JPH0772241B2 - Heat resistant and impact resistant resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention has an excellent balance between heat resistance and impact resistance, which is composed of a heat-resistant copolymer composed of specific components and compositions and a graft copolymer. It relates to a resin composition.

<Prior Art> A rubber-reinforced thermoplastic resin represented by ABS resin has excellent mechanical strength, moldability and appearance, and is widely used in many industrial fields including automobile parts and electric parts. Further, conventionally, heat resistant materials have been required in these fields, but as the material therefor, those in which the styrene component of the resin is replaced with α-methylstyrene have been used. However, recently, the fields of application have been expanded, and there is a strong demand for resins having higher heat resistance than α-methylstyrene resins.

On the other hand, it has been conventionally known that a resin obtained by introducing maleic anhydride or a maleimide-based monomer into a styrene resin has a very high heat resistance, and is trying to meet the above requirements. However, resins containing these monomers have the drawback of lacking toughness and being fragile, and their improvement is desired.

Further, as with the α-methylstyrene-based resin, a copolymer of styrene or methyl methacrylate and methacrylic acid is used as a resin having a certain degree of heat resistance and good mechanical properties (JP-A-49-85184). Or a styrene-methyl methacrylate-methacrylic acid type copolymer (JP-A-58-125712). The heat resistance of these copolymers is improved by the introduction of methacrylic acid, but even if the introduction amount is increased, those having high heat resistance such as those obtained by copolymerizing maleic anhydride or a maleimide-based monomer I can't get it.

<Problems to be Solved by the Invention> As described above, the conventionally proposed resin is inferior in either heat resistance or impact resistance, and it is hard to say that its physical property balance is good.

<Means for Solving Problems> The inventors of the present invention improve the drawbacks of each resin as described above and obtain a resin composition having a remarkably excellent balance between heat resistance and impact resistance. As a result of intensive studies, they have found that a composition of a heat-resistant copolymer and a graft copolymer, each of which has a specific component and composition, can sufficiently satisfy the object, and have reached the present invention.

That is, the present invention provides one or more monomers (A) selected from the group consisting of aromatic vinyl-based monomers, unsaturated carboxylic acid ester-based monomers, and unsaturated nitrile-based monomers. A heat-resistant co-polymer comprising an unsaturated dicarboxylic acid anhydride monomer and / or a maleimide monomer (B) and a (meth) acrylic acid monomer (C) and having a composition within a specific range. Graft copolymerization obtained by graft polymerizing the compound (I) and one or more monomers selected from the group consisting of the above monomers (A), (B) and (C) on a rubber-like substance. Coalescence (II)
A resin composition (first invention) having an excellent balance of heat resistance and impact resistance, and the above heat resistant copolymer (I) and graft copolymer (II), An excellent balance between heat resistance and impact resistance, characterized by comprising the above monomer (A) alone or a polymer (III) comprising (A) and (B) or (C), and being processable. The present invention provides a resin composition (second invention) having excellent properties.

Heat-Resistant Copolymer (I) The heat-resistant copolymer (I) in the present invention comprises the above-mentioned monomers (A), (B) and (C).

Here, as the aromatic vinyl-based monomer in the monomer (A), styrene, α-methylstyrene, α-chlorostyrene, P-methylstyrene, pt-butylstyrene, o-chlorostyrene. , P-chlorostyrene, 2,5-
Dichlorostyrene, 3,4-dichlorostyrene, 2,5-dibromostyrene and the like can be mentioned, and one kind or two or more kinds can be used. Of these, styrene is usually preferably used, but when heat resistance is further required, p-methylstyrene, pt-butylstyrene, α-
The use of methylstyrene is preferred. When flame retardancy is required, use of halogen-substituted styrene is preferable.

As the unsaturated carboxylic acid ester-based monomer, (meth)
Methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate,
Lauryl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, methyl maleate, ethyl maleate, maleic acid Butyl and the like can be used, and one kind or two or more kinds can be used. Of these, methyl methacrylate is usually preferably used, but when heat resistance is further required, the use of a substituted cyclic hydrocarbon such as cyclohexyl methacrylate is preferable. Further, in order to obtain a copolymer having an intermolecular crosslinked structure or an intramolecular cyclized structure by the reaction with (meth) acrylic acid which is a monomer (C) component, glycidyl (meth) acrylate or (meth) acrylic is used. When an aminoalkyl-substituted product such as dimethylaminoethyl acid salt or a hydroxyalkyl-substituted product such as 2-hydroxyethyl (meth) acrylate is used, there is an effect corresponding to the addition amount.

As the unsaturated nitrile-based monomer, acrylonitrile,
Methacrylonitrile, maleonitrile, fumaronitrile and the like can be mentioned, and one kind or two or more kinds can be used. Of these, acrylonitrile is usually preferably used.

The monomer (A) component may be one or more selected from the group consisting of the above-mentioned aromatic vinyl-based monomer, unsaturated carboxylic acid ester-based monomer and unsaturated nitrile-based monomer. Monomers are used.

Next, examples of the unsaturated dicarboxylic acid anhydride in the monomer (B) include maleic anhydride, itaconic anhydride, citraconic anhydride, aconitic anhydride, and hymic acid anhydride. One or more of them are used. be able to. Of these, maleic anhydride is particularly preferably used.

Examples of the maleimide-based monomer include maleimide, N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide and N-o-chlorophenylmaleimide. And one kind or two or more kinds can be used. Particularly, maleimide and N-phenylmaleimide are preferably used.

As the monomer (B) component, the above-mentioned unsaturated dicarboxylic acid anhydride and maleimide-based monomer can be used alone or in combination.

Further, the monomer (C) is acrylic acid and / or methacrylic acid, and these can be used alone or in combination, but methacrylic acid is particularly preferably used.

The heat-resistant copolymer (I) in the present invention comprises the above-mentioned monomers (A), (B) and (C), and its composition is represented by the following formulas (1), (2) and (3). Within the range represented by.

Here, the monomers (B) and (C) in the formula (2) are heat resistance imparting components of the heat resistant copolymer, but if the total amount of these is less than 2% by weight, the heat resistance improving effect is small. . The heat resistance generally increases by 1 to 3 ° C. for each 1% by weight increase of the component (B) or (C) in the heat resistant copolymer. On the other hand, if the amount exceeds 90% by weight, the mechanical strength of the heat-resistant copolymer is greatly reduced, which is not preferable.

A particularly preferable range of the total amount of the components (B) and (C) in the heat resistant copolymer is 5 to 70% by weight.

Further, the proportions of the monomers (B) and (C) are represented by the formula (3), but if the proportion of the component (B) is less than 5% by weight, it is difficult to obtain a polymer having high heat resistance, while 95% by weight is obtained. If the amount is larger than this, the effect of improving the mechanical properties becomes smaller.

The preferred range of component (B) in formula (3) is 10 to 90% by weight.

The composition of the heat-resistant copolymer can be determined by elemental analysis of carbon, hydrogen, nitrogen (CHN) and oxygen of the heat-resistant copolymer obtained by polymerization.

The heat-resistant copolymer (I) of the present invention is produced by a known bulk polymerization method,
It can be produced by a solution polymerization method, a bulk-suspension polymerization method, a suspension polymerization method, an emulsion polymerization method, an emulsion-suspension polymerization method, or the like.

The copolymerization is carried out in the presence of heat, light or a polymerization initiator. Known molecular weight regulators and other additives can be used. The order of addition of the monomers, the polymerization initiator, the molecular weight modifier, and other various additives, the addition method, and the polymerization conditions such as the polymerization temperature and the polymerization time are not particularly limited. For example,
Control of the polymerization reaction and control of the structure of the copolymer may be carried out by setting conditions as necessary, such as batch addition of raw materials, divided addition, polymerization by continuous addition, or polymerization by stepwise heating.

Further, among the monomer (B) components of the heat-resistant copolymer (I) of the present invention, the maleimide-based monomer component is prepared by synthesizing a copolymer containing maleic anhydride in advance, It can also be synthesized by imidizing with a primary amine or an isocyanate. It can also be synthesized by preparing a copolymer using maleic acid monoamide as a starting material and imidizing the copolymer. Furthermore, the (meth) acrylic acid component of the copolymer was previously synthesized by synthesizing a copolymer containing an easily heat-decomposable (meth) acrylic acid ester such as tertiary butyl (meth) acrylate and thermally decomposing it. Then, it can also be synthesized by converting to (meth) acrylic acid. Further, the (meth) acrylic acid component of the copolymer has a 6-membered cyclic acid anhydride structure and a glutarimide ring structure, respectively, according to the methods described in JP-A-58-217501 and JP-A-58-71928, respectively. It can be converted. Further, the unsaturated dicarboxylic acid component and the (meth) acrylic acid component of the copolymer can be converted into a monovalent carboxylic acid metal salt.

Graft Copolymer (II) The graft copolymer (II) used in the resin composition of the present invention comprises a rubber-like substance and the above-mentioned monomers (A) and (B).
And one or more monomers selected from the group consisting of (C) and (C).

The rubber-like substance used in the graft polymerization is rubber-like at room temperature, and its glass transition temperature is preferably 5 ° C. or lower.

Examples of this rubber-like substance include polybutadiene rubber,
Styrene-butadiene random or block copolymer, hydrogenated styrene-butadiene random or block copolymer, acrylonitrile-butadiene copolymer,
Neoprene rubber, chloroprene rubber, natural rubber, isobutylene rubber, ethylene-propylene rubber, ethylene-propylene-conjugated diene rubber, chlorinated polyethylene, chlorinated ethylene-propylene-conjugated diene rubber, acrylic rubber, ethylene-vinyl acetate copolymer Coalescence, ethylene-
(Meth) acrylic acid ester copolymer such as methyl (meth) acrylate, ethyl, propyl, butyl, glycidyl or dimethylaminoethyl, ethylene-vinyl acetate-glycidyl methacrylate copolymer, ethylene-methyl acrylate-methacrylic acid Examples thereof include glycidyl copolymer, polyvinyl butyral and polyester elastomer. These may be uncrosslinked or crosslinked, and may be used alone or in combination of two or more.

The graft copolymer can be produced by various polymerization methods as described in the section of producing the heat resistant copolymer. Further, the polymerization conditions may be selected such that the desired graft copolymer is produced.

The composition ratio of the rubber-like substance and the monomer of the graft copolymer is not particularly limited, but from the viewpoint of impact resistance and moldability, the rubber-like substance is 5 to 80% by weight and the monomer component is 95 to 20% by weight. It is preferably in the weight%. The composition ratio of the monomers is also not particularly limited, but a suitable composition may be selected from the viewpoint of compatibility with the heat resistant copolymer (I). From this point of view, it is generally desirable to increase the number of polar groups of the monomer in the graft copolymer as the number of polar groups of the heat resistant copolymer (I) increases.

In the graft polymerization, it is usually difficult to bond the entire amount of the monomer to the rubber-like substance by a graft reaction, and an ungrafted polymer is produced as a by-product. In the present invention, not only a true graft polymer in which the ungrafted polymer is positively separated and removed, but also a graft polymer containing the ungrafted polymer may be used. The graft copolymer (II)
Can be treated as

The structure of the graft copolymer is not limited, but the average particle diameter of the graft copolymer is 0.05 to 5 μm,
A graft ratio of 10 to 150% and a gel content of 50% or more are preferable in terms of balance of various physical properties.

Polymer (III) The polymer (III) used in the present invention is the above-mentioned monomer (A) alone or a polymer composed of (A) and (B) or (C).

More specifically, polystyrene, polymethylmethacrylate, styrene-methylmethacrylate copolymer, styrene-acrylonitrile copolymer and other copolymers composed of only the monomer (A), maleimide-styrene copolymer, A copolymer comprising a monomer (A) and a monomer (B) such as a maleic anhydride-styrene copolymer, an N-phenylmaleimide-styrene-acrylonitrile copolymer, a maleic anhydride-styrene-acrylonitrile copolymer. Polymers, further monomers (A) and monomers (C) such as methacrylic acid-styrene copolymer, methacrylic acid-methyl methacrylate-styrene copolymer, methacrylic acid-styrene-acrylonitrile copolymer ) And a copolymer consisting of.

Regarding the method for producing the polymer, the above heat-resistant copolymer (I) is used.
Various known polymerization methods such as those mentioned in the above section can be used. The composition of the polymer is also not limited, but if a suitable composition is selected from the viewpoints of compatibility with the heat resistant copolymer (I) and the graft copolymer (II), the physical property balance of the resin composition, and the like. Good. The intrinsic viscosity of the polymer (III) (dimethylformamide solution, 30 ° C) is preferably in the range of 0.3 to 1.5.

Resin composition The resin composition which is the first invention of the present invention comprises the heat resistant copolymer (I) and the graft copolymer (II), and there is no particular limitation on the blending ratio of both polymers. However, the range of 5 to 95 parts by weight of the heat resistant copolymer (I) and 95 to 5 parts by weight of the graft copolymer (II) is preferable from the viewpoint of the balance between heat resistance and impact resistance.

The resin composition of the second invention comprises the heat resistant copolymer (I), the graft copolymer (II), and the polymer (III) described above, and the blending ratio of these polymers is Although there is no particular limitation, the heat-resistant copolymer (I) to the graft copolymer (II) is 5 to 95 parts by weight to 95 to 5 parts by weight in view of the balance between heat resistance and impact resistance and workability. ,
The total of (I) and (II): 100 parts by weight of the polymer (III): 1
It is preferably about 50 parts by weight.

The production of the resin composition differs depending on the production method of the heat-resistant copolymer (I), the graft copolymer (II) and the polymer (III), for example, these are in a latex state, suspension slurry state, solution state, beads. It can be collected as a composition by mixing in a state, a powder state, a pellet state or a combination thereof. Further, these mixtures generally recovered as solids can be kneaded by a known melt-kneading machine such as a Banbury mixer, a roll mill, a single-screw or twin-screw extruder.

For the resin composition of the present invention, if necessary, an antioxidant,
Heat stabilizers, light stabilizers, lubricants, plasticizers, antistatic agents, inorganic and organic colorants, foaming agents, inorganic and organic fillers,
Surface gloss improver, matting agent, etc. can be added.

These various additives can be added during the manufacturing process of the resin composition or in the subsequent processing process.

The resin composition of the present invention can be used alone, and since it has a very good affinity with various polar materials, glass fiber, metal fiber, carbon fiber or powder thereof, calcium carbonate , Talc, gypsum, alumina,
Silica, mica, boron nitride, zirconia, silicon carbide,
It can be used as a composite material with potassium titanate or the like. Furthermore, polyethylene, polypropylene,
Polybutene-1, ethylene-butene-1 copolymer, propylene-butene-1 copolymer, propylene-ethylene block copolymer, ethylene-propylene rubber, maleic anhydride grafted polyolefin, chlorinated polyolefin, ethylene-vinyl acetate Copolymer, ethylene-vinyl alcohol copolymer, ethylene- (meth) acrylic acid and its metal salt copolymer, ethylene- (meth) acrylate methyl, ethyl, propyl, butyl, glycidyl, dimethylaminoethyl and the like ( (Meth) acrylic acid ester copolymer, polyvinyl butyral, polyvinyl chloride, butadiene rubber, styrene-butadiene random or block copolymer, hydrogenated styrene-butadiene random or block copolymer, acrylonitrile-butadiene rubber, isobutyrate Car parts, ship parts, etc. as resin compositions or laminates with rubber, acrylic rubber, polycarbonate, polyester, polyamide, polyimide, polyamideimide, polyetheretherketone, polysulfone, polyethersulfone, polyphenylene oxide, polyoxymethylene, etc. It can be widely used in many fields such as aircraft parts, building materials, electric parts, furniture, office supplies and so on.

The present invention will be described below with reference to examples, but the present invention is not limited thereto.

All parts and percentages given in the examples are by weight.

The compositions of the heat resistant copolymer (I) and the polymer (III) were determined by the following method.

The copolymer recovered after the polymerization was thoroughly washed with methanol to extract and remove residual monomers, and then dried samples were analyzed for carbon, hydrogen and nitrogen element analyzers (Yanamoto Co., Ltd., CHN Coder MT-2 type). And an elemental oxygen analyzer (manufactured by Mitamura Riken Co., Ltd., oxygen trace quantitative analyzer).

-Heat-resistant copolymer (I) -Reference Example 1 80 parts of pure water and 3 parts of 10% by weight sodium dodecylbenzenesulfonate aqueous solution were charged into a reactor equipped with a stirrer 10 and stirred in a nitrogen atmosphere at 300 rpm. Polymerization was carried out at 70 ° C. while continuously adding the following monomer solution, emulsifier solution and polymerization initiator solution for 5 hours. Then at 75 ℃ 2
Polymerization was completed by heating for an hour. The obtained copolymer latex was salted out with magnesium sulfate to recover a copolymer powder. The copolymer composition by elemental analysis is shown in Table 1.

Monomer solution Methyl methacrylate 75 parts N-Phenylmaleimide 20 parts Methacrylic acid 5 parts t-Dodecyl mercaptan 0.3 parts Emulsifier solution Pure water 30 parts Sodium dodecylbenzenesulfonate 2 parts Polymerization initiator solution Pure water 10 parts Potassium persulfate 0.4 Part Reference Example 2 The reactor used in Reference Example 1 was charged with 80 parts of pure water, 3 parts of a 10% aqueous solution of sodium dodecylbenzenesulfonate and 1 part of a 30% aqueous solution of potassium persulfate, and charged in a nitrogen atmosphere at 300 r.
While continuously adding the following monomer solution, emulsifier solution and polymerization initiator solution over 5 hours while stirring at 70 pm
Polymerized at ° C. Then, the mixture was heated at 75 ° C. for 2 hours to complete the polymerization.

Thereafter, the copolymer was recovered in the same manner as in Reference Example 1. The copolymer composition is shown in Table 1.

Monomer solution Styrene 55 parts Acrylonitrile 15 parts N-phenylmaleimide 20 parts Methacrylic acid 10 parts t-Dodecyl mercaptan 0.2 parts Emulsifier solution pure water 30 parts Sodium dodecylbenzenesulfonate 2 parts Polymerization initiator solution Pure water 10 parts Potassium persulfate 0.3 parts Reference Example 3 The copolymer composition obtained by repeating the method of Reference Example 2 except that the amounts of N-phenylmaleimide and methacrylic acid in Reference Example 2 were changed to 10 parts and 20 parts, respectively, is shown in Table 1.

Reference Example 4 The amounts of styrene, acrylonitrile, N-phenylmaleimide and methacrylic acid in Reference Example 2 were each 47
The method of Reference Example 2 was repeated, except that parts, 13, 20 and 20 parts were used. The copolymer composition is shown in Table 1.

Reference Example 5 70 parts of pure water, 0.8 part of sodium lauryl sulfate and 0.02 part of potassium persulfate were charged into the reactor used in Reference Example 1, and α-methylstyrene 25 was added under stirring at 300 rpm in a nitrogen atmosphere.
Part, acrylonitrile 10 parts and t-dodecyl mercaptan 0.2 part were added, and then the following monomer solution, emulsifier and polymerization initiator solution were continuously added over 5 hours respectively, and polymerization was carried out at 70 ° C. Then, the mixture was heated at 80 ° C. for 2 hours to complete the polymerization. Thereafter, the copolymer was recovered in the same manner as in Reference Example 1. The copolymer composition is shown in Table 1.

Monomer solution α-methylstyrene 25 parts Acrylonitrile 10 parts N-phenylmaleimide 15 parts Methacrylic acid 15 parts Emulsifier and polymerization initiator solution Pure water 50 parts Sodium lauryl sulphate 3 parts Potassium persulfate 0.5 parts Reference Example 6 In Reference Example 1 The reactor used was charged with 80 parts of pure water and 0.02 part of sodium dodecylbenzenesulfonate, and the following monomer solution, emulsifier and polymerization initiator solution were continuously added over 5 hours under stirring at 300 rpm in a nitrogen atmosphere. While
Polymerized at 70 ° C.

Then, the mixture was heated at 80 ° C. for 3 hours to complete the polymerization. Less than,
The copolymer was recovered in the same manner as in Reference Example 1. The copolymer composition is shown in Table 1.

Monomer solution Styrene 52 parts Acrylonitrile 23 parts Maleimide 20 parts Methacrylic acid 5 parts Emulsifier and polymerization initiator solution Pure water 40 parts Sodium dodecylbenzenesulfonate 2 parts Potassium persulfate 0.25 parts Reference Example 7 Styrene, acrylonitrile in Reference Example 2, The amounts of N-phenylmaleimide and methacrylic acid were each 32
The method of Reference Example 2 was repeated except that the parts, 8 parts, 30 parts and 30 parts were changed. The copolymer composition is shown in Table 1.

Reference Example 8 The method of Reference Example 1 was repeated except that the monomer in Reference Example 1 was changed to 51 parts of methyl methacrylate, 34 parts of styrene, 10 parts of N-phenylmaleimide and 5 parts of methacrylic acid. The copolymer composition is shown in Table 1.

Reference Example 9 300 parts of methyl ethyl ketone, 50 parts of styrene, 1.5 parts of azobisisobutyronitrile and 0.2 part of t-dodecyl mercaptan were charged into a reactor equipped with a stirrer 20 and then 50 parts of methyl ethyl ketone under stirring at 300 rpm in a nitrogen atmosphere. , Styrene 25 parts, maleic anhydride 15 parts and methacrylic acid 10
The solution in parts was polymerized at 70 ° C. with continuous addition over 4 hours and then heated at 80 ° C. for 2 hours. After the polymerization, 700 parts of methyl ethyl ketone was added to the reaction solution, and this solution was put into methanol to recover a copolymer. The copolymer composition is shown in Table 1.

Reference Example 10 40 parts of styrene and methacrylic acid were added to the reactor used in Reference Example 1.
Charge 10 parts, 0.2 part of lauroyl peroxide and 0.3 part of t-dodecyl mercaptan and replace the inside of the vessel with nitrogen.
While stirring at 00 rpm, a solution of 15 parts of styrene, 5 parts of acrylonitrile and 5 parts of maleic anhydride was continuously added over 3 hours to carry out polymerization at 70 ° C. After that, the temperature was maintained at 70 ° C for 20 minutes and then cooled to 30 ° C to obtain a viscous prepolymer. After adding 10 parts of acrylonitrile, 15 parts of N-phenylmaleimide and 0.3 part of bendyl peroxide to this, an aqueous solution of 150 parts of pure water, 0.2 parts of hydroxypropylmethylcellulose and 0.01 part of sodium lauryl sulfate was added, and the mixture was mixed at 70 ° C for 3 days. Polymerization was carried out for 2 hours at 90 ° C. for 2 hours. After the polymerization, steam was blown to remove unreacted monomers, and a bead-shaped polymer was recovered. First copolymer composition
Shown in the table.

Reference Example 11 The reactor used in Reference Example 1 was charged with an aqueous solution consisting of 100 parts of pure water, 0. 0 part of hydroxypropylmethylcellulose and 0.01 part of sodium dodecylbendene sulfonate, and then the inside of the reactor was replaced with nitrogen and stirred at 400 rpm. Styrene 70 below
Part, acrylonitrile 30 parts, lauroyl peroxide
A mixture of 0.6 parts and 0.3 part of t-dodecyl mercaptan was added, and the mixture was polymerized at 70 ° C for 4 hours and then at 80 ° C for 1 hour. After the polymerization, steam was blown to remove unreacted monomer, and a bead-shaped polymer was recovered. The copolymer composition is shown in Table 1.

Reference Example 12 Reference Example 2 except that 55 parts of styrene, 15 parts of acrylonitrile and 30 parts of N-phenylmaleimide were used as monomers.
The above method was repeated to obtain a copolymer. The copolymer composition is shown in Table 1.

Reference Example 13 Reference Example 2 except that 47 parts of styrene, 13 parts of acrylonitrile and 40 parts of N-phenylmaleimide were used as monomers.
The above method was repeated to obtain a copolymer. The copolymer composition is shown in Table 1.

Reference Example 14 A copolymer was obtained by repeating the method of Reference Example 9 except that the amount of maleic anhydride was changed to 25 parts without using methacrylic acid.
The copolymer composition is shown in Table 1.

Reference Example 15 A copolymer was obtained by repeating the method of Reference Example 1 except that N-phenylmaleimide was not used and the amounts of methyl methacrylate and methacrylic acid were changed to 73 parts and 27 parts, respectively.

Reference Example 16 The reactor used in Reference Example 1 was charged with dimethylformamide 300.
Parts, 5 parts of methyl methacrylate, N-phenylmaleimide
65 parts, methacrylic acid 30 parts, t-dodecyl mercaptan 0.
2 parts and lauroyl peroxide 0.2 parts were added, and the temperature was 65 ° C.
Polymerization was carried out for 5 hours and then at 75 ° C. for 3 hours. After the polymerization, 700 parts of dimethylformamide was added to the reaction solution, and this solution was put into methanol to recover a copolymer.

Reference Example 17 Monomer amount of styrene 71 parts, acrylonitrile 28 parts, N
The procedure of Reference Example 2 was repeated except that 0.5 part of phenylmaleimide and 0.5 part of methacrylic acid were used to obtain a copolymer. The copolymer composition is shown in Table 1.

-Graft Copolymer (II) -Reference Example 18 (ABS- (1)) Polybutadiene latex having a weight average particle diameter of 0.29 µm and a gel content of 85% was added to the reactor used in Reference Example 1 (solid content 50%).
200 parts, pure water 50 parts, dextrose 0.2 parts and sulfuric acid No. 1
After adding 0.01 part of iron and replacing the inside of the vessel with nitrogen, a mixed solution of 30 parts of acrylonitrile, 70 parts of styrene, 0.4 part of t-dodecyl mercaptan and 300 parts of pure water under stirring at 300 rpm and pure water 50
Part, 2 parts of sodium oleate and 0.32 part of cumene hydroperoxide were continuously added over 4 hours while polymerizing at 70 ° C, and then further heated at 75 ° C for 2 hours. The obtained latex was salted out with magnesium sulfate to recover a graft copolymer having a graft ratio of 52% and a rubber content of 51%.

Reference Example 19 (ABS- (2)) Weight average particle diameter of 0.21 instead of polybutadiene latex
The method of Reference Example 18 was repeated except that a styrene-butadiene rubber latex (solid content: 50%) having a particle size of 20 μm, a styrene content of 20%, and a gel content of 78% was used. As a result, a graft copolymer having a graft ratio of 47% and a rubber content of 52% was obtained.

Reference Example 20 (ABS- (3)) Weight average particle diameter of 0.17 instead of polybutadiene latex
μm, acrylonitrile content 15%, gel content 80% acrylonitrile-butadiene rubber latex (solid content
The method of Reference Example 18 was repeated except that 50%) was used.
As a result, a graft copolymer having a graft ratio of 51% and a rubber content of 51% was obtained.

Reference Example 21 (ABS- (4)) Polybutadiene latex having a weight average particle diameter of 0.27 μm and a gel content of 81% was added to the reactor used in Reference Example 1 (solid content 50%).
260 parts, pure water 40 parts, dextrose 0.2 parts and sulfuric acid first
After adding 0.01 part of iron and replacing the inside of the vessel with nitrogen, a mixed solution of 25 parts of acrylonitrile, 45 parts of styrene and 0.4 part of t-dodecyl mercaptan and pure water under stirring at 300 rpm and pure water 50
Part, 2.5 parts of sodium oleate and 0.37 part of cumene hydroperoxide were continuously added over 4 hours while polymerizing at 70 ° C, and then further heated at 75 ° C for 2 hours. The obtained latex was salted out with magnesium sulfate to obtain a graft copolymer having a graft ratio of 43% and a rubber content of 66%.

Reference Example 22 (AES) 100 reactor with n-hexane 400 parts, ethylene dichloride 20
0 part and iodine value 15.5, Mooney viscosity 57, propylene content 43%, ethylene-propylene-ethylidene norbornene polymer "EPDM" containing ethylidene norbornene as a diene component 30 parts "EPDM" was charged, and then in a nitrogen atmosphere 150
It was dissolved under stirring at rpm. Acrylonitrile 10
Parts, 20 parts styrene and 0.7 parts benzoyl peroxide added 6
Polymerization was carried out at 5 ° C for 10 hours. The reaction solution was poured into a large amount of methanol to obtain a graft copolymer having a graft ratio of 49% and a rubber content of 52%.

Reference Example 23 (AAS) In the reactor used in Reference Example 1, a butyl acrylate rubber latex with a weight average particle size of 0.18 μm and a gel content of 86% (solid content) was used.
50%) 200 parts, pure water 50 parts, dextrose 0.3 part and ferrous sulfate 0.007 part were charged, and the inside of the vessel was replaced with nitrogen, and then 300
A mixture of 6 parts of acrylonitrile, 14 parts of styrene and 0.1 part of benzoyl peroxide was added with stirring at rpm.
A mixture of 24 parts of acrylonitrile, 56 parts of styrene and 0.3 part of t-dodecyl mercaptan and pure water 50
Part, 2 parts of sodium lauryl sulfate and 0.4 part of cumene hydroperoxide were continuously polymerized at 70 ° C. for 4 hours and then heated at 80 ° C. for 3 hours. The obtained latex was salted out with magnesium sulfate to recover a graft copolymer having a graft ratio of 49% and a rubber content of 51%.

-Polymer (III) -Reference Example 24 An aqueous solution containing 150 parts of pure water and 0.5 part of sodium polyacrylate was charged into the reactor used in Reference Example 1, and 60 parts of methyl methacrylate, 40 parts of styrene, and terpinolene were added to the reactor.
A mixed solution of 0.3 part and benzoyl peroxide 0.4 part was added, and the mixture was polymerized in a nitrogen atmosphere at 300 rpm under stirring at 80 ° C. for 3 hours and then at 90 ° C. for 2 hours. The composition of the obtained polymer is shown in Table 2.

Reference Example 25 The reactor used in Reference Example 1 was charged with an aqueous solution consisting of 100 parts of pure water and 0.3 part of hydroxyethyl cellulose, and 30 parts of acrylonitrile, 70 parts of styrene, 0.4 part of t-dodecyl mercaptan and 0.5 part of lauroyl peroxide.
The mixture was added, and the mixture was polymerized in a nitrogen atmosphere at 300 rpm under stirring at 70 ° C for 4 hours and then at 80 ° C for 1 hour. The composition of the obtained polymer is shown in Table 2.

Reference Example 26 The reactor used in Reference Example 1 was charged with an aqueous solution consisting of 100 parts of pure water and 0.2 parts of hydroxypropylmethylcellulose, and 80 parts of methyl methacrylate, 10 parts of styrene, 10 parts of methacrylic acid, t-dodecyl mercaptan 0.2 And 0.5 part of lauroyl peroxide were added, and the mixture was polymerized in a nitrogen atmosphere with stirring at 300 rpm at 70 ° C. for 3 hours and then at 80 ° C. for 2 hours. The composition of the obtained polymer is second
Shown in the table.

Reference Example 27 The reactor used in Reference Example 1 was charged with an aqueous solution containing 100 parts of pure water and 0.2 part of sodium dodecylbenzenesulfonate, and then styrene 50 was added under stirring at 300 rpm in a nitrogen atmosphere.
Added parts. 18 parts of acrylonitrile, 22 parts of styrene
Part, 10 parts of N-phenylmaleimide and 0.3 part of t-dodecyl mercaptan, and 20 parts of pure water, an aqueous solution of 2 parts of sodium dodecylbenzenesulfonate and 0.4 parts of potassium persulfate while continuously added over 5 hours. After polymerizing at 70 ° C, it was further heated at 80 ° C for 2 hours. The obtained latex was salted out with magnesium sulfate to recover the polymer. The composition of the polymer is shown in Table 2.

Examples 1 to 10 The copolymers (I) produced in Reference Examples 1 to 10 were used, and the graft copolymer (II) was used in Reference Example 18
The one manufactured in 1. was used.

Add 60 parts of copolymer (I) and 40 parts of graft copolymer (II) to acid
Sumilizer as anti-oxidant BBM (Sumitomo Chemical) 0.2 parts
And 0.5 parts of barium stearate as a lubricant,
The mixture was kneaded with a Banbury mixer and then pelletized. This
The pellets of the above are made into the test piece by the injection molding machine at 270-290 ℃.
Then, the physical properties were measured. The results are shown in Table 1.

Comparative Examples 1 to 7 Compositions were prepared by the methods of Examples 1 to 10 except that the copolymers (I) prepared in Reference Examples 1 to 10 were replaced by the copolymers prepared in Reference Examples 11 to 17, respectively. The physical properties were measured. The results are shown in Table 1.

Examples 11 to 22 All the copolymers (I) produced by the method of Reference Example 2 were used. As the graft copolymer (II), those produced in Reference Examples 18 to 23 were used, and as the polymer (III), those produced in Reference Examples 24 to 27 were used.

The above polymers were blended in the proportions shown in Table 2, and test pieces were prepared by the method of Example 1 to measure the physical properties. The results are shown in Table 2.

Comparative Examples 8 to 11 The graft copolymers (II) prepared in Reference Examples 18 to 21 were used, and the copolymers prepared in Reference Example 12 were used. These were blended in the proportions shown in Table 2, and test pieces were prepared by the method of Example 1 to measure the physical properties. The results are shown in Table 2.

<Effects of the Invention> A heat-resistant resin composition formed by using a maleimide-based copolymer or a maleic anhydride-based copolymer as well as a resin composition including a conventionally known styrene-acrylonitrile copolymer and a graft copolymer. In comparison with the resin, the resin composition using the heat-resistant copolymer having the composition and composition ratio defined in the present invention is excellent in the balance between heat resistance and impact resistance. Further, a resin composition comprising a heat-resistant copolymer and a polymer as a graft copolymer is excellent in the balance between heat resistance and impact resistance and in processability.

Claims (2)

[Claims] 1. One or more monomers (A) selected from the group consisting of aromatic vinyl monomers, unsaturated carboxylic acid ester monomers and unsaturated nitrile monomers,
It is composed of an unsaturated dicarboxylic acid anhydride monomer and / or a maleimide monomer (B) and a (meth) acrylic acid monomer (C), and has a composition represented by the formulas (1), (2) and ( Heat-resistant copolymer (I) within the range represented by 3)
And a graft copolymer (II) obtained by graft-polymerizing one or more monomers selected from the group consisting of the above-mentioned monomers (A), (B) and (C) on a rubber-like substance. A heat-resistant and impact-resistant resin composition comprising: 2. One or more monomers (A) selected from the group consisting of aromatic vinyl monomers, unsaturated carboxylic acid ester monomers and unsaturated nitrile monomers,
It is composed of an unsaturated dicarboxylic acid anhydride monomer and / or a maleimide monomer (B) and a (meth) acrylic acid monomer (C), and has a composition represented by the formulas (1), (2) and ( Heat-resistant copolymer (I) within the range represented by 3)
And a graft copolymer (II) obtained by graft-polymerizing one or more monomers selected from the group consisting of the above-mentioned monomers (A), (B) and (C) on a rubber-like substance. And a monomer (A) alone or a polymer (III) comprising (A) and (B) or (C), a heat resistant and impact resistant resin composition.