included.

Table 1 Example 2, Comparative Examples 3 and 4 Graft copolymer (A) obtained in Reference Example 1, copolymer (C-1) obtained in Reference Example 2, Asl resin [Stylus manufactured by Asahi Kasei Kogyo ■] Rack (registered trademark) -As 789) and 4,
4'-Butylidene bis (3-methyl-6-butylphenol) was mixed and melted in a vented twin-screw extruder at the blending ratio shown in Table 2, and pelletized. These pellets were used to classify the pellets using various solvents, and predetermined test pieces were prepared by injection molding, and their physical properties were measured. The results obtained are shown in Table 2.

Table 2 (parts: parts by weight) *l Stylec (registered trademark) As 789$24
14'-Butylidenebis (3-methyl-6-butylphenol) If the amount of the insoluble part in the mixture of acetone and methylene chloride is small, the isodt impact strength will be significantly lowered, and from Comparative Example 4, if the amount of the methyl isobutyl ketone insoluble part is small, the heat distortion temperature will be significantly lowered. I understand.

Example 3, Comparative Example 5.6 66.51 parts of each of the copolymers (0-2), (C-3) and (C-4) obtained in Reference Examples 3 to 5 and that obtained in Reference Example 1 33.5 parts by weight of graft copolymer (A) and 4,4'-
0.3 parts by weight of butylidene bis (3-methyl-6-butylphenol) was mixed in a vented twin-screw extruder and pelletized. Using this pellet, compositional analysis of fraction 1 polymers with each solvent was performed, and prescribed test pieces were prepared by injection molding and physical properties were measured. The results obtained are shown in Table 3.

Table 3 Displayed in complete molti.

From Comparative Example 5, it can be seen that if the amount of acrylonitrile units is too large, the yellowness increases, and from Comparative Example 6, if the sum of the acrylonitrile units i and the N-phenylmaleimide units becomes too large, the yellowness increases significantly. I understand.

Examples 4 and 5. Comparative Example 7 Copolymers (C-5) and (C-6) obtained in Reference Examples 6 and 7
) and 66.5 parts by weight of each of the graft copolymer (A)
33.5 parts by weight and 0.3 parts by weight of 4,4'-butyritenebis (3-methyl-6-butylphenol) were mixed and pelletized using a vented twin-screw extruder. In addition, 23.5 parts by weight of the copolymer (C!') obtained from reference fIJ10, 33.5 parts by weight of the graft copolymer (A), 43.0 parts by weight of the copolymer (0-1), and 4.4 parts by weight of the copolymer (0-1) 0.3 parts by weight of '-butylidene bis (3-methyl-6-butylphenol) was similarly mixed and pelletized. Using these pellets, fractionation using each solvent and compositional analysis of the polymer were performed, and all predetermined test pieces were prepared by injection molding and physical properties were measured. The results obtained are shown in Table 4.

Table 4 *1 Soluble in acetone and methylene chloride mixture,
The composition of a polymer that is also insoluble in methyl isobutyl ketone is expressed in molten units.

*2 The amount of acetone insoluble portion in methylimptilactone insoluble portion is expressed in molten units.

Comparative Example 7 shows that when the amount of acrylonitrile units decreases and the amount of N-phenylmaleimide units increases, the Izod impact strength decreases, and at the same time, yellowness increases and chemical resistance decreases.

Example 6. Comparative Example 8 In Reference Example 8, 66.5 parts by weight of Tokunen copolymer (c-7), 33.5 parts by weight of graft copolymer (A), and 4,4'-butylidene bis(3-methyl-6-) were added. butylphenol) 0
．． 31 parts were mixed and pelletized using a vented twin-screw extruder. On the other hand, the copolymer obtained in Reference Example 9 (C-S
) latex and the graft copolymer of Reference Example 1 (66.5 parts by weight and 33.5 parts by weight of Shu latex in terms of solid content, respectively)
After mixing to give the same parts by weight, the mixture was added to a 2% aqueous aluminum sulfate solution at 85° C. for salting out, followed by dehydration and drying.

0.3 parts by weight of 4 per 100 parts by weight of this dry polymer.
．． 4'-Butylidenebis (3-methyl-6-butylphenol) was added and pelletized using a vented twin-screw extruder. Using this pellet If, we carried out fractionation using each solvent and analyzed the composition of the polymer.Specified test pieces were prepared by injection molding and physical properties were measured.The obtained results are shown in Table 5. It was shown to.

Table 5 *l Soluble in acetone and methylene chloride mixture.

The composition of a polymer that is also insoluble in methyl isobutyl ketone is expressed in molten units.

Tree 2 The amount of acetone insoluble portion in methyl isobutyl ketone insoluble portion is expressed in molten units.

Copolymer produced by emulsion polymerization from Comparative Example 8 (c-9)
It can be seen that the resin composition consisting of the and the graft copolymer (/-) has a significantly high degree of yellowness.

In the above Examples 1 to 6 and Comparative Examples 1 to 8, it was confirmed that the Izot impact strength was 10 to 9 cm/cm or more, the heating deformation temperature was 110°C or more, the yellowness was O, and the chemical resistance was satisfied. While the Examples achieved all four criteria, the Comparative Examples, which are not included in the scope of the claims of the present invention, did not achieve any one or more of the criteria.

Claims (1)

[Claims] 1(A) 80% by weight of polybutadiene or butadiene units
A graft copolymer obtained by grafting a copolymer containing the above with acrylonitrile and an aromatic vinyl compound, (B) at least one copolymer of acrylonitrile and an aromatic vinyl compound, and (C) acrylonitrile and N-phenylmaleimide. A composition comprising a copolymer of N-phenylmaleimide and an aromatic vinyl compound, or a mixture of this copolymer and a copolymer of N-phenylmaleimide and an aromatic vinyl compound, the composition comprising: (a) acetone and methylene chloride; The insoluble portion is 15 to 40% by weight and the soluble portion is 85 to 60% by weight in a mixed solvent with a weight ratio of 80:20; (b) The soluble portion is further soluble in methyl isobutyl ketone. ~80% by weight and 95 to 20% by weight of an insoluble part, and this insoluble part consists of 20 to 40 mol% of acrylonitrile units, 10 to 25 mol% of N-phenylmaleimide units, and 45 to 60 mol% of aromatic vinyl compound units. and (c) the insoluble part in (b) above further consists of 60 to 99% by weight of the soluble part and 40 to 1% by weight of the insoluble part in acetone, and this acetone insoluble part is an acrylonitrile unit. 1
~15 mol%, 30-50 N-phenylmaleimide units
mol% and an average composition of aromatic vinyl compound units of 45 to 60 mol%, 35 mol% or more of the aromatic vinyl compound units are styrene units, and the molar ratio of aromatic vinyl compound units to acrylonitrile units. is larger than 4.