JPH03163163A - Impact-resistant thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition excellent in heat resistance and low-temperature impact resistance by mixing a resin composition comprising a polyamide resin and a rubber-reinforced styrene graft copolymer with a specified copolymer containing an alpha,beta-unsaturated (di)carboxylic anhydride monomer component. CONSTITUTION:An impact-resistant thermoplastic resin composition is obtained by mixing 100 pts.wt. resin mixture comprising 20-80wt.% polyamide resin and 20-80wt.% rubber-reinforced styrene graft copolymer (comprising 40-60 pts.wt. conjugated diene rubber and 40-60 pts.wt. monomer component comprising 60-80wt.% aromatic vinyl monomer component and 20-40wt.% vinyl cyanide monomer component and having a mean particle diameter of graft rubber of 0.2-1.0mum, a degree of grafting of 40-80% and a relative viscosity of the resinous component of 0.05-0.10) with 0.01-40 pts.wt. unsaturated carboxylic acid. copolymer (comprising 50-80wt.% aromatic vinyl monomer component, 0.01-30wt.% alpha,beta-unsaturated carboxylic acid monomer component, 5-47wt.% vinyl cyanide monomer component and 0-30wt.% methyl methacrylate component).

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Field" The present invention relates to M impact thermoplastic resin compositions.More specifically, the present invention relates to M impact thermoplastic resin compositions. Naru O {Fabinuma. In compound, α
, β-monounsaturated carboxylic acid monomer component and/or α,
By blending a specific J(polymer) containing a β-unsaturated nocarboxylic acid anhydride monomer, it is possible to obtain a material with excellent impact resistance, particularly excellent notched Izod impact strength at low temperatures. This is related to Ift-kumi Kaimono from which you can obtain a gift.

``Jubei's Technology 1'' Boly7mide resin has traditionally been used as an engineering plastic for various mechanical parts due to its excellent properties such as wear resistance, electrical properties, mechanical strength, and chemical resistance. This polyamide #{# has disadvantages such as high water absorption and low Izod impact strength with /7 inch, especially at low temperatures.In addition, styrene-based heavy Compared to coalescence, it has disadvantages such as poor heat resistance under high loads and poor shapeability due to crystallinity.Because polyamide wood has these defects, it is not suitable as an engineering plastic. In some cases, the uses of polyamide PA resin were limited, and the excellent properties of polyamide PA resin could not be utilized.

As a method to improve these drawbacks of poly-7mide PA resin, it is known to mix it with a 7-crylonitrile-ptadiene-styrene copolymer (ABS resin) to create a blended resin. (For example,
(See Publication No. 8-23476). However, blends of polyamide resins and ABS resins have poor compatibility, and when made into molded products, a layering phenomenon occurs due to poor mixing, and mechanical strength such as tensile strength deteriorates. There are disadvantages such as severe deterioration. For this reason, poly7mide {M fat and A B
S l {As a method to improve compatibility with styrenic polymers such as fats, a styrene polymer containing an α,β monounsaturated carboxylic acid anhydride monomer component is added to a blend of both resins. , it has been proposed to incorporate it as a third component (see, for example, Japanese Patent Publication No. 60-47304). If this third precept is blended, it is true that a resin compound in which polyamide 135 resin and styrene polymer are physically finely dispersed can be obtained, but a resin compound made of three components can be obtained. There is almost no improvement in impact resistance.

As mentioned above, until now, in O-ring fabrics made of polyamide resin and styrene polymer, a resin material that combines the excellent properties of both materials and also has excellent impact resistance at low temperatures has not been obtained. is the current situation.

``Problems to be Solved by the Invention'' The present inventors have sought to solve the ``disclosure defect'' that has conventionally existed in resin compositions of polyamide resins and rubber-reinforced styrene-based graft copolymers. In other words, the present invention was arrived at as a result of extensive research. That is, an α,β monounsaturated carboxylic acid monomer component and/or an α,β monounsaturated dicarboxylic acid anhydride monomer component is added to a resin mixture consisting of a polyamide resin and a specific rubber-reinforced styrenic graft copolymer. By blending a specific copolymer containing body components, it is possible to obtain a molded product with excellent heat resistance and impact resistance, and in particular, the notched Izod impact strength at low temperatures is noticeably improved. It is an attempt to provide something. "Means for Solving the Problems" The gist of the present invention is that polyamide resin (A) 2
A monomer consisting of 0 to 80% by weight and 40 to 60 parts by weight of conjugated citric rubber, 60 to 80% by weight of aromatic vinyl monomer component and 20 to 40% by weight of vinyl cyanide monomer component. Ingredients 40~
60 parts by weight, and the average particle diameter of the graft rubber is 0.2 to 1.0 μ, the graft instep is 40 to 80%,
and the specific viscosity of the woody component consisting of the above monomer component is 0.
．． 05 to 0.10, or 100 parts by weight of a resin mixture consisting of 20 to 80% by weight of a graft copolymer (B) in which the weight average molecular weight of the lipid component is 220,000 to 450,000, aromatic vinyl Monomer component 50-80% by weight, α,β monounsaturated carboxylic acid monomer component and/or α,β monounsaturated dicarboxylic acid anhydride monomer component 0.01-30% heavy electric content
, a vinyl cyanide monomer component of 5 to 47% by weight, and a methyl methacrylate component of 0 to 30% by weight (however, the total monomer component is 100% by weight) (C) 0.01 ~40 parts by weight, and 60 to 90 weight% of the aromatic vinyl monomer component, 0 to 40 weight% of the vinyl cyanide monomer component, and 0 to 40 weight% of the methyl methacrylate component (however, the monomer Total number of precepts is 1
00% by weight. ) Ascending copolymer (D) 0-15
An impact-resistant thermoplastic resin composition comprising: The present invention will be explained in detail below.

The polyamide resin (A
) refers to a known nylon-based thermoplastic resin that can be injected or molded. Specific examples of the polyamide resin (A) include nylon 6, nylon 66, copolymerized nylon (copolymer of cabrolactam and hexamethylene diamine 7-dipic acid salt), nylon 610, nylon 612, nylon 11,
Examples include nylons known by common names such as nylon 12 and nylon MXDl3 (condensation polymer of metaxylylenenoamine and 7-dipic acid), copolymers containing these as main components, and mixtures thereof. It will be done. Among these examples, nylon 6, nylon 66, and copolymer nylon are particularly preferred. The graft copolymer (B) constituting the resinous material according to the present invention is 40 to 60 parts of conjugated rubber (preferably 45 to 60 parts by weight).
heavy IL part) and aromatic vinyl monomer component 60 to 80% by weight
and 40 to 60 parts by weight of a monomer component (preferably 40=, SS parts by weight) which is higher than 20 to 40 parts by weight of a vinyl cyanide monomer component, and a graft copolymer ( The average particle size of the grafted rubber in B) is 0.
2 to 1.0μ theory, Graph F wheel is 40 to 80%, and the specific viscosity of the resinous component of the unglazed 7F portion in the L-mer component is 0.05 to 0.1o, or the weight average molecule 2 songs
20.000 to 450.000. This graft copolymer (B) has optimized the content of conjugated diene rubber, the average particle size of the graft rubber, the grafting ratio, and the specificity or weight average molecular weight of the woody component, so that it can be used as a polyamide. By blending with the resin (A), it is effective as an impact modifier (impact resistance imparting agent).

In the present invention, the graft copolymer (B
) as an impact modifier, especially at low temperatures, a graft copolymer (B
) Select the average particle diameter of the grafted rubber in the range of 0.2 to 1.0μ, select the V1 graft ratio within the range of 40 to 80%, and set the specific viscosity of the lipid component in the final graph F part. 0.05
~0.10fl range, or weight average molecular weight of 220
,000 to 450,000.

Preferably, the weight average molecular weight of the above-mentioned $4{fm trade component is in the range of 250,000 to 400,000. Outside this range, the physical properties such as impact resistance at low temperatures of the resin composite according to the present invention may deteriorate. The improvement effect disappears. The conjugated diene rubber, which is a structural component of the graft copolymer (B), is a rubber containing 50% by weight or more of a conjugated diene monomer component such as butadiene, isoprene, chloroprene, etc., and has a glass transition temperature of 0°C or lower. refers to polymers with a shape of Specific examples of conjugated diene rubber include butadiene rubber (BR), styrene-butadiene rubber (SBR), acrylonitrino-butadiene rubber (NBR), and imprene rubber (IR).
)′! ? An example of this is the well-known Imaboshi rubber.

The above-mentioned conjugated diene rubber is supplied as a rubber latex or solid rubber, and is used in an emulsified state or a solution state according to the method for producing the graft copolymer (B).

Specific examples of the aromatic vinyl monomer component that is a component of the graft copolymer (B) include styrene, α-7-rukylstyrene such as a-methylstyrene, and 4-substituted monomers such as ρ-1/tinorestyrene. Examples include 7-olequinolestyrene and vinylnaphthalene. These include one or more types of pure water. It may be a current item.

The proportion of the aromatic vinyl monomer component in the monomer d component is in the range of 60 to 80%. If it is outside this range, the properties of the graft copolymer (B) such as impact resistance and miscibility with other resins will change, making it impossible to produce a wood composite with excellent physical properties.

Specific examples of the cy7-vinyl monomer which is a structural component of the graft copolymer (13) mentioned above include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and the like. These may be used alone or in a mixture of two or more.

Vinyl cyanide! The proportion of the lt-mer component in the monomer component is in the range of 20 to 40% by weight. If it is outside this range, the properties of the graft copolymer (B), such as impact resistance and miscibility with other fats, will change, making it impossible to produce a jufu-kumi kaimono with excellent physical properties.

The above graft copolymer (B) is a conjugated diene rubber 4
0 to 60 parts by weight, preferably 45 to 60 parts by weight, and 40 to 60 parts by weight of a monomer component consisting of an aromatic vinyl monomer component and a vinyl cyanide monomer component, preferably 4 parts by weight.
It is composed of a component ratio of 0 to 55 parts by weight. If this ratio is exceeded, it will not be possible to optimize the conjugated diene rubber content, graft size, specific viscosity, or average molecular weight of the graft copolymer (B), so the properties as an Impact Mod 7T ear will deteriorate and the properties of the graft copolymer (B) will deteriorate. It is not possible to make an excellent woodwork. When the conjugated diene rubber content is less than the above component ratio, ! This is particularly undesirable since the impact resistance of the l1r& object at low temperatures decreases.

In the present invention, the average particle diameter of the graft rubber in the graft copolymer (B) is in the range of 0.2 to about 0.5 μm, as defined by Coulter Electronics Ltd., USA! Il! "Coulter Nano-Sizer Tl"
), the raw rubber latex before graft polymerization is
It refers to the weight average particle size measured in a system dispersed in water at 3°C. For the range of about 0.5 to 1.0μ, using the Coulter Counter Model T A l'[. It refers to the weight average particle diameter measured at 23°C in a solution containing a small amount of potassium thiocyanate.

In the present invention, the grafting rate is expressed by the following formula: Graft copolymer (B) is dispersed and dissolved in acetone at 23°C, and then centrifugation is performed to obtain the a7ton T solution (graft rubber). ) and 77 tons of the soluble component and the resinous component), and the resulting graft copolymer (B) is obtained by subtracting the rubber content in the graft copolymer (r3) from the weight of the dried acetone-insoluble component. It refers to the ratio (%) to the rubber content inside.

In the present invention, the specificity refers to the degree of specificity in the Ill electric component composed of the aromatic vinyl monoelectric component and the vinyl cyanide monoacid component produced in the graft copolymer (B). It refers to the specific viscosity (ηsIl) of the lipid component of the terminal graft portion. Specifically, first, the acetone soluble content obtained from the graft copolymer (B) is dried using the same method and procedure as in 1. for measuring the graft ratio, and the tree mY! Get ta. This is the specific viscosity (ηsp) measured using an Ubbelohde viscometer at 25°C using the obtained resinous component as a solution of 0.1% (g/100 ml) methyl ethyl ketone. In addition, since the specific viscosity (ηsp) has a relatively large measurement error of 1 to 1, it is more preferable to display it as the weight average molecule fl (MW) measured by GPC described below.
.

In the present invention, the weight average molecular weight means 'Il.' in the graft copolymer (B). It refers to the weight average molecular weight (Mw) obtained by measuring the resinous component in the ungraphed portion of the graph by GPC. Specifically, the above-mentioned resinous component obtained by drying the a-7ton soluble content in the graft copolymer (B) is first dissolved in tetrahydro7-ran.
Then, the obtained tetrahydro7rane solution was subjected to GPC (
The weight average molecular weight (Mw) is obtained as a weight average molecular weight (Mw) in terms of polystyrene.

The graft copolymer (B) in the present invention is produced by adding aromatic vinyl monomers and cyanide vinyl mf to the bottom of the rubber spine by emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization, etc.
It can be produced by graft copolymerizing a monomer mixture containing the i-isomer as a main component by a known method.

In particular, the emulsion polymerization method is preferred because it is easy to control the average particle diameter of the graft rubber in the graft copolymer (B), the graph F ratio, the rubber content wP, etc. The TJ4 resin mixture constituting the inventive resin composition includes the polyamide resin (A) in an amount of 20 to 80% by weight, preferably 30 to 70% by weight, and the graft copolymer (B).
) in a range of 20 to 80% by weight, preferably in a range of 30 to 70% by weight. The above resin mixture is the base resin composition of the present invention, and must be blended within the above range in order to obtain the desired physical properties. However, as for the blending method, it is necessary to mix and knead only the above f2 resin (A) and the above graft copolymer (B) in advance before blending the below-mentioned copolymer (C) or the below-mentioned copolymer (D). It is sufficient that it is finally contained in the resin composition of the present invention within the above range. If this blending ratio is out of the above range, the physical properties of the resulting resin MLIR product, such as mechanical strength, heat resistance, or machinability, will deteriorate. The copolymer (C) constituting the resin composition of the present invention includes an aromatic vinyl monomer component of 50 to 80% by weight, an α,β monounsaturated carboxylic acid monomer component, and V/or α, β monounsaturated nocarboxylic anhydride monomer component 0.01 to 30% by weight,
Consisting of 5 to 47% by weight of vinyl cyanide monomer and 0 to 30% by weight of methyl methacrylate component (however, the total monomer component is 100% by weight. The same applies hereinafter). The copolymer (C) is a thermoplastic hard resin. Moreover, the copolymer (C) is a polyamide resin (A)
It is added to the mixture of the polymer and the graft no-q polymer (B) to improve the dispersibility and miscibility of the two, thereby improving properties such as impact resistance and mechanical strength at low temperatures. The aromatic vinyl monomer component and vinyl cyanide monomer component, which are the vt components of the above copolymer (C), are those exemplified as the components of the copolymer (B) in the graph above. It has the same meaning as each vinyl monomer component. The proportion of the aromatic vinyl monomer component in the copolymer (C) shall be in the range of 50 to 8 (l%). Outside this range, the heat resistance of the copolymer (C) and other factors may be affected. properties such as miscibility with the resin change, making it impossible to produce a tree auxiliary composition with excellent physical properties.

α,β-unsaturated carbon il! which is a V# component of the above copolymer (C)! 2 Monoplane components include acrylic acid,
An example is notacrylic acid. Further, examples of the α,β-unsaturated dicarboxylic acid anhydride monomer component include maleic anhydride. Among these, maleic anhydride, which is an α,β-monounsaturated dicarboxylic acid anhydride monomer component, is particularly preferred. α, β monounsaturated carboxylic acid monomer component and/
Alternatively, the proportion of the α,β-unsaturated dicarboxylic acid anhydride monomer component in the copolymer (C) is in the range of 0.01 to 30%. Preferably, this ratio is 0.1 to 1
0 parts by weight is good. The copolymer (C) containing an α,β monounsaturated carboxylic acid monomer component and/or an α,β monounsaturated dicarboxylic acid anhydride monomer component within this range is a polyamide resin (A) and a polyamide resin (A). F copolymer (B),
+3 {Jet? We can manufacture knitted items.

The proportion of the vinyl cyanide monomer component in the copolymer (C) is in the range of 5 to 47% by weight. Preferably 1
A range of 0 to 35 double bases% is good. If it is outside this range, the heat resistance of the obtained resin composition and the miscibility between the resins will decrease, so in the present invention, the copolymer of methyl methacrylate component (
The ratio in C) is 0 to 30% by weight, but
It is preferably in the range of 0 to 10% by weight. If the amount exceeds 30% by weight, the physical properties of the resulting copolymer will change, making it impossible to obtain the desired resin composition.

The method for producing the above copolymer (C) includes copolymer (C)
) was used as a raw material for polymerization, 50 to 80% by weight of aromatic vinyl monomer, α,β monounsaturated carboxylic acid! 11-mer and/or α,β-unsaturated dicarboxylic acid anhydride monomer 0.0 1 to 30% heavy electric charge, vinyl cyanide Ill. Body 5'. , 47% by weight, and 0 to 30% by weight of methyl methacrylate. By copolymerizing a mixture of 11(1) and 11(1), it is possible to produce J(polymer (C)), which has an ordinary structure.

Specific operations include bulk polymerization method, solution polymerization method, suspension polymerization method, and/or emulsion polymerization method, and can be carried out by either a quarter-section method or a continuous method. good. The polymerization methods and methods described above can be combined as appropriate. In addition, as treatment methods after the copolymerization operation is completed, known extraction, precipitation, distillation, coagulation, separation, washing,
Single operations such as drying and pelletizing can be employed in appropriate combinations. Copolymer (C) can be obtained by such post-treatment.

The copolymer (D) constituting the composition of the present invention includes 60 to 90% by weight of an aromatic vinyl monomer component, 0 to 40% by weight of a vinyl cyanide monomer component, and a predominant component of methyl methacrylate. It is a thermoplastic resin consisting of ~40% by weight.

The aromatic vinyl monomer and vinyl cyanide monomer, which are the constituent components of the above-mentioned copolymer (D), refer to each of the vinyl monomers exemplified as the precepts of the above-mentioned graft copolymer (B). Synonymous with monomouse. The proportions of components that should be kept in mind in the copolymer (D) are as described above.If the proportions are outside this range, the characteristics of the copolymerized resin will change, and the miscibility with the resin in the mixing pond will become poor, making it difficult to meet the intended purpose. It is undesirable because it lowers the heat resistance or impact resistance of the material at low temperatures.

The method and polymerization conditions for the copolymer (D) include, for example, a known 7-crylonitrile-styrene copolymer (AS resin).
of! ! ! ``According to technology a, emulsion polymerization method, suspension polymerization method,
Methods such as solution polymerization method and bulk polymerization method can be appropriately selected from batch or continuous methods.

Moreover, this copolymer (D) is a graft copolymer (B)
In the polymerization operation of and/or copolymer (C), they can be produced simultaneously in the same polymerization system, or they can be produced by setting a separate polymerization method and polymerization conditions.

The resin composition according to the present invention comprises the above-described polyamide resin 1l'ff (A) and the graft copolymer (B).
More! Based on 100 fR parts of the jt m mixture, add copolymer (coo, oi to 40 m' parts, preferably 1
~20 parts by weight, and copolymer (D)O' = 1
Five layers! It is weighed out and mixed preferably in a range of O -, 10 parts. The mixed compound may be left as a dry blend, but it may be further subjected to a tf# melt kneading step to form a melt F.
Aft1 It is more preferable to do it now. Each one? If the blending amount of H fat is out of the range 2, the desired physical properties such as heat resistance and impact resistance at low temperatures will not be obtained, and the thermoplastic resin will not have good processability. Can not do it. In order to blend, mix and knead the constituent components of the wood composite of the present invention, known mixing and cross-mixing methods may be used.

For example, a mixture of one or more of these resins and copolymers in the form of powder, beads, seven lakes, or pellets is placed in an extrusion chamber such as a one-sleeve extrusion chamber, a two-wheel extrusion chamber, or
It can be made into a resin ffi mold using a mixer such as a bumperley mixer, pressurizing machine, two rolls, etc. In some cases, one or more of these copolymers that have been polymerized may be mixed in an undried state,
A method of precipitating, washing, drying, and kneading can also be used. As for the order of this mixing and kneading, three or four types of component resins or copolymers may be mixed and mixed at the same time.
Also, first of all, the component resin or copolymer 11! Alternatively, two or more types may be mixed and kneaded, and a mixture of one type or 2F1 or more may be mixed and kneaded later to produce the desired resin composite. In addition, if volatile matter remains in the wood composition, physical properties such as heat resistance may deteriorate, so when mixing and kneading using an extruder, it is necessary to forcibly devolatilize the material. It is better to perform two kneading operations. The wood Wt composite thus obtained is used as it is or after being dried for use in processing, etc.

The tree composition according to the present invention includes a class A and millet lubricant that does not impair the properties of the resin, a mold release agent, a foil coloring agent, an antistatic IL agent,
Various resin additives such as flame retardants, ultraviolet absorbers, light resistance stabilizers, heat resistance stabilizers, fillers, and nucleating agents can be added in appropriate combinations. The filler ε includes glass m fibers, metal m&fibers, carbon a fibers, fibrous reinforcing agents such as potassium titanate whiskers, talc, clay, calcium carbonate,
Mica, glass 7 lake, milled fiber, metal flakes, metal powder, etc. can be mentioned, and these can be used alone or 2! 'It or more can also be combined. The resin composition according to the present invention can be produced by injection molding method, extrusion molding method,
By various processing methods such as compression molding, it can be made into molded parts such as automobile parts, electrical parts, industrial parts, sports equipment, etc., and can be used in applications that require excellent heat resistance and impact resistance at low temperatures. ．． "Effects of the Invention" The present invention has been described above, and has the following particularly remarkable effects, and its industrial utility value is extremely large.

(1) The u4 fat composition according to the present invention is a poly7amide fat (
A) and a specific graft as an FJII impact imparting agent (polymer (B) containing an α,β monounsaturated carboxylic acid.
By blending a specific copolymer (C) containing a monomer component and/or an α,β monounsaturated dicarboxylic acid anhydride monomer component, surprisingly, hitherto unanticipated results can be obtained. Notched Izod impact strength measured at 23°C is 70 kg.
・Notched Izoft impact strength that is excellent at low temperatures, i.e., the value measured at -20℃ is 4.
0k.・6 thermoplastic resin materials with cta/eta or higher can be used. (2) The resin composition according to the present invention comprises an α,β-unsaturated carboxylic acid monoemulsion component and/or α,β-1′:#J
in:tJ, Il-J7. -a
m 11 & IN 纂 & rj} Ak j &
Since +-→←Polymer (C) is blended, it is possible to obtain an attractive product that exhibits good miscibility and processability, as well as excellent heat resistance and rock mechanical strength. (3) Since the resin composite according to the present invention has each constituent component optimized and blended, each NItI&
A molded product with low hygroscopicity and excellent chemical resistance, which combines the characteristics of saibun, can be obtained.

(4) The resin molding material according to the present invention has excellent resin molding processability because each component is optimized and blended.

(5) Since the resin composition according to the present invention has excellent miscibility with other materials, for example, by mixing and kneading with glass fiber etc. to form a composite, the resin composition can be reinforced with glass fibers with excellent heat resistance and rigidity. It can be made into a resin composition. ``Example 1'' Next, the present invention will be specifically explained based on Examples and Comparative Examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

Iri τ/r% sea bream 1yu◆! −) Lee “Drinking gong reto! Ha I↓”
Represents the presence and partner. Production example (1) Production of graft polymer (polymer (B) 1) Styrene (
Hereinafter, it will be abbreviated as St. ) and 30 parts of 7-crylonitrile (hereinafter abbreviated as AN) was prepared. Stir Vcrl! , reflux condenser,
Styrene-putadiene-rubber latex (St component content in the rubber: 10% by weight, rubber solids concentration: 37% by weight, rubber average ladle diameter: 0.38 μ- 330 parts (including water) and 100 parts of deionized water were charged, and the internal temperature was raised to 68°C while stirring under a nitrogen stream.0. 01 part, dextrose 0.25
1 part of sodium pyrophosphate was added to the polymerization system. Next, 25 parts (0.5 parts) of an aqueous dispersion of cumene hydroperoxide (hereinafter abbreviated as C H P O) was added to the flask.
Contains 5 parts CHPO. ) was continuously added over a period of 120 minutes, and the entire amount of monomer mixture (1) was continuously added over a period of 90 minutes, and the polymerization reaction was started at the same temperature. Ninety minutes after starting the polymerization reaction, 0.2 part of sodium dodecylbenzenesulfonate was added to the polymerization system. After starting the polymerization, the graft copolymerization reaction was continued at the same temperature for 150 minutes.

The latex obtained after the graft copolymerization reaction is
The graft copolymer (
B)-1 was obtained.

As a result of analysis and measurement of the obtained graft copolymer (B)-r, the graft A was 60%, and the specific viscosity of the resin component was 0.0.
7 3, and the fn amount average molecule ffi (
Mw) was 320,000.

(2) 70 parts of graft copolymer (B)-n product St;
A monomer mixture (It) consisting of 30 parts of AN and 1.1 parts of t-dodecylbutane was prepared.

Styrene-butadiene-rubber latex (St content 10% by weight, rubber solids concentration 37% by weight, rubber average particle size 0 .30 μm) (including water) and 100 parts of deionized water were charged, and the internal temperature was raised to 70°C while stirring under a nitrogen stream. Ferrous sulfate o. dissolved in a small amount of deionized water. oi parts, 0.8 parts of dextrose, and 1 part of sodium birophosphate were added to the polymerization system. Next, 25 parts of the C H P O aqueous dispersion (containing 0.5 part of C I { P O ) was added to the seven rasps over a period of 180 minutes, and the total amount of the monomer mixture (n) was added over a period of 140 minutes. Then, continuous addition was started, and the polymerization reaction started at the same temperature. 120 minutes after starting the polymerization reaction, 0.2 part of sodium dodecynolebenzene snolephonate was added to the polymerization system. After starting the polymerization, the graft polymerization reaction was continued at the same temperature for 210 minutes.

Gu? 71 The latex obtained after completing the polymerization reaction is
It was added dropwise to a 4% aqueous magnesium sulfate solution heated to ℃, salted out, dehydrated, and dried to obtain a powdery graft copolymer (B).
-1T was obtained.

The ratio was 40%, the specificity was 0.035, and the average molecular weight was 90.000.

(3) Production of graft copolymer ([3)-III to 7] In the example of Production Example (2), the rubber average particle diameter of the styrene-butadiene-rubber latex and the rubber in the graph F copolymer (B) The production conditions of the graft copolymer (B) were changed so that the content ratios became the compositions shown in Table 1, and graft copolymers (B)-■ to and ■ were obtained. The obtained graft copolymer (r3)-■H-■ was analyzed and measured.

The results are shown in the fjSl table.

fjS1 Table (4) Production of copolymer (C)-1 St.
67 parts of AN, 29 parts of AN, and 200 parts of methyl ethyl ketone were charged, and the humidity was raised to 77°C while blowing nitrogen gas. On the other hand, a solution was prepared in which 10 parts of notylethyl ketone, 3 parts of AN, part S of anhydrous maleic PIIO, and 0.5 part of azobisisoputyronitrile were dissolved (hereinafter abbreviated as W# solution A). Then, this W# liquid A was divided into 5 equal parts. After the polymerization reaction system reached 77°C, solution A was divided into 5 equal parts.
Polymerization was started by adding the split portion. While maintaining the system at 77°C, one portion of each of the five equal parts of solution A was added at intervals of 0.5, 1.0, 2.0, and 3.0 hours after the start of polymerization. Polymerization was completed 5 hours after the start of polymerization, and the mixture was cooled. After cooling, the reaction mixture was reprecipitated with a large amount of methanol to obtain a dried copolymer (C)-1. The polymerization conversion rate was 60%. As a result of analysis by GPC, the obtained copolymer (C)-1 had a weight average molecular weight of 70,000 in terms of polystyrene. In addition, as a result of analysis by liquid chromatography 7E, the content of upstream 7 crylonitrile was 30% by weight. The content of maleic anhydride is 0.83% by weight, calculated from the polymerization conversion rate.
Met. (5) Copolymer (C)-I1 g1''a 67 parts of St, AN29 in a 7-lask made by Russ Co., Ltd. equipped with a cooler and a stirring device
200 parts of ethyl ethyl ketone were charged, and the temperature was raised to 77°C while blowing nitrogen gas. On the other hand, 10 parts of methyl ethyl ketone, 3 parts of AN, 0.5 parts of maleic anhydride, and 0 parts of azobisisobutyronitrile.
A solution was prepared by dissolving 3 parts of NIB (hereinafter abbreviated as dissolved NIB). And this melt 8! Divide B into 6 equal parts. After the polymerization reaction system reaches 72°C, ff#? l! Polymerization was started by adding one portion of B divided into six equal parts. While maintaining the system at 72°C, the polymerization was started at 1.0, 2.0, 3.0, 4.
After every 0 and 5.0 hours, one portion of each of the six equal portions of Solution B was added. Eight hours after the start of polymerization, the polymerization was completed and cooled. After cooling, the reaction mixture was reprecipitated with a large amount of methanol and dried to obtain copolymer (C)-1I. The polymerization conversion rate was 53%. As a result of analysis by GPC, the obtained copolymer (C)-111 had a weight average molecular weight of 110,000 in terms of polystyrene. In addition, from the analysis results of liquid chromatography 7E, 7
Crylonitrile was 30% by weight. The content of maleic anhydride was calculated from the polymerization conversion rate and was 0.94% by weight. (6) Copolymer (D) Styrene/acrylonitrile = 70/30 (fi amount ratio)
The one with a specific viscosity of 0.11 was used. Example 1
-5, Comparative Examples 1-8 Nylon 6 (N O
V● AMID 1010, Mitsubishi Ka & Co., Ltd.! ! ), the graft copolymer (B), copolymer (C) and copolymer (D) obtained by the method described in the above production example were mixed in the blending ratios (parts) listed in Table 2. ) to weigh the amount of excess,
Mix with a tampufu, mix the obtained mixture with a pen Ll hakama 9 Tsumugi sho car side part m, and mix it with a pen Ll hakama 9 Tsumugi sho car side part m and f rin profit now to the middle part.
Created Beleft of the fJTff assembly. From the left of this resin assembly, test pieces for measuring physical properties were shaped using the injection molding method. Regarding the square test piece, the tensile strength, Izod impact strength (measured at 2°C with a notch and at -20°C), and melt 7 roll rate were measured in an absolutely dry state by the method described in the ftIJ1 table. It was measured. The results are shown in Table 2. ．． Measured based on IIS K7113.

Measured at 23°C and -20°C in accordance with J r S K7 1 1 0.

Kyo3: JIS K7210 B method (load 10k
gf, temperature 260″C).

Book 2: [J Kami 1 tree l: From Table 2, the following becomes clear.

(1) Since the Il resin composition according to the present invention has optimized the composition of the graft copolymer (B) to be blended, low temperature (
-20°C) excellent notched Izo flli
Has impact strength (more than 40 kg・Cω/Cω) (tjS2
(See Table Examples 1 to 5).

On the other hand, the notched Izosite impact strength at low temperature (-20°C) of the 1flt tree composite containing the graft copolymer (B) outside the scope of the present invention is low (see Comparative Examples 1 to 8 in Table 2). .

(2) Since the resin composite according to the present invention contains an appropriate amount of the optimized lIl copolymer (C), it exhibits unexpected properties at room temperature and low temperature (-20°C). It has a high notched Izod impact strength even when inserted (see Examples 1 to 5). On the other hand, those containing no copolymer (C) at all (see Comparative Example 8) have low notched Izod impact strength (3) Tree IJ according to the present invention}? Since the composition contains appropriate amounts of each O, it has excellent tensile strength, Izod impact strength at 23°C and -20°C, and mechanical strength as shown in melt 7 roll rate, heat resistance and The shape processability is well balanced (Examples 1 to 5).

In addition, resin composites obtained outside the framework of the present invention have the disadvantage that the balance between them is poor and at least one of the physical properties is poor (see Comparative Examples 1 to 8).

Claims (3)

[Claims] (1) 20 to 80% by weight of polyamide resin (A), 40 to 60 parts by weight of conjugated diene rubber, 60 to 80% by weight of aromatic vinyl monomer component, and 20 to 40% by weight of vinyl cyanide monomer component Monomer component 40 consisting of
60 parts by weight, and the average particle diameter of the grafted rubber is 0.2 to 1.0 μm, and the grafting rate is 40 to 80%.
and the specific viscosity of the resinous component consisting of the above monomer component is 0.
．． 100 parts by weight of a resin mixture consisting of 20 to 80% by weight of graft copolymer (B) having a molecular weight of 05 to 0.10, 50 to 80% by weight of aromatic vinyl monomer components, α, β
-Unsaturated carboxylic acid monomer component and/or α, β-
Unsaturated dicarboxylic anhydride monomer component 0.01 to 30% by weight, vinyl cyanide monomer component 5 to 47% by weight, and methyl methacrylate component 0 to 30% by weight (however,
The total amount of monomer components is 100% by weight. ), 0.01 to 40 parts by weight of copolymer (C), 60 to 90% by weight of aromatic vinyl monomer component, 0 to 40% by weight of vinyl cyanide monomer component, and 0 to 40% of methyl methacrylate component. Copolymer (D) 0-1 consisting of 40% by weight (however, the total monomer component is 100% by weight)
5 parts by weight of an impact-resistant thermoplastic resin composition. (2) 20-80% by weight of polyamide resin (A), 45-60 parts by weight of conjugated diene rubber, 60-80% by weight of aromatic vinyl monomer component and 20-40% by weight of vinyl cyanide monomer component Monomer component 40 consisting of
55 parts by weight, and the average particle diameter of the grafted rubber is 0.2 to 1.0 μm, and the grafting rate is 40 to 80%.
and 100 parts by weight of a resin mixture consisting of 20 to 80% by weight of a graft copolymer (B) in which the weight average molecular weight of the resinous component consisting of the above monomer components is 220,000 to 450,000, aromatic vinyl monomer body component 50 to 80% by weight, α,β-unsaturated carboxylic acid monomer component and/or α,β-unsaturated dicarboxylic acid anhydride monomer component 0.01 to 30% by weight
, a vinyl cyanide monomer component of 5 to 47% by weight, and a methyl methacrylate component of 0 to 30% by weight (however, the total monomer component is 100% by weight) (C) 0.01 ~40 parts by weight, and 60 to 90% by weight of aromatic vinyl monomer component, 0 to 40% by weight of vinyl cyanide monomer component, and 0 to 40% by weight of methyl methacrylate component (however, the total monomer component is An impact-resistant thermoplastic resin composition comprising 0 to 15 parts by weight of a copolymer (D) consisting of 100% by weight. (3) In accordance with JISK7110 (Izod impact test method for hard plastics), the notched Izod impact strength measured at 23°C is 70 kg cm/cm or more, and the notched Izod impact measured at -20°C The impact-resistant thermoplastic resin composition according to claim 1 or claim 2, which has a strength of 40 kg·cm/cm or more.