JPH051188A - Weather-and impact-resistant polymer composition excellent in oil resistance - Google Patents

Abstract

PURPOSE:To obtain a polymer composition having oil, weather, impact and heat resistance and fluidity and excellent appearance. CONSTITUTION:A polymer composition is obtained by blending (A) 10-50 wt.% spherical polymer of a complex structure composed of (A1) a spherical rubber- like polymer which is a mixture of an acrylic acid ester crosslinked polymer with a copolymer composed of methacrylic acid ester units and acrylic acid ester units and has <=-30 deg.C glass transition temperature, (A2) a copolymer, composed of aromatic vinyl units and unsaturated nitrile units and/or a copolymer, composed of the aromatic vinyl, the unsaturated nitrile and the acrylic acid ester units of the construction in the component (A1) and dispersed in the interior of the component (A1),and (A3) a copolymer, composed of the aromatic vinyl and the unsaturated nitrile and/or a copolymer, composed of the aromatic vinyl, the unsaturated nitrile and the acrylic acid ester of the construction in the component (A1) and surrounding the exterior of the component (A1) with (B) 90-50wt.% thermoplastic polymer composed of the unsaturated nitrile units, the aromatic vinyl units, etc.

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 acrylic acid ester-based rubber graft copolymer and a specific AS-based polymer. More specifically, the present invention relates to a polymer composition which has oil resistance, weather resistance, impact resistance, fluidity, heat resistance, and excellent appearance, or has excellent balance characteristics of these.

[0002]

2. Description of the Related Art ABS resin has excellent impact resistance, excellent balance of mechanical properties, and easy molding process.
It is widely used in the fields of automobiles, electric parts, etc. because of its relatively low price. On the other hand, however, ABS resin has a drawback in weather resistance because it uses polybutadiene as one of the constituents, and is not suitable for the field of outdoor use, and the weather resistance of ABS resin is remarkably improved. The advent of plastics has long been a desire.

Therefore, the present inventors have improved weather resistance and impact resistance by previously combining (a) a specific acrylic acid ester-based multilayer structure polymer and (b) a specific thermoplastic polymer. He found that he could do so and applied for a patent (Japanese Patent Application No. 1-320435). However, in Japanese Patent Application No. 1-320435 filed previously by the present inventors, when the amount of unsaturated nitrile units introduced is increased, the oil resistance is improved, but the impact resistance is significantly lowered. It turned out to do.

Further, in JP-A-2-155945, (a) a copolymer in which a vinyl cyanide compound and an aromatic vinyl compound are graft-copolymerized on a rubbery polymer,
(B) A resin composition comprising a copolymer of a vinyl cyanide compound and an aromatic vinyl compound, wherein the vinyl cyanide content in the composition is 35 to 50%, and the specific copolymer Compositions having a coalescing composition distribution are disclosed.

Although the composition of the publication is excellent in oil resistance and impact resistance, it is inferior in weather resistance and is limited in industrial use. That is, in this publication, regarding a graft copolymer having an acrylate ester rubber as an essential component, there is no technical disclosure about a method for obtaining a composition excellent in oil resistance, impact resistance, and weather resistance. Because not.

[0006]

SUMMARY OF THE INVENTION In view of the above situation, the present invention has no problems as described above, namely, oil resistance,
It is an object of the present invention to provide a polymer composition which has weather resistance, impact resistance, fluidity, heat resistance and excellent appearance, or which has an excellent balance of these properties.

[0007]

Means for Solving the Problems As a result of intensive investigations by the present inventors to improve the oil resistance and impact resistance of a polymer composition containing an acrylic ester-based rubber graft copolymer,
(A) (a) a specific copolymer composition, (b) a specific rubber particle diameter, and (c) an acrylic ester-based rubber graft copolymer (a double-structured polymer A) having a specific morphology, and (b) ) By combining an AS-based polymer (thermoplastic polymer B) having a specific copolymerization composition in a specific amount ratio,
Surprisingly, it has become possible to dramatically improve oil resistance, impact resistance and heat resistance while maintaining weather resistance, fluidity and excellent appearance, and the present invention has been achieved.

That is, the present invention is;
A polymer composition C comprising 50% by weight and 90 to 50% by weight of a thermoplastic polymer B, wherein the multi-structured polymer A is an essentially spherical crosslinked rubber body and has the following form: (A) a mixture of an acrylic acid ester cross-linked polymer and a copolymer composed of a methacrylic acid ester unit and an acrylic acid ester unit, which has a composition and has a glass transition temperature of -30 ° C or lower, Is a spherical rubbery polymer (α part),

(B) A polymer dispersed in the above-mentioned α portion, which is a copolymer comprising an aromatic vinyl unit and an unsaturated nitrile unit and / or an aromatic vinyl unit, an unsaturated nitrile unit and an α portion. A copolymer (β portion) composed of acrylic acid ester units constituting the polymer, and (c) a polymer which surrounds the outside of the α portion in a layered manner, the copolymer comprising an aromatic vinyl unit and an unsaturated nitrile unit, and And / or an aromatic vinyl unit, an unsaturated nitrile unit, and a copolymer (γ portion) composed of an acrylic acid ester unit constituting an α portion, and the copolymer composition thereof is

(A) Methacrylic acid ester unit 2-3
0% by weight, and (b) acrylic acid ester unit 50 to
80% by weight, and (C) unsaturated nitrile unit 5 to 3
0% by weight, and (d) aromatic vinyl unit 10 to 10
30% by weight, and the weight ratio of the unsaturated nitrile unit / the aromatic vinyl unit is 35/65 to 50/50.
Is a multi-structured polymer A which is

The average diameter of the essentially spherical α portion is 10
0 to 3,900 Å, the average layer thickness of the γ part surrounding the α part is 10 to 450 Å, and the average diameter of the entire particles of the double-structured polymer Å is 1,000 to 4,000 Å, (A) The degree of swelling of the acetone-insoluble portion with respect to (a) acetone is 1.5 to 10, and (b) the tensile modulus is 1,000.
A multi-structured polymer having a molecular weight of up to 10,000 kg / cm ² ,

The thermoplastic polymer B comprises 35 to 50% by weight of unsaturated nitrile units and 65 to 50% by weight of aromatic vinyl units.
And one or more monomer units 0 to 5 copolymerizable with them
The present invention provides a weather-resistant and impact-resistant polymer composition having excellent oil resistance, which is a thermoplastic polymer composed of 0% by weight.

The present invention will be described in detail below. The polymer composition of the present invention comprises: (a) a specific acrylic ester-based rubber graft copolymer (multi-structured polymer A; hereinafter referred to as polymer A); and (b) a specific thermoplastic polymer B ( Hereinafter referred to as Polymer B)) provides surprising advantages.

The reason for this will be described below. The polymer composition of the present invention comprises a rubber component (polymer A) and a resin component (mainly polymer B). In order to improve oil resistance and heat resistance, it is preferable that the content of the unsaturated nitrile monomer in the resin component, which is the acetone-soluble component of the composition, is large, but since the fluidity is remarkably reduced, in terms of balance, The unsaturated nitrile monomer should be 35 to 50% by weight.

When the unsaturated nitrile monomer is in the above range, the entanglement of the molecular chain is increased as compared with the low nitrile polymer of less than 35% by weight, resulting in impact resistance, especially tensile elongation. It was found that the ductility behaviour, while improving the strength and maintaining the rigidity. Furthermore, the present inventors have found that impact resistance is further improved by having a specific unsaturated nitrile composition distribution.

On the other hand, the polymer A, which is a rubber component, is an AS-based (unsaturated nitrile / aromatic vinyl-based) graft copolymer using an acrylic ester rubber from the viewpoint of weather resistance. In particular, the main mechanism of impact resistance expression is (a) it is important to have a morphology in which the AS-based polymer is dispersed inside the spherical rubber-like polymer, which apparently increases the rubber content, Improved impact resistance and rigidity,

(B) The compatibility with the resin component is improved by the content of the specific unsaturated nitrile monomer, and (c) the generation and propagation of crazes and the shear band are efficiently achieved by the specific rubber particle diameter. Based on the principle of generating.

In particular, in the case of a high nitrile polymer, it has been found that the oil resistance and the impact resistance are balanced only when the particle size is made smaller than the optimum particle size found by the present inventors in Japanese Patent Application No. 1-320435. ..

First, the polymer A (multi-structured polymer) will be referred to. (A) Composition of multi-structured polymer (polymer A); The multi-structured polymer in the present invention has compositionally (a) methacrylic acid alkyl ester unit, (b) acrylic acid alkyl ester unit, and (c) It is a multi-structured polymer composed of a saturated nitrile unit and (d) aromatic vinyl unit, and further containing (e) a polyfunctional crosslinking agent.

Examples of the (a) methacrylic acid alkyl ester unit constituting the double-structured polymer include methyl methacrylate, ethyl methacrylate, propyl methacrylate and the like, and methyl methacrylate is particularly preferably used. (B) Examples of the alkyl acrylate unit include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and the like, and butyl acrylate is preferably used.

Examples of (c) unsaturated nitrile units include acrylonitrile and methacrylonitrile, and acrylonitrile is preferably used. (D) Examples of the aromatic vinyl unit include styrene, α-methylstyrene, halogenated styrene, and the like, and styrene is preferably used.

Further, as the (e) polyfunctional crosslinking agent, C
= C crosslinkable monomer having at least two double bonds, and examples thereof include esters of triallyl isocyanurate and unsaturated alcohols such as triallyl cyanurate and triallyl isocyanurate; divinyl compounds such as divinylbenzene; diallyl. Compounds, dimethacryl compounds such as ethylene glycol dimethacrylate,
Although generally known crosslinking agents can be used, triallyl isocyanurate is preferably used.

(B) Composition ratio of multi-structured polymer (polymer A); On the other hand, the composition ratio of multi-structured polymer is basically
(A) Methacrylic acid alkyl ester unit 2 to 30% by weight, preferably 5 to 15% by weight, (b) acrylic acid alkyl ester unit 50 to 80% by weight, preferably 55 to
70 wt%, (c) unsaturated nitrile unit 5 to 30 wt%, preferably 6 to 20 wt%, (d) aromatic vinyl unit 10 to 30 wt%, preferably 8 to 25 wt% and (e) poly It is necessary that the functional crosslinking agent is 0.05 to 5% by weight.

If it deviates from this range, it is not preferable in terms of impact resistance. Furthermore, the weight ratio of unsaturated nitrile unit / aromatic vinyl unit is 35/65 to 50/50,
It is important that it is preferably 40/60 to 45/55. However, if it is out of this range, the compatibility with the polymer B is lowered and the impact resistance is remarkably lowered (see Examples 1 to 3 described later).
And Comparative Examples 8 and 9).

(C) Swelling degree of the double-structured polymer; the swelling degree of the acetone-insoluble portion with respect to acetone is 1.5 to 10,
Furthermore, the tensile and elastic modulus is 1,000 to 10,000 kg /
It must be cm ² . If it deviates from this range, it may be inferior in impact resistance, which is not preferable.

(D) Particle diameter of multi-structured polymer (Polymer A); Particle diameter of Polymer A (number average particle diameter) is 1,0
It must be in the range of 00 to 4,000Å. If it is less than 1,000 Å, the surface gloss is excellent, but the impact resistance is low. On the other hand, if it exceeds 4,000 Å, the oil resistance is excellent, but the surface gloss is inferior (Examples 1 and 4 described later). 5 and Comparative Examples 10 and 11).

(E) Fine structure of double-structured polymer: The double-structured polymer of the present invention has a structure in which β parts are dispersed in α parts, and the average diameter of the α parts is 100 to 3,900Å, It has a very special structure that the average thickness of the γ part covering the periphery is 10 to 450Å.

Due to this special structure, it is considered that the surface gloss is greatly improved while maintaining the impact resistance and the weather resistance. This was difficult to expect from the following composite structures that have been conventionally proposed.

On the other hand, in the method disclosed in Japanese Patent Publication No. 47-109811, when a grafting agent such as allyl methacrylate or a cross-linking agent is used during the polymerization of the hard polymer in the first step, , Α-part is a spherical first-stage (crossed) hard polymer which is not stained with osminic acid. More specifically, it is a multi-structured polymer including two regions, that is, a part in which small particles of β part are microscopically dispersed in α part and a spherical part in which β part does not exist at all (independent). In this case, the reduction of impact strength is a serious problem.

Therefore, in the multi-structured polymer of the present invention,
If the α part is not covered with the γ part, the impact resistance and weather resistance are inferior, and if the β part is not dispersed in the α part, the surface gloss and It is not possible to obtain one that satisfies the impact properties at the same time.

Further, the average diameter of the α part is 100 to 3,9.
It is necessary to have 00Å, and preferably 1,000 to
It is 2,000Å. If it is less than 100Å, the impact resistance is lowered, while if it exceeds 3,900Å, the surface gloss is lowered. Further, the average thickness of the γ portion covering the periphery of the α portion is 1
Need to be 0 ~ 450Å, preferably 100 ~ 300
It is Å. If it is less than 10Å, the compatibility with the polymer B is lowered and the impact resistance is poor. On the other hand, if it exceeds 450Å, the compatibility is improved and the two-phase system collapses and becomes the same as a single substance. Is reduced.

In the multi-structured polymer of the present invention, in order to disperse a plurality of β parts in the α part as a whole, the composition of α part, the molecular weight, the crosslink density and the distance between crosslink points should be proper. is necessary. In the double-structured polymer of the present invention, the β part being dispersed in the α part means a state in which a plurality of small particles of the β part are relatively uniformly dispersed in the entire α part. Therefore,
It is said that the conventional composite structure having two regions, that is, a portion in which small particles of β portion are dispersed in α portion and a spherical portion in which β portion does not exist at all (independent), is dispersed. I can not say.

As a mode in which the β portion is dispersed in the α portion, it is preferable that the β portion is dispersed in the entire α portion, but the embodiment is not limited thereto. The number of small particles in the β-part is not particularly limited, and may be any number, but it is more preferable that a relatively large number of particles are uniformly dispersed. Further, it is preferable that the sizes of the small particles in the β portion are relatively uniform, but there may be some variations.

The double-structured polymer of the present invention itself, the α part, the β
The part also has a substantially spherical shape, and the γ part exists as a layer surrounding the spherical α part. The shape of these particles is not limited as long as the object of the present invention is achieved.

Taking the α part as an example, a representative preferable form thereof is essentially spherical. When the α-part is spherical, observing the cross-sectional shape of the double-structured polymer shows that the γ-part 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 elliptical shape having a major axis or a minor axis, a kidney shape, or a gourd shape, as shown in the cross-sectional shape of FIG. Alternatively, it may have a shape as shown in FIG. Further, the shape is not necessarily symmetrical and may be indefinite.

The γ portion preferably surrounds the entire α portion, but the α portion may be partially exposed at a portion where the γ portion does not exist. It is more preferable that the variation in the thickness of the α portion is small.

(F) Method for producing double-structured polymer: The method for producing a double-structured polymer of the present invention comprises a known emulsion polymerization method carried out in the presence of a monomer, an emulsifier, a polymerization initiator, a chain transfer agent and the like. It is advantageous to use. Further, in order to form such a double-structured polymer, it is advantageous to use a seed polymerization method capable of forming a double-structured polymer by sequentially adding and reacting each monomer or monomer mixture. Is.

A typical example of the method for producing the double-structured polymer of the present invention is specifically shown below. <First Stage Polymerization> Methacrylic acid alkyl ester 2 to
30% by weight and acrylic acid alkyl ester 1 to 6% by weight
The monomer mixture liquid of (1) is polymerized with an emulsifier and a polymerization initiator at a monomer / water ratio of 0.3 to 1.0. If a crosslinking agent or a graft crossing agent is used at this stage, the impact resistance becomes low.

<Second-stage polymerization> A part of the seed latex obtained in the first stage can be used for polymerization in the same monomer mixture as in the first stage to control the particle size. .. This second-stage polymerization can be omitted. <Third stage polymerization> Alkyl acrylate 45-
A monomer liquid 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 2 to 10% by weight Aromatic vinyl 4 to 8% by weight Crosslinking agent 0.005 to 0.5% by weight Monomer liquid Is emulsion polymerized with an emulsifier and a polymerization initiator.

<Fifth Stage Polymerization> Acrylic acid alkyl ester 0 to 2 wt% unsaturated nitrile 1 to 20 wt% aromatic vinyl 3 to 38 wt% A monomer solution is emulsion-polymerized together with an emulsifier and a polymerization initiator.

At this time, when carrying out the third and subsequent polymerizations, it is necessary to select conditions that suppress the formation of new particles as much as possible. It can be realized by making the concentration less than the micelle concentration. Further, the presence or absence of new particle generation can be confirmed by observation with an electron microscope.

Further, in order to control the particle diameter (diameter) of each layer of the multi-structured polymer within a specific range, one of the seed latex of the hard polymer (those obtained by the first-stage polymerization) of the innermost layer is used. It is possible to adjust the amount of seed latex to be taken out and control the number of particles of the seed latex when continuing to carry out the seed polymerization by taking out a part and adding ion-exchanged water, an emulsifier and a monomer.

To control the degree of swelling within a specific range,
It can be carried out depending on the amount of the crosslinking agent added. That is, when the degree of swelling is decreased, the amount of the crosslinking agent is increased, while when the degree of swelling is increased, it is decreased.

Suitable 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. in each polymerization step.

The emulsifier used in the polymerization is not particularly limited, and any emulsifier conventionally used can be selected. For example, C ₂ -C ₂₂ carboxylic acids, C ₆ -C ₂₂ alcohols or sulfonates of alkylphenols, anionic emulsifiers, nonionic emulsifiers in which alkylene oxides are added to aliphatic amines or amides, or quaternary ammonium-containing compounds. Examples of such cationic emulsifiers include long-chain alkylcarboxylic acid salts and alkylbenzene sulfonic acid salts.

The polymerization initiator used at this time is not particularly limited, and examples thereof include water-soluble peroxides such as alkali metal salts and ammonium salts of persulfate: inorganic initiators such as perborate salts. An azo compound such as hydrogen peroxide or azobisbutyronitrile may be used alone or in combination with a sulfite or thiosulfate as a redox initiator. Further, redox initiators such as oil-soluble organic peroxide / ferrous salt and organic peroxide / sodium sulfoxylate can be used.

Further, as the chain transfer agent used,
alkyl mercaptans such as t-dodecyl mercaptan,
Toluene, xylene, chloroform, halogenated hydrocarbon and the like can be mentioned.

The monomer may be added all at once, but it is preferable to add the monomer in several times or continuously add it. In that case, a polymerization reaction can be controlled and overheating and solidification can be prevented.

In order to advantageously produce the multi-structured polymer of the present invention, each layer may be subjected to a method adjusted as follows. The formation of the rubber-like elastic body may be carried out by completing the polymerization reaction of the acrylic acid ester crosslinked body and then successively polymerizing it by adding the monomer for the rubbery elastic body, or by completing the polymerization of the acrylic acid ester crosslinked body. Without doing so, unsaturated nitrile (c), aromatic vinyl (d), etc. may be added to form the rubber-like elastic body while leaving the unreacted monomer.

(G) Others: The multi-structured polymer having a special structure obtained by such a polymerization method is subjected to treatments such as salting out, washing and drying by a known method from the state of the polymer latex. , As a particulate solid. Such a double-structured polymer is usually
Since it can be obtained as a mixture of a pure double-structured polymer itself which is insoluble in a solvent such as acetone and a polymer which is soluble in a solvent such as acetone and which is not grafted, the double-structured polymer referred to here includes the double-structured polymer. The combination itself and a mixture of the multi-structured polymer and the non-grafted polymer are included.

The double-structured polymer having a special structure of the present invention can be basically obtained by the polymerization method described in (f) above. The characteristics of the polymer obtained at each polymerization step are:
The polymer obtained by the first-stage and second-stage polymerization plays a role of increasing the elastic modulus of the double-structured polymer, and is important in the sense of determining the final particle size of the double-structured polymer in the sheet polymerization. is there.

In particular, when a grafting agent or a crosslinking agent is present during the first-stage polymerization, only a double-structured polymer having low impact resistance can be obtained (formed by the first-stage and second-stage polymerizations). The layer is referred to as the first layer.).

The acrylic acid ester crosslinked product obtained mainly by the third stage polymerization serves to impart impact strength (the layer formed by this polymerization is referred to as the second layer). The rubber-like elastic body mainly obtained by the fourth-stage polymerization is composed of the hard polymer of the first-second polymerization and the acrylic polymer cross-linked body of the third-stage polymerization and the final polymer. And plays a role of improving the adhesiveness (the layer formed by this polymerization is referred to as a third layer).
The final polymer obtained by the final-stage 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 polymer B is composed of an unsaturated nitrile unit, an aromatic vinyl unit, and one or more monomer units copolymerizable with them. Here, the unsaturated nitrile as an essential component is acrylonitrile, methacrylonitrile or the like, and acrylonitrile is particularly preferable, but a copolymer mainly containing acrylonitrile and containing methacrylonitrile may be used.

Another essential component, aromatic vinyl, is styrene, α-methylstyrene, paramethylstyrene, p
-Chlorostyrene, p-bromostyrene, 2,4,5-
Tribromostyrene and the like are preferable, and styrene is most preferable, but a copolymer obtained by mixing styrene as a main component with the other aromatic vinyl may be used.

As the component of the polymer B, at least one monomer component copolymerizable with unsaturated nitrile and aromatic vinyl may be introduced. When it is necessary to further improve the blendability with the polymer A or to reduce the melt viscosity at the time of blending, an acrylate ester composed of an alkyl group having 1 to 8 carbon atoms can be used. Further, when it is necessary to enhance the heat resistance of the sheet, it is selected from monomers such as acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleimide.

The unsaturated nitrile unit in the composition of the polymer B is 35 to 50% by weight, preferably 40 to 45% by weight, and the aromatic vinyl unit is 65 to 50% by weight, preferably 60 to 55% by weight. The one or more copolymerizable monomer units must be in the range of 0 to 50% by weight, and outside this range, oil resistance, heat resistance, fluidity and impact resistance cannot be balanced.

That is, when the unsaturated nitrile unit is less than 35% by weight, the effect of improving oil resistance and heat resistance is small, which is 5
When it exceeds 0% by weight, the fluidity is remarkably lowered (see Examples 1, 6, 7 and Comparative Examples 12, 13 described later).

As the distribution of the unsaturated nitrile unit in the composition of the polymer B, the half value width D defined in the general formula (I) is preferably 0.01 to 10% by weight, more preferably 0.01 to It is 5% by weight. General formula (I); D = Σdi (where di is the half value width of the peak height of peak i by nitrile analysis by liquid chromatography, as shown in FIG. 1, and D is D It is the sum of the half width of each peak.)

When D exceeds 10% by weight, the compatibility with the polymer A is lowered and the impact resistance is remarkably lowered. On the other hand, D
Is less than 0.01% by weight, the fluidity is lowered (see Examples 1, 8 and 9 described later). And this polymer B is manufactured by the usual method of solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization. The copolymer composition can be controlled by changing the composition of the charged monomers.

When acrylonitrile is used as the unsaturated nitrile monomer and styrene is used as the aromatic vinyl monomer, a specific compounding composition (azeotropic composition) can be obtained at 25% by weight of acrylonitrile. Generally, in a high nitrile polymer, the composition distribution is widened because the composition is largely deviated from the azeotropic composition.

Therefore, in order to form a narrow composition distribution having a half-value width D of 10% by weight or less, for example, in continuous solution polymerization, polymerization is carried out at a uniform temperature and a uniform copolymerization composition in a complete mixing reactor. ..

The polymer composition C of the present invention also contains the polymer A.
It is possible to add a compatible polymer to B and B. Thereby, a special function can be given to the molded product. For example, methacrylic resin imparts scratch resistance, vinyl cyanide-aromatic vinyl-acrylic acid ester copolymer imparts fluidity, and vinyl cyanide-aromatic vinyl-N-substituted maleimide copolymer imparts heat resistance. The polycarbonate resin imparts heat resistance and impact resistance, and the vinyl chloride resin imparts flame retardancy.

Regarding the amount ratio of the polymer A and the polymer B constituting the polymer composition C of the present invention, A is 10 to 50% by weight, preferably 30 to 40% by weight, and B is 90 to 50% by weight. %, Preferably 70 to 60% by weight. Outside the above range, impact resistance, rigidity, oil resistance and heat resistance cannot be balanced. That is, when the content of the polymer A is less than 10% by weight, there is no effect of improving the impact resistance, and when it exceeds 50% by weight, the rigidity, oil resistance and heat resistance are deteriorated (see Examples 1, 10, 11 and Comparative Examples described later). See Examples 14-16).

The polymer composition C of the present invention can be obtained by melt-kneading each of the above polymers with a commercially available single-screw extruder or a twin-screw extruder, in which case an ultraviolet absorber, a stabilizer, Lubricants, fillers, reinforcing materials, dyes, pigments and the like can be added as necessary.

The composition of the present invention thus obtained is combined with oil resistance, weather resistance, impact resistance, fluidity and excellent appearance by, for example, injection molding or extrusion molding, or Thus, a molded product in which those properties are balanced is obtained.

[0068]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. The measurements in Examples and Comparative Examples were performed using the following methods or measuring instruments. Preparation of sample for electron microscope; average diameter of α layer and average thickness of γ layer of the multilayer structure polymer of the present invention are measured as follows. That is, the multi-layer structure polymer is treated with PMMA (delpet 8
0N: Asahi Kasei Co., Ltd. AS-3 manufactured by Nakatani Kikai Seisakusho
Knead with a 0,30 mmφ twin-screw extruder. Next, 0.5m
An ultrathin section of m square or less is prepared, and the surface is cut with a diamond knife to finish. This sample in a closed container,
It was exposed to the vapor of a 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 is composed of a portion which is stained with ruthenium and a portion which is not stained with ruthenium acid. The ring-shaped α-layer is surrounded by a ring and the portion stained with ruthenic acid is the γ-layer, and the small particles in the α-layer stained with ruthenic acid and a plurality of dispersed small particles are the β-layer.

Average diameter (particle diameter), average thickness: As described above, a transmission electron micrograph (photograph magnification: 100,000 times) of an ultrathin section obtained by staining a sample cut from a molded article with ruthenic acid was prepared. The diameter of 100 randomly selected particles is measured, and the arithmetic mean is used to calculate the average diameter (particle diameter).
And At this time, when the particles cannot be regarded as spherical, the major axis and the minor axis thereof were determined, and the value obtained by arithmetically averaging was defined as the average diameter (particle diameter).

The thickness was also randomly selected 1
The measurement was performed on 00 particles, and the average was calculated to obtain the average thickness. At this time, when the thickness is uneven, the maximum thickness and the minimum thickness were measured, and the value obtained by arithmetical averaging was taken as the thickness.

Swelling degree: 30 ml of acetone is added to about 0.5 g of pellets, immersed at 25 ° C. for 24 hours, shaken for 5 hours, and centrifuged at 5 ° C. and 18,000 rpm for 1 hour. After removing the supernatant liquid by decantation, 30 ml of acetone was newly added, and the mixture was shaken at 25 ° C. for 1 hour, and 5
Centrifuge at 18,000 rpm for 1 hour. The supernatant is removed and the weight is weighed (W ₁ ). Then 100
Vacuum dry at 2 ° C. for 2 hours and weigh the residue (W ₂ ).

The degree of swelling is calculated by the following formula.

[Equation 1]

Compositional analysis: The acetone-soluble portion was obtained by pouring the supernatant obtained by the acetone separation into a large amount of methanol and vacuum-drying the precipitate. For the acetone-insoluble portion, a sample obtained by acetone fractionation was used. The composition of each sample was analyzed by pyrolysis gas chromatography.

Unsaturated nitrile distribution (composition distribution) of polymer B; analyzed by developing the CN group in polymer B with a filler having a nitrile (CN) bond using liquid chromatography. Specifically, LC-6A manufactured by Shimadzu Corporation was used as liquid chromatography, and ZorbaxCN manufactured by DuPont was used as a column.
The mixed solvent of heptane was used as a mobile phase and developed at 45 ° C.
The distribution of nitrile was measured from the absorption value at a wavelength of 254 nm with a V detector.

The determination of the nitrile content and distribution in the sample is performed, for example, by preparing a calibration curve using an AS resin (acrylonitrile-styrene copolymer) whose nitrile content is known in advance, and based on the calibration curve. Calculated. A nitrile distribution chart is shown in FIG. When a parallel line was drawn from the midpoint of the height of the peak to the baseline, the line segment cut off by the peak was defined as the half-width and used as a measure of the distribution of unsaturated nitrile. When there are a plurality of peaks, the general formula (I)
Is used, the sum D of the half widths di of each peak is used. General formula (I); D = Σdi

Tensile elastic modulus (acetone insoluble part): The insoluble part obtained by acetone fractionation was compression molded at 150 ° C. to prepare a film, from which a width of 15 ± 0.5 mm, a thickness of 0.50 ± 0.05 mm, A test piece having a length of 70 mm was produced. The measurement was performed using a tensile tester at a chuck distance of 50 mm and a pulling speed of 50 mm / min.

Surface gloss; ASTM-D523-62
Based on T, the specular glossiness at an incident angle of 60 degrees was calculated. Weather resistance: 6 using a Suga Test Instruments Co., Ltd. depanel optical control weather meter (DPWL-5 type)
Irradiation was carried out at 0 ° C., and a weather resistance accelerating test was carried out at 40 ° C. in a cycle of wet condensation. The percentage of the ratio between the physical property value after 20 days irradiation and the initial value was defined as the physical property retention rate, and the weather resistance was evaluated. Here, the physical properties evaluated for weather resistance are Izod impact strength, tensile elongation, and gloss.

Tensile Strength, Tensile Elongation: Measured by the method according to ASTM-D638. (10) Flexural strength and flexural modulus: Measured by a method according to ASTM-D790. (11) Izod impact strength: Measured by a method according to ASTM-D256 (V notch, 1/4 "test piece).

(12) Melt flow rate (MFR): Measured by a method in accordance with ASTM-D1238 as an index of fluidity. 10 under load of 10kg and melting temperature of 220 ℃
It was determined from the extrusion rate per minute (g / 10 minutes). (13) Oil resistance; the weight of a molded article made of the polymer composition of the present invention when fully dried is W ₃ , and the molded article is 23
After dipping in gasoline at 20 ° C. for 20 hours, the surface gasoline was sufficiently wiped off, and the weight was taken as W _4, and the oil absorption rate was calculated by the following formula and used as a scale of oil resistance.

[0081]

[Equation 2] (14) Vicat softening temperature: Measured by a method according to ASTM-D1525 and used as a measure of heat resistance.

[0082]

Example 1 (a) Production of polymer A (1) Polymerization of hard polymer in the innermost layer (first layer), 248.3 parts by weight of ion-exchanged water in a reactor, sodium hexylsulfosuccinate 1.00 After adding parts by weight and thoroughly performing nitrogen substitution with stirring, the temperature is raised to an internal temperature of 75 ° C.
After adding 0.02 parts by weight of ammonium persulfate to this reactor, 8 parts by weight of methyl methacrylate and 2 parts of butyl acrylate were added.
Parts by weight of the mixture were added continuously over 50 minutes. After the addition, the reaction was continued at 75 ° C. for 45 minutes. Polymerization rate is 99
%Met.

(2) Polymerization of acrylic acid ester cross-linked product (second stage polymerization), (second layer): Ammonium persulfate of 0.1% in the presence of the latex of (1).
01 parts by weight, sodium dihexyl sulfosuccinate 0.
After adding 05 parts by weight, a mixture of 63 parts by weight of butyl acrylate and 0.6 parts by weight of triallyl isocyanurate as a crosslinking agent was continuously added at 70 ° C. for 80 minutes. After the addition was completed, the reaction was continued at 70 ° C. for 20 minutes. First
The rate of polymerization through the layer and the second layer was 85%.

(3) Polymerization of rubber-like elastic material (third stage polymerization), (third layer); 11 parts by weight of butyl acrylate unreacted in the polymerization of (2),
In the presence of 0.18 parts by weight of triallyl isocyanurate, after adding 0.045 parts by weight of ammonium persulfate and 0.45 part by weight of sodium dihexylsulfosuccinate, 6.8 parts by weight of acrylonitrile, 8.4 parts by weight of styrene,
A mixture of 0.025 parts by weight of t-dodecyl mercaptan was continuously added at 75 ° C over 90 minutes. Polymerization rate is 9
It was 3%.

Further, the amount of residual monomers in the latex was measured by gas chromatography to calculate the copolymerization composition ratio of the third layer. As a result, acrylonitrile / styrene /
The butyl acrylate ratio was 18/25/47, respectively.

(4) Polymerization of final polymer (4th stage polymerization), (4th layer); In the presence of the latex of (3), acrylonitrile 5.
A mixture of 3 parts by weight, 6.5 parts by weight of styrene and 0.02 part by weight of t-dodecyl mercaptan was continuously added at 75 ° C. over 70 minutes. To further complete the polymerization, 8
The reaction was continued for 1 hour at 5 ° C. The polymerization rate was 97%.

The amount of residual monomers in the latex was measured by gas chromatography to calculate the copolymerization composition ratio of the fourth layer. As a result, acrylonitrile / styrene /
The butyl acrylate ratio was 41/48/11, respectively.

The latex thus obtained was mixed with 3
Pour into a warm wt% sodium sulfate aqueous solution, salt out and coagulate, then repeat dehydration and washing, then dry,
Polymer A-1 was obtained. When the polymer ratio of acrylonitrile and styrene was determined by thermal decomposition gas chromatography using the polymer A-1 obtained here, it was 43/57. In addition, other analysis results are shown in Table 2.

(B) Morphology of multi-structured polymer (Polymer A) (i) Staining with ruthenic acid and electron microscopic observation: Further, a test piece was prepared by the method described above, and stained with ruthenic acid from the test piece. When an ultrathin section was prepared and observed with a transmission electron microscope, as shown in the schematic view of FIG.
A state in which island phases 2 made of a multi-structured polymer are scattered in a sea phase 1 made of a thermoplastic resin is observed.

The average particle size of the α portion 4 which is not dyed with ruthenic acid is 1,800Å, and the entire island 2
(Compound structure polymer) has an average particle diameter of 2,100Å,
The average thickness of the γ part 3 dyed with ruthenic acid is 15
It is 0Å. Α part 4 not stained with ruthenic acid
In, a plurality of portions (β portion) 5 stained with ruthenic acid were dispersed almost entirely.

Considering the characteristics of each monomer for the hard polymer, the monomer for the rubber elastic body, and the monomer for the acrylic acid ester cross-linking body used for polymerizing the multi-structured polymer, (a) α part Part 4 is composed of a butyl acrylate for a hard polymer by the first polymerization, a methyl methacrylate unit, and a butyl acrylate for a cross-linked acrylic ester by the second polymerization, a crosslinking agent or a grafting agent unit. Thought to be the main ingredient,

(B) The γ part 3 is composed of butyl acrylate, styrene and acrylonitrile units for the rubber elastic body obtained by the third stage polymerization, and styrene and acrylonitrile for the final polymer obtained by the fourth stage polymerization. The remaining butyl acrylate units are believed to be the major component. further,
(C) It is considered that the β portion 5 dispersed in the α portion 4 is formed by the polymerization of a part of the hard component such as styrene mainly charged in the γ portion 3 into the α portion 4 for polymerization. Be done.

(C) Production of Polymer B 28.4 parts by weight of acrylonitrile, 42.6 parts by weight of styrene, 29 parts by weight of ethylbenzene and t as an initiator.
-Butyl-peroxyisopropyl carbonate 300
The mixed solution of ppm is 2.1 L at a rate of 1.9 L / hr.
Was continuously fed to the completely mixed reactor of Example 1 to carry out polymerization at 130 ° C. The polymerization liquid is continuously guided to the extruder with a vent,
Unreacted monomer and solvent were removed under the conditions of 260 ° C. and 40 Torr, and the polymer was continuously cooled and solidified to obtain a particulate polymer B-1.

It consisted of 40.0% by weight of acrylonitrile units and 60.0% by weight of styrene units. When the average composition and distribution of acrylonitrile of this polymer were determined by liquid chromatography, the average acrylonitrile content was 40.0% by weight, and the full width at half maximum of the peak was 2.5% by weight.

(D) Preparation and Evaluation of Composition The weight ratio of the polymer A-1 and the polymer B-1 is 35/65.
After mixing for 20 minutes with a Henschel mixer at the ratio of
Twin screw extruder with 30mm vent (Nakaya Machinery Co., Ltd., A
The pellets obtained by performing pelletization at 260 ° C. using an in-line screw injection molding machine (manufactured by Toshiba Machine Co., Ltd., IS-75S type) at a molding temperature of 2
Predetermined test pieces were prepared under the conditions of 60 ° C. and mold temperature of 60 ° C., and physical properties were measured. The results are shown in Table 1. Table 1
According to the above, it is understood that the polymer composition of the present invention has weather resistance, impact resistance, rigidity, heat resistance, oil resistance and excellent appearance.

[0096]

[Comparative Example 1] (Low nitrile AAS resin) (a) Production of double-structured polymer (1) Polymerization of hard polymer in innermost layer (first stage of seed) 248.3 parts by weight of ion-exchanged water in a reactor, After charging 0.05 part by weight of sodium dihexyl sulfosuccinate and thoroughly performing nitrogen substitution with stirring, the temperature was raised to an internal temperature of 75 ° C.
To After 0.02 part by weight of ammonium persulfate was added 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 99%
Met.

(2) Polymerization of hard polymer in innermost layer (second stage of seed) 1/4 (2.5 parts by weight in terms of solid content) of the latex obtained in (1) was taken out, and further ion-exchanged water 186. 2 parts by weight and 0.03 part by weight of sodium dihexyl sulfosuccinate are charged into a reactor, and nitrogen replacement is sufficiently performed with stirring, and then the temperature is raised to an internal temperature of 75 ° C. After adding 0.02 part 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 complete the reaction. The polymerization rate was 98%.

(3) Polymerization of acrylic acid ester crosslinked product (third stage polymerization), (second layer) In the presence of the latex of (2), 0.01 parts by weight of ammonium persulfate and sodium dihexyl succinate. After adding 0.05 part by weight, a mixture of 63 parts by weight of butyl acrylate and 0.6 part by weight of triallyl isocyanurate as a crosslinking agent was continuously added at 70 ° C. for 80 minutes. After the addition was completed, the reaction was 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 material (fourth stage polymerization) (third layer) 11 parts by weight of butyl acrylate not reacted in the polymerization of (3),
In the presence of 0.18 part by weight of triallyl isocyanurate, after addition of 0.045 part by weight of ammonium peroxide and 0.45 part by weight of sodium dihexylsulfosuccinate, 3.8 parts by weight of acrylonitrile, 11.4 parts by weight of styrene, A mixture of 0.025 parts by weight of t-dodecyl mercaptan was continuously added at 75 ° C over 90 minutes. The polymerization rate was 93%.

Further, the residual monomer amount in the latex was measured by gas chromatography to calculate the copolymerization composition ratio of the third layer. As a result, the acrylonitrile / styrene / butyl acrylate ratio was 10/43/47, respectively. It was

(5) Polymerization of final polymer (fifth stage polymerization), (fourth layer) In the presence of the latex of (4), acrylonitrile 2.
A mixture of 95 parts by weight, 8.86 parts by weight of styrene and 0.02 part by weight of t-dodecyl mercaptan was continuously added at 75 ° C. over 70 minutes. The reaction was continued for 1 hour at 85 ° C. to complete the polymerization. The polymerization rate was 97%.

The amount of residual monomer in the latex was measured by gas chromatography to calculate the copolymerization composition ratio of the fourth layer. As a result, acrylonitrile / styrene /
The butyl acrylate ratio was 24/65/11, respectively. The latex thus obtained was put into a 3% by weight hot aqueous solution of sodium sulfate for salting out and coagulation,
Then, after dehydration and washing are repeated, the polymer a is dried.
-1 was obtained.

Using the polymer a-1 thus obtained, the weight ratio of acrylonitrile and styrene was determined by pyrolysis gas chromatography to be 3.26 / 74. The average particle size of the polymer a-1 was 5,000Å.

(B) Polymer b-1 AS resin [(acrylonitrile-styrene copolymer)
(Acrylonitrile / styrene = 29/71 weight ratio) The product name "Styrac" (registered trademark> AS-783) manufactured by Asahi Kasei Kogyo Co., Ltd.] is referred to as a polymer b-1, and the distribution of this acrylonitrile is determined. Half-width is 2.
It was 3% by weight.

(C) Preparation and Evaluation of Composition In Example 1, instead of the polymers A-1 and B-1,
Other than using the polymers a-1 and b-1, respectively,
After obtaining pellets in the same manner as in Example 1, a molded product was prepared and the physical properties were evaluated. The results are shown in Tables 1-2. According to Tables 1-2, acrylonitrile content is 35% by weight
It can be seen that the low nitrile AAS resin of less than 1 is inferior in oil resistance and heat resistance.

[0106]

Comparative Example 2 (High Nitrile AAS Resin-Large Particle Diameter Rubber) (a) Production of Double-Structured Polymer In the production of the polymer a-1 of Comparative Example 1, the fourth stage and the fifth stage The same experiment was repeated, except that the amount ratio of acrylonitrile and styrene in the polymerization was changed as follows:
Polymer a-2 was obtained.

(4) Polymerization of elastic body for rubber (4th stage polymerization) (third layer) Modification Acrylonitrile 3.8 parts by weight 6.8 parts by weight Styrene 11.4 parts by weight 8.4 parts by weight (5) Polymerization of final polymer (fifth stage polymerization) (fourth layer) Modified acrylonitrile 2.95 parts by weight → 5.3 parts by weight Styrene 8.86 parts by weight → 6.51 parts by weight

Using the polymer a-2 thus obtained, the weight ratio of acrylonitrile and styrene was determined by pyrolysis gas chromatography to be 3.44 / 56. The average particle size of the polymer a-2 was 5,300Å.

(B) Preparation and Evaluation of Composition After preparing pellets in the same manner as in Example 1 except that the polymer a-2 was used instead of the polymer A-1, A molded product was prepared and its physical properties were evaluated. The results are shown in Tables 1-2. From Tables 1 and 2, it can be seen that even with a high nitrile AAS resin having an acrylonitrile content of 35 to 50% by weight, when the average particle diameter of the polymer A exceeds 4,000 Å, the impact resistance is significantly lowered.

[0110]

[Comparative Example 3] (Low nitrile ABS resin) Instead of the polymer composition of Example 1, an ABS resin (acrylonitrile content of 225% by weight) [Asahi Kasei Co., Ltd. trade name <Styrac-ABS> registered trade name <200 >] Was used to manufacture a molded product in the same manner as in Example 1, and the physical properties were evaluated. The results are shown in Tables 1-2. The average acrylonitrile content of the acetone-soluble component in the composition was 25.1% by weight, and the full width at half maximum was 3.2% by weight. From Tables 1 and 2, it can be seen that the ABS resin having a low nitrile content is inferior in weather resistance and oil resistance.

[0111]

Comparative Example 4 (High Nitrile ABS Resin) (a) Production of Polymer a Polybutadiene rubber (weight average particle diameter 3,000Å) 16 parts by weight of rubber solid content, 100 parts by weight of deionized water, potassium rosinate 1. 0 part by weight was placed in a polymerization tank equipped with a reflux condenser, and the gas phase was heated to 70 ° C. while substituting with nitrogen. 33.6 parts by weight of acrylonitrile, 50.4 parts by weight of styrene, 0.1 part by weight of cumene hydroperoxide, t-
A mixed solution of 0.85 parts by weight of dodecyl mercaptan, and 50 parts by weight of deionized exchanged water, 0.2 parts by weight of sodium formaldehyde sulfoxylate, and 0.004 of ferrous sulfur.
Parts by weight, sodium ethylenediaminetetraacetate 0.0
A solution in which 4 parts by weight was dissolved was continuously added and reacted for 6 hours. During this period, the temperature of the polymerization system was controlled at 70 ° C., and after the additional addition was completed, the state was maintained for 1 hour to complete the polymerization. To the obtained copolymer latex,
1.3 parts by weight of magnesium sulfate was added to coagulate and wash,
After dehydration, it was dried with hot air at 90 ° C to obtain a resin powder (polymer a-3).

(B) Preparation and evaluation of composition Except that the polymer a-3 is used as the polymer A,
After obtaining pellets in the same manner as in Example 1, a molded product was prepared and the physical properties were evaluated. The results are shown in Table 1. According to Table 1, it can be seen that the ABS resin has poor weather resistance.

[0113]

[Table 1]

[0114]

[Table 2]

[0115]

[Comparative Example 5] (a) Production of a double-structured polymer (1) The polymerization of the hard polymer of the innermost layer was carried out in the same manner as in Example 1 except that 0.19 part by weight of allyl methacrylate was added. It was (2) Polymerization of acrylic acid ester crosslinked product (second-stage polymerization) Ammonium persulfate was added in the presence of the latex of (1).
13 parts by weight, sodium dihexyl succinate 0.0
After adding 5 parts by weight, a mixture of 63 parts by weight of butyl acrylate and 0.6 part by weight of triallyl isocyanurate as a crosslinking agent was continuously added at 80 ° C. for 80 minutes. After the addition was completed, the reaction was continued at 80 ° C. for 90 minutes. Through the polymerizations of (1) and (2), the polymerization rate was 99.5%.

(3) Polymerization of final polymer (third stage polymerization) Ammonium persulfate was added in the presence of the latex of (2).
045 parts by weight, sodium dihexyl succinate 0.
After adding 045 parts by weight, a mixture of 12.15 parts by weight of acrylonitrile, 14.8 parts by weight of styrene and 0.045 parts by weight of t-dodecylmercaptan was continuously added at 75 ° C. over 160 minutes. Furthermore, in order to complete the polymerization,
The reaction was continued at 85 ° C for 1 hour. The polymerization rate was 98%. The amount of residual monomer in the latex was measured by gas chromatography to calculate the copolymerization composition ratio of the fourth layer. As a result, the acrylonitrile / styrene / butyl acrylate ratio was 40/60/0, respectively. The latex thus obtained was treated in the same manner as in Example 1 to obtain a polymer a-4.

(B) Morphology of the multi-structured polymer (polymer a-4) As a result of electron microscopic observation, as shown in the schematic view of FIG. 3, the multi-structured polymer was contained in the sea phase 1 made of a thermoplastic resin. Are dispersed in an island phase 2. The island phase 2 is composed of two layers and has an average diameter of an inner layer (α portion) portion 4 inside the particle 1.
The thickness was 900 Å, and the average thickness of the outer layer (γ portion) portion 3 surrounded by layers was 140 Å. Not present in α part 4 in Example 1, not stained with osmic acid, diameter 450
An independent spherical layer 6 of Å was observed. There was no β portion 5 dispersed in this spherical layer 6.

(C) Preparation and Evaluation of Composition After obtaining pellets in the same manner as in Example 1 except that the above-mentioned double-structured polymer a-4 was used, a molded product was prepared and the physical properties were evaluated. The results are shown in Tables 3-4. In summary of Tables 3 to 4 and the results of electron microscope observation, when a grafting agent (crosslinking agent) was introduced during the polymerization of the hard polymer of the innermost layer, an independent spherical layer was present, and β was present in this spherical layer. It can be seen that the mechanical strength is low because the parts are not dispersed.

[0119]

[Comparative Example 6] (a) Production of double-structured polymer (1) Polymerization of cross-linked acrylic ester ester 248.3 parts by weight of ion-exchanged water and 1.05 part by weight of sodium dihexylsulfosuccinate were charged in a reactor and stirred. After sufficiently replacing the lower nitrogen, raise the temperature to 70 ° C.
To After adding 0.02 part by weight of ammonium persulfate to this reactor, a mixture of 73 parts by weight of butyl acrylate and 0.68 parts by weight of triallyl isocyanurate as a crosslinking agent was continuously added over 80 minutes. After the addition is completed, 70 ℃
The reaction was continued for 20 minutes. The polymerization rate was 85%.

(2) Polymerization of rubber-like elastic material 11 parts by weight of butyl acrylate not reacted in the polymerization of (1),
In the presence of 0.18 parts by weight of triallyl isocyanurate, after adding 0.045 parts by weight of ammonium persulfate and 0.45 parts by weight of sodium dihexyl succinate, 6.8 parts by weight of acrylonitrile, 8.4 parts by weight of styrene, t
-Dodecyl mercaptan 0.025 parts by weight of the mixture 7 parts
It was added continuously at 5 ° C over 90 minutes. Polymerization rate is 93
%Met.

The amount of residual monomer in the latex was measured by gas chromatography to calculate the copolymerization composition ratio of the third layer. As a result, acrylonitrile / styrene /
The butyl acrylate ratio was 19/24/47, respectively.

(3) Polymerization of the final polymer In the presence of the latex of (2), acrylonitrile
A mixture of 3 parts by weight, 6.5 parts by weight of styrene and 0.02 part by weight of t-dodecyl mercaptan was continuously added at 75 ° C. over 70 minutes. 85 to further complete the polymerization
The reaction was continued for 1 hour at ℃. The polymerization rate was 97%.

The amount of residual monomers in the latex was measured by gas chromatography to calculate the copolymerization composition ratio of the final polymer. As a result, the acrylonitrile / styrene / butyl acrylate ratio was 42/47/11, respectively. It was

The latex thus obtained was mixed with 3
Pour into a warm wt% sodium sulfate aqueous solution to salt out and coagulate, then repeat dehydration and washing, then dry,
A multi-structured polymer a-5 was obtained.

(B) Preparation and Evaluation of Composition After obtaining pellets in the same manner as in Example 1 except that the above-mentioned double-structured polymer a-5 was used, a molded product was prepared and the physical properties were evaluated. The results are shown in Tables 3-4. According to Tables 3 to 4, it can be seen that the polymer composition using the double-layered polymer without the hard polymer in the innermost layer composed of the methacrylic acid alkyl ester and the acrylic acid alkyl ester is inferior in impact resistance and gloss.

[0126]

[Table 3]

[0127]

[Table 4]

[0128]

Comparative Example 7 The same experiment as in Example 1 was carried out except that the crosslinking agent triallyl isocyanurate was not used in the polymerization of the acrylic ester crosslinked product of Example 1. The copolymer having no triallyl isocyanurate has an Izod impact strength of 2.9 Kgcm / cm, which shows that the impact resistance is significantly inferior to that of the molded product of Example 1. When observed by an electron microscope, the γ part and the α part were not present.

[0129]

Examples 1 to 3 and Comparative Examples 8 to 9 (Effect of Composition Ratio of Acrylonitrile and Styrene of Polymer A) In the production of the polymer A-1 of Example 1, the copolymerization ratio of acrylonitrile and styrene In order to obtain a different polymer A, acrylonitrile was added during (3) polymerization of the rubber-like elastic body (third stage polymerization) and (4) polymerization of the final polymer (fourth stage polymerization). Seed polymerization was carried out by changing the composition of styrene. The latex thus obtained was treated in the same manner as in Example 1 to prepare a polymer composition by using the polymer A obtained here in place of the polymer A-1, and the evaluation was made. did. The results are shown in Tables 5-6.

[0130]

[Table 5]

[0131]

[Table 6]

According to Tables 5 and 6, the acrylonitrile / styrene weight ratio of polymer A was 35/65 to 50/50.
It can be seen that good impact resistance is exhibited only within the range.

[0133]

Examples 1, 4, 5 and Comparative Examples 10, 11 (Effect of Particle Diameter of Polymer A) Polymer A-1 of Example 1
In the production of, a polymer A having the same copolymer composition as A-1 but different particle diameter was obtained. For that purpose, during the polymerization of the hard polymer of the innermost layer, the amount of sodium dihexyl sulfosuccinate is increased and the seed polymerization is continued to
-1 or make the particles smaller than -1, or divide the polymerization of the hard polymer in the innermost layer into two stages, take out a part of the latex obtained in the first stage polymerization, add ion-exchanged water, an emulsifier, and a monomer. And continue the second stage seed polymerization. At that time,
The amount of seed latex taken out was adjusted to limit the number of particles of the seed latex to make the particles larger than A-1.

The latex thus obtained was treated in the same manner as in Example 1, except that the polymer A-1 was replaced by the polymer A-1.
Using the polymer A obtained here, a polymer composition was prepared and evaluated. The results are shown in Table 7.

[0135]

[Table 7]

According to Table 7, when the particle diameter is less than 1,000 Å, the gloss is excellent, but the impact resistance is poor. On the other hand, when it exceeds 4,000 Å, the oil resistance is excellent, but the impact resistance is low. It turns out that the gloss is inferior.

[0137]

Examples 1, 6, 7 and Comparative Examples 12, 13 (Effect of composition ratio of acrylonitrile and styrene of polymer B) In the production of the polymer B-1 of Example 1, different acrylonitrile and styrene were used. In order to obtain the polymer B having a copolymerization composition, polymerization was performed while changing the composition of the charged monomers. Using the polymer B thus obtained in place of the polymer B-1 of Example 1, the same experiment as in Example 1 was conducted and evaluated. The results are shown in Tables 8-9.

[0138]

[Table 8]

[0139]

[Table 9]

From Tables 8 to 9, it can be seen that good impact resistance, oil resistance and heat resistance are exhibited only when the weight ratio of acrylonitrile / styrene is in the range of 35/65 to 50/50.

[0141]

Examples 1, 8 and 9 (Effect of Distribution of Acrylonitrile Monomer of Polymer B) In the production of the polymer B-1 of Example 1, the composition of the monomers charged was changed to obtain acrylonitrile and styrene. Polymers having different copolymer compositions were prepared. Then, a plurality of the above polymers are mixed so that the average content of acrylonitrile is 4
Polymers differing only in the distribution of acrylonitrile were obtained at 0% by weight.

The polymer thus obtained was used in Example 1.
The same experiment as in Example 1 was conducted and evaluated by using the polymer B-1 instead of the polymer B-1. The results are shown in Tables 10-11.

[0143]

[Table 10]

[0144]

[Table 11]

From Tables 10 to 11, it can be seen that the impact resistance is lowered when the half width of the peak exceeds 10% by weight.

[0146]

Examples 1, 10, 11 and Comparative Examples 14, 15, 16 (Effect of Composition Ratio of Polymers A and B) Polymer A of Example 1
-1 and B-1 are mixed to prepare a polymer composition,
evaluated. The results are shown in Tables 12 to 13.

[0147]

[Table 12]

[0148]

[Table 13] According to Tables 12 to 13, the polymer A is 10 to 50% by weight,
It can be seen that impact resistance, rigidity, heat resistance and oil resistance are balanced only when the content of the polymer B is in the range of 90 to 50% by weight.

[0150]

As described above, the polymer composition of the present invention has improved weather resistance as compared with conventional ABS resins and the like, and has oil resistance, heat resistance, impact resistance, rigidity and It is an unprecedented new weather resistant and impact resistant polymer composition having excellent appearance.

This composition is used for a wide range of applications such as automobile parts and electronic parts which are required to have heat resistance, oil resistance, impact resistance, etc., especially for outdoor use which has conventionally been applied with coated materials such as metal materials or ABS resin. It can be used unpainted for various purposes and plays a major role in these industries.

[Brief description of drawings]

FIG. 1 is a liquid chromatography chart showing the composition distribution of unsaturated nitrile in an unsaturated nitrile / aromatic vinyl copolymer.

FIG. 2 is a schematic view of a transmission electron microscope photograph of a ruthenic acid-stained ultrathin section of a multilayer structure polymer according to the present invention and a thermoplastic resin composition containing the same.

FIG. 3 is a schematic diagram of a transmission electron microscope photograph of a ruthenic acid-stained ultrathin section of a multilayer structure polymer and a thermoplastic resin containing the same according to a comparative example.

FIG. 4 is a schematic view showing an example of the particle shape of the double-structured polymer of the present invention.

FIG. 5 is a schematic view showing an example of the particle shape of the double-structured polymer of the present invention.

[Explanation of symbols]

 1 Sea phase 2 Island phase 3 γ layer 4 α layer 5 β layer 6 Independent layer d Half-width

Claims (1)

Claim: What is claimed is: 1. A polymer composition C comprising 10 to 50% by weight of a double-structured polymer A and 90 to 50% by weight of a thermoplastic polymer B. Is an essentially spherical crosslinked rubber body having the following morphology and composition:
(A) A mixture of an acrylic acid ester crosslinked polymer and a copolymer composed of a methacrylic acid ester unit and an acrylic acid ester unit, which has a glass transition temperature of −30 ° C. or lower and is essentially spherical. Rubbery polymer (α part)
And (b) a polymer dispersed inside the α portion, which is a copolymer comprising an aromatic vinyl unit and an unsaturated nitrile unit and / or constitutes an aromatic vinyl unit, an unsaturated nitrile unit and an α portion. And (c) a polymer that surrounds the outside of the α portion in a layered manner, the copolymer comprising an aromatic vinyl unit and an unsaturated nitrile unit, and Or a copolymer (γ part) composed of an aromatic vinyl unit, an unsaturated nitrile unit and an acrylic acid ester unit constituting an α part, and the copolymerization composition thereof is (a) a methacrylic acid ester unit.
~ 30 wt% and (b) acrylic acid ester unit 50 ~
80% by weight, and (c) unsaturated nitrile unit 5 to
30% by weight, and (d) aromatic vinyl unit 10
To 30% by weight of the unsaturated nitrile unit /
The weight ratio with the aromatic vinyl unit is 35/65 to 50 /
In the multi-structured polymer A of 50, the average diameter of the essentially spherical α portion is 100 to 3,900 Å, and the average layer thickness of the γ portion surrounding this α portion is 10 to 450 Å,
And the average diameter of the entire particles of the multi-structured polymer A is 100
0 to 4,000Å, which is insoluble in acetone,
The degree of swelling in acetone is 1.5 to 10, and (b)
A thermoplastic polymer B having a tensile elastic modulus of 1,000 to 10,000 kg / cm ² and containing 35 to 50% by weight of an unsaturated nitrile unit and 6 units of an aromatic vinyl unit.
It is a thermoplastic polymer composed of 5 to 50% by weight and 0 to 50% by weight of one or more kinds of monomer units copolymerizable therewith, and is excellent in oil resistance, weather resistance and impact resistance. Polymer composition.