JPH01168752A - Impact-resistant resin composition - Google Patents

Abstract

PURPOSE:To provide an impact-resistant resin composition excellent in moldability, weather resistance, colorability, appearance of molding, etc., by mixing two specified graft copolymer resins with a specified copolymer resin. CONSTITUTION:80-97.9wt.% (2-12C) alkyl acrylate is mixed with 19.9-2wt.% copolymeriazable vinyl monomer and 0.1-2wt.% polyvinyl monomer, and the obtained mixture is emulsion-polymerized to produce an acrylic rubber of a rubber particle diameter of 0.08-0.18mum. 100 pts.wt. this rubber is mixed with 25-400 pts.wt. monomer mixture M comprising 10-90wt.% aromatic vinyl monomer, 40-10wt.% vinyl cyanide monomer and 80-0wt.% methyl methacrylate, and the resulting mixture is subjected to graft polymerization to obtain a graft copolymer resin A. Separately, 200-900 pts.wt. monomer mixture is added to 100 pts.wt. EPDM rubber, and the resulting mixture is subjected to graft polymerization to obtain a graft copolymer resin B of a rubber particle diameter of 0.2-0.5mum. The graft copolymer resins A and B are mixed with a copolymer resin obtained by polymerizing the monomer mixture M to obtain an impact-resistant resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to impact-resistant resin compositions. More specifically, thermoplastic resin (hereinafter abbreviated as AAS resin), which is obtained by graft polymerizing aromatic vinyl monomers etc. to acrylic rubber, and acrylonitrile/ethylene/propylene φ non-conjugated diene/styrene copolymer ( The present invention relates to an impact-resistant resin composition blended with ABS resin (hereinafter abbreviated as ABS resin) and having excellent coloring properties, surface gloss, and good appearance of molded products.

``Prior art'' Many methods are known for blending rubber with hard resins to obtain impact-resistant resins reinforced by this rubber. ABS resin is a typical example of this type of resin. , diene rubber is mainly used as the base rubber component.Due to the poor weather resistance of this base rubber, outdoor use of ABS resin based on tsene rubber is restricted; This is the biggest drawback of resin.

From this point of view, the use of materials other than diene rubbers as the base rubber has come to be considered, and various examples using saturated rubbers with good weather resistance have been proposed. Acrylate rubber-like polymers (hereinafter abbreviated as acrylic rubber) and ethylene-propylene-non-conjugated diene copolymer rubber (hereinafter abbreviated as EPDM) are often used as examples of these. .

However, even if acrylic rubber is simply substituted for the diene rubber of ABS resin as the base rubber and graft polymerized, a resin with satisfactory lightness properties cannot be obtained. Compared to ABS resin, the weather resistance is greatly improved, but there are problems with the colorability of the resin, the surface gloss and appearance of molded products, and mechanical properties such as impact strength, making it unsatisfactory for practical use. It's hard to say it's something that should be done.

A rubber-resin two-component resin reinforced with acrylic rubber or the like is usually produced by graft polymerizing a monomer mixture that forms a branch component of a graft copolymer onto a latex-like rubber component. Acrylic rubber, which is used as a rubber component with good weather resistance, has a disadvantage that it has a lower optical refractive index than diene rubber, is softer, has a lower elastic modulus, and has slow elastic recovery and is prone to plastic deformation. have. When a rubber-resin two-component resin is manufactured using such soft acrylic rubber with a low refractive index and molded by injection molding or other methods as a molding material, the surface of the molded product will have a pearl-like luster. The product value tends to decrease as it becomes difficult to express the depth (saturation) of the color, especially when it is colored, as light is reflected by the rubber particles and becomes whitish.

The appearance of the molded surface and mechanical properties such as V impact strength of such molded products vary greatly depending on the flow direction during molding and the location of the molded product. This has the disadvantage of causing poor physical properties.

In addition, EPDM cannot usually be produced by emulsion radical polymerization and is produced by solution-type coordination anion polymerization, so it can be obtained as a latex-like water-dispersed rubber with a rubber particle size of less than about 0.5μ. For this reason, it is difficult to perform a graft polymerization reaction using emulsion polymerization, and as a two-component rubber-resin resin, it is extremely difficult to achieve a good molded product appearance. A drawback of ABS resin is that it is not possible to produce a material with a rubber particle size distribution and rubber component content suitable for V impact resistance.

On the other hand, it has been proposed to mix AAS resin and ABS resin to obtain a resin composition with improved weather resistance and impact resistance (for example, Japanese Patent Publication Nos. 53-34212 and 60-4545). (see official bulletin). However, although such resin compositions do have improved impact resistance,
Properties such as the colorability of the resin composition and the surface gloss and appearance of the molded article are hardly improved.

As mentioned above, the conventional AAS resin and AE30
It has been difficult to obtain molded articles that exhibit excellent weatherability, impact resistance, and colorability, and have excellent surface gloss and appearance with resin compositions containing wildflower oil.

[Problems to be Solved by the Invention] The present inventors have solved the above-mentioned shortcomings that existed in conventional rubber-resin two-component resins using acrylic rubber or EPDM as the base rubber. With the purpose of
As a result of extensive research, we have arrived at the present invention.

That is, first, an acrylic rubber with an average rubber particle size adjusted to a specific range was produced by an emulsion polymerization method, and an acrylonitrile/acrylic rubber/styrene copolymer (A A S resin) was further produced by a graft polymerization reaction.
Acrylonitrile with rubber particle diameter adjusted to a specific range.
By blending EPDM/styrene copolymer (AES resin) and acrylonitrile/styrene copolymer (hereinafter referred to as A S 1.4 (abbreviated as fat)) with a specific range of composition in a specific ratio. The object of the present invention is to provide an impact-resistant resin composition that has good moldability and weather resistance, as well as excellent coloring properties, surface gloss, and a good appearance of molded products.

[Means for solving the 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 a furkyl 7 acrylate monomer of No. 12, 2 to 19.9% by weight of a vinyl monomer copolymerizable with the above alkyl acrylate, and 0.1 to 19.9% by weight of a polyfunctional vinyl monomer. Obtained by emulsion polymerization of a monomer mixture consisting of 9% by weight (however, the total monomer mixture is 100% by weight), and has a rubber particle size of 0.08 to 0.18 μla.
100 parts by weight of acrylic rubber, 10-90% by weight of aromatic vinyl monomer and 10-4% by weight of vinyl cyanide monomer.
0% by weight, and methyl methacrylate 0-80% by weight
(However, the monomer mixture consists of a total of 1
00% by weight. ) 25 to 400 parts by weight of graft copolymer resin (A) obtained by graft polymerization, ethylene propylene non-conjugated diene copolymer rubber (E
PDM) 100 parts by weight, 10 to 9 aromatic vinyl monomers
0% by weight, vinyl cyanide monomer 10-40% by weight, and methyl methacrylate 0-80% by weight (however, the total monomer mixture is 100% by weight) 200-900% by weight The rubber particle size obtained by graft polymerization is 0.2 μm to 0.5 μm.
and a graft copolymer resin (B) which is less than
A copolymer resin (C) obtained by polymerizing a monomer mixture consisting of 80% by weight (however, the total monomer mixture is 100% by weight). Existing in impact-resistant resin compositions.

The present invention will be explained in detail below.

Graft copolymer t constituting the resin composition according to the present invention
jlN(A) is produced by further performing a graft polymerization process on an acrylic rubber obtained by emulsion polymerization, which will be described later. This graft copolymer tree JIW (A) is a type of acrylonitrile-acrylic rubber-styrene copolymer (AAS resin), and it provides the resin composition of the present invention with excellent coloring properties, surface gloss, and weather resistance. It is something that is given.

In the present invention, the acrylic rubber for producing the graft copolymer resin (A>) has a furkyl group having 2 to 1 carbon atoms.
80 to 97.9% by weight of the furkyl acrylate monomer of No. 2
, 2 to 19.9% by weight of a vinyl monomer copolymerizable with the above alkyl acrylate, and 0 polyfunctional vinyl monomer.
．． A monomer mixture (■) consisting of 1 to 19.9% by weight (however, the total monomer mixture is 100% by weight. The same applies hereinafter) is produced by - emulsion polymerization, and the average rubber particle size is 0.08 to 0.18 μl.

The alkyl acrylate monomer, which is a constituent component of the acrylic rubber, refers to an alkyl acrylate whose furkyl group has 2 to 12 carbon atoms. Specific examples include furkyl acrylates such as ethyl acrylate, probyl acrylate, n-butyl acrylate, butyl acrylate, amyl acrylate, hexyl 7-acrylate, otatyl acrylate, 2-ethylhexyl acrylate, cyclohexyl 7-acrylate, and dodecyl acrylate. can give. These may be 1 m or a mixture of two or more types.

Monomer mixture (1) used for producing the acrylic rubber
The above alkyl acrylate monomer is 80 to 97.9
It must be contained within the range of % by weight. Content is 80
If it is less than % by weight, the modulus of elasticity of the acrylic rubber increases, which is not preferable. The content of this alkyl acrylate monomer does not exceed 97.9% by weight since the monomer mixture (1) contains other components.

Vinyl monomers copolymerizable with the alkyl 7-acrylate include aromatic vinyl monomers described later, vinyl cyanide monomers described later, acrylamide, methacrylamide, vinylidene chloride, alkyl vinyl ethers, alkyl methacrylates, and their like. Examples include halogen-substituted compounds. These may be used alone or in a mixture of two or more. Preferably, the vinyl cyanide monomers described below are appropriately selected.

The amount of this copolymerizable vinyl monomer to be included in the monomer mixture (I) must be selected within the range of 2 to 19.9% by weight. However, if it is less than 19.9% by weight, it is not preferable because the viscosity of the acrylic rubber becomes very low. Moreover, if it exceeds 19.9% by weight, the elastic modulus increases and various properties as an acrylic rubber deteriorate, which is not preferable.

The polyfunctional vinyl monomer in the present invention refers to a vinyl monomer containing two or more vinyl groups in one monomer molecule for crosslinking acrylic rubber. Specific examples of vinyl monomers include aromatic polyfunctional vinyl monomers such as divinylbenzene and divinyltoluene, heptadacrylates and acrylates of polyhydric alcohols such as ethylene glycol no methacrylate, trinotyrol propane triacrylate, and diallyl polymers. rate, diallyl 7
Examples include malate, triallyl isocyanurate/diallyl maleate, allyl tutaacrylate, allyl acrylate, and the like. These may be used alone or in a mixture of two or more.

The amount of this polyfunctional vinyl monomer to be included in the monomer mixture <r> must be selected within the range of 0.1 to 2 double weight. If the polyfunctional vinyl monomer is less than 0.1% by weight, the resulting acrylic rubber will not be crosslinked and will easily undergo plastic deformation, which is undesirable. If it exceeds 19.9% by weight, the resulting graft This is not preferable because the swelling ratio and graph F ratio of the acrylic rubber of the copolymer (A) become poor, and various properties of the rubber deteriorate.

The acrylic rubber in the present invention is produced by a known emulsion polymerization method using water as a medium, including the types and amounts of emulsifiers and polymerization catalysts, their addition methods, addition methods of each monomer, polymerization temperature, rubber particle adjustment method, etc. It can be manufactured by appropriately selecting and combining various conditions.

The above acrylic rubber has an average rubber particle diameter of 0.08 to 0.
．． Must be 18 μm. The average rubber particle diameter is 0.
If the diameter is smaller than 08 μm, the resulting graft copolymer (A) will have low impact resistance, which is not preferable. When the average rubber particle size exceeds 0.18 microns, it is possible to produce a resin composition with excellent coloring properties and surface gloss.

In the acrylic rubber of the present invention, when using a mixture of two or more acrylic rubbers with different rubber particle sizes, the acrylic rubber with a rubber particle size of 0.20 μm or less is used as the total acrylic rubber. It is preferable to mix it in a range such that it is contained in the rubber in an amount of 80% by weight or more. If the range of the acrylic rubber is out of the above range, the colorability of the resulting resin composition and the appearance of the molded product will be poor, so it is not preferable (1° In the present invention, the rubber particle diameter of the acrylic rubber dispersed in water and is manufactured by Coulter Electronics, Inc.
Nanosizer (C) manufactured by electronics Ltd.
ulter@Nano-3izer”),
It refers to the weight average rubber particle diameter measured in a system in which latex is dispersed in water at 23°C.

The graft copolymer resin (A) in the present invention is prepared by adding 100 parts by weight of the acrylic rubber to 100 parts by weight of the acrylic rubber, 10 to 90% by weight of aromatic vinyl monomer, 10 to 40% by weight of vinyl cyanide monomer, and methyl methacrylate 0-8
It can be produced by adding 25 to 400 parts by weight of monomer mixture (II) containing 0% by weight and performing graft polymerization.

Specific examples of the aromatic vinyl monomer that is a component of the monomer mixture (II) include styrene, a-furkylstyrene such as a-methylstyrene, nuclear-substituted alkylstyrene such as p-methylstyrene, and vinylxylene. , halo-substituted styrenes such as monochlorostyrene and dichlorostyrene, and vinylnaphthalene. These may be used alone or in a mixture of two or more.

The proportion of the aromatic vinyl monomer in the monomer mixture (II) must be in the range of 10 to 90% by weight.

If this ratio is outside the above range, the resulting resin will have poor compatibility when mixed with other thermoplastic resins, making it impossible to effectively achieve the object of the present invention.

Specific examples of vinyl cyanide monomers include 7-acrylonitrile, methacrylonitrile, and the like. these are,
It may be one type or a mixture of two or more types. The proportion of vinyl cyanide monomer in the monomer mixture (n) is:
It must be in the range of 10 to 40% by weight. If this ratio is out of the above range, the compatibility and dispersibility of the graft polymerized resin with other thermoplastic resins will decrease, and the molding processability of the resin composition will deteriorate. This is not preferable because it becomes defective.

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

When producing the graft copolymer (A) in the present invention, 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,
Carry out graft polymerization. The monomer mixture added at this time (
If the amount of II) is less than 25 parts by weight, a sufficient amount of resin cannot be generated by graft polymerization to coat the surface of the rubber particles of the acrylic rubber latex, and the graft ratio becomes small, resulting in a graft copolymer. This is undesirable because it lowers the impact resistance and dispersibility of the material. If the amount added exceeds 400 parts by weight, the grafting rate becomes saturated and remains constant, only the amount of resin that has not been 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 steps of the graft polymerization may be carried out by a normal emulsion polymerization method using water as a medium. When the surface is coated with Graph F resin and it becomes possible to disperse only the rubber particles in organic solvents (monomer mixtures, etc.), it is possible to disperse the rubber particles into other systems such as emulsion systems, suspension systems, solution systems, or block systems. It is also possible to adopt a method in which the graft polymerization is continued by transferring to the polymerization system shown in FIG.

After graft polymerization, the polymerization system is subjected to appropriate known post-treatments, such as salting out, separation, washing, dehydration, drying, mixing, mixing, devolatilization, pelletization, etc., selected and combined as appropriate. By doing so, the graft copolymer resin (A) can be obtained.

The graft copolymer resin (B) constituting the composition of the present invention is composed of 100 parts by weight of EPDM and 10 parts by weight of aromatic vinyl monomer.
~90% by weight, vinyl cyanide monomer 10-40% by weight
, 200 to 900 parts by weight of a monomer mixture (III) consisting of 0 to 80% by weight of methyl methacrylate is added, and the rubber particle size obtained by graft polymerization is 0.2 μm to 0.
．． Refers to those with a ring size of less than 5μ. This graft copolymer resin (B) is a type of acrylonitrile-EPDM-styrene copolymer (AEStj (fat)), and it imparts excellent weather resistance and impact resistance to the resin composition according to the present invention. It is something that is given.

EP, which is a constituent component of the graft copolymer resin (B)
Any known DM can be used without any special restrictions.

EPDM is a rubber obtained by appropriately combining components such as ethylene, propylene, and non-conjugated diene, and performing coordination anion polymerization.

Among these components, what is important in graft polymerization is the type and amount of non-conjugated diene, which serves as the starting point for the branch components of graft polymerization.
It is used in EPDM in a proportion of 0.1 to 20% by weight.

The aromatic vinyl monomer and vinyl cyanide monomer, which are the components of the monomer mixture (III), are the same as those previously exemplified as components used in the graft polymerization step for producing the graft copolymer resin (A). It is the same type as each vinyl monomer. The monomer mixture (III) is comprised of 10 to 90% by weight of aromatic vinyl monomer, 10 to 40% by weight of vinyl cyanide monomer, and 80 to 80% by weight of methyl methacrylate.

If it is outside this range, the graft polymerizability will not only change, making it necessary to change the polymerization conditions, but also change the characteristics of the graft-polymerized resin and limit the types of other resins to be mixed, which is not preferable.

This monomer mixture (II
I) in a range of 200 to 900 parts by weight, preferably 25 parts by weight.
It is added in a range of 0 to 600 parts by weight and graft polymerization is carried out. If the amount of monomer mixture (III) added at this time is less than 200 parts by weight, the viscosity of the solution will be high, making it impossible to form the desired EPDM rubber particles. Therefore, the impact resistance and E of the graft copolymer resin (B)
This is not preferred because it reduces the dispersibility of PDM rubber particles. When the amount added exceeds 900, only the amount of resin that has not been graft-polymerized increases, and the amount of E in the graft copolymer If fat increases.
This is not preferable because it lowers the concentration of the PDM component.

*In addition, when graft polymerization is carried out by a bulk polymerization method (including solution bulk polymerization method, solution bulk-suspension polymerization method, bulk-suspension polymerization method, etc.) described later, EPDM is mixed with a monomer mixture (I[
), the amount added is particularly preferably selected from the range of 250 to 600 parts by weight.

This graft polymerization is carried out using the known bulk polymerization method, solution (bulk)
Methods such as a polymerization method, a suspension polymerization method, and/or an emulsion polymerization method can be employed in a batch or continuous manner, or in appropriate combinations of these methods and methods.

To give an example of the solution bulk polymerization method, first, a solution system is formed in which EPDM is completely dissolved in the monomer mixture (11) and the EPDM solvent, and then a polymerization initiator and a molecular weight regulator are added to this system. It is added batchwise or continuously, and polymerization is carried out while applying shear stress in at least one polymerization tank of a multi-tank polymerization system.

Then, after the EPDM graft rubber particles are stably formed, a devolatilization polymerization step is carried out to complete the polymerization and at the same time, the EPDM solvent is recovered. As a solvent for EPDM, various known solvents can be used alone or as a mixture, and for example, saturated hydrocarbons such as n-hebutane and cyclohexane, and aromatic hydrocarbons such as toluene and xylene are most often used. .

In this graft polymerization, a known polymerization initiator for acrylonitrile-rubber component-styrene copolymer and
If necessary, auxiliary agents such as molecular weight regulators, stabilizers, antioxidants, surfactants, lubricants, and suspension stabilizers may be used in appropriate combinations.

EP D of the graft copolymer resin (B) in the present invention
The rubber particle size of M r& is adjusted within the range of 0.2 μm to less than 0.5 μm depending on the shear stress of the polymerization system.

If the particle diameter of the EPDM component rubber is smaller than 0.2 μm, it is not preferable because the impact resistance of the resin composition cannot be improved. If it is 0.5 μm or more, properties such as the coloring property of the resulting resin composition and the surface gloss and appearance of the molded product are deteriorated, which is not preferable.

In the present invention, the rubber particle diameter of the EPDM component contained in the graft copolymer resin (B) is defined as the ffi It refers to the weight average rubber particle diameter determined by taking a photograph and performing statistical processing based on a sample exposed to sublimated steam of sectioned ruthenium (Rub) for 30 minutes to 1 hour.

The copolymer tree m<c> constituting the composition of the present invention contains 10 to 90% by weight of aromatic vinyl monomer, 10 to 40% by weight of vinyl cyanide monomer, and 0 to 8% of methyl methacrylate.
Polymerize the monomer mixture (■) consisting of 0% by weight! !
! be left behind. This copolymer resin (C) is a known 7-acrylonitrile-styrene copolymer (AS resin) having a molecular weight and composition suitable for the resin composition according to the present invention.

The polymerization method and polymerization conditions for the above monomer mixture (IV) are based on known AS resin manufacturing techniques, such as emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization, either batchwise or continuously. The method can be selected as appropriate. The aromatic vinyl monomer and vinyl cyanide monomer that are the components of the monomer mixture (■) are the vinyl monomers listed above.

The monomer mixture (IV) contains 10 to 9 aromatic vinyl monomers.
0% by weight, 10 to 40% by weight of vinyl cyanide monomer, and 0 to 80% by weight of methyl methacrylate. Outside this range, the polymerization conditions may need to be changed and the type and composition of other graft copolymer resins to be blended will be limited, which is not preferable.

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

At this time, the ratio of the acrylic rubber component polished to the graft copolymer resin (A) and the EPDM component polished to the graft copolymer resin (B) is acrylic rubber component/EPDM component = 90 by weight. It is preferable to select a combination within the range of /10 to 40/60, and particularly preferred within this range is acrylic rubber component/EPDM component = 80
/20 to 50150. Apart from this ratio of the acrylic rubber component and EPDM component, if the content of the EPDM component is too little or too much, the impact resistance tends to decrease, so it is better to select and combine them within the above ratio range. .

Further, it is preferable that the total amount of the acrylic rubber component and the EPDM component contained in the resin composition of the present invention is within the range of 5 to 40% by weight based on the entire resin composition. . Acrylic rubber component and EP
If the total amount of DM components is outside the above range and is too small, the impact resistance tends to decrease, and if it is too large, the rigidity, melt flowability, etc. of the resin composition decreases, and the appearance of the molded product is unfavorable. Therefore, it is best to keep it within the above range.

Graft copolymer resin (A), graft copolymer resin (
B) and the copolymer resin (C) may be blended and mixed and kneaded by any known mixing and kneading method.

For example, one or 2f of these copolymer resins in powder, bead, or pellet form! The above mixture can be made into a resin composition using an extruder such as a -screw extruder or a twin-screw extruder, or a kneading machine such as a Banbury mixer 1 pressurized knee goo or two rolls. Also, in some cases,
One or more of these copolymer resins that have completed polymerization are mixed in an undried state, precipitated, washed,
A drying and kneading method may also be used.

As for the order of this mixing and kneading, three types of component resins may be mixed and kneaded at the same time, or one of the component resins may be mixed and kneaded first.
A desired resin composition may be obtained by mixing and kneading one or more types, and then separately kneading one or more types and kneading them together afterwards.

The PAIIIF composition according to the present invention can be used as it is for molding and the like. *Other thermoplastic resins, such as polystyrene, polymethyl methacrylate, polyvinyl chloride, polycarbonate, polyamide, polybutylene thiolate, polyphenylene oxide, acrylonitrile/N7! It can be mixed with imidized products of nilmaleimide/styrene copolymer, styrene/maleic anhydride copolymer, etc., and used as a weather-resistant and impact-resistant resin.

The resin composition according to the present invention includes lubricants, mold release agents, colorants, ultraviolet #X@ absorbers, light resistance stabilizers, heat resistance stabilizers, fillers, and hardening agents in types and amounts that do not inhibit the properties of the resin. Various resin additives such as refractories and antifungal agents can be added in appropriate combinations.

The resin composition according to the present invention can be produced by injection molding method, extrusion molding method,
It can be made into desired molded products by various processing methods such as compression molding, and used in applications that require excellent weather resistance and impact resistance.

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

(1) The resin composition according to the present invention contains the optimized graft copolymer resin (A), graft copolymer resin (B), and copolymer resin (C), so it has excellent It has colorability, surface gloss and appearance of molded products.

(2) The resin composition according to the present invention has the ratio of each rubber component and the ratio of each rubber component to the acrylic rubber component in the graft copolymer resin (A) and the EPDM component in the graft copolymer resin (B). Since the total blending amount and the diameter of each rubber particle are optimized and blended, it can be used as a thermoplastic resin with excellent impact resistance.

(3) The resin composition according to the present invention has extremely excellent weather resistance because the base rubber is an acrylic rubber having a main chain of saturated carbon bonds and EPDM.

(4) The resin composition according to the present invention has excellent compatibility with other hard thermoplastic resins, so by cross-mixing, a different type of resin composition with excellent weather resistance and impact resistance can be produced. can do.

"Examples" 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.

Production example (1) Production of graft copolymer resin (A) (i)
Production of acrylic yarn seed rubber particles 937.5 g of butyl acrylate (hereinafter abbreviated as BA), acrylonitrile (
Hereinafter, it will be abbreviated as AN. ) and 5 g of allyl methacrylate (hereinafter abbreviated as AMA) were weighed and mixed to prepare a monomer mixture (■).

1520g of deionized water in a 31y lath 917 flask equipped with a stirring device, reflux condenser, thermometer, and auxiliary agent addition processing device.
, 20 g of higher fatty acid soap (mainly composed of sodium salt of a fatty acid with 18 carbon atoms), and 10 g of sodium hydrogen carbonate (hereinafter abbreviated as Na HCOs) were prepared, and the internal temperature was adjusted to 75°C under a nitrogen stream. Do not raise the temperature to Then,
In this flask, 20ml of potassium persulfate (hereinafter abbreviated as KPS) aqueous solution (contains 0.75g of KPS).
Then, 40 g of monomer mixture (1) was added, and the polymerization reaction was started at the same temperature. 20 minutes after starting the polymerization reaction, the remaining monomer mixture (1) '965
g was continuously added to the polymerization system at an addition rate of approximately 60 g/10 minutes.

20 minutes after starting the polymerization reaction, add 20% of KPS aqueous solution.
m1 (contains 0.75 g of KPS), 1:1030
High fatty acid soap after 10 minutes. was added.

Addition of monomer mixture (I) was completed 3 hours after starting the polymerization reaction. Furthermore, the internal 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.
Acrylic type 1 rubber particles were obtained.

The conversion rate of the monomers used 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) The acrylic yarn type obtained by the method described in (i) above was placed in a glass flask with a capacity of 31 equipped with a stirrer, a reflux condenser, a thermometer, and an auxiliary agent addition device. Rubber particles, deionized water, and NaHCO3 were weighed and charged in the amounts listed in Table 1, and the internal temperature of the flask was raised to 70°C. 30 ml of KPS aqueous solution (containing 0.9 g of KPS) was added to prepare for polymerization.

On the other hand, 6fjS2 was prepared by preparing each monomer mixture (1) having the composition listed in the tjtJ2 table to be added to the polymerization system.
The monomer mixture (1) listed in the table was added at a constant addition rate for 30 minutes.
It was continuously added to the flask over a period of 30 minutes to start the polymerization reaction.

After starting the polymerization reaction, 10 ml of soap aqueous solution (10 ml of soap aqueous solution ) containing the total amount of higher fatty acid soap listed in Table 1 divided into seven equal parts, and after 1 hour,
After hours, 15 ml of KPS aqueous solution (KPS0.46
After starting the polymerization reaction, the addition of monomer mixture (I) was completed after 3 hours and 30 minutes, and then the temperature was raised to 80°C, and further addition was carried out at the same temperature. 1 hour 3
The reaction was continued for 0 minutes, and the polymerization reaction was completed. The conversion rates of the monomers used were all 99% or higher.

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 (A
R-5) Into the same 3 liter glass flask as described in (i) above, add 500 g (solid content equivalent) of the acrylic seed rubber particles obtained by the method described in (i) above, and deionized water. 685g
, Sodium dodecylbenzenesulfonate (hereinafter referred to as D
Abbreviated as BS. ) 5 g of a 10% aqueous solution was charged, and the internal temperature was raised to 50° C. under a nitrogen stream.

While gently stirring the contents of the flask, add 2.5 liters of phosphoric acid.
% aqueous solution was added over about 1 minute at the same temperature. After stirring gently for 2 minutes, add potassium hydroxide 25% water ff# solution 22.4F1 and DBS2 to the flask.
14 g of a 5% aqueous solution was added and stirring was returned to normal. The rubber particle diameter of the obtained acrylic rubber was measured. The results are shown in Table 3.

(iii) Production of graft copolymer resin (A) by graft polymerization. 500 g (solid content equivalent) of each acrylic rubber (listed in Table 3), 40 g of deionized water
0 g and 5 g of Na HCOz were charged, and the internal temperature of the flask was raised to 80°C. Under stirring, 30 ml of KPS aqueous solution (containing 0.85 g of KPS), and AM
A2,5. was added to start the polymerization reaction. Five minutes after starting the polymerization reaction, styrene (hereinafter abbreviated as St)
350. , and a monomer mixture consisting of 150 g of AN (
JT) was added continuously at an addition rate of 27.8 g/10 minutes.

30 minutes, 1 hour, and 1 hour 30 minutes after starting polymerization
After minutes, after 2 hours, after 2 hours and 30 minutes, and after 3 hours,
Each soap aqueous solution 10a + I (higher fatty acid soap 0.95g
6) containing 1 hour and 30 minutes later, KP
After 3 hours, 20 ml of S aqueous solution (containing 052 g of KPSO) and 5 g of Terpircin were added to 15 ml of KPS aqueous solution.
1 (containing 0.35 g of KPS) was added to each of the 0
Three hours after starting the polymerization reaction, the monomer mixture (I
Addition of t) was completed, followed by an additional 1 hour at the same temperature.
The reaction was continued for 0 minutes, and the graft polymerization reaction was completed.

The powdering ratio of the monomers used was 98 to 99%.The latex polymerized with 6 grams was salted out by a conventional method, thoroughly washed with water, and dried to obtain each graft copolymer. A combined resin (A) was obtained.

(2) Production of graft copolymer resin (B) (i) Graft copolymer resin (B)-1 560 g of St was placed in a 31 autoclave equipped with a high shear stirring device, a thermometer, and an auxiliary agent addition device.

EPDM (A-2-viscosity ML, (100"C) 45
, has an iodine value of 25, and has ethylidenenorbornene as its first main component. ) 200g,) 990g of luene, and AN240
After charging and purging with nitrogen, heat at 50'C for 3 hours,
It was completely dissolved by stirring at 0 rpm.

Then, the internal temperature was raised to 80°C, and benzoyl peroxide O,
aSg% t-butyl peracetate 0.2 g.

0.85 g of t-dodecyl mercaptan, and 10.0 g of toluene. was added and under the same stirring conditions, the polymerization reaction started. 3 hours after starting the polymerization reaction, the internal temperature was raised to 90°C, the reaction was continued at the same temperature for 3 hours, and after 6 hours, the internal temperature was increased to 90°C. The temperature was raised to 110°C, and at the same temperature and under the same stirring conditions, it was further heated for 2
The reaction continued for hours.

Thereafter, the graft polymerization reaction was completed by natural cooling. The conversion rate of the monomers used was approximately 95%.

The syrup obtained by graft polymerization was extruded under vacuum at 60°C, devolatilized, dried, and pulverized.

The pulverized Graph F copolymer was heated to 40IaIIl with a vent.
Copolymer resin (B)-1 was obtained by melt-kneading using an extrusion mill, extruding and pelletizing while devolatilizing.

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

(ii) Graft copolymer resin (B)-2 In the example described in Production Example (2) (i) above, except that the stirring conditions were changed to 80 rpm from immediately after the start of the polymerization reaction until 3 hours had passed. , graft polymerization was carried out in the same procedure as in ipsilateral (2) (i). The conversion rate of the monomers used was approximately 92%.

The copolymer resin (B)-2 was obtained by pelletizing according to the same procedure as in (2) (i) on the same side. The rubber particle diameter of the obtained resin was measured.

The results are shown in table m3.

(iii) Graft copolymer resin (B)-3 2 1 equipped with an Ikari type stirring device, a thermometer, and an auxiliary agent addition device
In the autoclave, St552g.

EPDM (as described in Production Example (2) (i) above)
After charging 140 g and 100 g of n-hebutane and purging with nitrogen, complete dissolution was achieved by stirring at 150 rpm for 2 hours at 50°C.

Then, under the same stirring, 258 g of AN was charged at a rate of 40 g/10 minutes, and then 0.0 g of di-t-butyl peroxide was added.
．． 5 g, 0.13 g of t-butyl peracetate and 0.2 sg of Turbirun were charged, and bulk polymerization was carried out at 97° C. for 7 hours and 20 minutes. About 30 minutes before the end of bulk polymerization, 1.5 g of di-t-butyl peroxide and 1.5 g of turbilsin were dissolved in 50 g of St and charged into EPDM at the end of 6-polymerization.
The rubber particle size was 0.8 μm.

The syrup obtained in the bulk polymerization step was added to 1100 g of water.
Suspending agent (acrylic acid/alkyl acrylate copolymer)
2,5. 3 1 autoclave containing an aqueous solution (3
The aqueous suspension system was charged into a stirrer (equipped with a swept blade stirrer) and purged with nitrogen. The aqueous suspension system was subjected to suspension polymerization at 130°C and 500 rpm for 2 hours, and then heated to 150°C. , stripping was performed for 1 hour. The obtained resin composition was washed with water and then dried at 100°C to obtain 950 g of graft copolymer resin (B)-3.

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

Examples 1 to 7, Comparative Examples 1 to 4 Graft copolymer resin (A) obtained by the method described in Production Example (1), graft copolymer resin obtained by the method described in Production Example (2) Resin (B), acrylonitrile-styrene copolymer (SAN''-C1 manufactured by Mitsubishi Monsanto Chemical Co., Ltd.), and styrene-acrylonitrile-N-phenylmaleimide resin (average set r&: styrene/acrylonitrile/N-7!nilmaleimide) = 45/25/30, styrene/acrylonitrile/maleic anhydride copolymer imidized with aniline) were weighed according to the ratios shown in Table 3, and the temperature was adjusted to 180°C using a test Banbury mixer. The mixture was kneaded to prepare pellets of a resin composition having a total rubber content of 20% by weight.

The pellets of this resin composition were molded into test pieces for impact resistance measurement and light intensity evaluation at 230° C. using a 7 oz injection molding machine. In accordance with JIS K7110, Izotsu impact strength (with notch) is JIS K7105.
The gloss by reflectance at an incident angle of 60° was measured according to the following. The results are shown in Table 3.

In order to evaluate the colorability, when the raw materials for the composition were kneaded using the test Pamba 17-mixer, carbon black for color was mixed and added, and a colored resin composition was prepared by the same operation as above. pellets were made.

The pellets of this resin composition were molded into test pieces using an injection molding machine. The colorability and appearance of the molded test pieces were visually judged based on the following criteria. The results are shown in Table 3.

Judgment criteria for colorability and appearance ◎: Good colorability. It becomes a deep black (jet black).

Pearl-like luster (, weld line (resin melt bonding line)
is almost never accepted.

○: Colorability is normal. The black lacks depth and requires an increased amount of colorant to match. No pearly luster. Some weld lines are visible.

Δ: Colorability is slightly poor. The blacks lack depth and require a significant increase in colorant to match. It exhibits pearl-like luster and weld lines are clearly visible.

×: Poor colorability. A dull gray-like black color 1
Even if the amount of colorant is increased, it is difficult to match the jet black color.

It exhibits pearl-like luster and some delamination is observed. Weld lines are clearly visible.

From Table 3, the following becomes clear.

(1) The resin composition according to the present invention comprises the acrylic rubber of the graft copolymer resin (A) and the graft copolymer resin (A).
Since the rubber particle diameters of B) and EPDM are optimized, the molded product has excellent coloring properties and surface gloss (see Examples 1 to 7).

On the other hand, in the case of comparative examples in which the rubber particle size is large or EPDM rubber is blended alone, the colorability and surface gloss are poor (see Comparative Example 1.2.4).

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

Furthermore, resin compositions obtained outside the scope of the present invention have poor impact resistance (see Comparative Example 3).

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

Claims (3)

[Claims] (1) 80 to 97.9% by weight of an alkyl acrylate monomer whose alkyl group has 2 to 12 carbon atoms, and 2 to 19.9% by weight of a vinyl monomer copolymerizable with the above alkyl acrylate.
, and a monomer mixture consisting of 0.1 to 2% by weight of a polyfunctional vinyl monomer (however, the total monomer mixture is 100% by weight), obtained by emulsion polymerization, and the rubber particle size is 0
．． To 100 parts by weight of acrylic rubber having a diameter of 08 to 0.18 μm, a monomer consisting of 10 to 90 weight % of an aromatic vinyl monomer, 10 to 40 weight % of a vinyl cyanide monomer, and 0 to 80 weight % of methyl methacrylate is added. mer mixture (however,
The total amount of the monomer mixture is 100% by weight. )25-40
0 parts by weight of the graft copolymer resin (A) obtained by graft polymerization, 100 parts by weight of ethylene propylene non-conjugated diene copolymer rubber (EPDM), and 10 to 90 parts by weight of the aromatic vinyl monomer. % by weight, vinyl cyanide monomer 10-40% by weight, and methyl methacrylate 0-8
Add 200 to 900 parts by weight of a monomer mixture consisting of 0% by weight (however, the total monomer mixture is 100% by weight), and perform graft polymerization to obtain a rubber particle size of 0.2%.
Graft copolymer resin (B) having a diameter of μm to less than 0.5 μm, and 10 to 90% by weight of aromatic vinyl monomer
, a 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 monomer mixture is 100% by weight).
An impact-resistant resin composition characterized by containing a copolymer resin (C) obtained by polymerizing the following. (2) The ratio of the acrylic rubber component derived from the graft copolymer resin (A) to the EPDM component derived from the graft copolymer resin (B) is acrylic rubber component/EPDM component = 90 by weight. The impact-resistant resin composition according to claim (1), characterized in that the composition is blended within the range of /10 to 40/60. (3) A patent claim characterized in that 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 based on the entire resin composition. The impact-resistant resin composition according to any one of item (1) and item (2).