JPH04342750A - Weather-resistance, impact-resistance composition having excellent colorability - Google Patents

Abstract

PURPOSE:To obtain a weather-resistant, impact-resistant polymer composition having excellent colorability and appearance. CONSTITUTION:A polymer composition comprising (a) an acrylic acid ester-based rubber graft copolymer having a specific structure, (b) an AS-based resin (acrylonitrile-styrenic polymer) of a specific copolymerization composition and (c) a methacrylic polymer of a specific copolymerization composition. Having colorability (coloring properties), weather resistance, impact resistance and excellent appearance, the composition is suitable for a wide range of application including automobile parts and electric parts.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer composition comprising a specific acrylate rubber graft copolymer, a specific AS polymer, and a specific methacrylic polymer. More specifically, the present invention relates to a polymer composition that has colorability, weather resistance, impact resistance, and excellent appearance, or has an excellent balance of these properties.

0002

[Prior Art] Among plastics, polycarbonate and methacrylic resin have relatively good weather resistance, but
These resins are not necessarily well-balanced in terms of mechanical strength, processability, price, etc., so their range of application is narrowed.

On the other hand, ABS resin is widely used in fields such as automobiles and electrical parts because of its excellent impact resistance, excellent balance of mechanical properties, ease of molding, and relatively low price. It is being However, on the other hand, AB
Since S resin uses polybutadiene as one of its constituent components, it has poor weather resistance and is considered unsuitable for outdoor use.For many years, plastics with significantly improved weather resistance than ABS resin have appeared. This was the request of

From this background, it has been considered to use rubbers other than diene rubbers, and various proposals have been made to use saturated rubbers. A which is an acrylic acid ester polymer
AS resin is one example of this, and although weather resistance is improved by this method, on the other hand, impact resistance and appearance of molded products are deteriorated, and problems remain in practical use.

[0005] For example, Japanese Patent Publication No. 55-27576 discloses a method for producing a multistage, sequential structure polymer consisting of a hard polymer in the first stage, a rubber-like elastic polymer in the intermediate stage, and a hard polymer in the third stage. has been disclosed, but in this method, by using a grafting agent and a crosslinking agent in the first step, not only a low haze impact resistant resin composition is obtained, but also the impact strength is low, and the practical use range is low. is limited. Furthermore, Japanese Patent Publication No. 59-36645 discloses a method for producing a multi-stage polymer consisting of a methacrylic acid ester and an acrylic acid ester, but the impact strength is insufficient.

[0006] The present inventors first attempted to improve weather resistance by combining (a) a specific acrylic ester multilayer structure polymer and (b) a specific thermoplastic polymer.
It was discovered that the impact resistance could be improved and an application was filed (Japanese Patent Application No. 1-320435).

However, when a molded article was produced by adding a coloring agent to the polymer composition of the publication, it lacked clarity and depth, especially in vivid colors and dark colors, compared to ABS resin. A problem has arisen in that a large amount of coloring agent is required to achieve the same level of color depth.

[0008] Against this background, the present inventors have conducted intensive studies to improve the colorability of polymer compositions containing acrylic acid ester rubber graft copolymers.
It was concluded that it is important to reduce the reflected light at the interface between the matrix resin and the rubber particles.

The mechanism will be explained based on FIG. FIG. 1 shows the spectral reflectance of a red colorant, rubber particles, and a molded article colored with a red colorant. Red colorant is 400-600
It has absorption in the nm range and reflection in the complementary color range of 600 to 700 nm. Furthermore, rubber particles reflect in the entire visible light range. Therefore, the reflection of the colored molded product is observed as a composite reflection of both. This means that 400 to 600 nm
Reflection is observed in the region, which means that the absorption in that region (red) decreases, resulting in a thinning of the molded product.

[0010] Therefore, in order to improve the colorability, an important point is how to reduce reflection on the rubber particle surface. Generally, an AS resin containing an ertel acrylate rubber has a refractive index of the rubber (for example, that of butyl polyacrylate is 1.47), and a refractive index of the matrix resin (
For example, since there is a large difference from that of AS resin (1.57), the reflection on the rubber particle surface is significant.

Therefore, conventional techniques for reducing the above-mentioned reflection include (a) introducing a high refractive index monomer to increase the refractive index of the acrylic ester rubber; and (b) increasing the refractive index of the matrix resin. In order to lower the refractive index, a method of introducing a low refractive index polymer is known.

Regarding the above method (a), there is an example of copolymerization with an aromatic ester monomer, but this increases the glass transition temperature of the rubber and significantly reduces the impact resistance. Regarding method (b), it is known that a methacrylic resin having a low refractive index (refractive index 1.49) is blended with an AS resin (acrylonitrile-styrene resin) serving as a matrix resin. For example, Japanese Patent Application No. 1-54737 discloses the use of methacrylic resin as a matrix resin in acrylic ester rubber. Although this method reduces reflection on the surface of the rubber particles and improves colorability, the impact resistance is significantly lowered.

Furthermore, as an example of a blend of methacrylic resins, Japanese Patent Publication No. 63-64467 discloses a resin composition comprising an AES resin made of EPDM, an AS resin, and a methacrylic resin. Although the resin composition of this publication has excellent weather resistance and colorability, it does not have sufficient impact resistance. (a) Specific copolymerization composition ratio and specific rubber particle diameter of the rubber-based graft copolymer, (b) Specific copolymerization composition ratio of the AS-based resin, and (c) Specific copolymerization ratio of the methacrylic resin. This is because the specificity of improving the balance between impact resistance and colorability by combining composition ratios is not disclosed.

[0014]

[Problems to be Solved by the Invention] In view of the current situation, the present invention has been developed to eliminate the above-mentioned problems, that is, to improve colorability,
The object of the present invention is to provide a polymer composition that has weather resistance, impact resistance, and excellent appearance, or has an excellent balance of these properties.

[0015]

[Means for Solving the Problems] As a result of extensive research into improving the colorability and impact resistance of polymer compositions containing acrylic acid ester-based rubber graft copolymers, the present inventors found that (
a) An acrylic ester rubber graft copolymer (multi-structure polymer A) having (a) a specific copolymer composition, (b) a specific rubber particle diameter, and (c) a specific morphology.
and (b) an AS-based polymer (thermoplastic polymer B) with a specific copolymerization composition, and (c) a methacrylic polymer (thermoplastic polymer C) with a specific copolymerization composition in a specific quantitative ratio. By combining these materials, it is surprisingly possible to dramatically improve colorability and impact resistance while maintaining weather resistance and excellent appearance, and the present invention has been achieved.

That is, the present invention is; Multi-structure polymer A10-5
0% by weight, 70 to 10% by weight of thermoplastic polymer B, and 20 to 80% by weight of thermoplastic polymer C, wherein the multistructure polymer A is essentially a spherical crosslinked rubber body. is a mixture of (a) an acrylic ester crosslinked polymer and a copolymer consisting of methacrylic ester units and acrylic ester units, having the following form and composition, an essentially spherical rubbery polymer (α portion) having a glass transition temperature; and (b) a polymer dispersed within the α portion, comprising aromatic vinyl units and unsaturated nitrile units. A copolymer and/or a copolymer (β portion) consisting of an aromatic vinyl unit, an unsaturated nitrile unit, and an acrylic acid ester unit constituting the α portion, and (c) a polymer surrounding the outside of the α portion in a layered manner. A copolymer consisting of an aromatic vinyl unit and an unsaturated nitrile unit, and/or a copolymer consisting of an aromatic vinyl unit, an unsaturated nitrile unit, and an acrylic acid ester unit constituting the α portion (γ portion). The copolymerization composition is

(a) Methacrylic acid ester unit 2-
30% by weight and (b) acrylic acid ester unit
50 to 80% by weight and (c) unsaturated nitrile units
5 to 20% by weight, and (d) aromatic vinyl unit.
5 to 40% by weight, and the weight ratio of the unsaturated nitrile unit/the aromatic vinyl unit is
A multi-structure polymer A having a ratio of 10/90 to 30/70,

The average diameter of the essentially spherical α portion is 19
00 to 5900 Å, the average layer thickness of the γ part surrounding this α part is 10 to 1000 Å, and the multistructure polymer A
The average diameter of the entire particle is 2000 to 6000 Å,
The acetone-insoluble portion has (a) a degree of swelling in methyl ethyl ketone of 1.5 to 10, and (b) a tensile modulus of 1,
000 to 10,000 kg/cm2,

The thermoplastic polymer B contains (a) 10 to 30% by weight of unsaturated nitrile units and (b) 9 aromatic vinyl units.
0 to 70% by weight, and (c) 0 to 50% by weight of one or more monomer units copolymerizable therewith,

The thermoplastic polymer C comprises (a) 50 to 99% by weight of methacrylic acid ester units and (
b) A thermoplastic polymer consisting of 1 to 50% by weight of one or more monomer units selected from acrylic acid ester units, unsaturated nitrile units, and monomers copolymerizable with these units. The present invention provides a weather-resistant and impact-resistant polymer composition with excellent colorability.

The present invention will be explained in detail below. The polymer composition of the present invention comprises (a) a specific acrylic ester-based rubber graft copolymer (multi-structure polymer A; hereinafter referred to as polymer A), and (b) a specific thermoplastic polymer B ( (hereinafter referred to as polymer B), and (c) a specific thermoplastic polymer C (
It will be referred to as Polymer C hereinafter. ) results in surprising advantages.

[0022] First, polymer A (multi-structure polymer) will be mentioned. (a) Composition of the multi-structure polymer; The multi-structure polymer in the present invention is composed of (a) methacrylic acid alkyl ester units, (b) acrylic acid alkyl ester units, (c) unsaturated nitrile units, and (c) unsaturated nitrile units. d) It is a multi-structure polymer composed of aromatic vinyl units and further contains (e) a polyfunctional crosslinking agent.

Examples of the methacrylic acid alkyl ester unit (a) constituting the multi-structure polymer include methyl methacrylate, ethyl methacrylate, and propyl methacrylate, with methyl methacrylate being particularly preferably used. (b) Examples of the acrylic acid alkyl ester unit include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and butyl acrylate is preferably used. (c) Examples of the unsaturated nitrile unit include acrylonitrile and methacrylonitrile, with acrylonitrile being preferably used. (iv) Examples of the aromatic vinyl unit include styrene, α-methylstyrene, and halogenated styrene, with styrene being preferably used.

Furthermore, (e) as the polyfunctional crosslinking agent, C
=C A crosslinkable monomer having at least two double bonds, such as esters of triallyl isocyanurate and unsaturated alcohols such as triallyl cyanurate and triallyl isocyanurate; divinyl compounds such as divinylbenzene; diallyl compounds, such as dimethacrylic compounds such as ethylene glycol dimethacrylate,
Although commonly known crosslinking agents can be used, triallylisocyanurate is preferably used.

(b) Composition ratio of the multi-structure polymer (polymer A); On the other hand, the composition ratio of the multi-structure polymer is basically (a)
2-30% by weight of methacrylic acid alkyl ester units, preferably 5-15% by weight, (b) 50-80% by weight of acrylic acid alkyl ester units, preferably 55-70% by weight, (c) 5-5% of unsaturated nitrile units. 20% by weight, preferably 6 to 10% by weight, (d) 5 to 4 aromatic vinyl units
0% by weight, preferably 8 to 35% by weight, and (e) 0.05 to 5% by weight of the polyfunctional crosslinking agent.

If it deviates from this range, it is unfavorable in terms of impact resistance. Furthermore, the weight ratio of unsaturated nitrile units/aromatic vinyl units is 10/90 to 30/70,
It is important that the ratio is preferably 15/85 to 25/75. However, outside this range, the compatibility with polymers B and C decreases, resulting in a significant decrease in impact resistance. (See Examples 1 to 3 and Comparative Examples 4 and 5 described later)

(c) Swelling degree of the multi-structure polymer; the degree of swelling of the acetone-insoluble portion with respect to methyl ethyl ketone is 1.5 to 1.
0, and the tensile modulus is 1,000 to 10,0.
00 kg/cm2. If it deviates from this range, a product with poor impact resistance will be obtained, which is not preferable.

(d) Particle diameter of the multi-structure polymer (polymer A); the particle diameter (number average particle diameter) of the polymer A is 2.0
It must be in the range of 00 to 6,000 Å. However, if the thickness is less than 2000 Å, the surface gloss is excellent, but
Impact resistance and colorability are low; on the other hand, when it exceeds 6,000 Å, colorability is excellent but surface gloss is poor (see Examples 1 and 4 and Comparative Examples 6 and 7 described later).

(e) Fine structure of the multi-structure polymer; The multi-structure polymer of the present invention has a structure in which the β part is dispersed in the α part, and the average diameter of the α part is 1900 to 5900 Å. It has a very special structure in which the average thickness of the γ portion covering the periphery is 10 to 1000 Å. It is thought that this special structure greatly improves surface gloss while maintaining impact resistance and weather resistance. This was difficult to predict from the following composite structures that have been proposed in the past.

On the other hand, in the method disclosed in Japanese Patent Publication No. 47-109811, when a grafting agent or a crosslinking (crosslinking) agent such as allyl methacrylate is used during the first stage of polymerization of the hard polymer, , a spherical first-stage (crossed) hard polymer that is not stained with osminic acid is present in the α region. More specifically, it is a multi-structure polymer that includes two regions: a part in which small particles of the β part are microdispersed in the α part, and an (independent) spherical part in which the β part does not exist at all. In this case, a significant decrease in impact strength is a problem.

[0031] Therefore, in the multi-structure polymer of the present invention,
If the α part is not covered with the γ part, a product with poor impact resistance and weather resistance will be obtained, and if the β part is not dispersed in the α part, the surface gloss and resistance will be poor. It is not possible to obtain a product that satisfies impact resistance at the same time.

Furthermore, the average diameter of the α section is 1900 to 59
00 Å, preferably 3000 to 4
000 Å. If it is less than 1900 Å, the impact resistance will decrease, while if it exceeds 5900 Å, the surface gloss will decrease. In addition, the average thickness of the γ part surrounding the α part is 10~
1000 Å is required, preferably 200 to 500 Å
It is. If it is less than 10 Å, the compatibility with polymer B decreases,
On the other hand, if it exceeds 1000 Å, the compatibility becomes good, the two-phase system collapses, and the impact resistance decreases because the two-phase system collapses and becomes similar to a single substance.

In the multi-structure polymer of the present invention, in order to completely disperse a plurality of β parts in the α part, the composition, molecular weight, crosslinking density, and distance between crosslinking points of the α part should be appropriate. It is necessary. In the multi-structure polymer of the present invention, the term "β part dispersed in the α part" refers to a state in which a plurality of small particles of the β part are dispersed relatively evenly throughout the α part. Therefore, like the above-mentioned conventional composite structure, a structure containing two regions, a part in which small particles of the β part are dispersed in the α part and an (independent) spherical part in which the β part does not exist at all, has a dispersed structure. It can not be said.

[0034] As a mode of dispersing the β part in the α part, it is preferable that the β part is dispersed throughout the α part, but the present invention is not limited thereto. Further, the number of small particles in the β portion is not particularly limited, and may be any number, but it is more preferable that a relatively large number of small particles are uniformly dispersed. Further, although it is preferable that the small particles in the β portion are relatively uniform in size, there may be some variation.

[0035] The multistructure polymer itself of the present invention, the α part, and the β part
The shape of the part is also essentially spherical, and the γ part exists as a layer surrounding this spherical α part. The shape of these particles is not limited in any way as long as the object of the present invention is achieved.

Taking the α part as an example, a typical preferred shape thereof is essentially spherical. If the α portion is spherical, observing the cross-sectional shape of the multistructure polymer reveals that γ
It can be seen that the section exists as a layer whose cross-sectional shape is essentially ring-shaped. In addition to the spherical shape, the shape of the α portion may be an ellipse having a long axis and a short axis, a kidney shape, a gourd shape, etc., as the cross-sectional shape is schematically shown in FIG. Alternatively, it may be of the form shown in FIG. 5, which has irregularities thereon. Also, it is not necessarily symmetrical,
It may be of an amorphous shape.

It is preferable that the γ part surrounds the entire α part, but the α part may be partially exposed where the γ part is not present. It is more preferable that the variation in thickness of the α portion is small.

(f) Method for producing a multi-structure polymer; The method for producing a multi-structure polymer of the present invention employs a known emulsion polymerization method carried out in the presence of monomers, emulsifiers, polymerization initiators, chain transfer agents, etc. It is advantageous to use Furthermore, in order to form such a multi-structure polymer, it is advantageous to use a seed polymerization method in which a multi-structure polymer can be formed by sequentially adding and reacting each monomer or monomer mixture. It is.

A typical example of the method for producing the multi-structure polymer of the present invention is as follows. <First stage polymerization> Methacrylic acid alkyl ester 2~
30% by weight and 1-6% by weight of acrylic acid alkyl ester
The monomer mixture is polymerized together with an emulsifier and a polymerization initiator at a monomer/water ratio of 0.3 to 1.0. Note that if a crosslinking agent or a grafting agent is used at this stage, the impact resistance will be lowered.

<Second stage polymerization> A part of the seed latex obtained in the first stage is used for polymerization with the same monomer mixture as in the first stage, and the particle size can be controlled. . This second stage polymerization can also be omitted. <Third stage polymerization> Acrylic acid alkyl ester 45~
A monomer solution containing 70% by weight and a crosslinking agent of 0.05 to 5% by weight is emulsion polymerized together with an emulsifier and a polymerization initiator.

<Fourth stage polymerization> Acrylic acid alkyl ester 4-8% by weight Unsaturated nitrile 4-8% by weight Aromatic vinyl 2-5% by weight Crosslinking agent 0.005-0
．． A 5% by weight monomer solution is subjected to emulsion polymerization together with an emulsifier and a polymerization initiator.

<Fifth stage polymerization> Acrylic acid alkyl ester 0 to 2% by weight Aromatic vinyl 1 to 16% by weight Unsaturated nitrile 3 to 38% by weight of the monomer liquid is mixed with an emulsifier,
Emulsion polymerization is carried out together with a polymerization initiator. At this time, when conducting the third and subsequent stages of polymerization, it is necessary to select conditions that suppress the generation of new particles as much as possible, but for this purpose, the amount of emulsifier used must be lower than the critical micelle concentration. This can be achieved by doing. In addition, the presence or absence of new particle generation is determined by
This can be confirmed by observation using an electron microscope.

In addition, in order to control the particle size (diameter) of each layer of the multi-structure polymer within a specific range, it is possible to When seed polymerization is continued by adding ion-exchanged water, an emulsifier, and a monomer, the amount of seed latex taken out may be adjusted to control the number of particles of the seed latex.

[0044] Furthermore, in order to control the degree of swelling within a specific range,
This can be done by changing the amount of crosslinking agent added. That is, when decreasing the degree of swelling, the amount of crosslinking agent is increased, while when increasing the degree of swelling, it is decreased.

The appropriate polymerization temperature for forming the polymer and/or copolymer in each polymerization step is selected within the range of 30 to 120°C, preferably 50 to 100°C.

There are no particular restrictions on the emulsifier used in the polymerization, and any emulsifier can be selected from those conventionally used. For example, anionic emulsifiers of C2-C22 carboxylic acids, C6-C22 alcohols or sulfonates of alkylphenols, nonionic emulsifiers with alkylene oxide added to aliphatic amines or amides, or cationic emulsifiers such as quaternary ammonium-containing compounds. Emulsifiers may be mentioned, but long-chain alkyl carboxylates, alkylbenzene sulfonates, and the like are preferably used.

The polymerization initiator used at this time is not particularly limited; for example, water-soluble peroxides such as alkali metal salts of persulfuric acid and ammonium salts; inorganic initiators such as perborates; Azo compounds such as hydrogen peroxide and azobisbutyronitrile can be used alone or in combination with sulfites, thiosulfates, etc. as redox initiators. Additionally, redox initiators such as oil-soluble organic peroxides/ferrous salts, organic peroxides/sodium sulfoxylates can also be used. Furthermore, examples of the chain transfer agent used include alkyl mercaptans such as t-dodecyl mercaptan, toluene, xylene, chloroform, and halogenated hydrocarbons.

Regarding the method of adding the monomer, it is possible to add the monomer all at once, but it is better to add the monomer in several portions or to add the monomer continuously. In that case, the polymerization reaction can be controlled and overheating and coagulation can be prevented.

[0049] When advantageously producing the multi-structure polymer of the present invention, each layer may be prepared by a method adjusted as follows. The rubber-like elastic body may be formed by completing the polymerization reaction of the acrylic ester cross-linked product, and then adding a rubber-like elastic body monomer and polymerizing it sequentially, or by completing the polymerization of the acrylic ester cross-linked product. A rubber-like elastic body may be formed by adding unsaturated nitrile (c), aromatic vinyl (d), etc., with unreacted monomer remaining.

(g) Others: A multi-structure polymer with a special structure obtained by such a polymerization method can be obtained by performing treatments such as salting out, washing, drying, etc. from the polymer latex state by known methods. , obtained as a particulate solid. Such multi-structure polymers are usually
Since it is obtained as a mixture of a pure multilayer polymer itself that is insoluble in solvents such as acetone, and a non-grafted polymer that is soluble in solvents such as acetone, the multilayer polymer referred to here includes the multilayer polymer itself. Included are the coalescence itself and mixtures of the bistructured polymer and the non-grafted polymer described above.

[0051] The multi-structure polymer having a special structure of the present invention is basically obtained by the polymerization method as explained in (f) above, but the characteristics of the polymer obtained at each polymerization step are as follows:
■ The polymer obtained in the first and second stages of polymerization plays a role in increasing the elastic modulus of the multi-structure polymer, and is also important in sheet polymerization because it determines the final particle size of the multi-structure polymer. It is. In particular, if a grafting agent or crosslinking agent is present during the first stage polymerization, only a multi-structure polymer with low impact resistance can be obtained (the layers formed during the first and second stage polymerizations). (referred to as the first layer)

[0052] The acrylic acid ester crosslinked product mainly obtained in the third stage polymerization plays the role of imparting impact strength. (The layer formed by this polymerization is called the second layer.) ■ The rubber-like elastic body obtained mainly in the fourth stage polymerization is the hard polymer of the first to second stage polymerization, the third stage polymerization, and the third stage polymerization. It serves to improve the adhesion between the acrylic ester crosslinked product of the polymerization step and the final polymer. (The layer formed by this polymerization is called the third layer.)
■ The final polymer obtained in the final stage of polymerization serves to improve the compatibility with the thermoplastic resin to be further blended. (The layer formed by this polymerization is called the fourth layer.)

00
[53] On the other hand, polymer B consists of unsaturated nitrile units, aromatic vinyl units, and one or more monomer units copolymerizable with these units. Here, the unsaturated nitrile as an essential component includes acrylonitrile, methacrylonitrile, etc., and acrylonitrile is particularly preferred, but a copolymer mainly composed of acrylonitrile and containing methacrylonitrile may also be used.

Another essential component, aromatic vinyl, includes styrene, α-methylstyrene, paramethylstyrene, p-
-chlorostyrene, p-bromostyrene, 2,4,5-
Tribromostyrene, etc., and styrene is the most preferred, but a copolymer mainly composed of styrene and other aromatic vinyls mentioned above may also be used.

As a component of polymer B, one or more monomer components copolymerizable with unsaturated nitrile and aromatic vinyl may be introduced. When it is necessary to further improve the blendability of polymers A and C or to lower the melt viscosity during blending, an acrylic ester consisting of an alkyl group having 1 to 8 carbon atoms can be used.

In addition, when it is necessary to improve the heat resistance of the sheet, acrylic acid, methacrylic acid, maleic anhydride,
Selected from monomers such as N-substituted maleimides. The unsaturated nitrile units in the composition of polymer B are 10 to 30
% by weight, preferably 15-25% by weight, aromatic vinyl units 90-70% by weight, preferably 85-75% by weight,
One or more monomer units copolymerizable with these are 0 to 5
It is necessary that the content be in the range of 0% by weight; outside this range, the blendability with polymers A and C will decrease, and the impact resistance of the molded article will decrease.

[0057] As described above, it cannot be expected based on conventional knowledge that compatibility with Polymer C, which is a methacrylic polymer, is achieved only by using a specific amount of the unsaturated nitrile units. there were. (See Examples 1, 5, and 6 and Comparative Examples 8 and 9, which will be described later.) This polymer B is produced by a conventional solution polymerization, suspension polymerization, or emulsion polymerization method.

[0058] Polymer C is a component for improving colorability, and contains (a) methacrylic acid ester units and (b)
One or two selected from acrylic acid ester units, unsaturated nitrile units, and monomer units copolymerizable with these units.
Consists of more than one species of monomeric units. Here, the essential component methacrylic ester includes methyl methacrylate, ethyl methacrylate, propyl methacrylate, etc., and methyl methacrylate is particularly preferred. Furthermore, acrylic esters include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and methyl acrylate is particularly preferred. The unsaturated nitrile is exemplified in the explanation of the components of polymer B.

As a component of this polymer C, one or more monomers copolymerizable with methacrylic ester, acrylic ester, and unsaturated nitrile may be introduced. If it is necessary to improve processability and moisture resistance, use aromatic vinyl such as styrene, α-methylstyrene, paramethylstyrene, p-chlorostyrene, p-bromostyrene, 2,4,5-tribromostyrene, etc. Can be polymerized. Moreover, when it is necessary to improve the heat resistance of the polymer composition, monomers such as acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleimide can be used.

The content of (a) methacrylic acid ester units in the composition of polymer C is 50 to 99% by weight, preferably 70% by weight.
~95% by weight, (b) 1 to 50% by weight of one or more monomer units selected from acrylic acid ester units, unsaturated nitrile units, and monomers copolymerizable with these;
Preferably, the amount needs to be in the range of 30 to 5% by weight; outside this range, the colorability and impact resistance will be unbalanced. This polymer C can be obtained by ordinary solution polymerization.
Manufactured by suspension polymerization and emulsion polymerization methods.

Furthermore, it is possible to add a polymer capable of making polymers A, B, and C compatible with each other to the polymer composition of the present invention. This allows a special function to be imparted to the molded product. For example, vinyl cyanide - vinyl aromatic -
Acrylic acid ester copolymer provides fluidity,
The vinyl cyanide-aromatic vinyl-N-substituted maleimide copolymer provides heat resistance, the polycarbonate resin provides heat resistance and impact resistance, and the vinyl chloride resin provides flame retardancy.

Polymer A constituting the polymer composition of the present invention
Regarding the quantitative ratio of polymer B and polymer C, A is 10 to
50% by weight, preferably 20-40% by weight, B is 70-40% by weight
10% by weight, preferably 50-30% by weight, C 20-
It should be 80% by weight, preferably in the range 30-50% by weight. Outside the above range, impact resistance and colorability will not be balanced. In particular, with regard to colorability, if Polymer C is less than 20% by weight, there is no effect, while if it exceeds 80% by weight, although colorability is excellent, impact resistance is significantly reduced. (See Examples 1, 7, 8 and Comparative Examples 10 to 14 described below)

The polymer composition of the present invention can be obtained by melt-kneading the above-mentioned polymers in a commercially available single-screw extruder or twin-screw extruder. Fillers, reinforcing materials, dyes, pigments, etc. can be added as necessary. By injection molding or extrusion molding, for example, the composition of the present invention obtained in this manner, it is possible to obtain a composition that has colorability, weather resistance, impact resistance, and excellent appearance, or has a balance of these properties. A molded product is obtained.

[0064]

EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto in any way. Note that measurements in Examples and Comparative Examples were performed using the following methods or measuring instruments. (2) Preparation of sample for electron microscopy: The average diameter of the α layer and the average thickness of the γ layer of the multilayer structure polymer of the present invention are measured as follows. That is, the multilayer structure polymer was PMMA (Delpet 80N; manufactured by Asahi Kasei Corporation), and the multilayer structure polymer was
Knead using a 0.30 mmφ twin screw extruder. Next, 0.5m
An ultra-thin section of m square or less is prepared, and the surface is cut and finished using a diamond knife. This sample is placed in a closed container.
It was exposed to the vapor of 1% ruthenic acid aqueous solution for several hours in a light-shielded state and dyed. When the composition is observed with an electron microscope, it has a sea-island structure, and the island portion consists of a portion that is stained with ruthenium and a portion that is not.The portion that is not stained with ruthenic acid is the α layer, and the portion outside the α layer is the α layer. The part surrounding the layer in a ring shape and dyed with ruthenic acid is called the γ layer, and the plurality of dispersed small particles in the α layer dyed with ruthenic acid are called the β layer.

■ Average diameter (particle size), average thickness;
As mentioned above, a transmission electron micrograph (100,000x magnification) of an ultrathin section of a sample cut from a molded product was stained with ruthenic acid, and the diameters of 100 randomly selected particles were measured. and the average diameter (particle diameter) defined in general formula [I]

[Chemical formula 1] At this time, if the particle cannot be considered spherical, determine its major axis and minor axis, and calculate the arithmetic average value as the average diameter (particle diameter).

[Case 2] And so.

Regarding the thickness, 1 was similarly selected at random.
Measurements were made for 00 particles, and the results were arithmetic averaged to obtain the average thickness. At this time, if the thickness is uneven, the maximum thickness and minimum thickness were measured, and the arithmetic average value was taken as the thickness.

General formula [I]:

[Equation 1] (Here, ni is the number of particles of the polymer A having a particle diameter Di.) ■ Swelling degree: Add 30 ml of methyl ethyl ketone to about 0.5 g of pellets, soak at 25°C for 24 hours, and then soak for 5 hours. Shake and centrifuge at 18,000 rpm for 1 hour at 5°C. After removing the supernatant by decantation, 30 ml of methyl ethyl ketone is newly added, shaken at 25°C for 1 hour, and centrifuged at 5°C and 18,000 rpm for 1 hour. The supernatant liquid is removed and the weight is measured (W3). Thereafter, it is vacuum dried at 100° C. for 2 hours, and the weight of the residue is weighed (W4).

The degree of swelling is calculated using the following formula.

[Formula 2] (2) Compositional analysis: The acetone-soluble portion was obtained by pouring the supernatants (a) and (b) obtained from the acetone separation into a large amount of methanol, and drying the precipitate under vacuum. For the acetone-insoluble portion, a sample obtained by acetone fractionation was used. Compositional analysis of each sample was performed by pyrolysis gas chromatography.

■ Tensile modulus: The insoluble part obtained by acetone fractionation was compression molded at 150°C to prepare a film, which had a width of 15 ± 0.5 mm and a thickness of 0.50 ± 0.0.
A test piece with a diameter of 5 mm and a length of 70 mm was prepared. Using a tensile testing machine, the distance between chucks was 50 mm, and the tensile speed was 50 mm/
Measured in minutes.

■Surface gloss; ASTM-D523-6
Based on 2T, specular gloss was determined at an incident angle of 60 degrees. (2) Weather resistance: A weather resistance acceleration test was conducted using a Dupanel Light Control Weather Meter (DPWL-5 model) manufactured by Suga Test Instruments Co., Ltd. under a cycle of irradiation at 60°C and wet condensation at 40°C. The percentage of the ratio of the Izod impact strength after 20 days of irradiation to that at the initial stage was defined as the retention rate of Izod impact strength, and was used as an evaluation of weather resistance.

■ Tensile strength, tensile elongation: ASTM-D
It was measured by a method based on 638. ■ Bending strength, bending elastic modulus: Measured by a method based on ASTM-D790. (10) Izod impact strength: Measured in accordance with ASTM-D256 (V-notch, 1/4" test piece).

(11) Evaluation of colorability; A. Coloring Conditions The following red colorant was mixed with 100 parts by weight of the polymer composition, and the mixture was mixed using a twin screw extruder. (a) Titanium oxide
0.10
Weight part (b) Color index number “Solvent Red-135”

0.10 parts by weight (c) Color index number “Solvent Red-1”
50"

0.10 parts by weight (d) Manufactured by Sumitomo Chemical Co., Ltd., product name “Sumiplast Yellow-HLR”

0
．． 005 parts by weight The above color index means "
The Society of dies and c
oloristsAmerican Associate
ion of textile chemists a
This is the compound number described in ``And Colorists''.

B. Evaluation of colorability From the above colored polymer composition, 7 cm x 5 cm square, thickness 5
A flat plate with a diameter of mm was prepared using ICS manufactured by Sakata Inx Co., Ltd.
-TEXICON MM9000 “Color M
400 to 700 nm spectral reflectance was used. Here, the reflectance at 640 nm was used to evaluate the colorability. The deeper the red (the better the coloring), the lower the reflectance at 640 nm.

[0074]

[Example 1] (a) Production of a multi-structure polymer (polymer A) (1) Polymerization of the innermost layer of hard polymer (seed first stage), 248.3 parts by weight of ion-exchanged water in the reactor, 0.05 parts by weight of sodium dihexyl sulfosuccinate was added as an emulsifier, and after thorough nitrogen substitution with stirring, the temperature was raised to 75°C. After adding 0.02 parts by weight of ammonium persulfate to this reactor, a mixture of 8 parts by weight of methyl methacrylate and 2 parts by weight of butyl acrylate was continuously added over 50 minutes. After the addition, 0.01 part by weight of ammonium persulfate was further added, and the reaction was continued at 75° C. for 45 minutes. Polymerization rate is 99%
Met.

(2) Polymerization of the hard polymer in the innermost layer (second stage of seeds) 1/4 of the latex obtained in (1) (2.5 in terms of solid content)
186.2 parts by weight of ion-exchanged water and 0.03 parts by weight of sodium dihexylsulfosuccinate were added to the reactor, and after sufficiently purging with nitrogen while stirring, the temperature was raised to bring the internal temperature to a Bring to 75℃. After adding 0.02 parts by weight of ammonium persulfate to this reactor, a mixture of 6.0 parts by weight of methyl methacrylate and 1.5 parts by weight of butyl acrylate was continuously added over 50 minutes. After the addition was completed, the reaction was continued at 75° C. for 45 minutes to further complete the reaction. The polymerization rate was 98%.

(3) Polymerization of acrylic acid ester crosslinked product (
(3rd stage polymerization), (2nd layer) In the presence of the latex of (2), ammonium persulfate 0
．． 01 parts by weight, sodium dihexyl sulfosuccinate 0
．． After adding 05 parts by weight, 63 parts by weight of butyl acrylate,
A mixture of 0.6 parts by weight of triallylisocyanurate as a crosslinking agent was continuously added at 70° C. over 80 minutes. After the addition was completed, the reaction was further continued at 70°C for 20 minutes. The polymerization rate through the first layer and the second layer was 85%. (4) Polymerization of rubber-like elastic body (4th stage polymerization), (3rd stage polymerization)
layer)

In the presence of 11 parts by weight of butyl acrylate and 0.18 parts by weight of triallylisocyanurate that were unreacted in the polymerization of (3), 0.045 parts by weight of ammonium persulfate,
After adding 0.45 parts by weight of sodium dihexyl sulfosuccinate, 3.0 parts by weight of acrylonitrile and 12 parts by weight of styrene.
．． A mixture of 2 parts by weight and 0.025 parts by weight of t-dodecylmercaptan was added continuously at 75°C over 90 minutes. The polymerization rate was 93%. In addition, the amount of residual monomer in the latex was measured by gas chromatography.
As a result of calculating the copolymerization composition ratio of the third layer, the acrylonitrile/styrene/butyl acrylate ratio was 11/42, respectively.
/47.

(5) Polymerization of final polymer (5th stage polymerization) (4th layer) In the presence of the latex of (4), acrylonitrile 2.
A mixture of 4 parts by weight of styrene, 9.4 parts by weight of styrene, and 0.02 parts by weight of t-dodecylmercaptan was continuously added at 75° C. over 70 minutes. In order to further complete the polymerization, 8
The reaction continued for 1 hour at 5°C. The polymerization rate was 97%. In addition, the amount of residual monomer in the latex was measured by gas chromatography, and the copolymerization composition ratio of the fourth layer was calculated. As a result, the acrylonitrile/styrene/butyl acrylate ratio was 21/68/11, respectively. .

[0079] The latex thus obtained was
Pour into a warm aqueous solution of sodium sulfate (wt%) to salt out and solidify, then repeat dehydration and washing, and then dry.
Polymer A-1 was obtained. Using the polymer A-1 obtained here, the polymerization ratio of acrylonitrile and styrene was determined by pyrolysis gas chromatography and was found to be 20/80. Further, other analysis results are shown in Table 1.

(b) Morphology of the multi-structure polymer (polymer A) (i) Staining with ruthenic acid and observation with an electron microscope: In addition, a test piece was prepared by the method described above, and the test piece was stained with ruthenic acid. When ultra-thin sections were prepared and observed with a transmission electron microscope, as shown in the schematic diagram in Figure 2, island phases 2 made of a multi-structure polymer were scattered within a sea phase 1 made of thermoplastic resin. condition is observed.

[0080] The average particle diameter of the α part 4 which is not stained with ruthenic acid is 5000 Å, and the average particle diameter of the entire island 2 (multi-structure polymer) is 5350 Å, which is stained with ruthenic acid. The average thickness of γ part 3 is 350 Å
It is. A plurality of portions (β portions) 5 stained with ruthenic acid were dispersed almost entirely in the α portion 4 that was not stained with ruthenic acid.

[0081] Considering the characteristics of each of the monomers for hard polymers, monomers for rubber elastic bodies, and monomers for crosslinked acrylic esters used to polymerize this multi-structure polymer, (a) the α part Portion 4 contains butyl acrylate, methyl methacrylate units for the hard polymer from the first and second stage polymerizations, and butyl acrylate, crosslinker or graft for the acrylic ester crosslinked product from the third stage polymerization. It is thought that the main component is the oxidizing agent unit,

[0082]
(b) The γ portion 3 contains butyl acrylate, styrene, and acrylonitrile units for the rubber elastic body obtained by the fourth stage polymerization, and styrene, acrylonitrile, and residual acrylic units for the final polymer obtained by the fifth stage polymerization. It is believed that acid butyl units are the main component. Furthermore, (c) the β part 5 dispersed in the α part 4 is formed by a part of the hard component, mainly styrene, charged in the γ part 3 flowing into the α part 4 and polymerizing. it is conceivable that.

(c) Production of Polymer B 14.2 parts by weight of acrylonitrile, 56.8 parts by weight of styrene, 29 parts by weight of ethylbenzene and t as an initiator.
-Butyl-peroxyisopropyl carbonate 300
ppm mixed solution at a rate of 1.9L/hr with a volume of 2.1L
was continuously supplied to a complete mixing type reactor, and polymerization was carried out at 130°C. The polymerization liquid is continuously led to a vented extruder,
Unreacted monomers and solvent were removed under conditions of 260° C. and 40 Torr, and the polymer was continuously cooled and solidified to obtain particulate polymer B-1. It consists of 20% by weight of acrylonitrile units and 80% by weight of styrene units, and GPC
Analysis shows that Mw is 165,800 and MwMn is 1.
．． It was 86.

(d) Polymer C Polymer C was a methacrylic resin [(methyl methacrylate/methyl acrylate = 98/2 (weight ratio) Asahi Kasei Corporation (
Co., Ltd. Product name, <Delpet> Registered trademark <80N>
] (referred to as Polymer C-1) was used. (E) Preparation and evaluation of the composition After mixing the polymer A-1, polymer B-1, and polymer C-1 at a weight ratio of 35/30/35 for 20 minutes in a Henschel mixer, a 30 mm Twin screw extruder with vent (
Pelletization was performed at 260° C. using a model A (manufactured by Nakatani Kikai Co., Ltd.).

[0085] Using the obtained pellets, a specified test piece was prepared using an in-line screw injection molding machine (manufactured by Toshiba Machine Co., Ltd., model IS-75S) at a molding temperature of 260°C and a mold temperature of 60°C. Physical properties were measured. The results are shown in Table 1.

On the other hand, the pellet and measurement method 11
After mixing the coloring agents described in the column for evaluation of colorability using the above-mentioned twin-screw extruder, a flat plate was prepared, and the colorability was evaluated. The results are shown in Table 1. According to Table 1, it can be seen that the polymer composition of the present invention has weather resistance, impact resistance, rigidity, excellent appearance, and good colorability.

[0087]

[Comparative Example 1] (A) Production of multi-structure polymer (I) Production of large particle polymer (1) Polymerization of innermost layer hard polymer (1st stage of seeds) and (2) Innermost layer hard polymer The polymerization (seed second stage) of
The same method as in Example 1 for producing LTX-(I) was performed except that 0.19 parts by weight of allyl methacrylate was added.

(3) Polymerization of acrylic acid ester crosslinked product (
3rd stage polymerization) In the presence of the latex of (2), ammonium persulfate 0
．． 13 parts by weight, sodium dihexyl sulfuccinate 0.
After adding 0.5 parts by weight, a mixture of 63 parts by weight of butyl acrylate and 0.6 parts by weight of triallylisocyanurate as a crosslinking agent was continuously added at 80° C. over 80 minutes. After the addition was completed, the reaction was further continued at 80°C for 90 minutes. Through the polymerization of (1) to (3) above, the polymerization rate was 99.5%.
Met.

(4) Polymerization of the final polymer (4th stage polymerization) In the presence of the latex of (3), ammonium persulfate 0
．． 045 parts by weight, sodium dihexyl sulfuccinate 0
．． After adding 0.045 parts by weight, a mixture of 5.4 parts by weight of acrylonitrile, 21.6 parts by weight of styrene, and 0.045 parts by weight of t-dodecylmercaptan was continuously added at 75° C. over 160 minutes. 85°C to further complete polymerization.
The reaction was continued for 1 hour. The polymerization rate was 98%. Further, the amount of residual monomer in the latex was measured by gas chromatography and the copolymerization composition ratio of the fourth layer was calculated, and as a result, the acrylonitrile/styrene/butyl acrylate ratio was 20/80/0. The latex thus obtained was subjected to the same treatment as in Example 1, and polymer a-1
I got it.

(b) Morphology of the multi-structure polymer (polymer a-1) As a result of electron microscopic observation, as shown in the schematic diagram of FIG. 3, the multi-structure polymer is present in the sea phase 1 made of thermoplastic resin. The island phase 2 consists of two layers, and the average major axis of the inner layer (α part) part 4 inside the particle is 490.
0 Å, the average thickness of the outer layer (γ part) portion 3 surrounding the layered layer is 3
It was 40 Å. Not present in Example 1 in α part 4, not stained with osmic acid, diameter 1200 Å
An independent spherical layer 6 was observed. There was no β part 5 dispersed in this spherical layer 6.

(c) Preparation and evaluation of composition Pellets were obtained in the same manner as in Example 1, except that the above-mentioned multi-structure polymer a-1 was used, and then molded articles were prepared and their physical properties were evaluated. The results are shown in Table 1.

[0092]

[Table 1] Combining Table 1 and the results of electron microscopy observation, when a grafting agent (crosslinking agent) is introduced during the polymerization of the innermost hard polymer, an independent spherical layer exists, and within this spherical layer, It can be seen that the mechanical strength is low because the β part is not dispersed.

[0093]

[Comparative Example 2] (A) Production of multi-structure polymer (I) Production of large particle polymer (1) Polymerization of acrylic acid ester crosslinked product (first stage of seeds), 248.3 g of ion-exchanged water in the reactor parts by weight, and 0.05 parts by weight of sodium dihexylsulfosuccinate, and after sufficiently purging with nitrogen while stirring, the temperature was raised to bring the internal temperature to 7.
Bring to 5℃. This reactor contains 0.02 ammonium persulfate.
After adding parts by weight, a mixture of 10 parts by weight of butyl acrylate and 0.1 parts by weight of triallylisocyanurate as a crosslinking agent was continuously added over 50 minutes. After the addition, 0.01 part by weight of ammonium persulfate was further added, and the temperature was increased to 45°C at 75°C.
The reaction continued for minutes. The polymerization rate was 99%.

(2) Polymerization of acrylic acid ester crosslinked product (
2nd stage of seeds), 1/4 of the latex obtained in (1) (2.5 in terms of solid content)
186.2 parts by weight of ion-exchanged water and 0.03 parts by weight of sodium dihexylsulfosuccinate were added to the reactor, and after sufficient nitrogen purging with stirring, the internal temperature was brought to 70°C. . After adding 0.01 part by weight of ammonium persulfate to this reactor, 70.5 parts by weight of butyl acrylate and 0.6 parts by weight of triallylisocyanurate as a crosslinking agent.
7 parts by weight of the mixture was added continuously over 80 minutes at 70°C. After the addition was completed, the reaction was further continued at 70°C for 20 minutes. The polymerization rate was 85%.

(3) Polymerization of rubber-like elastic body In the presence of 11 parts by weight of butyl acrylate and 0.18 parts by weight of triallylisocyanurate, which were unreacted in the polymerization of (2), 0.045 parts by weight of ammonium persulfate, After adding 0.45 parts by weight of sodium dihexyl sulfuccinate, 3.0 parts by weight of acrylonitrile was added.
A mixture of 0 parts by weight, 12.2 parts by weight of styrene, and 0.025 parts by weight of t-dodecylmercaptan was continuously added at 75° C. over 90 minutes. The polymerization rate was 93%. Further, the amount of residual monomer in the latex was measured by gas chromatography, and the copolymerization composition ratio of the third layer was calculated. As a result, the acrylonitrile/styrene/butyl acrylate ratio was 11/42/47, respectively.

(4) Polymerization of the final polymer In the presence of the latex of (3), acrylonitrile 2.
A mixture of 4 parts by weight of styrene, 9.4 parts by weight of styrene, and 0.02 parts by weight of t-dodecylmercaptan was continuously added at 75° C. over 70 minutes. 85 to further complete the polymerization.
The reaction was continued for 1 hour at °C. The polymerization rate was 97%. In addition, the amount of residual monomer in the latex was measured by gas chromatography and the copolymerization composition ratio of the final polymer was calculated, and the acrylonitrile/styrene/butyl acrylate ratio was 21/68/11, respectively. . The latex thus obtained was poured into a 3% by weight warm aqueous solution of sodium sulfate for salting out and coagulation, followed by repeated dehydration and washing, followed by drying to form the multistructure polymer a-2. Obtained.

(B) Preparation and Evaluation of Composition Pellets were obtained in the same manner as in Example 1, except that the multi-structure polymer a-2 was used, and then molded products were produced and their physical properties were evaluated. The results are shown in Table 1. According to Table 1, it can be seen that the resin composition using a multi-structure polymer without a hard polymer in the innermost layer consisting of an alkyl methacrylate ester and an alkyl acrylate ester has poor impact resistance and gloss.

[0098]

[Comparative Example 3] The same experiment as in Example 1 was conducted except that triallylisocyanurate as a crosslinking agent was not used in the polymerization of the acrylic ester crosslinked product in Example 1. The copolymer without triallylisocyanurate has an Izod impact strength of 3.2 Kgcm/cm, which shows that the impact resistance is significantly inferior to that of the molded article of Example 1. When observed by electron microscopy, γ and α parts were not present.

0099

[Examples 1 to 3 and Comparative Examples 4 and 5] (Effect of the composition ratio of acrylonitrile and styrene in polymer A) In the production of polymer A-1 of Example 1, the copolymerization ratio of acrylonitrile and styrene was In order to obtain different polymers A, (4) polymerization of the rubbery elastomer (fourth stage polymerization) and (5) polymerization of the final polymer (fifth stage polymerization).
At this time, seed polymerization was performed by changing the charging composition of acrylonitrile and styrene. The latex thus obtained was treated in the same manner as in Example 1 to obtain polymer A-1.
Instead, a polymer composition was prepared using the polymer A obtained here and evaluated. The results are shown in Table 2.

[0100]

Table 2 shows that polymer A exhibits good impact resistance only when the acrylonitrile/styrene weight ratio is in the range of 10/90 to 30/70.

[0101]

[Examples 1 and 4 and Comparative Examples 6 and 7] (Effect of particle diameter of polymer A) In the production of polymer A-1 of Example 1, the copolymer composition was the same as that of A-1, and the Polymers A having different particle diameters were obtained. To achieve this, it is necessary to reduce the amount of latex obtained by the first seed polymerization of the innermost layer hard polymer and continue seed polymerization to make the particles larger than A-1, or to By increasing the amount of sodium dihexyl sulfosuccinate in the first seed stage and continuing seed polymerization, particles were made smaller than A-1.

The latex thus obtained was subjected to the same treatment as in Example 1, and instead of polymer A-1,
A polymer composition was prepared using the polymer A obtained here and evaluated. The results are shown in Table 3.

[0103]

[Table 3] According to Table 3, when the particle diameter is less than 2000 Å, the gloss is excellent, but the impact resistance and coloring properties are poor, while when it exceeds 6000 Å, the coloring properties are excellent, but the gloss is poor. I can see that

[0104]

[Examples 1, 5, 6 and Comparative Examples 8, 9] (Effect of composition ratio of acrylonitrile and styrene in polymer B) Example 1
In the production of Polymer B-1, in order to obtain Polymer B with a different copolymer composition of acrylonitrile and styrene,
Polymerization was carried out by changing the monomer charge composition. The polymer B thus obtained was used in place of the polymer B-1 of Example 1, and the same experiment as in Example 1 was conducted and evaluated. The results are shown in Table 4.

[0105]

Table 4 shows that good impact resistance is exhibited only when the weight ratio of acrylonitrile to styrene is in the range of 10/90 to 30/70.

[0106]

[Examples 1, 7, 8 and Comparative Examples 10 to 14] (Effect of composition ratio of polymers A, B, and C) Various types of polymers A-1, B-1, and C-1 of Example 1 were mixed. to prepare a polymer composition,
evaluated. The results are shown in Table 5.

[0107]

[Table 5] According to Table 5, 10 to 50% by weight of polymer A, 10 to 50% by weight of polymer B,
It can be seen that impact resistance, rigidity, and colorability are balanced only when Polymer C is in the range of 70 to 10% by weight and Polymer C is in the range of 20 to 80% by weight.

[0108]

[Example 1 and Comparative Examples 15 and 16] (Comparative evaluation with ABS resin and AES resin) Instead of the polymer composition of Example 1, ABS resin [Asahi Kasei Kogyo Co., Ltd.]
Manufactured by Product Name <Switarac-ABS> Registered Trademark <20
0> and AES resin [manufactured by Japan Synthetic Rubber Co., Ltd., product name <
The same experiment as in Example 1 was conducted and evaluated using JSR-AES>Registered Trademark <115>. The results are listed in Table 6.

[0109]

[Table 6] According to Table 6, ABS resin has poor weather resistance, while AE
It can be seen that the S resin has poor coloring properties.

[0110]

Effects of the Invention As is clear from the above, the present invention provides
It is a novel polymer composition that has improved weather resistance compared to BS resin, and combines excellent appearance, impact resistance, rigidity, and excellent colorability. This composition is
It can be used unpainted for a wide range of applications including automobile parts and electronic parts, especially for outdoor applications where previously painted products such as metal materials or ABS resin were used, and it plays a major role in these industries.

[Brief explanation of the drawing]

FIG. 1 diagrammatically explains the mechanism by which coloration occurs using spectral reflectance.

FIG. 2 is a schematic diagram of a transmission electron micrograph of an ultrathin section stained with ruthenic acid of a multilayered polymer according to the present invention and a thermoplastic resin composition containing the same.

FIG. 3 is a schematic diagram of a transmission electron micrograph of an ultrathin section stained with ruthenic acid of a multilayer polymer and a thermoplastic resin containing the polymer according to a comparative example.

FIG. 4 is a schematic diagram showing an example of the particle shape of the multi-structure polymer of the present invention.

FIG. 5 is a schematic diagram showing an example of the particle shape of the multi-structure polymer of the present invention.

[Explanation of symbols]

1　Marine phase 2 Island phase 3 γ layer 4 α layer 5 β layer 6. Independent layer

Claims (1)

[Claims] Claim 1: 10 to 50% by weight of multi-structure polymer A, 70 to 10% by weight of thermoplastic polymer B, and thermoplastic polymer C2
0 to 80% by weight, the multi-structure polymer A is essentially a spherical crosslinked rubber body,
A mixture of (a) an acrylic ester crosslinked polymer and a copolymer consisting of methacrylic ester units and acrylic ester units, having the following form and composition, -
an essentially spherical rubbery polymer (α portion) having a glass transition temperature of 30° C. or less; and (b) a polymer dispersed inside said α portion, comprising an aromatic vinyl unit and unsaturation. A copolymer consisting of a nitrile unit and/or a copolymer consisting of an aromatic vinyl unit, an unsaturated nitrile unit, and an acrylic acid ester unit constituting the α portion (β portion); (c)
A polymer surrounding the outside of the α portion in a layered manner, the copolymer consisting of an aromatic vinyl unit and an unsaturated nitrile unit, and/or an acrylic ester comprising an aromatic vinyl unit, an unsaturated nitrile unit, and the α portion. A copolymer consisting of units (
The copolymerization composition is (a) 2 to 30% by weight of methacrylic acid ester units, (b) 50 to 80% by weight of acrylic acid ester units, and (c) 5 to 50% of unsaturated nitrile units. 20% by weight and (d) aromatic vinyl unit.
5 to 40% by weight, and the weight ratio of the unsaturated nitrile unit to the aromatic vinyl unit is 10/90 to 30.
/70, the average diameter of the essentially spherical α part is 1900 to 5900 Å, the average layer thickness of the γ part surrounding this α part is 10 to 1000 Å, and The average diameter of the entire particles of the multi-structure polymer A is 20
00 to 6,000 Å, (a) the degree of swelling of the acetone-insoluble portion to methyl ethyl ketone is 1.5 to 10, and (b) a tensile modulus of 1,000 to 10,000 kg/
cm2, and the thermoplastic polymer B comprises (a) 10 to 30% by weight of unsaturated nitrile units and (
b) A thermoplastic polymer consisting of 90 to 70% by weight of aromatic vinyl units and (c) 0 to 50% by weight of one or more monomer units copolymerizable with them, and the thermoplastic polymer C is , (a) 50 to 99% by weight of methacrylic acid ester units and (
b) A thermoplastic polymer consisting of 1 to 50% by weight of one or more monomer units selected from acrylic acid ester units, unsaturated nitrile units, and monomers copolymerizable with these units. A weather-resistant and impact-resistant polymer composition with excellent colorability.