JPH04258655A - Weather-resistant high-impact resin composition excellent in solvent resistance - Google Patents

Abstract

PURPOSE:To provide the title compsn. excellent also in heat resistance and appearance. CONSTITUTION:The title compsn. comprises a double-structured polymer based on an acrylic ester rubber, a polyamide resin, an AS resin contg. an alpha,beta-unsatd. carboxylic acid (e.g. an acrylonitrile-styrene resin), and a resin compatible with the foregoing resins. It is excellent in weatherability, solvent resistance, heat resistance, mechanical strengths, and appearance, and hence is suitable for wide application areas including automotive parts, such as an automotive exterior panel, and electronic parts.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a weather-resistant and impact-resistant resin made of a novel acrylic ester rubber. More specifically, the present invention relates to a weather-resistant and impact-resistant resin composition made of an acrylic ester rubber that has solvent resistance, heat resistance, moisture resistance, high rigidity, and excellent appearance.

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 due to its excellent impact resistance, excellent balance of mechanical properties, ease of molding, and relatively low price. . but,
On the other hand, since ABS resin uses polybutadiene as one of its constituent components, it has poor weather resistance and is considered unsuitable for outdoor use. Its appearance has been a long-standing desire.

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 this method improves weather resistance, it also leads to a decrease in impact resistance and appearance of molded products, and depending on the field of application, it also reduces solvent resistance,
The heat resistance was also insufficient and problems remained in practical use.

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.

[0005] Also, Japanese Patent Publication No. 59-36645,
A method for producing a multi-stage polymer consisting of a methacrylic ester and an acrylic ester has been disclosed, but the impact strength was insufficient. On the other hand, in order to improve solvent resistance, impact resistance, and heat resistance, polymer blends of ABS resins and AAS resins with solvent-resistant, heat-resistant, and tough resins can be considered. One example is polyamide resin. However, ABS resin or AAS resin and polyamide resin are not compatible with each other, and simply blending them results in phase separation and no impact strength is developed. (See Comparative Example 6 described later) For example, regarding the compatibilization of both resins, JP-A-62-11
Publication No. 760 discloses a rubber-modified nylon composition comprising an ABS resin, a polyamide resin, and a compatibilizer containing a functional monomer that can react with the polyamide resin. Although it has excellent mechanical strength, it has poor weather resistance.

[0006] Furthermore, JP-A-56-50931 discloses a copolymer of a random copolymer of an α,β-unsaturated carboxylic acid anhydride and a styrene compound and a polyamide resin. , which has excellent solvent resistance but poor impact strength. Furthermore, JP-A-63-162751
The publication discloses a composition including an acrylic ester-based graft rubber composition, a polyamide resin, and a compatibility-imparting polymer containing a functional monomer that can react with the polyamide resin. Although it has excellent properties such as hardness and solvent resistance, its impact strength is not sufficient, which limits its industrial use. As a result of intensive research into improving the solvent resistance and heat resistance of acrylic acid ester-based weather-resistant and impact-resistant resins, the present invention was developed by combining a specific multi-structure polymer, a specific thermoplastic resin, and a polyamide resin. It has become possible to dramatically improve solvent resistance, heat resistance, and moisture resistance while maintaining impact resistance and excellent appearance.

[0007]

[Problems to be Solved by the Invention] In view of the current situation, the present invention has been developed to provide a material that does not have the above-mentioned problems, that is, has solvent resistance, heat resistance, moisture resistance, high rigidity, and excellent appearance. The object of the present invention is to provide a weather-resistant and impact-resistant resin composition made of acrylic ester rubber.

[0008]

[Means for Solving the Problems] That is, the present invention consists of 10 to 80% by weight of a multistructure polymer A and 1% by weight of a polyamide resin.
A resin composition comprising 0 to 80% by weight of a thermoplastic resin B, 1 to 80% by weight of a thermoplastic resin B, and 0 to 30% by weight of a thermoplastic resin C, wherein the multi-structure polymer A comprises (a) an alkyl methacrylate ester; Units 2-30% by weight, (b) Acrylic acid alkyl ester units 50-80
% by weight, (c) 5 to 20% by weight of unsaturated nitrile units, (
d) A multi-structure polymer A consisting of 5 to 40% by weight of aromatic vinyl units and (e) 0.05 to 5% by weight of a polyfunctional crosslinking agent, the multi-structure polymer A comprising: (a) unsaturated nitrile; unit, a polymer consisting of an aromatic vinyl unit and an acrylic acid alkyl ester unit (α part)
and (b) a polymer (β portion) consisting of an acrylic acid alkyl ester unit, a methacrylic acid alkyl ester unit, and a polyfunctional crosslinking agent, and (c) an unsaturated nitrile unit, an aromatic vinyl unit, and an acrylic acid alkyl ester unit. It has multiple structures composed of polymers (γ part),
(d) the β part is essentially particulate and has an average diameter of 2000 to 6500 Å; α is a layer surrounding the β part in a layered manner; The thickness is 10 to 1000 Å, the γ part is essentially fine particles, and multiple particles are present dispersed in the β part, and (e) the acetone-insoluble part has a swelling degree of (i) methyl ethyl ketone of 1.5 to 10. and (b) the tensile modulus is 1000
~10,000 Kg/cm2, and the thermoplastic resin B has 20 to 45 vinyl cyanide units.
wt% and aromatic vinyl units 75-55 wt% and α,β-
A thermoplastic resin consisting of 0.1 to 5.0% by weight of an unsaturated carboxylic anhydride and 0 to 30% by weight of one or more monomer units copolymerizable with these, and the thermoplastic resin C is
The present invention provides a weather-resistant and impact-resistant resin composition with excellent solvent resistance, which is characterized by being a thermoplastic resin that can be made compatible with a multi-structure polymer A, a polyamide resin, and a thermoplastic resin B.

The present invention will be explained in detail below. The weatherable impact resistant resin composition of the present invention provides surprising advantages by combining a specific bistructured polymer A, a polyamide resin, a specific thermoplastic B, and a specific thermoplastic resin C. First, let's talk about multi-structure polymers. (a). Composition of the multi-structure polymer: The multi-structure polymer in the present invention compositionally includes (a) methacrylic acid alkyl ester units, (b) acrylic acid alkyl ester units, (c) unsaturated nitrile units, and (d) aromatic It is a multi-structure polymer composed of group vinyl units and further containing (v) a polyfunctional crosslinking agent.

Examples of the methacrylic acid alkyl ester unit (a) constituting the multi-structure polymer include methyl methacrylate, ethyl methacrylate, propyl methacrylate and the like, 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) the polyfunctional crosslinking agent is a crosslinking monomer having at least two C=C double bonds, such as triallyl isocyanurate and unsaturated alcohol such as triallyl cyanurate and triallyl isocyanurate. Commonly known crosslinking agents can be used, such as esters with; divinyl compounds such as divinylbenzene; diallyl compounds, and dimethacrylic compounds such as ethylene glycol dimecrylate;
Triallylisocyanurate is preferably used. (b). Composition ratio and degree of swelling of the multi-structure polymer On the other hand, the composition ratio of the multi-structure polymer is basically (i) 2 to 30% by weight of methacrylic acid alkyl ester units, preferably 5 to 15% by weight.
Weight %, (b) Acrylic acid alkyl ester unit 50~
80% by weight, preferably 55-70% by weight, (c) 5-20% by weight of unsaturated nitrile units, preferably 6-10% by weight, (d) 5-40% by weight of aromatic vinyl units, preferably 8-10% by weight. 35% by weight and (e) polyfunctional crosslinking agent 0.05~
It is necessary that the content be 5% by weight.

[0012] If it deviates from this range, it is unfavorable in terms of impact resistance. In addition, the swelling degree of the acetone-insoluble part with respect to methyl ethyl ketone is 1.5 to 10, and the tensile and elastic modulus is 1,000 to 10,000 Kg/cm2.
It is necessary that If it deviates from this range, a product with poor impact resistance will be obtained, which is not preferable. (c). Fine structure of the multi-structure polymer: The multi-structure polymer of the present invention has a structure in which a plurality of γ parts are microdispersed throughout the β part, and the average diameter of the β part is 2,000 to 2,000. 6
, 500 Å, and the average thickness of the α part surrounding it is
It has a very special structure with a thickness of 10 to 1000 Å.

[0013] Due to this special structure, it is thought that the surface gloss is greatly improved while maintaining impact resistance and weather resistance. This was difficult to predict from the following composite structures that have been proposed so far. 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 polymerization of the hard polymer, the β part In the first stage, which is not stained with osminic acid (
(crossed) hard polymer exists in a spherical shape. More specifically, there is a part in which small particles of the γ part are microdispersed in the β part, and a part in which the small particles of the γ part are microdispersed in the β part.
This results in a multi-structure polymer containing two regions of (independent) spherical parts in which no part exists.

[0014] In this case, a significant decrease in impact strength is a problem. Therefore, in the multi-structure polymer of the present invention, β
If the α part is not covered with the α part, a product with poor impact resistance and weather resistance will be obtained, and if the β part does not have multiple γ parts dispersed microscopically, the surface will deteriorate. It is not possible to obtain a product that satisfies gloss and impact resistance at the same time.

Furthermore, the average diameter of the β portion is 2000 to 65
00 Å, preferably 2500 to 4
000 Å. If it is less than 2000 Å, impact resistance will decrease, while if it exceeds 6500 Å, surface gloss will decrease. In addition, the average thickness of the α part that covers the β part is 10~
1000 Å is required, preferably 300 to 400 Å
It is. If it is less than 10 Å, the compatibility between the polyamide resin and thermoplastic resins B and C decreases, resulting in poor impact resistance;
When it exceeds 1000 Å, the compatibility improves and the two-phase system collapses to become similar to a single substance, resulting in a decrease in impact resistance.

In the multi-structure polymer of the present invention, in order to microdisperse a plurality of γ parts in the β part, the composition, molecular weight, crosslinking density, and distance between the crosslinking points of the β part should be adjusted appropriately. It is necessary to do so. In the multi-structure polymer of the present invention, a plurality of γ parts are microdispersed throughout the β part means that a plurality of small particles of the γ part are dispersed relatively evenly throughout the β part. Refers to the state. Therefore, as in the conventional composite structure described above, there are two parts: a part in which small particles of the γ part are microdispersed in the β part, and a spherical part (independent) in which the γ part does not exist at all.
Something that includes two areas cannot be said to be microdispersed as a whole.

As an embodiment in which a plurality of γ parts are microdispersed throughout the β part, it is preferable that a plurality of γ parts are uniformly microdispersed throughout the β part. Not restricted. Further, the number of small particles in the γ portion is not particularly limited and may be any number, but it is more preferable that a relatively large number of small particles be uniformly microdispersed. Further, although it is preferable that the small particles in the γ portion are relatively uniform in size, there may be some variation.

Both the multistructure polymer of the present invention itself and the β part have γ
The shape of the part is essentially particulate, and the α part exists as a layer surrounding the particulate β 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 β part as an example, a typical preferred shape is essentially spherical.

When the β part is spherical, observing the cross-sectional shape of the multistructure polymer shows that the α part exists as a layer whose cross-sectional shape is essentially ring-shaped. In addition to the spherical shape, the shape of the β 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. 4, which has irregularities thereon.

[0020] Furthermore, the shape is not necessarily symmetrical, and may be irregularly shaped. Although it is preferable that the α portion surrounds the entire β portion, the β portion may be partially exposed in a portion where the α portion is not present. It is more preferable that the variation in thickness of the α portion is small. (d). Method for producing a multi-structure polymer: The method for producing a multi-structure polymer according to the present invention is advantageous by using a known emulsion polymerization method that is carried out in the presence of a monomer, an emulsifier, a polymerization initiator, a chain transfer agent, etc. .

Furthermore, in order to form such a multi-structure polymer, a seed polymerization method can be used in which a multi-structure polymer can be formed by sequentially adding and reacting each monomer or monomer mixture. is advantageous. A typical example of the method for producing the multi-structure polymer of the present invention is specifically shown below. <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.

[0022] 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 to 8% by weight Unsaturated nitrile 4 to 8% by weight Aromatic vinyl 2 to 5% by weight Crosslinking agent 0.005 to 05% by weight of the monomer liquid as an emulsifier and polymerization initiation emulsion polymerization with the agent. <5th stage polymerization> Acrylic acid alkyl ester 0
~2% by weight Aromatic vinyl 1-1
6% by weight unsaturated nitrile
A 3 to 38% by weight monomer liquid is emulsion polymerized together with an emulsifier and a polymerization initiator.

At this time, when conducting the third and subsequent stages of polymerization, it is necessary to select conditions that suppress the formation of new particles as much as possible, but for this purpose, the amount of emulsifier used must be adjusted to a critical level. This can be achieved by lowering the micelle concentration. Moreover, the presence or absence of new particle generation 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, a part of the seed latex of the innermost layer hard polymer (obtained in the first stage polymerization) is removed. This can be done by adjusting the amount of seed latex taken out and controlling the number of particles of the seed latex when adding ion-exchanged water, an emulsifier, and a monomer to continue seed polymerization.

The appropriate polymerization temperature for forming the polymer and/or copolymer in each polymerization step is selected in the range of 30 to 120°C, preferably 50 to 100°C. There are no particular limitations on the emulsifier used in the polymerization, and any emulsifier can be selected from conventionally used emulsifiers. 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, the chain transfer agent used is:
alkyl mercaptans such as t-dodecyl mercaptan;
Examples include toluene, xylene, chloroform, halogenated hydrocarbons, and the like. Regarding the method of adding the monomer, it is possible to add it all at once, but it is also possible to add the monomer in several parts.
Or it is better to add it continuously. In that case, the polymerization reaction can be controlled and overheating and coagulation can be prevented.

[0027] 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 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., while leaving unreacted monomers. (e). Others: Multi-structure polymers with special structures obtained by such polymerization methods can be converted into particulate solids by performing treatments such as salting out, washing, and drying from the state of polymer latex using known methods. can get.

[0028] Such a multi-structure polymer usually has the following properties:
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.

The multi-structure polymer having a special structure of the present invention is basically obtained by the polymerization method as explained in (d) 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 multistructure polymer with low impact resistance can be obtained. (The layer formed in the first and second stage polymerization is called the first layer.) ■ The acrylic ester crosslinked product mainly obtained in the third stage polymerization plays a role in imparting impact strength. do. (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 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 referred to as 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 referred to as the fourth layer.) On the other hand, the polyamide resin is used to impart solvent resistance, heat resistance, and impact resistance to the resin composition of the present invention. repeating unit

[0031]

[Chemical formula 1] or

[0032]

[Image Omitted] Or has a structure that is a mixture of both. Examples of such polyamide resins include polycaprolactam (nylon-6), polyhexamethylene adipamide (nylon-6,6), polyhexamethylene sebaamide (nylon-6,10), and nylon 6,6. /6,10 copolymer,
Nylon 6,6/6 copolymer, polylauryllactam (
Nylon 12), polyhexamethylene azeramide (nylon 6,9), polyhexamethylene dodecanodiamide (
Examples include nylon 6,12), poly γ-butyrolactam (nylon 4), poly 7-aminoheptanoic acid (nylon 7), poly 8-aminocaprylic acid (nylon 8), and furthermore terephthalic acid and isophthalic acid. Also included are aromatic polyamides containing residues. As the method for polymerizing the polyamide resin, commonly known melt polymerization, solid phase polymerization, or a combination thereof can be employed.

[0033] The thermoplastic resin B is used to impart compatibility between the multi-structure polymer A and the polyamide resin in the resin composition of the present invention, and contains 20 to 45 vinyl cyanide units by weight. % and aromatic vinyl units 75-55% by weight
and α,β-unsaturated carboxylic acid anhydride 0.1 to 5.0% by weight, and one or more monomer units copolymerizable with these 0
~30% by weight. Here, the vinyl cyanide which is an essential component is 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, is styrene, α-methylstyrene, paramethylstyrene, p-chlorostyrene, p-bromostyrene, 2,4
, 5-tribromostyrene, etc., and styrene is the most preferred, but a copolymer containing styrene as a main component and other aromatic vinyls mentioned above may also be used.

[0034] Still another essential component, α,β-unsaturated carboxylic acid anhydride, is maleic anhydride, methylmaleic anhydride, chloromaleic anhydride, itaconic anhydride, aconitic anhydride or citraconic anhydride. Maleic anhydride is particularly preferred, but a copolymer consisting mainly of maleic anhydride mixed with other α,β-unsaturated carboxylic acid anhydrides may also be used.

As a component of the thermoplastic resin B, one or more monomer components copolymerizable with the aromatic vinyl cyanide and the α,β-unsaturated carboxylic acid anhydride may be introduced. When it is necessary to further improve the blendability with the multilayer structure polymer A 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. Moreover, when it is necessary to improve the heat resistance of the molded article, monomers such as acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleimide are selected.

In the composition of thermoplastic resin B, the cyanide vinyl units are 20 to 45% by weight, and the aromatic vinyl units are 7% by weight.
5-55% by weight, α,β-unsaturated carboxylic acid anhydride is 0
．． 1 to 5.0% by weight, and one or more monomer units copolymerizable with these need to be in the range of 0 to 30% by weight, and outside this range, the The effect of imparting compatibility is small, and the mechanical properties of the molded article deteriorate.

[0037] This thermoplastic resin B is produced by a conventional solution polymerization, suspension polymerization, or emulsion polymerization method. Furthermore, the thermoplastic resin C is not particularly limited as long as it is a thermoplastic resin that can be made compatible with the multi-structure polymer A, the polyamide resin, and the thermoplastic resin B, and can thereby impart special functions to the molded product. Can be done. For example, methacrylic resin provides scratch resistance, vinyl cyanide-aromatic vinyl-acrylic acid ester copolymer provides fluidity, and 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.

Regarding the quantitative ratio of the multi-structure polymer A, the polyamide resin, the thermoplastic resin B, and the thermoplastic resin C constituting the resin composition of the present invention, A is 10 to 80% by weight, and the polyamide resin is 10 to 80% by weight. 80% by weight, B from 1 to 80% by weight, C
It is essential that the amount is in the range of 0 to 30% by weight. Outside the above range, solvent resistance, heat resistance, moisture resistance, and mechanical strength will not be balanced.

The resin composition of the present invention can be obtained by melt-kneading multi-structure polymer A, polyamide resin, thermoplastic resin B, and thermoplastic resin C using a commercially available single-screw extruder or twin-screw extruder. However, at that time, ultraviolet absorbers, stabilizers, lubricants, fillers, reinforcing agents, dyes, pigments, etc. can be added as necessary. By injection molding or extrusion molding the composition of the present invention thus obtained, a molded product with all the six characteristics of weather resistance, impact resistance, solvent resistance, moisture resistance, heat resistance, and excellent appearance can be obtained. can get.

[0040]

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. 1. Preparation of sample for electron microscopy: The average diameter of the β portion and the average thickness of the α portion of the multistructure polymer of the present invention are measured as follows.

That is, the multi-structure polymer is kneaded with PMMA (Delpet <registered trademark>80N; manufactured by Asahi Kasei Corporation) using an AS-30, 30 mmφ twin-screw extruder manufactured by Nakatani Kikai Seisakusho. Next, an ultra-thin section of 0.5 mm square or less is prepared, and the surface is cut and finished using a diamond knife. This sample was exposed to the vapor of a 1% ruthenic acid aqueous solution for several hours in a closed container in a light-shielded state for staining.

When the composition is observed under 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, and the portion that is not stained with ruthenic acid is called the β portion and the outside of the β portion. The ring-shaped part surrounding the β layer and dyed with ruthenic acid is called the α part, and the small particles in the β part, which are dyed with ruthenic acid and dispersed in plurality, are called the γ part. 2. Average diameter (particle size) Average thickness: As mentioned above, samples cut from the molded product were stained with ruthenic acid, ultrathin sections were prepared using a transmission electron microscope (photo magnification: 100,000 times), and randomly selected. The diameters of 100 particles were measured and arithmetic averaged to obtain the average diameter (particle diameter).

At this time, if the particles cannot be regarded as spherical, the major axis and minor axis were determined, and the arithmetic average value was taken as the average major axis (particle diameter). The thickness was similarly measured for 100 randomly selected particles, and the average thickness was taken as the arithmetic mean. 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. 3. Swelling degree: Add 30 ml of methyl ethyl ketone to about 0.5 g of pellets, soak at 25°C for 24 hours, shake for 5 hours, and centrifuge at 5°C and 18,000 rpm for 1 hour. 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.

[0045]

[Math. 1] 4. Composition analysis: The acetone-soluble portion was obtained by pouring the supernatants (a) and (b) obtained from 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. 5. Tensile modulus: the insoluble part obtained by acetone fractionation is 1
A film is made by compression molding at 50°C, and the width is 1.
5±0.5mm, thickness 0.50±0.05mm, length 7
A 0 mm test piece was prepared.

[0046] Using a tensile tester, the gap distance was 50 mm.
, measured at a tensile speed of 50 mm/min. 6. Tensile strength and tensile elongation: Measured according to ASTM-D638. 7. Bending strength, bending elastic modulus: Measured according to ASTM-D790. 8. Izod impact strength: Measured according to ASTM-D256 (V-notch, 1/4" test piece). 9. Glossiness: 60 based on ASTM-D523-62T.
The degree of specular gloss was calculated based on the angle of incidence in degrees. 10. Vicat softening temperature: Measured by a method based on ASTM-D1525, and used as a measure of heat resistance. 11. Solvent resistance: 25 times the amount of methyl ethyl ketone (ME
After repeating the operation of immersing the resin composition of the present invention in K), shaking for 2 hours, and removing the supernatant with a centrifuge three times, the weight of the composition obtained by drying and the initial composition are The percentage by weight of MEK was defined as the MEK insoluble content (%), and was used as a measure of solvent resistance. 12. Moisture resistance: The weight of a molded article made of the resin composition of the present invention when sufficiently dried is W1, and the molded article is 80%
After 5 hours of immersion in hot water at 0.degree. C., the weight after thoroughly wiping off the water on the surface was taken as W2, and the water absorption rate was determined using the following formula, which was used as a measure of moisture resistance.

[0047]

[Math 2] 13. 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 Izod after 20 days of irradiation to the initial Izod was defined as the retention rate of Izod impact strength, and weather resistance was evaluated.

[0048]

[Example 1] (a) Production of multi-structure polymer A (1) Polymerization of the innermost layer of hard polymer (seed first stage), 248.3 parts by weight of ion-exchanged water, sodium dihexyl sulfosuccinate in the reactor After charging 0.05 parts by weight and thoroughly purging with nitrogen while stirring, the temperature is 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 addition, further add 0.01 part by weight of ammonium persulfate and then heat to 75°C.
The reaction was continued for 45 minutes. The polymerization rate was 99%. (2) Polymerization of the innermost layer of hard polymer (seed second stage), (
1/4 of the latex obtained in 1) (2.5 parts by weight in terms of solid content) was taken out, and further 186.2 parts by weight of ion-exchanged water,
After charging 0.03 parts by weight of sodium dihexyl sulfosuccinate into a reactor and thoroughly purging with nitrogen while stirring,
Raise the temperature to 75°C. After adding 0.02 parts by weight of ammonium persulfate to this reactor, 6 parts of methyl methacrylate was added.
．． A mixture of 0 parts by weight 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 complete the reaction. The polymerization rate was 98%. (3) Polymerization of acrylic acid ester crosslinked product (third stage polymerization), (second layer) 0.01 part by weight of ammonium persulfate and 0.05 part by weight of sodium dihexylsulfosuccinate in the presence of the latex of (2) After adding 1.5 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 70° C. over 80 minutes. After the addition was completed, the reaction was further continued at 70°C for 20 minutes. Polymerization rate through the first and second layers is 85%
Met. (4) Polymerization of rubber-like elastic body (4th stage polymerization), (3rd stage polymerization)
Layer) 0.045 parts by weight of ammonium persulfate and 0.45 parts by weight of sodium dihexylsulfosuccinate were added 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 layer (3). After addition,
A mixture of 3.8 parts by weight of acrylonitrile, 11.4 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%.

In addition, the amount of residual monomer in the latex was measured by gas chromatography, and the copolymerization composition ratio of the third layer was calculated.
The butyl acrylate ratio was 10/43/47, respectively. (5) Polymerization of final polymer (5th stage polymerization), (4th layer) In the presence of the latex of (4), acrylonitrile 2.
A mixture of 0.05 parts by weight, 8.86 parts by weight of styrene, and 0.02 parts by weight of t-dodecyl mercaptan was continuously added at 75° C. over 70 minutes. Furthermore, the reaction was continued at 85° C. for 1 hour to complete the polymerization. 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.
The butyl acrylate ratio was 24/65/11, 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-1. Obtained. (b) Production of thermoplastic resin B 21.5 parts by weight of acrylonitrile, 49.5 parts by weight of styrene, 1.0 parts by weight of maleic anhydride, 2 parts by weight of ethylbenzene
8 parts by weight and 300 ppm of t-butylperoxasiisopropyl carbonate as an initiator.
It was continuously supplied to a complete mixing type reactor with a capacity of 2.1 liters at a rate of liter/hr, and polymerization was carried out at 130°C. The polymerization solution is continuously led to a vented extruder and heated at 260°C.
Unreacted monomers and solvent were removed under the condition of 40 Torr, and the polymer was continuously cooled and solidified to obtain particulate thermoplastic resin B-1. It consists of 28.5% by weight of acrylonitrile units, 70.0% by weight of styrene units, and 1.5% by weight of maleic anhydride units according to an infrared absorption spectrum, and has an Mw of 165,800 and an Mw/Mn of 1.5% by GPC analysis. It was 1.86. (c) Preparation and evaluation of composition The above-mentioned multi-structure polymer A-1, polyamide resin [polycaprolactam (nylon-6) (trade name "Leona" (registered trademark) 2300, manufactured by Asahi Kasei Industries, Ltd.)], The thermoplastic resin B-1 and AS resin [(acrylonitrile-styrene copolymer) (acrylonitrile/styrene = 29/
71 weight ratio) Asahi Kasei Kogyo Co., Ltd. product name "Stylac"<registeredtrademark> AS-783)] was 35/4 in weight ratio.
After mixing for 20 minutes in a Henschel mixer at a ratio of 0/8/17, a 30 mm vented twin screw extruder (Nakatani Kikai)
Pelletization was carried out at 270° C. using Type A) manufactured by Co., Ltd.

[0051] 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 270°C and a mold temperature of 60°C. Physical properties were measured. The results are shown in Table 1. According to Table 1, it can be seen that the resin composition of the present invention has weather resistance, impact resistance, high rigidity, solvent resistance, moisture resistance, heat resistance, and excellent appearance. (d) Analysis of multi-structure polymers, etc.; (i) Staining with ruthenic acid and observation with an electron microscope: In addition, a test piece was prepared using the method described above, and an ultrathin section stained with ruthenic acid was prepared from the test piece. However, when observed with a transmission electron microscope, as shown in the schematic diagram in Figure 1, a state in which island phases 2 made of a multi-structure polymer are scattered in a sea phase 1 made of a thermoplastic resin is observed. .

[0052] The average particle diameter of the β part 4 that is not stained with ruthenic acid is 5,000 Å, and the whole island 2 (
The average particle diameter of the multi-structure polymer is 5,7000 Å, and the average thickness of the α part 3 dyed with ruthenic acid is 3.
It is 50 Å. In the β part 4 which was not stained with ruthenic acid, a plurality of parts (γ part) 5 which were stained with ruthenic acid were dispersed almost entirely microscopically.

[0053] Considering the characteristics of each hard polymer monomer, rubber elastic body monomer, and acrylic acid ester crosslinked monomer used to polymerize this multi-structure polymer, (a) β 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 curing agent unit, and (b) the α part 3 contains butyl acrylate, styrene, and acrylonitrile units for the rubber elastic body in the fourth stage polymerization, and the styrene and acrylonitrile units in the fifth stage polymerization. Styrene, acrylonitrile and residual butyl acrylate units for the final polymer are believed to be the main components. Furthermore, (c) the γ part 5 microscopically dispersed in the β part 4 is formed when a part of the hard component, mainly styrene, charged in the α part 3 flows into the β part 4 and polymerizes. It is thought that the This mechanism is only a guess, and the reason for this is not clearly clear. (ii) Swelling degree, tensile modulus: The swelling degree of the multilayer polymer with respect to methyl ethyl ketone was 3.5. The tensile modulus of the film was 2,500 Kg/cm2. (iii) Composition analysis: The results of composition analysis by pyrolysis gas chromatography were MMA 7.0% by weight, BA65
．． 9% by weight, St 20.0% by weight, and AN 7.1% by weight.

[0054]

[Comparative Example 1] (a) Production of multi-structure polymer (1) Polymerization of the hard polymer in the innermost layer (first stage of seeds) and (2) Polymerization of the hard polymer in the innermost layer (second stage of seeds) , except that 0.19 parts of allyl methacrylate was added, in the same manner as in Example 1. (3) Polymerization of acrylic acid ester crosslinked product (third stage polymerization) Ammonium persulfate 0.0.
13 parts by weight, sodium dihexyl sulfuccinate 0.0
After adding 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. Said (1
) to (3), the polymerization rate was 99.5%. (4) Polymerization of final polymer (4th stage polymerization), (3)
ammonium persulfate in the presence of latex of 0.045
Part by weight, sodium dihexyl sulfuccinate 0.045
After adding parts by weight, 6.75 parts by weight of acrylonitrile, 20.25 parts by weight of styrene, 0 parts by weight of t-dodecylmercaptan.
．． 045 parts by weight of the mixture were added continuously over 160 minutes at 75°C. 1 at 85°C to complete the polymerization.
The reaction continued for hours. The polymerization rate was 98%. In addition, as a result of measuring the amount of residual monomer in the latex by gas chromatography and calculating the copolymerization composition ratio of the fourth layer,
Acrylonitrile/styrene/butyl acrylate ratio is 2
It was 5/75/0. The latex thus obtained was subjected to the same treatment as in Example 1 to obtain a multi-structure polymer a-
I got 1. (b) Preparation and evaluation of composition Pellets were obtained in the same manner as in Example 1 except that the multistructure polymer a-1 was used, and then molded products were produced and their physical properties were evaluated. The results are shown in Table 1.

Furthermore, as a result of electron microscopic observation, as shown in the schematic diagram of FIG. 2, island phases 2 made of a multi-structure polymer are scattered in the sea phase 1 made of a thermoplastic resin. Phase 2
consists of two layers, the inner layer (β part) inside the particle has an average major diameter of 4,900 Å, and the outer layer (α part) surrounds the particle in a layered manner.
The average thickness of portion 3 was 340 Å. An independent spherical layer 6 with a diameter of 1,200 Å was observed in the β region 4, which was not present in Example 1 and was not stained with osmic acid. There were no micro-dispersed γ parts 5 in this spherical layer 6.

Combining Table 1 and the results of electron microscopy, it can be seen that when a grafting agent (crosslinking agent) is introduced during polymerization of the innermost hard polymer, an independent spherical layer exists, and γ It can be seen that the mechanical strength is low because the parts are not microdispersed.

[0057]

[Examples 2 and 3 and Comparative Examples 2 and 3] In Example 1,
Seed polymerization was continued by decreasing the amount of latex obtained in the first seed stage polymerization of the innermost layer hard polymer. Further, the amount of sodium dihexyl sulfosuccinate in the first seed stage was increased and seed polymerization was continued. The latex thus obtained was subjected to the same treatment as in Example 1 and evaluated. The results are listed in Table 1.

According to Table 1, when the average diameter of the β part and the average thickness of the α part are smaller than 2,000 Å and 10 Å, respectively, the gloss is excellent, but the mechanical strength is low;
, 500 Å, or 1,000 Å, the mechanical strength is excellent but the gloss is low.

[0059]

[Comparative Example 4] (a) Production of multi-structure polymer (1) Polymerization of crosslinked acrylic acid ester (first stage of seeds) 248.3 parts by weight of ion-exchanged water and 0.0 parts by weight of sodium dihexyl sulfosuccinate were placed in the reactor. After adding 05 parts by weight and thoroughly purging with nitrogen while stirring, the temperature was raised to an internal temperature of 75°C.
Make it. After adding 0.02 parts by weight of ammonium persulfate to this reactor, 5 parts by weight of a mixture of 10 parts by weight of butyl acrylate and 0.1 parts by weight of triallylisocyanurate as a crosslinking agent were added.
It was added continuously for 0 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. The polymerization rate was 99%. (2) Polymerization of acrylic acid ester crosslinked product (seed second stage), 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 replacement with stirring, the internal temperature was brought to 70°C. . After adding 0.01 parts by weight of ammonium persulfate to the reactor, 70 parts by weight of butyl acrylate was added.
5 parts by weight, 0 triallylisocyanurate as crosslinking agent
．． 67 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 11 parts by weight of unreacted butyl acrylate in the polymerization of (2),
In the presence of 0.18 parts by weight of triallylisocyanurate, after adding 0.045 parts by weight of ammonium persulfate and 0.45 parts by weight of sodium dihexylsulfuccinate, 3.8 parts by weight of acrylonitrile, 11.4 parts by weight of styrene, t
- 7 parts by weight of a mixture of 0.025 parts by weight of dodecyl mercaptan
Additions were made continuously over 90 minutes at 5°C. Polymerization rate is 93
%Met.

[0060] Furthermore, the amount of residual monomer in the latex was measured by gas chromatography, and the copolymerization composition ratio of the third layer was calculated.
The butyl acrylate ratio was 10/43/47, respectively. (4) Polymerization of the final polymer In the presence of the latex of (3), acrylonitrile 2.
A mixture of 0.05 parts by weight, 8.86 parts by weight of styrene, and 0.02 parts by weight of t-dodecyl mercaptan was continuously added at 75° C. over 70 minutes. Furthermore, the reaction was continued at 85° C. for 1 hour to complete the polymerization. The polymerization rate was 97%.

[0061] Furthermore, the amount of residual monomer in the latex was measured by gas chromatography, and the copolymerization composition ratio of the final polymer was calculated. As a result, the acrylonitrile/styrene/butyl acrylate ratio was 24/65/11, respectively. there were. The latex thus obtained was 3% by weight.
The mixture was poured into a hot aqueous solution of sodium sulfate for salting out and coagulation, followed by repeated dehydration and washing, followed by drying to obtain a multi-structure polymer a-2. (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 articles 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 and an alkyl acrylate has poor impact resistance and gloss.

[0063]

[Example 4] In Example 1, acrylonitrile-styrene-butyl acrylate copolymer (acrylonitrile/styrene/butyl acrylate = 2
7/63/10 weight ratio) (product name manufactured by Asahi Kasei Industries, Ltd.)
The same experiment was repeated except that Styrac (registered trademark) AS-T8704) was used, and various physical properties were evaluated. The results are shown in Table 2.

According to Table 2, it can be seen that the resin composition of the present invention has weather resistance, impact resistance, high rigidity, solvent resistance, moisture resistance, heat resistance, and excellent appearance.

[0065]

[Example 5] In Example 1, methacrylic resin (methyl methacrylate/methyl acrylate = 98/2 weight ratio) (product name "Delpet" manufactured by Asahi Kasei Industries, Ltd. <registered trademark) was used instead of AS resin. The same experiment was repeated except that a pressure of >80N) was used, and various physical properties were evaluated. Table 2 shows the results.
It was shown to.

According to Table 2, it can be seen that the resin composition of the present invention has weather resistance, impact resistance, high rigidity, solvent resistance, moisture resistance, heat resistance, and excellent appearance.

[0067]

[Example 6] Example 1 except that an acrylonitrile-styrene-N-phenylmaleimide copolymer (acrylonitrile/styrene/N-phenylmaleimide = 16/51/33 weight ratio) is used instead of the AS resin. The same experiment was repeated and various physical properties were evaluated. The results are shown in Table 2.

According to Table 2, it can be seen that the resin composition of the present invention has weather resistance, impact resistance, high rigidity, solvent resistance, moisture resistance, heat resistance, and excellent appearance.

[0069]

Comparative Example 5 The same experiment as in Example 1 was conducted except that triallyl isocyanurate as a crosslinking agent was not used in the polymerization of the acrylic ester crosslinked product of Example 1. It can be seen that the copolymer without triallylisocyanurate has an Izod impact strength of 5.1 Kgcm/cm, which is significantly inferior to the molded article of Example 1 in impact resistance. When observed by electron microscopy, α and β parts were not present.

[0070]

[Example 7] In Example 1, multi-structure polymer A-1,
The same experiment was repeated except that the weight ratios of polyamide resin, thermoplastic resin B-1, and AS resin were changed to 35/20/4/41, respectively, and various physical properties were evaluated. The results are shown in Table 3. According to Table 3, it can be seen that the resin composition of the present invention has weather resistance, impact resistance, high rigidity, solvent resistance, moisture resistance, heat resistance, and excellent appearance.

[0071]

[Comparative Example 6] In Example 1, only the multi-structure polymer A-1 and the polyamide resin were used, and the weight ratio was changed to 3.
Repeat the same experiment except for changing to 5/65,
Various physical properties were evaluated. The results are shown in Table 3. According to Table 3, it can be seen that the composition without thermoplastic resin B has significantly poor impact resistance.

[0072]

[Comparative Example 7] In Example 1, only polyamide resin and thermoplastic resin B-1 were used, and their weight ratio was 5.
Repeat the same experiment except for changing it to 0/50,
Various physical properties were evaluated. The results are shown in Table 3. According to Table 3, it can be seen that the impact resistance of the composition without the dual structure polymer A-1 is significantly poor.

[0073]

[Comparative Example 8] The same experiment as in Example 1 was repeated except that only the multi-structure polymer A-1 and thermoplastic resin B-1 were used and the weight ratio was changed to 35/65. , various physical properties were evaluated. The results are shown in Table 3. Table 3
According to the composition without polyamide resin, solvent resistance,
It can be seen that the heat resistance is significantly inferior.

[0074]

[Comparative Example 9] Same as Example 1 except that only the multi-structure polymer A-1, polyamide resin and thermoplastic B-1 were used and the weight ratio was changed to 50/5/45. The experiment was repeated and various physical properties were evaluated. The results are shown in Table 3. According to Table 3, the composite structure polymer A-1 is 40
It can be seen that when the content of the polyamide resin exceeds 10% by weight and is less than 10% by weight, the heat resistance and solvent resistance are poor.

[0075]

[Comparative Example 10] In Example 1, double structure polymer A-1
Except for using only polyamide resin and thermoplastic B-1 and changing the weight ratio to 5/30/65, respectively.
The same experiment was repeated and various physical properties were evaluated. The results are shown in Table 3. According to Table 3, the double structure polymer A-1 has 1
It can be seen that if the amount is less than 0% by weight, the impact resistance is significantly inferior.

[0076]

[Comparative Example 11] In Example 1, double structure polymer A-1
Except for using only polyamide resin and thermoplastic B-1, and changing the weight ratio to 10/85/5, respectively.
The same experiment was repeated and various physical properties were evaluated. The results are shown in Table 3. According to Table 3, it can be seen that when the polyamide resin exceeds 80% by weight, the water absorption rate is high and the moisture resistance is poor.

[0077]

[Comparative Example 12] (1) Production of ABS resin 70 parts by weight of polybutadiene rubber, 0.0 parts of dihexysulfuccinic acid ester
An aqueous emulsion containing 5 parts by weight of ammonium persulfate, 0.02 parts by weight of ammonium persulfate, and 200 parts by weight of ion-exchanged water was charged into a reactor, and the internal temperature was controlled at 75°C. Next, 30 parts by weight of a monomer mixture of 25% by weight of acrylonitrile and 75% by weight of styrene was added continuously over 2 hours, and after the addition was completed, polymerization was continued for an additional 2 hours to complete the graft co-existence. A polymer was obtained. The reaction rate was 98%. The weight ratio of acrylonitrile units to styrene units in this polymer was 25/75. Also, according to electron microscopy,
The average rubber particle diameter was 0.4 μm. (2) Preparation and Evaluation of Composition Pellets were obtained in the same manner as in Example 1 except that the above-mentioned graft copolymer was used, and then molded articles were produced and their physical properties were evaluated. The results are shown in Table 4.

According to Table 4, it can be seen that ABS resin has poor weather resistance.

[0079]

[Table 1]

[0080]

[Table 2]

[0081]

[Table 3]

[0082]

[Table 4]

[0083]

Effects of the Invention As explained above, the resin composition of the present invention has improved weather resistance compared to conventional ABS resins, etc., and has excellent solvent resistance, heat resistance, moisture resistance, and mechanical properties. An unprecedented new type of weather resistance that combines strength and excellent appearance.
It is an impact-resistant resin. This resin is suitable for a wide range of applications, including automotive parts such as automobile exterior panels and electronic parts, which require heat and solvent resistance, and especially for outdoor applications where conventionally painted products such as metal materials or ABS resin were used. It is an unpainted product that can be used for many years, and it plays a major role in these industries.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram of a transmission electron micrograph of an ultrathin section stained with ruthenic acid of a multilayer structure polymer according to the present invention and a thermoplastic resin composition containing the same.

FIG. 2 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. 3 is a schematic diagram showing an example of the particle shape of the multi-structure polymer of the present invention.

FIG. 4 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 α layer 4 β layer 5 γ layer 6. Independent layer

Claims (1)

[Claims] Claim 1: Multi-structure polymer A 10 to 80% by weight
A resin composition comprising 10 to 80% by weight of a polyamide resin, 1 to 80% by weight of a thermoplastic resin B, and 0 to 30% by weight of a thermoplastic resin C, wherein the composite structure polymer A
(a) 2 to 30 methacrylic acid alkyl ester units
Weight %, (b) Acrylic acid alkyl ester unit 50~
80% by weight, (c) 5-20% by weight of unsaturated nitrile units
, (d) A multi-structure polymer A consisting of 5 to 40% by weight of aromatic vinyl units and (e) 0.05 to 5% by weight of a polyfunctional crosslinking agent.
(a) a polymer (α portion) consisting of an unsaturated nitrile unit, an aromatic vinyl unit, and an acrylic acid alkyl ester unit;
and (b) a polymer (β portion) consisting of an acrylic acid alkyl ester unit, a methacrylic acid alkyl ester unit, and a polyfunctional crosslinking agent, and (c) an unsaturated nitrile unit, an aromatic vinyl unit, and an acrylic acid alkyl ester unit. It has multiple structures composed of polymers (γ part),
essentially particulate, (d) the β part is essentially particulate and has an average diameter of 2000 to 6500 Å;
The α part is a layer surrounding the β part and has an average layer thickness of 10 to 1000 Å, the γ part is essentially fine particles, and a plurality of particles are present dispersed in the β part, (e) 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 1000.
~10,000 Kg/cm2, and the thermoplastic resin B has 20 to 45 vinyl cyanide units.
wt% and aromatic vinyl units 75-55 wt% and α,β-
A thermoplastic resin consisting of 0.1 to 5.0% by weight of an unsaturated carboxylic anhydride and 0 to 30% by weight of one or more monomer units copolymerizable with these, and the thermoplastic resin C is
A weather-resistant and impact-resistant resin composition with excellent solvent resistance, which is a thermoplastic resin that can be made compatible with a multi-structure polymer A, a polyamide resin, and a thermoplastic B.