JPH02132140A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition having excellent mechanical properties, moldability and appearance of molded article by compounding specific amounts of a specific maleimide copolymer, a polyamide and a modified polyolefin polymer. CONSTITUTION:The objective composition containing dispersed particles of a maleimide copolymer having particle diameter of 0.01-1mum, preferably 0.05-0.3mum is produced by compounding (A) 10-50wt.% of a maleimide copolymer composed of 30-70mol% of an aromatic vinyl monomer group, 30-50mol% of a maleimide monomer group, 3-20mol% of an unsaturated dicarboxylic acid anhydride group and 0-50mol% of other copolymerizable monomer group, (B) a polyamide (e.g., nylon 6), (C) 3-40wt.% of a modified polyolefin polymer modified with 0.1-10wt.% of an unsaturated dicarboxylic acid anhydride monomer group and/or an unsaturated carboxylic acid monomer group and, as necessary, (D) 0.01-5wt.% of an organic acid metal salt and/or a fatty acid amide.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thermoplastic tree-cultivated product that has excellent properties, moldability, and appearance of molded products. More specifically, Atagawa's proprietary resin is made of polyamide and a specific maleimide copolymer, and has improved hygroscopicity, heat resistance, and moldability of polyamide, and also provides molded products with excellent appearance!
Regarding the 6J1 product. [Conventional technology Copolyamides have excellent properties such as mechanical properties, chemical resistance, abrasion resistance, and electrical properties, but have poor impact resistance (notched)
, they have low heat resistance, high molding shrinkage, and are prone to problems such as sink marks and warpage in molded products. Furthermore, due to its high hygroscopicity, it not only tends to cause defects in the appearance of the molded product during the molding process, but also tends to cause large changes in the dimensions or shape of the molded product, as well as the mechanical properties of the molded product. Are known. In addition, the viscosity of the molten resin is low, and during injection molding, molten resin tends to flow out of the nozzle of the molding machine as if pulling a string, which is likely to occur.
The disadvantage is that the molding operation is complicated. In order to improve these drawbacks of polyamide, attempts have been made to mix or react various polymeric substances with polyamide. For example, styrene resins such as polystyrene or styrene-acrylonitrile copolymers were melt-blended (Japanese Patent Publication No. 3B-23476).
No. 40-7380, U.S. Patent No. 3,243,47
No. 8, No. 3, 243, 479, West German Published Patent No. 2, 403, 8894! i. These (Dm resins) have poor compatibility with polyamide, so a layered peeling phenomenon was observed in the molded product made from the obtained string composite, and the mechanical properties were also poor. An attempt was made to mix a copolymer of 100% and an unsaturated dicarboxylic anhydride monomer (JP-A-56-50931), but the resulting composition had poor thermal stability. For the purpose of improvement, a three-component composition is known in which a copolymer of styrene and an unsaturated dicarboxylic anhydride monomer is used as a compatibilizer between the styrenic resin and polyamide ( Tokukai Showa 6
No. 0-195157), the resulting composition was improved in compatibility and thermal stability, but its effects were insufficient. A copolymer containing an imide compound of unsaturated dicarboxylic acid and polyamide? A copolymer in which both polymer chains are bonded is known (Japanese Patent Application Laid-Open Nos. 57-577-19 and 57-141-426), which is produced by fusion mixing, but the properties of the obtained copolymer are was susceptible to the effects of manufacturing conditions using a melting machine and a mixer, which was an industrial disadvantage. Furthermore, the Fj4p properties and impact resistance of the obtained copolymer were not necessarily sufficient. A composition comprising an unsaturated dicarboxylic anhydride monomer, an aromatic vinyl copolymer, a polyamide, and a modified polyolefin is also known (Japanese Patent Application Laid-Open No. 2003-31-171).
No. 751), these are insufficient in heat resistance and thermal stability. As an improvement on this, a three-component composition consisting of a copolymer of a maleimide monomer, a polyamide, and a modified polyolefin is known (Japanese Patent Laid-Open No. 62-5964
No. 7, No. 62-179546), and the molded product made from the obtained composition showed defective phenomena on the surface in the vicinity of the gate, had peeling and hazy properties, and had poor impact properties such as straightness, elongation, and rigidity. It was inadequate in terms of balance. [Problems to be Solved by the Invention] As mentioned above, many attempts have been made to improve the various properties of polyamide, but the effects have not been sufficient for practical use. The purpose of the present invention is to provide a polyamide-based resin silk composition that has good heat resistance and impact resistance, a good balance of elongation and rigidity, and has a beautiful appearance. [Means for solving the problem] That is, in the present invention, 30 to 70 mol% of aromatic vinyl monomer groups
, 10 to 50 ffi, a maleimide co-modal polymer consisting of 30 to 50 mol% of maleimide monomer groups, 3 to 20 mol% of unsaturated dicarboxylic anhydride monomer groups, and 0 to 50 mol% of acrylic monomer groups Weight% and polyamide 40-80% by weight
, unsaturated dicarbon II1!2 anhydride monomer group and/
or unsaturated carboxylic acid monomer group 0. 1~10ff
Modified polyolefin polymer 3 modified with lffi%
-40% by weight, a composition in which a maleimide copolymer forms dispersed particles, characterized in that the particle size of the dispersed particles is 0.01 to LO microns. In the case of thermoplastic resin string composites, the obtained M
It has been found that the first product has a good balance of impact resistance, elongation, rigidity, fA thermal properties, etc., has low moldability and low moisture absorption, and gives molded products with a beautiful appearance.
Furthermore, in the present invention, it is preferable that the modified polyolefin polymer is also dispersed as dispersed particles in independent amorphous shapes of several microns or less and substantially uniformly dispersed. There are no particular limitations on the method for producing the maleimide copolymer used in the present invention, and for example, radicals of aromatic vinyl monomers, maleimide monomers, unsaturated dicarboxylic acid anhydride monomers, and acrylic monomers are used. It can be produced by copolymerization. Specific examples of aromatic vinyl monomers include styrene, α-
Examples of maleimide monomers include methylstyrene, vinyltoluene, t-butylstyrene, etc., and specific examples of maleimide monomers include maleimide, N-methylmaleimide, N-ethylmaleimide, N-probylmaleimide, N-hexylmaleimide,
Examples of unsaturated dicarboxylic anhydride monomers include N-cyclohexylmaleimide, N-phenylmaleimide, and N-1lylmaleimide. Specific examples of unsaturated dicarboxylic anhydride monomers include maleic anhydride, methylmaleic anhydride, and 1,2-dimethyl anhydride. Maleic acid, ethyl maleic anhydride, phenyl maleic anhydride, etc. Specific examples of acrylic monomers include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, etc. Acrylate, cyclohexyl (meth)acrylate, decyl (meth)acrylate, octadecyl (meth)acrylate, hydroxyethyl (meth)acrylate, methoxyethyl (meth)acrylate, glycidyl (meth)acrylate, etc., and these can be used alone or in combination. It can be used as However, here methyl (meta)
Acrylate refers to methyl acrylate or methyl methacrylate. There are no particular restrictions on the method of copolymerizing these monomers, and any known radical copolymerization method can be employed. Another method for producing the maleimide copolymer used in the present invention is to combine an aromatic vinyl monomer, an unsaturated dicarboxylic anhydride monomer, and an acrylic monomer with ammonia or a primary amine. An example of a method for imidizing an acid anhydride group by reacting with The imidization reaction between a polymeric substance having an acid anhydride group in its molecular chain and an amine compound is well known, for example, as described in Japanese Patent Publication No. 61, No.
According to the method disclosed in No. 26938 or No. 82-8456, a desired maleimide copolymer having an imide group can be produced by reacting a polymeric substance with an amine compound. Examples of primary amines used in imidization reactions are:
Methylamine, ethylamine, probylamine, butylamine, hexylamine, cyclohexylamine, decylamine, aniline, toluidine, naphthylamine,
These include chlorophenylamine, dichlorophenylamine, promophenylamine, and dibromophenylamine. The imidization reaction can be carried out in a solution state, bulk molten state, or suspension state using an autoclave. It is also possible to carry out the reaction in a molten state using a melt kneading device such as a screw extruder. Any solvent can be used in the solution reaction, such as acetone, methyl ethyl ketone, methyl isobutyl ketone,
Ketones such as cyclohexanone, tetrahydrofuran, 1. Examples include ethers such as 4-dioxane, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethyl sulfoxide, and N-methyl-2-pyrrolidone. 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. Although the imidization reaction does not necessarily require the presence of a catalyst,
If used, trimethylamine, tonoethylamine,
Tertiary amines such as tributylamine, N,N-dimethylaniline, N,N-zoethylaniline and the like are preferred. The maleimide copolymer used in the present invention contains 30 to 70 mol% of aromatic vinyl monomer groups, 30 to 50 mol% of maleimide monomer groups, and 3 to 20 mol% of unsaturated dicarboxylic anhydride monomer groups. mol% and 0 to 50 mol% of acrylic monomer groups. More preferred ranges are 50 to 60 mol% of aromatic vinyl monomer groups and 40 to 50 mol% of maleimide monomer groups.
mol%, unsaturated dicarboxylic anhydride monomer groups 3 to 10 mol%, and acrylic monomer groups 0 to 30 mol%.
If the aromatic vinyl monomer group is less than 30 mol %, it is difficult to industrially produce a polymer having a homogeneous silk composition with good reproducibility, and it is difficult to produce a polymer having a homogeneous silk composition industrially, and it is difficult to produce a polymer having a homogeneous silk composition by mixing the maleimide copolymer with a polyamide. The resulting silk products have poor properties such as thermal stability, moldability, and mechanical strength. Also, aromatic vinyl Qlffi
If the body group exceeds 70 mol% or if the maleimide monomer group is ungrooved by 30 mol%, the resulting composition will have poor ship resistance, and if the maleimide monomer group exceeds 50 mol%. The moldability of the resulting composition is poor. If the unsaturated dicarboxylic acid anhydride monomer group is less than 3 mol%, the compatibility of the morning product obtained by mixing with the polyamide will be poor, and the particle size of the maleimide copolymer dispersed particles will increase. , mechanical strength is poor, and peeling phenomenon is observed in the molded product. In addition, the unsaturated dicarboxylic anhydride monomer group has 2
If it exceeds 0 mol%, the particle size of the maleimide-based copolymer-dispersed particles in the strand becomes too small, resulting in poor molding processability, poor thermal stability of the molded product, and the surface becoming rough like a shark's skin. There is also. The polyamide used in the present invention is not particularly limited, and may be a polyamide obtained from an aliphatic, aromatic or alicyclic dicarboxylic acid and a diamine, a polyamide obtained from an aminocarboxylic acid or a cyclic lactam, etc. Specific examples include aliphatic polyamides such as nylon 6, nylon 6/6, nylon 6l9, nylon 6-10, nylon 6*12, nylon 4-6, nylon 11, and nylon 12, and poly(hexamethylene terephthalamide). ), poly(hexamethylene isophthalamide), poly(m-xylylene adivamide), and other polyamides containing aromatic rings, and these can be used alone or in combination.In the present invention, Maleimide copolymer 10-50Mf!L
% polyamide, 40-801i weight %, and modified polyolefin polymer 3-40 l weight % are mixed to make a silk composition. Unfortunately, the degree of improvement in heat resistance, moldability, or moisture absorption of the obtained composition is insufficient, and the 71-neumide copolymer content exceeds 50% by weight, or the polyamide content is less than 4011ffi%. The mechanical strength, chemical resistance, and abrasion resistance of the cast material are poor. Furthermore, if the modified polyolefin polymer contains 3% by weight of the ungrooved material, the effect of improving the equilibrium U value is low, and if the modified polyolefin polymer contains 1% by weight or more of 40I, the decrease in rigidity is too large. The modified polyolefin polymer used in the present invention is a modified polyolefin polymer modified with an unsaturated dicarboxylic anhydride monomer and/or an unsaturated carboxylic acid monomer, and preferably has rubber-like elasticity. The modified polyolefin polymer refers to a modified product of monomer or co-i1i polymer of olefin monomers, and specific examples of the olefin monomers used include ethylene, brobylene, 1-butene, isobutylene, and 2-butene. , cyclobutem, 3-methyl-1-butene, 4-methyl-1-butene, 4-methyl-1-pentene, cyclobentene, 1-hexene, cyclohexene, 1-octene, 1-decene, 1-dodecene, and the like. In addition, the modified polyolefin polymer may be used as a non-conjugated polymer such as 4-ethylidenenorbornene, dicyclopentadiene, etc., if necessary. ．． Acrylic monomers, etc., which have already been exemplified as the co-doplexing monomers constituting the ffi-form and the maleimide-based copolymer, may be copolymerized within a range that exhibits rubber elasticity. Examples of preferred composition ranges include: 20 to 90 mol% ethylene, 10 to 90 mol% α-olefin monomer
It is particularly preferable that the ethylene content is 80 mol% and other monomers O to 10 mol%, and the ethylene content is 50 to 86 mol%. Further, the Tg of these modified polyolefin polymers is -10°C or lower, particularly preferably -30°C or lower. As the unsaturated dicarboxylic acid anhydride monomer constituting the modified polyolefin polymer, those already exemplified as monomers constituting the maleimide copolymer can be used, but
Maleic anhydride is particularly preferred, and unsaturated carboxylic acid monomers include acrylic acid, methacrylic acid, and the like. The content of unsaturated dicarboxylic anhydride monomer groups or unsaturated carboxylic acid groups in the modified polyolefin polymer is 0.
．． 1 to 101 tffi% is preferable, and 0.1 to 5
B! % is particularly preferable, but if it is less than 0.1 mft%, the mechanical strength of the resulting composition will be insufficient, and a peeling phenomenon may often be observed in molded products.
If the amount exceeds 1L, mechanical strength or thermal stability may be impaired. Modification in the present invention refers to monomer groups used for modification to the main chain or I4 chain of the polyolefin polymer, for example,
This indicates the presence of maleic anhydride groups, and modification can be carried out using known techniques such as random copolymerization and graft polymerization. The modification method is not particularly limited, and is disclosed in, for example, Japanese Patent Publication No. 39-6810, Japanese Patent Publication No. 52-43877, Japanese Patent Publication No. 53-57-16, Japanese Patent Publication No. 56-9925, Japanese Patent Publication No. 5B-445, etc. The denaturation can be carried out according to the method described above. In addition, it is preferable to use a graft that has been modified as a graft rather than introduced into the main chain in terms of low-temperature impact value. Furthermore, the amount of unreacted monomer remaining is 0.5ffif1
% or less, the better. There is no particular restriction on the molecular weight of the modified polyolefin 1 combination, but it is preferably 50,000 to 500,000, particularly preferably 100,000 to 300,000, in view of the balance between impact resistance and moldability. Examples of commercially available modified polyolefin-based polymers include Tafmer MPO 820 (Mitsui Petrochemical). In the silk composition of the present invention, the maleimide-based copolymer forms dispersed particles, and The particle diameter of the dispersed particles is 0.01~
It must be 1.0 micron. A particularly preferred particle size is 0.04 to 5 microns. More preferably, it is 0.05 to 0.3 micron. However, the particle diameter of the dispersed particles is the value determined by C measurement by observing an ultrathin section cut from a sample treated with hydrazine hydrate and stained with osmic acid using a transmission electron microscope. If the dispersed particle size is less than 0.01 micron, the melt viscosity of the string composite obtained by mixing with polyamide will be high, and a shark-skinned defective phenomenon will occur on the surface of the molded product. If the dispersed particle size exceeds 1.0 micron, the mechanical strength of the composition will be poor. It is also desirable to form dispersed particles in the modified polyolefin polymer, which are independent, amorphous, and almost uniformly dispersed. According to the findings of the present inventors, when the same amount of the same polyamide is used, the factors that are particularly important for determining the diameter of dispersed lachrymal particles in the silk composition are those in the maleimide copolymer. It is the content of saturated dicarboxylic anhydride monomer groups; when the content is low, the particle size is large, and when the content is high, the particle size is small. In addition, the content of organic acid groups in the modified polyolefin polymer is equally important.
It exhibits the same effect as the unsaturated dicarboxylic anhydride monomer group in the imidized resin copolymer. The composition of the present invention preferably contains a metal acid salt and/or a fatty acid amide compound. Containing these compounds has the advantage of improving the impact strength of the resulting cake. The organic acid metal salts used in the present invention include lauric acid, myristylic acid, valmitic acid, steanone acid, behenic acid, oleic acid,
Because of linole, fatty acids such as ricinoleic acid and hydroxystearic acid, aromatic carboxylic acids such as phthalic acid, and sodium, potassium, lithium, magnesium, calcium, strontium, barium, and zinc. It is a salt with metals such as cadmium, aluminum, tin, and lead. Divalent metal salts such as magnesium, calcium, barium, and zinc are preferred. Further, the fatty acid amide is a primary amide or a secondary amide of the aforementioned fatty acid, and the secondary amide may be a bisamide such as methylene bisstearylamide or ethylene bisstearylamide. The content of organic acid metal salt and/or fatty acid amide in the morning preparation of the present invention is 0.01-5% by weight, preferably 0.01-5% by weight.
The content is in the range of 0.05 to 2% by weight, more preferably 0.2 to 1% by weight. 0. No effect of addition was observed when the Ol weight% was not grooved, and 5! If the amount exceeds %, properties such as heat resistance and rigidity may deteriorate, and the effect of improving impact value may be small. Particularly preferably, these organic acid metal salts and fatty acid amide are used in combination, and the ratio of the organic acid metal salt and fatty acid amide to be used is not particularly limited as long as it is within the above-mentioned amounts, but it is preferably around 1:l. It is also possible to contain antioxidants, and the use of phenolic antioxidants is preferable because of discoloration. As a phenolic antioxidant, octadecyl-3-(3.5-di-t-butyl-4-hydroxyphenyl)probionate (for example, Irganox 107
6), N-N'hexamethylenebis(3.6-di-t-
Butyl-4-hydroxycinnamamide (e.g. Irganox 1098), 3,5-di-t-butyl-4
-Hydroxytoluene, 2,2'-methylenebis(4
-methyl-6-t-butylphenol), 4,4'-methylenebis(2,6-di-t-butylphenol), 4
◆4'-butylidenebis-6-t-butyl-m-cresol, 2,6-bis(2'-hydroxy-3't-butyl-6'-methylbenzyl)-4-methylphenol, 1,1,3-tris (2'methyl-5'-t-butyl-4'-hydroxyphenyl)butane, 1, 3, 5
-trimethyl-2,4,6-tris(3' 6゜-
(di-t-b-f-ru-4'-hydroxybenzyl)
Benzene, 4,4'-thiobis(2'-methyl-6'-
t-butylphenol), 2,2'-thiobis(4'-
Methyl-6'-t-butylphenol), 4●4'-thiobis(3-methyl-6-t-butylphenol),
1-1 1-tetrakis(methyl-3-(3.5-
di-t-butyl-4-hydroxyphenyl)probionate]methane, 2,2'-thiodiethylbis[3-(
:3,5-di-t-butyl-4-hydroxyphenyl)
monobrobionate], N-lauroyl p-7 mininophenol, and N-stearoyl p-aminophenol, and it is preferable to use a combination of those for general nylon and for olefin. In addition, it is of course also possible to use chelate-based antioxidants.
Another factor is that the dispersed particle size depends on the mixing method of the maleimide copolymer, polyamide, and modified polyolefin polymer. The maleimide copolymer, polyamide, and modified polyolefin polymer can be mixed using a normal melt kneading device, but suitable melt kneading devices include a screw extruder, a Banbury mixer, a co-kneader, and a mixing roll. etc. The composition of the present invention can be made into a composition by adding other additives or modifiers depending on the purpose. Specifically, reinforcing fibers such as glass fibers, carbon fibers, aramid fibers, etc. These include fillers such as talc, silica, clay mica, and calcium carbonate, ultraviolet absorbers, flame retardants, lubricants, and colorants. [Example] The present invention will be explained in more detail with reference to Examples below.
All parts and percentages used in Examples and Comparative Examples are ffL.
It is based on quantity. Furthermore, these are merely illustrative and do not limit the content of the present invention. The methods for measuring various properties are as follows. Dispersed particle size in the composite: A pre-trimmed sample was mixed in hydrazine hydrate and left at 60°C for 48 hours. After washing with water, this sample was immersed in a 1% aqueous Sumic acid solution and left at room temperature for 24 hours for staining. Ultrathin sections were cut from the stained samples and transmission electron micrographs were taken. The obtained images were analyzed to determine the particle size. Heat resistance: A
In accordance with STM D-648, the heat distortion temperature (H DT ) was measured using an injection molded product with a thickness of 1/4# at a load of 18.6 J/am2. Impact strength: According to ASTM D-256, thickness 1
/4# extrusion molded product was used to measure the notched iso-to. The ambient temperature is 23℃. Fluidity: ASTM
According to D-1238, temperature 265°C, load I! tl
The melt flow rate was measured using okg. Appearance: A molded product with bosses, ribs, and openings on the back side was molded using a 5-ounce injection molding machine, and the appearance of the molded product was visually evaluated. Molding temperature is 260℃. (1) Polyamide (B) The following nylon 6, nylon 12, and nylon 66 obtained by the i'a Ta fi 1 method were used. b-1) Nylon 6: Nylon 6 obtained from ε-cabrolactam with a sulfuric acid relative viscosity of 2.65.

b-2) Nylon 12; Nylon 12 obtained from 12-aminododecanoic acid with a relative viscosity of 2.40.

b-3) Nylon 66; Relative viscosity of sulfuric acid obtained from equimolar salts of hexamethylene diamine and adivic acid 2.
55 nylon 66, (2) maleimide copolymer (
A) The maleimide copolymer was prepared by placing 100 parts of styrene in an autoclave with a stirrer in place, purging the system with the desired gas, and then heating it to a temperature of 80°C. To this was added 8 parts of a solution of 67 parts of maleic anhydride and 0.2 parts of penzoin peroxide dissolved in 300 parts of methyl ethyl ketone. After the addition, the temperature was kept at 80°C for an additional 4 hours. To the above copolymer, 1.2 parts of triethylamine and 38 parts of aniline. 1 part was added and the reaction was carried out at 130°C for 7 hours. The reaction solution was cooled to room temperature, poured into 300 parts of vigorously stirred methanol, filtered and evaporated to obtain a maleimide-based copolymer (a-3). Other maleimide copolymers were prepared in the same way. These are shown in Table 1. (3)
Modified polyolefin polymer ethylene alpha-olefin copolymer Beret with ethylene content of 80 mol%} 10 kg, powdered anhydrous malein! 12
0g, 2ψ5-dimethyl - 2 Pour into a shell mixer,
Stir for 5 minutes to blend uniformly, and use a 40lφ extruder (L/T-28, Dalmage type, manufactured by Nitgyo wo Ryutsu).
Form into pellets. Cylinder temperature is polymer temperature 2
The temperature was adjusted to 40°C, and the graft reaction product (c-3
) was obtained (the amount of maleic anhydride introduced into the copolymer was 0.
9! fit%). Other modified polyolefin polymers were prepared in the same manner. These are shown in Table 2. Examples-1 to 1 day and Comparative Examples-1 to 5 0.0 kg of barium stearate was added to 10 kg of the above nylon-6 (b-1).
Blend 05ffi amount% in 2OL Henschel, 4
560kg of pelletized material extruded with a 0Bφ1 trowel at 240°C, 20! After adding 0.5 ffl weight % of ethylene bisstearylamide into Henschel and blending, maleimide copolymer resin (a-2) 3. 5kg
．． Modified polyolefin polymer (c-3) 1.5 kg,
Antioxidant (octadecyl-3-(3,5-T)
-butyl)monohydroxyphenyllube nate 0. 2 Add 51 fLm% OyoUN-N' hexamethylenebis(3,5-di-butyl)monohydroxyhydrocinnamamide 0.5ffiffi%), blend, and then add CTM (manufactured by Kobe Steel) to a 40-φ It was extruded using an extruder at 290°C and formed into an L knot. The dispersed particle size of the maleimide copolymer in the obtained composition was 0.17t.
It was rn. Also, weird. The condition of the dispersed particles of the polyolefin polymer is also good. Using this pellet, a test mold for measuring physical properties was created using an injection molding machine, and various physical properties were measured. The results are shown in the table. Similarly, Example-2~
15. Comparative Examples 1 to 5 were also conducted. Comparative example-1 and 2
The maleic anhydride content in the maleimide copolymer is out of range. In Comparative Example 3, the maleic anhydride content in the modified polyolefin compound was outside the range. Comparative Examples-4 and 5 are
The content of modified polyolefin polymer is out of range. The molding temperature was set at 270''C as a standard, and was slightly modified depending on the condition of the molded product.

The following is clear from the results of Examples and Comparative Examples. From Example 2 and Comparative Example 1, it is clear that if the maleimide-based sympathic polymer does not contain the unsaturated dicarboxylic anhydride monomer 2, the impact value improvement effect will be small and the elongation will be low, making it impractical. In addition, the dispersion of the maleimide copolymer at this time was poor and the dispersed particle size became large.Furthermore, as in Comparative Example 2, even if the amount of unsaturated dicarboxylic anhydride was too large, the impact value did not improve. However, it causes poor appearance and a decrease in moldability (flow).From Example 2 and Comparative Example 3, the presence of dicarboxylic acid anhydride in the polyolefin system 1 is essential, but is it not present? It can be seen that the effect of improving the gj impact value is small and the appearance becomes poor.As mentioned above, the physical property balance is achieved only when both contain suitable unsaturated carboxylic acid anhydrides (grafting, copolymerization). Furthermore, as is clear from the Examples and Comparative Examples, the dispersion state of the maleimide-based sympathic polymer is also important for the physical properties, and neither large nor small particle diameters are good. The electron micrographs of the resin silk compositions obtained in Example 2 and Comparative Examples 1 and 3 are shown in Figure 1, Figure 2, and Figure 3.
It is shown in the figure. As can be seen from FIG. 1, in the resin composite of the present invention, the particle size of the maleimide copolymer is 0. 1 μm, and the modified polyolefin polymer is almost uniformly dispersed in a semi-continuous layer. In Comparative Example-1, the dispersed particle size of the maleimide copolymer is large, and the dispersed particle size of the modified polyolefin polymer is also poor, unlike in Example-1.

In Comparative Example 3, the dispersed particle size of the maleimide copolymer was small, and the modified polyolefin polymer was unevenly dispersed. 4,

[Brief explanation of drawings]

FIG. 1, FIG. 2, and FIG. 3 show Example-2, respectively.
This is an electron [1 mirror photograph] showing the dispersion state of the maleimide copolymer particles of the resin compositions obtained in Comparative Examples 1 and 3. Second

Claims (1)

[Claims] 1. (A) 30 to 70 mol % of aromatic vinyl monomer groups, 30 to 50 mol % of maleimide monomer groups, 3 to 20 mol % of unsaturated dicarboxylic anhydride monomer groups. % and other copolymerizable monomer groups 10 to 50% by weight, (B) polyamide 40 to 50% by weight
80% by weight, and (C) unsaturated dicarboxylic anhydride monomer group and/or unsaturated carboxylic acid monomer group 0.1
Thermoplastic, characterized in that a maleimide copolymer containing 3 to 40% by weight of a modified polyolefin polymer modified at 10% by weight forms dispersed particles of 0.01 to 1.0 microns. Resin composition. 2. The thermoplastic resin composition according to claim 1, wherein the modified polyolefin polymer is amorphous and substantially uniformly dispersed. 3. The composition according to claim 1 or 2, containing an organic acid metal salt and/or a fatty acid amide.