JPH0681799B2 - Impact resistant resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION “Industrial field of application” The present invention relates to an impact resistant resin composition. More specifically, a thermoplastic resin obtained by graft-polymerizing an aromatic vinyl monomer or the like on an acrylic rubber (hereinafter, abbreviated as AAS resin) and acrylonitrile / ethylene / propylene /
The present invention relates to an impact-resistant resin composition containing a non-conjugated diene / styrene copolymer (hereinafter abbreviated as AES resin), which has excellent coloring properties, surface gloss, and good appearance of molded articles.

"Prior Art" Conventionally, it is well known that a hard resin is mixed with rubber to obtain an impact resistant resin reinforced by the rubber. ABS resin is a typical one of this type, but a diene rubber is mainly used as a rubber component of a base. Due to the poor weather resistance of this base rubber, ABS resin based on diene rubber is restricted in outdoor use,
This is the biggest drawback of this resin.

From such a point of view, use of a base rubber other than a diene rubber has been considered, and various examples of using a saturated rubber having good weather resistance have been proposed. Acrylate rubber-like polymers (hereinafter abbreviated as acrylic rubber) and ethylene / propylene / non-conjugated diene copolymer rubbers (hereinafter abbreviated as EPDM), etc. are often used as these examples. .

However, a resin having satisfactory properties cannot be obtained by simply substituting an acrylic rubber as a base rubber for a diene rubber of an ABS resin as a base rubber and performing graft polymerization.
Certainly, compared with ABS resin based on diene rubber, it is greatly improved in terms of weather resistance, but mechanical properties such as resin coloring, surface gloss and appearance of molded products, impact strength, etc. There is a problem with the physical properties and it is hard to say that it is practically satisfactory.

A rubber-resin two-component resin reinforced with an acrylic rubber or the like is usually produced by graft-polymerizing a latex-based rubber component with a monomer mixture forming a branch component of a graft copolymer. Compared with diene rubber, acrylic rubber used as a rubber component having good weather resistance has an optically small refractive index and is softer so that the elastic modulus is low, elastic recovery is slow, and plastic deformation easily occurs. have. When a rubber-resin two-component resin is manufactured using such a soft acrylic rubber with a small refractive index, and molding such as injection molding is performed as a molding material, a pearly luster appears on the surface of the molded product. The rubber particles cause light to diffusely reflect and the appearance becomes whitish, and it becomes difficult to express the depth (saturation) of the color, especially when coloring, so that the commercial value tends to decrease.

In such molded products, the appearance of the molding surface and mechanical properties such as impact strength greatly differ depending on the flow direction at the time of molding and the location of the molded product, and the appearance such as color and gloss and mechanical properties such as cracks in different directions. There is a drawback that it causes the defect of.

EPDM cannot be usually produced by an emulsion radical polymerization method and is produced by a solution-type coordinated anionic polymerization method. Therefore, it is a technical idea to obtain a latex-like water-dispersed rubber having a rubber particle diameter of less than about 0.5 μm. It was extremely difficult economically and economically. For this reason, it is difficult to carry out a graft polymerization reaction using an emulsion polymerization method, and as a rubber-resin two-component resin, a rubber particle size distribution suitable for a good molded article appearance and impact resistance, and a rubber component content rate. The problem with AES resin is that it cannot produce materials with

On the other hand, it has been proposed to mix AAS resin and AES resin to obtain a resin composition having improved weather resistance and impact resistance (for example, JP-B-53-34212, JP-A-60-4545).
(See the official gazette). However, although such a resin composition is certainly improved in impact resistance, properties such as colorability of the resin composition, surface gloss and appearance of a molded product are hardly improved.

As described above, the resin composition containing the AAS resin and the AES resin so far exhibits excellent weather resistance and impact resistance, and excellent colorability, and a molded article having excellent surface gloss and appearance is obtained. It was difficult.

“Problems to be Solved by the Invention” The present inventors have solved the above-mentioned various drawbacks existing in a conventional rubber-resin two-component resin using an acrylic rubber or EPDM as a base rubber. As a result of intensive studies, the present invention has been achieved. That is, first, by an emulsion polymerization method, an acrylic rubber in which the average rubber particle size is adjusted to a specific range is prepared, and then acrylonitrile / acrylic rubber / styrene copolymer (AAS resin) and rubber produced by a graft polymerization reaction. Acrylonitrile / EPDM / styrene copolymer (AES resin) having a particle size adjusted to a specific range, and acrylonitrile / styrene copolymer (hereinafter abbreviated as AS resin) having a composition in a specific range are specified. By blending in proportions, it is intended to provide an impact-resistant resin composition having good moldability and weather resistance, and having excellent colorability, surface gloss and good appearance of molded articles.

“Means for Solving Problems” The gist of the present invention is that the alkyl group has 2 to 2 carbon atoms.
80 to 97.9% by weight of 12 alkyl acrylate monomers, 2 to 2 vinyl monomers copolymerizable with the above alkyl acrylate
A monomer mixture consisting of 19.9% by weight and 0.1 to 2% by weight of a polyfunctional vinyl monomer (however, the monomer mixture is the total
100% by weight. ) Is obtained by emulsion polymerization, and 100 parts by weight of an acrylic rubber having a rubber particle diameter of 0.08 to 0.18 μm, 10 to 90% by weight of an aromatic vinyl monomer and 10 to 40% by weight of a vinyl cyanide monomer. , And methyl methacrylate 0 to
Graft copolymer resin (A) obtained by adding 25 to 400 parts by weight of a monomer mixture of 80% by weight (however, the total amount of the monomer mixture is 100% by weight) and ethylene.・ Propylene / non-conjugated diene copolymer rubber (EP
DM) 100 parts by weight, aromatic vinyl monomer 10 to 90% by weight,
Monomer mixture consisting of 10 to 40% by weight of vinyl cyanide monomer and 0 to 80% by weight of methyl methacrylate (however, the total amount of the monomer mixture is 100% by weight) 200 to 900
Graft copolymer resin (B) having a rubber particle size of 0.2 μm to less than 0.5 μm, obtained by graft-polymerizing 1 part by weight, and 10 to 90% by weight of an aromatic vinyl monomer, vinyl cyanide Copolymer resin obtained by polymerizing a monomer mixture consisting of 10 to 40% by weight of a monomer and 0 to 80% by weight of methyl methacrylate (however, the total amount of the monomer mixture is 100% by weight). C), and an impact-resistant resin composition comprising:

Hereinafter, the present invention will be described in detail.

The graft copolymer resin (A) constituting the resin composition according to the present invention is produced by further subjecting an acrylic rubber obtained by emulsion polymerization described below to a graft polymerization step. This graft copolymer resin (A) is acrylonitrile
It is a kind of acrylic rubber / styrene copolymer (AAS resin) and imparts excellent colorability, surface gloss and weather resistance to the resin composition according to the present invention.

The acrylic rubber for producing the graft copolymer resin (A) in the present invention means an alkyl group having 2 to 12 carbon atoms.
Alkyl acrylate monomer of 80-97.9% by weight, vinyl monomer 2-1 copolymerizable with the above alkyl acrylate
9.9% by weight and 0.1-2% by weight of polyfunctional vinyl monomer
A monomer mixture (I) consisting of 100% by weight of the monomer mixture (the same applies hereinafter), which is produced by emulsion polymerization and has an average rubber particle diameter of 0.08 to 0.18 μm. Say.

The alkyl acrylate monomer which is a constituent of the acrylic rubber is an alkyl acrylate having an alkyl group having 2 to 12 carbon atoms. Specific examples include ethyl acrylate, propyl acrylate, n-butyl acrylate,
Examples thereof include alkyl acrylates such as butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, and dodecyl acrylate. These may be one kind or a mixture of two or more kinds.

Monomer mixture (I) used for producing the acrylic rubber
80 to 97.9% by weight of the above alkyl acrylate monomer
Must be contained within the range of. If the content is less than 80% by weight, the elastic modulus of the acrylic rubber increases, which is not preferable. The content of the alkyl acrylate monomer does not exceed 97.9% by weight because the monomer mixture (I) contains other components.

Examples of the vinyl monomer copolymerizable with the alkyl acrylate include aromatic vinyl monomers described below, vinyl cyanide monomers described below, acrylic amide, methacrylamide, vinylidene chloride, alkyl vinyl ethers, alkyl methacrylates and halogens thereof. Substitution compounds and the like can be mentioned. These may be one kind or a mixture of two or more kinds. Preferably, the vinyl cyanide monomer described below is appropriately selected.

The amount of the copolymerizable vinyl monomer contained in the monomer mixture (I) must be selected in the range of 2 to 19.9% by weight. The content of this copolymerizable vinyl monomer is 2
If it is less than wt%, the viscosity of the acrylic rubber (rubber) becomes large, which is not preferable. Further, if it exceeds 19.9% by weight, the elastic modulus becomes large, and various properties as an acrylic rubber are deteriorated, which is not preferable.

The polyfunctional vinyl monomer in the present invention means a vinyl monomer containing two or more vinyl groups in one molecule of the monomer in order to crosslink the acrylic rubber. Specific examples of the polyfunctional vinyl monomer include aromatic polyfunctional vinyl monomers such as divinylbenzene and divinyltoluene, and methacrylates and acrylates of polyhydric alcohols such as ethylene glycol dimethacrylate and trimethylolpropane triacrylate. , Diallyl malate, diallyl fumarate, triallyl isocyanurate, diallyl phthalate, allyl methacrylate, allyl acrylate and the like. These may be one kind or a mixture of two or more kinds.

The amount of the polyfunctional vinyl monomer contained in the monomer mixture (I) must be selected in the range of 0.1 to 2% by weight. When the content of this polyfunctional vinyl monomer is less than 0.1% by weight, the resulting acrylic rubber is not crosslinked and is easily plastically deformed, which is not preferable. If it exceeds 2% by weight, the resulting swelling ratio and graft ratio of the acrylic rubber of the graft copolymer (A) will be poor, and various properties of the rubber will be deteriorated, such being undesirable.

Acrylic rubber in the present invention, by the known emulsion polymerization method using water as a medium, the type and amount of the emulsifier and the polymerization catalyst and the addition method thereof, the addition method of each monomer, the polymerization temperature, the adjustment method of the rubber particles, etc. Can be manufactured by appropriately selecting and combining the various conditions of.

The acrylic rubber has an average rubber particle diameter of 0.08 to 0.18 μm.
must be m. When the average rubber particle diameter is smaller than 0.08 μm, the impact resistance of the obtained graft copolymer (A) becomes low, which is not preferable. The average rubber particle size is
If it exceeds 0.18 μm, a resin composition having excellent colorability and surface gloss cannot be produced.

When two or more acrylic rubbers having different rubber particle diameters are blended in the acrylic rubber of the present invention, an acrylic rubber having a rubber particle diameter of 0.20 μm or less is used among all acrylic rubbers. It is preferable to mix it in such a range that it contains 80% by weight or more. If the range of the acrylic rubber is out of the above range, the coloring property of the obtained resin composition and the appearance of the molded product will be poor, which is not preferable.

In the present invention, rubber particles of acrylic rubber dispersed in water
The diameter is the Coulter Electron
cs Ltd. Nanosizer (Coulter  Nano-Size
r^TM), The latex was dispersed in water at 23 ° C.
The measured weight average rubber particle diameter.

The graft copolymer resin (A) in the present invention is prepared by emulsion polymerization, wherein 100 parts by weight of the acrylic rubber, 10 to 90% by weight of an aromatic vinyl monomer and 10 to 40% of a vinyl cyanide monomer are used.
It can be produced by adding 25 to 400 parts by weight of a monomer mixture (II) consisting of 0 to 80% by weight of methyl methacrylate and graft polymerization.

Specific examples of the aromatic vinyl monomer that is a component of the above-mentioned monomer mixture (II) include styrene, α-alkylstyrene such as α-methylstyrene, n-substituted alkylstyrene such as p-methylstyrene and vinylxylene, Examples thereof include halo-substituted styrenes such as monochlorostyrene and dichlorostyrene, vinyl niphthalene and the like. These may be one kind or a mixture of two or more kinds.

The proportion of the aromatic vinyl monomer in the monomer mixture (II) should be in the range of 10 to 90% by weight. If the ratio is out of the above range, the compatibility of the obtained resin with other thermoplastic resins becomes poor, and the object of the present invention cannot be effectively achieved.

Specific examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile. These may be one kind or a mixture of two or more kinds. The proportion of vinyl cyanide monomer in the monomer mixture (II) should be in the range of 10 to 40% by weight. If this ratio is out of the above range, the compatibility dispersibility of the graft-polymerized resin and the other thermoplastic resin decreases, and the moldability of the resin composition becomes poor, which is not preferable.

If necessary, methyl methacrylate can be mixed with the monomer mixture (II) in the range of 0 to 80% by weight. If it exceeds this range, the compatibility between the graft-polymerized resin and the other resin or the moldability of the obtained resin composition becomes poor, which is not preferable.

When the graft copolymer (A) of the present invention is produced, the monomer mixture (II) is added in an amount of 25 to 400 parts by weight to 100 parts by weight of the acrylic rubber to carry out graft polymerization. . If the amount of the monomer mixture (II) added at this time is less than 25 parts by weight, a sufficient amount of resin cannot be generated by graft polymerization to cover the surface of the rubber particles of the acrylic rubber latex. However, the graft ratio is reduced and the impact resistance and dispersibility of the graft copolymer are reduced, which is not preferable. If the addition amount exceeds 400 parts by weight, the graft ratio is saturated and becomes constant, only the resin not graft-polymerized increases, and the concentration of acrylic rubber in the resin decreases, which is not preferable.

In carrying out the graft polymerization of the graft copolymer (A), all the steps of the graft polymerization may be carried out by a usual emulsion polymerization method using water as a medium. When the surface is coated with a graft resin and it is possible to disperse it in an organic solvent (monomer mixture, etc.) using only rubber particles, a polymerization system such as an emulsion system, a suspension system, a solution system, or a bulk system. It is also possible to adopt a method in which the graft polymerization is continued and the graft polymerization is continued.

For the polymerization system that has completed the graft polymerization, known appropriate post-treatments such as salting out, separation, washing, dehydration, drying, mixing, kneading, devolatilization, and pelletizing are appropriately selected and combined. Thus, the graft copolymer resin (A) can be obtained.

The graft copolymer resin (B) constituting the composition of the present invention means 100 parts by weight of EPDM, 10 to 90% by weight of an aromatic vinyl monomer, 10 to 40% by weight of a vinyl cyanide monomer, and 0% of methyl methacrylate. ~ 80% by weight of monomer mixture (III) 200
˜900 parts by weight is added, and the rubber particles obtained by graft polymerization have a diameter of 0.2 μm to less than 0.5 μm.
The graft copolymer resin (B) is a kind of acrylonitrile / EPDM.styrene copolymer (AES resin) and imparts excellent weather resistance and impact resistance to the resin composition according to the present invention. is there.

EPDM which is a constituent component of the above graft copolymer resin (B)
Known materials can be used without any special restriction. EPDM
Is a rubber obtained by coordinating anionic polymerization of components such as ethylene, propylene, and non-conjugated dienes in an appropriate combination. Of these components, what is important in the case of graft polymerization is the type and amount of the non-conjugated diene which is the starting point of the branch component of the graft polymerization, and usually ethylidene norbornene and the like are contained in EPDM in a proportion of 0.1 to 20 wt%. Used in.

The aromatic vinyl monomer and vinyl cyanide monomer, which are the components of the above-mentioned monomer mixture (III), are exemplified as the components used in the graft polymerization step for producing the graft copolymer resin (A). It is the same kind as each vinyl monomer.
The above-mentioned monomer mixture (III) contains 10 to 9 aromatic vinyl monomers.
It comprises 0% by weight, 10 to 40% by weight of vinyl cyanide monomer, and 0 to 80% by weight of methyl methacrylate.
If it is out of this range, not only the graft polymerizability changes, it is necessary to change the polymerization conditions, but also the characteristics of the graft polymerized resin change and the types of other resins to be mixed are limited, which is not preferable.

200 parts of this monomer mixture (III) was added to 100 parts by weight of the above EPDM.
To 900 parts by weight, preferably 250 to 600 parts by weight, and graft polymerization is carried out. If the amount of the monomer mixture (III) added at this time is less than 200 parts by weight, the solution viscosity is high and the desired EPDM rubber particles cannot be formed. Therefore, the impact resistance of the graft copolymer resin (B) and the dispersibility of the EPDM rubber particles are deteriorated, which is not preferable. If the amount added exceeds 900 parts by weight, only the resin not graft-polymerized increases and the concentration of the EPDM component in the graft copolymer resin decreases, which is not preferable. When the graft polymerization is carried out by a bulk polymerization method described later (including solution bulk polymerization method, solution bulk-suspension polymerization method, bulk-suspension polymerization method, etc.), EPDM is added as a monomer mixture (III). Therefore, it is particularly preferable that the addition amount is selected from the range of 250 to 600 parts by weight.

This graft polymerization is a known bulk polymerization method, solution (bulk)
A method such as a polymerization method, a suspension polymerization method, and / or an emulsion polymerization method can be employed in a batch or continuous manner, and these methods and methods can be appropriately combined and employed.

As an example of the solution bulk polymerization method, first, a solution system in which EPDM is completely dissolved in a monomer mixture (III) and a solvent for EPDM is once formed, and then a polymerization initiator and a molecular weight modifier are added to this system. Polymerization is carried out while applying shear stress in at least one polymerization tank of a multi-tank polymerization system by adding batchwise or continuously. Then, after the EPDM graft rubber particles are stably formed, the process proceeds to the devolatilization polymerization step to complete the polymerization and recover the EPDM solvent. As the solvent for EPDM, various known solvents can be used alone or as a mixture,
For example, saturated hydrocarbons such as n-heptane and cyclohexane, and aromatic hydrocarbons such as toluene and xylene are most often used.

In this graft polymerization, a known polymerization initiator of acrylonitrile-rubber component-styrene-based copolymer and, if necessary, a molecular weight modifier, stabilizer, antioxidant, surfactant, lubricant, suspension stabilizer. Auxiliary agents such as the above can be appropriately combined and used.

The rubber particle size of the EPDM component of the graft copolymer resin (B) in the present invention is adjusted within the range of 0.2 μm to less than 0.5 μm by the shear stress of the polymerization system. If the EPDM component rubber particle size is smaller than 0.2 μm, the impact resistance of the resin composition cannot be improved, which is not preferable. When it is 0.5 μm or more, the properties such as the coloring property of the obtained resin composition, the surface gloss and the appearance of the molded article are deteriorated, which is not preferable.

In the present invention, the rubber particle size of the EPDM component contained in the graft copolymer resin (B) means the ultra-high density obtained from the compression molding test piece of the graft copolymer resin (B) using a transmission electron microscope. 30 pieces of ruthenium oxide (RuO ₄ ) sublimation vapor on the section
The weight average rubber particle diameter is obtained by taking a photograph and statistically processing the sample exposed for 1 minute to 1 hour.

The copolymer resin (C) constituting the composition of the present invention comprises 10 to 90% by weight of an aromatic vinyl monomer and 10 to 90% of a vinyl cyanide monomer.
It is produced by polymerizing a monomer mixture (IV) consisting of 40% by weight and 0 to 80% by weight of methyl methacrylate. This copolymer resin (C) is a known acrylonitrile-styrene copolymer (AS resin) having an appropriate molecular weight and composition in accordance with the resin composition according to the present invention.

The polymerization method and polymerization conditions of the above monomer mixture (IV) are
A method such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, and a bulk polymerization method can be appropriately selected from batch or continuous methods according to known AS resin production techniques. The aromatic vinyl monomer and vinyl cyanide monomer, which are the components of the monomer mixture (IV), are the respective vinyl monomers exemplified above. The monomer mixture (IV) is an aromatic vinyl monomer 10
.About.90% by weight, vinyl cyanide monomer 10 to 40% by weight, and methyl methacrylate 0 to 80% by weight. Outside of this range, not only is it necessary to change the polymerization conditions, but also the types and compositions of other graph copolymer resins to be blended are limited, which is not preferable.

The resin composition according to the present invention comprises a graft copolymer resin (A), a graft copolymer resin (B),
And a copolymer resin (C) are mixed, and mixed and kneaded to produce.

At this time, it is derived from the acrylic rubber component derived from the graft copolymer resin (A) and the graft copolymer resin (B).
The weight ratio of EPDM component is acrylic rubber component / E
It is recommended to selectively combine PDM components within the range of 90/10 to 40/60. Particularly preferred within this range is acrylic rubber component / PEDM component = 80/20 to 50/50. Since the impact resistance tends to decrease when the content of the EPDM component is too small or too large apart from the ratio of the acrylic rubber component and the EPDM component, it is preferable to select and combine in the range of the ratio. .

Further, it is preferable that the total of the acrylic rubber component and the EPDM component contained in the resin composition according to the present invention is in the range of 5 to 40% by weight based on the whole resin composition. . If the total of the acrylic rubber component and the EPDM component is too small outside the above range, the impact resistance tends to decrease, and if it is excessive, the rigidity of the resin composition, the melt fluidity, etc. will decrease, and the appearance of the molded product will decrease. Since it has an unfavorable effect on the above, it is preferable to set it in the above range.

To mix and knead the graft copolymer resin (A), the graft copolymer resin (B) and the copolymer resin (C), a known mixing and kneading method may be used.

For example, one or a mixture of two or more of these copolymer resins in the form of powder, beads, or pellets is added to an extruder such as a single-screw extruder or a twin-screw extruder, or a Banbury mixer, a pressure kneader, or two extruders. The resin composition can be prepared by using a kneader such as a roll. Also, in some cases,
One or two or more of these copolymer resins that have been polymerized are mixed in an undried state, precipitated, washed,
A method of drying and kneading can also be adopted.

As the order of this mixing and kneading, three kinds of component resins may be mixed and kneaded at the same time.
One kind or two kinds may be mixed and kneaded, and one kind or two or more kinds may be separately kneaded and kneaded together to obtain a desired resin composition.

The resin composition according to the present invention can be directly used for molding and the like. Further, other thermoplastic resins such as polystyrene, polymethylmethacrylate, polyvinyl chloride, polycarbonate, polyamide, polybutylene terephthalate, polyphenylene oxide, acrylonitrile / N-phenylmaleimide / styrene copolymer, styrene / maleic anhydride copolymer It can be used as a weather resistant and impact resistant resin by mixing and kneading it with a combined imidized product.

The resin composition according to the present invention, a kind and amount of lubricant that does not impair the properties of the resin, a release agent, a colorant, an ultraviolet absorber,
Various resin additives such as a light resistance stabilizer, a heat resistance stabilizer, a filler, a flame retardant, and a fungicide can be added in an appropriate combination.

The resin composition according to the present invention includes an injection molding method, an extrusion molding method,
It is made into a desired molded product by various processing methods such as compression molding, and can be used in applications where excellent weather resistance and impact resistance are required.

"Effects of the Invention" As described above, the present invention has particularly remarkable effects as described below, and its industrial utility value is extremely large.

(1) The resin composition according to the present invention comprises an optimized graft copolymer resin (A), graft copolymer resin (B),
And, since it contains the copolymer resin (C), it has excellent coloring properties, surface gloss and appearance of the molded product.

(2) In the resin composition according to the present invention, the ratio of each rubber component and each rubber component of the acrylic rubber component in the graft copolymer resin (A) and the EPDM component in the graft copolymer resin (B) are changed. Since the total compounding amount and the respective rubber particle diameters are optimized and compounded, it can be used as a thermoplastic resin having excellent impact resistance.

(3) Since the resin composition according to the present invention uses the acrylic rubber having a saturated carbon bond main chain and EPDM as the base rubber, it has excellent weather resistance.

(4) Since the resin composition according to the present invention has excellent compatibility with other hard thermoplastic resins, a different type of resin composition having excellent weather resistance and impact resistance can be produced by kneading and mixing. be able to.

[Examples] Next, the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited to the following examples unless it exceeds the gist.

Production Example (1) Production of Graft Polymer Resin (A) (i) Production of Acrylic Seed Rubber Particles Butyl acrylate (hereinafter abbreviated as BA) 937.5 g, acrylonitrile (hereinafter abbreviated as AN) 62.5 g, and A monomer mixture (I) 'was prepared by weighing and mixing 5 g of allylmethitaacrylate (hereinafter abbreviated as AMA).

In a 3 liter glass flask equipped with a stirrer, a reflux condenser, a thermometer, and an auxiliary additive addition device, 1520 g of deionized water, 20 g of higher fatty acid soap (mainly containing sodium salt of fatty acid having 18 carbon atoms), and Sodium hydrogen carbonate (hereinafter NaHCO ₃
Is abbreviated. ) 10 g was charged and the internal temperature was 75 ° C under a nitrogen stream.
The temperature was raised to. Then, 20 ml of an aqueous solution of potassium persulfate (hereinafter abbreviated as KPS) (containing 0.75 g of KPS) was added to the flask, and subsequently, 40 g of the monomer mixture (I) was added.
Was added and the polymerization reaction was started at the same temperature. After 20 minutes from the start of the polymerization reaction, the remaining monomer mixture (I) '96
5 g was continuously added to the polymerization system at an addition rate of about 60 g / 10 minutes.

20 minutes after starting the polymerization reaction, 20 ml of KPS aqueous solution
(Containing 0.75 g of KPS), 1 hour and 30 minutes later, 10 g of higher fatty acid soap was added. The addition of the monomer mixture (I) 'was completed within 3 hours after starting the polymerization reaction. Furthermore, the internal temperature
The temperature was raised to 80 ° C. and the polymerization reaction was continued at the same temperature for 1 hour and 30 minutes to complete the reaction to obtain acrylic seed rubber particles. The conversion of the used monomer was 99%. The rubber particle diameter of the obtained latex was 0.078 μm.

(Ii) Production of acrylic rubber (ii) -1 Production of acrylic rubber by seed polymerization (AR-1 to AR-4) A capacity equipped with a stirrer, a reflux condenser, a thermometer, and an auxiliary addition device In a 3 L glass flask, the acrylic seed rubber particles obtained by the method described in (i) above, deionized water,
And NaHCO ₃ were weighed and charged as shown in Table 1,
The temperature inside the flask was raised to 70 ° C. 30 ml of KPS aqueous solution (0.9 g
Including KPS. ) Was added to prepare for polymerization.

On the other hand, each monomer mixture (I) having the composition shown in Table 2 to be added to the polymerization system was prepared.

The monomer mixture (I) shown in Table 2 was continuously added to the flask at a constant addition rate over 3 hours and 30 minutes to initiate the polymerization reaction.

30 minutes, 1 hour, 1 hour 30 minutes after starting the polymerization reaction
After 2 minutes, 2 hours, 2 hours and 30 minutes, 3 hours, and 3 hours and 30 minutes, 10 ml of each aqueous soap solution (including the total amount of the higher fatty acid soap listed in Table 1 divided into seven equal parts) .)
Then, after 1 hour and 3 hours, 15 ml of an aqueous KPS solution (containing 0.46 g of KPS) was additionally added. 3 hours and 30 minutes after the start of the polymerization reaction, the addition of the monomer mixture (I) was completed, the temperature was raised to 80 ° C., and the reaction was continued at the same temperature for an additional 1 hour and 30 minutes. It's finished. The addition rate of the used monomers was 99% or more in all cases. The rubber particle diameter of each of the obtained acrylic rubbers was measured.

The results are shown in Table 3.

(Ii) -2 Production of acrylic rubber by particle size enlargement (AR
-5) In the same 3 liter glass flask described in (i) above,
Acrylic seed rubber particles 500 g (as solid content) obtained by the method described in (i), deionized water 685 g, sodium dodecylbenzenesulfonate (abbreviated as DBS hereinafter) 10
% Aqueous solution (5 g) was charged and the internal temperature was raised to 50 ° C. under a nitrogen stream. Phosphoric acid 2.
320 g of a 5% aqueous solution was added at the same temperature for about 1 minute. Then, after gently stirring for 2 minutes, 22.4 g of 25% aqueous potassium hydroxide solution and 14 g of 25% aqueous DBS solution were added to the flask, and the stirring was returned to normal. The rubber particle size of the obtained acrylic rubber was measured. The results are shown in Table 3.

(Iii) Production of Graft Copolymer Resin (A) by Graft Polymerization In the same 3 l glass flask as described in (ii) above,
Each latex of acrylic rubber obtained by the method described in (ii) -1 and (ii) -2 (as described in Table 3) 500 g (as solid content), deionized water 400 g, and NaHC
5 g of O ₃ was charged, and the temperature inside the flask was raised to 80 ° C. With stirring, 30 ml of KPS aqueous solution (containing 0.85 g of KPS) and AMA.
2.5 g was added to start the polymerization reaction. Five minutes after starting the polymerization reaction, a monomer mixture (II) consisting of 350 g of styrene (hereinafter abbreviated as St) and 150 g of AN was added at a rate of about
It was continuously added at 27.8 g / 10 minutes.

Thirty minutes, one hour, one hour and thirty minutes, two hours, two hours and thirty minutes, and three hours after starting the polymerization, 10 ml of an aqueous soap solution (containing 0.95 g of higher fatty acid soap) was used. Each time, 1 hour and 30 minutes later, 20 ml of KPS aqueous solution (KPS0.
Including 52g. ), And 5 g of terpinolene after 3 hours K
15 ml of PS aqueous solution (containing 0.35 g of KPS) was added. 3 hours after starting the polymerization reaction, the addition of the monomer mixture (II) was completed, and then at the same temperature for another hour.
The reaction was continued for 30 minutes to complete the graft polymerization reaction.

The conversion rates of the monomers used were all 98 to 99%.
The graft-polymerized latex was salted out by a conventional method, washed well with water, and dried to obtain each graft copolymer resin (A).

(2) Manufacture of graft copolymer resin (B) (i) Graft copolymer resin (B) -1 3l equipped with a high shear stirrer, thermometer, auxiliary addition conversion device
St560g, EPDM (Mooney viscosity ML during autoclave
_{1 + 4} (100 ℃) 45, iodine value 25, ethylidene norbornene is the third component. ) 200g, toluene 990g, and AN240g
Was charged and the atmosphere was replaced with nitrogen, and then completely dissolved by stirring at 50 rpm for 3 hours at 100 rpm.

Next, the internal temperature was raised to 80 ° C and benzoyl peroxide 0.85 was added.
g, t-butyl peracetate 0.2 g, t-dodecyl mercaptan 0.85 g, and toluene 10 g were added, and the polymerization reaction was started under the same stirring conditions. After 3 hours from the start of the polymerization reaction, the internal temperature was raised to 90 ° C and the reaction was continued at the same temperature for 3 hours. After 6 hours, the internal temperature was raised to 110 ° C and the stirring temperature was the same. Then, the reaction was continued for another 2 hours. After this,
The mixture was naturally cooled to complete the graft polymerization reaction. The conversion of the used monomer was about 95%.

The syrup obtained by the graft polymerization was extruded at 60 ° C. under reduced pressure in a vacuum, devolatilized, dried and pulverized. The crushed graft copolymer was melt-kneaded with a vented 40 mm extruder,
While extruding, extrude and pelletize. Copolymer resin (B) -1 was obtained.

The rubber particle size of the obtained resin was measured. The results are shown in Table 3.

(Ii) Graft copolymer resin (B) -2 In the example described in the above Production Example (2) (i), the stirring condition is 80 rpm from immediately after the initiation of the polymerization reaction until 3 hours have elapsed.
Graft polymerization was performed in the same manner as in Example (2) (i) except that the above procedure was changed. The conversion of the monomer used was about 92%.

By the same procedure as in Example (2) (i), pelletization was performed to obtain a copolymer resin (B) -2. The rubber particle size of the obtained resin was measured.

The results are shown in Table 3.

(Iii) Graft copolymer resin (B) -3 equipped with an icari type stirring device, a thermometer, and an auxiliary additive addition device
St552 g, EPDM (described in the above Production Example (2) (i)) 140 g, and n-heptane 100 g were charged in a 2 l autoclave, and the atmosphere was replaced with nitrogen, and then at 50 ° C. for 2 hours at 150 rpm.
It was completely dissolved by stirring.

Then, under the same stirring, 258 g of AN was charged at a rate of 40 g / 10 minutes, and then 0.5 g of di-t-butyl peroxide, 0.13 g of t-butyl peracetate and 0.25 g of terbinolene were charged.
Bulk polymerization was carried out at ℃ for 7 hours and 20 minutes. About 30 minutes before the end of the bulk polymerization, 1.5 g of di-t-butyl peroxide and 1.5 g of terbinolene were dissolved in 50 g of St and charged. EPDM at the end of polymerization
The rubber particle size was 0.8 μm.

2.5g of suspension agent (acrylic acid / alkyl acrylate copolymer) was added to the syrup obtained in the bulk polymerization process in 1100g of water.
Was charged into a 3 l autoclave (equipped with a three-blade reversing blade stirrer) containing the above aqueous solution and replaced with nitrogen, and then this aqueous suspension system was subjected to suspension polymerization at 130 ° C. and 500 rpm for 2 hours. Then, the temperature was raised to 150 ° C. and stripping was performed for 1 hour. The obtained resin composition was washed with water and dried at 100 ° C. to obtain 950 g of a graft copolymer resin (B) -3.

The rubber particle size of the obtained resin was measured. The results are shown in Table 3.

Examples 1 to 7, Comparative Examples 1 to 4 Graft copolymers obtained by the method described in Production Example (1)
Resin (A), obtained by the method described in Production Example (2)
Copolymer resin (B), acrylonitrile / styrene
Copolymer (SAN -C, Mitsubishi Monsanto Kasei Co., Ltd.
), And styrene / acrylonitrile / N-phenyl
Lumaleimide resin (average composition: styrene / acrylonit
Ryl / N-phenylalleymid = 45/25/30, styrene
Acrylonitrile / maleic anhydride copolymer with aniline
Imidized one) so that it becomes the ratio in Table 3
Test Banbury Miki weighed each and adjusted to 180 ℃
Of the resin composition having a total rubber content of 20% by weight.
Pellets were made.

The pellets of the resin composition, by 7 _OZ injection molding machine, 2
Test pieces for impact resistance measurement and gloss evaluation were molded at 30 ° C. According to JIS K7110, Izod impact strength (with notch) according to JIS K7105. The gloss due to the reflectance at an incident angle of 60 ° was measured. The results are shown in Table 3.

In order to evaluate the colorability, when the raw materials for the composition are kneaded by the test Banbury mixer, carbon black for color is mixed and added, and by the same operation as above, pellets of the colored resin composition are added. It was created.

A test piece was molded from the pellet of the resin composition by an injection molding machine. With respect to the molded test piece, the colorability and the appearance were visually judged based on the following criteria. The results are shown in Table 3.

Criteria for judging colorability and appearance ⊚: Colorability is good. It becomes deep black (black). Weld line (resin fusion line) with no pearly luster
Is hardly recognized.

◯: Colorability is normal. The depth of black is lacking, and it is necessary to increase the amount of colorant for color matching. There is no pearly luster. Weld lines are slightly recognized.

Δ: Colorability is slightly poor. It lacks the depth of black and requires a significant increase in colorant for color matching. It has a pearly luster and a clear weld line.

X: Poor colorability. It becomes a dull gray-like black color. Even if the amount of the coloring agent is increased, it is difficult to match the jet black color. It has a pearly luster and some delamination is observed. Weld lines are clearly visible.

The following is clear from Table 3.

(1) In the resin composition according to the present invention, the rubber particle diameters of the acrylic rubber of the graft copolymer resin (A) and the EPDM of the graft copolymer resin (B) are optimized, It has excellent colorability and surface gloss of molded products (see Examples 1 to 7).

On the other hand, in the case of the comparative example having a large rubber particle diameter or blending EPDM rubber alone, the colorability and surface gloss are poor (see Comparative Examples 1, 2, and 4).

(2) The resin composition according to the present invention has an excellent impact resistance because the graft copolymer resin (A), the graft copolymer resin (B) and the copolymer resin (C) are optimized and blended. (See Examples 1 to 7).

Further, the resin composition obtained outside the scope of the present invention is inferior in impact resistance (see Comparative Example 3).

(3) The resin composition according to the present invention has excellent compatibility with other hard thermoplastic resins, and another type of resin composition having excellent coloring properties, surface gloss and impact resistance can be obtained (implementation). See Example 5).

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Nobuaki Ito 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Monsanto Kasei Co., Ltd. Yokkaichi Laboratory (56) Reference JP-A-60-4545 (JP, A) JP-A-SHO 47-30751 (JP, A)

Claims (3)

[Claims] 1. An alkyl acrylate monomer having an alkyl group having 2 to 12 carbon atoms in an amount of 80 to 97.9% by weight, a vinyl monomer copolymerizable with the above alkyl acrylate in an amount of 2 to 19.9% by weight, and a polyfunctional vinyl monomer. Obtained by emulsion polymerization of a monomer mixture consisting of 0.1 to 2% by weight (however, the total amount of the monomer mixture is 100% by weight), and having a rubber particle diameter of 0.08 to 0.18.
A monomer mixture consisting of 10 to 90% by weight of an aromatic vinyl monomer, 10 to 40% by weight of a vinyl cyanide monomer, and 0 to 80% by weight of methyl methacrylate per 100 parts by weight of an acrylic rubber having a size of μm ( However, the total monomer mixture is 100% by weight.
And ) Graft copolymer resin (A) obtained by adding 25 to 400 parts by weight and graft polymerizing, ethylene / propylene / non-conjugated diene copolymer rubber (EP
DM) 100 parts by weight, aromatic vinyl monomer 10 to 90% by weight,
Monomer mixture consisting of 10 to 40% by weight of vinyl cyanide monomer and 0 to 80% by weight of methyl methacrylate (however, the total amount of the monomer mixture is 100% by weight) 200 to 900
Graft copolymer resin (B) having a rubber particle size of 0.2 μm to less than 0.5 μm, obtained by graft-polymerizing 1 part by weight, and 10 to 90% by weight of an aromatic vinyl monomer, vinyl cyanide Copolymer resin obtained by polymerizing a monomer mixture consisting of 10 to 40% by weight of a monomer and 0 to 80% by weight of methyl methacrylate (however, the total amount of the monomer mixture is 100% by weight). C), and an impact resistant resin composition comprising: 2. A weight ratio of the acrylic rubber component derived from the graft copolymer resin (A) and the EPDM component derived from the graft copolymer resin (B) is acrylic rubber component / EPDM component. = 90/10 to 40/60. The impact resistant resin composition according to claim (1), characterized in that it is blended in the range of 90/10 to 40/60. 3. The total of the acrylic rubber component and the EPDM component contained in the impact resistant resin composition is in the range of 5 to 40% by weight with respect to the entire resin composition, The impact resistant resin composition according to any one of claims (1) and (2).