JPH04325536A - Weather-and impact-resistant polymer composition of excellent appearance - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in weathering resistance, impact resistance, rigidity and appearance when oriented. CONSTITUTION:A polymer composition comprising a complex structure polymer comprising an acrylic ester rubber specified in copolymer composition, morphology, particle diameter, particle diameter distribution and degree of swelling and an acrylonitrile/styrene copolymer of a specified composition. Because this composition excels in weathering resistance, impact resistance, rigidity and appearance when oriented, it is desirable in the fields of injection molding for outdoor use such as automobile components and electronic components or in the fields of sheets and films for electronic devices and housing equipment.

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 polymer composition comprising a novel acrylic ester rubber. More specifically, the present invention relates to a weather-resistant and impact-resistant polymer composition comprising an acrylic ester rubber that has weather resistance, impact resistance, high rigidity, and excellent appearance when oriented.

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 weather resistance is improved by this method, on the other hand, impact resistance and appearance of molded products are deteriorated, and problems remain in practical use.

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. Therefore, the present inventors first attempted to improve weather resistance and impact resistance by combining (a) a specific acrylic ester multilayer structure polymer and (b) a specific thermoplastic polymer. He discovered this and filed an application (Japanese Patent Application No. 1-320435). However, when a molded article is produced from the polymer composition of the publication under low orientation conditions, although the above advantages are produced, the highly oriented molded article produced by a high-speed injection molding machine or the stretched sheet and film have a pearly tone (pearlescent luster). ), which caused a problem of loss of product value.

[0006] Against this background, the present inventors have conducted intensive studies to improve the pearlescent tone of high-speed injection molded products or stretched sheets and films. The conclusion was reached that it was caused by interference of reflected light. The mechanism will be explained based on FIG. In a non-stretched (non-oriented) state, light is diffusely reflected on the surface of the rubber particles and no interference occurs, but in a stretched (orientated) state, the rubber particles become flat and the diffused reflection is reduced. By the way, in general, acrylic ester rubber is soft and easily deformed, and the refractive index of the rubber (for example, that of butyl polyacrylate is 1.47) and the refractive index of the matrix resin (for example, AS-based rubber are 1.47). There is a large difference from that of resin (1.57).

For this reason, the reflection of the incident light on the surface of the rubber particle significantly exceeds the transmission, and as a result, interference occurs between the surface of the rubber particle and the light reflected on the inner surface of the rubber particle.
It has a pearl color. Therefore, as conventional techniques for reducing the above-mentioned interference, there are known methods of (a) reducing the refractive index difference between the rubber particles and the matrix resin, and (b) increasing the hardness of the rubber particles to prevent deformation. .

Regarding the above method (a), methacrylic resin with a low refractive index (refractive index 1.49) is added to the AS resin (acrylonitrile-styrene resin) as the matrix resin.
It is known to blend. For example,
JP-A-54737 discloses the use of methacrylic resin as a matrix resin in acrylic ester rubber. Although this method reduces interference and improves pearl color upon stretching, impact resistance is significantly reduced.

Regarding the above method (b), for example, JP-A-2-292351 discloses a resin composition containing acrylic ester rubber particles having a three-layer structure, and the rubber particles are The inner layer includes a hard crosslinked resin layer, a highly crosslinked acrylic acid ester polymer layer thereon, and an AS graft polymer layer thereon. In this method, by increasing the hardness of the rubber particles, there is less deformation and the pearl color tone is improved, but the impact resistance is significantly lowered.

[0010] Therefore, the present inventors investigated ways to improve the pearl color tone during orientation, and found that by making the rubber particles smaller, reflection and interference within the same particle were reduced, so that the pearl color tone was eliminated. I discovered that. However, due to the reduction in particle size, the craze generation and propagation ability was poor, and the impact resistance was significantly lowered.

[0011] As a result of intensive studies to overcome the above-mentioned drawbacks, and to find a composition that has excellent weather resistance and impact resistance, and does not exhibit a pearl color tone during orientation, the present inventors found that (a) and (b) specific Copolymer composition, (b) specific morphology, (c)
Combining a multi-structure polymer made of an acrylic ester rubber having a specific particle diameter, a specific particle diameter distribution, and (d) a specific degree of swelling, and (b) an AS polymer having a specific copolymer composition. As a result, surprisingly, it has become possible to eliminate the pearlescent tone and dramatically improve the appearance while maintaining weather resistance and impact resistance, and the present invention has been achieved.

On the other hand, regarding a resin made of acrylic ester rubber having a wide rubber particle diameter distribution similar to the present invention, for example, Japanese Patent Application Laid-open No. 63-202644 discloses,
A graft polymer in which a vinyl aromatic monomer, ethylenically unsaturated nitrile, and methyl methacrylate are grafted onto an acrylic acid ester rubber core, and the particle size of the graft copolymer is high gloss consisting of large particles and small particles. Acrylate rubber modified weathering resins are disclosed. Although the polymer disclosed in this publication has excellent gloss and impact resistance, because it does not contain a hard resin layer in the acrylic ester rubber, the rubber particles are significantly deformed during stretching, resulting in a pearlescent color. Problems remain.

[0013]

[Problems to be Solved by the Invention] In view of the current situation, the present invention has been developed to avoid the above-mentioned problems, that is, to achieve weather resistance,
The present invention relates to a weather-resistant, impact-resistant polymer composition that has both impact resistance and excellent appearance when oriented.

[0014]

[Means for Solving the Problems] That is, the present invention provides a polymer comprising 10 to 80% by weight of a multi-structure polymer A (Polymer A) and 90 to 20% by weight of a thermoplastic polymer B (Polymer B). (a) a composite composition in which the multistructure polymer A is essentially a spherical crosslinked rubber body and has the following form and composition;
A mixture of an acrylic ester crosslinked polymer and a copolymer consisting of methacrylic ester units and acrylic ester units, which is essentially a spherical rubbery polymer having a glass transition temperature of -30°C or lower. (b) a polymer dispersed within the α portion, the copolymer consisting of an aromatic vinyl unit and an unsaturated nitrile unit and/or an aromatic vinyl unit and an unsaturated nitrile unit; and α
(c) a copolymer consisting of acrylic acid ester units constituting the part (β part), and (c) a polymer surrounding the outside of the α part in a layered manner,
A copolymer consisting of an aromatic vinyl unit and an unsaturated nitrile unit and/or a copolymer consisting of an aromatic vinyl unit, an unsaturated nitrile unit, and an acrylic ester unit constituting the α part (γ part), The copolymerization composition is (a)
2 to 30% by weight of methacrylic ester units, (b) 50 to 80% of acrylic ester units, and (c) 5 to 20 unsaturated nitrile units.
Weight% and (d) aromatic vinyl units
A multi-structure polymer A consisting of 5 to 40% by weight,
Essentially, the average diameter of the spherical α portion is 1900 to 590
0 Å, and the average layer thickness of the γ part surrounding this α part is 10~
1000 Å, and the number average particle diameter defined in general formula [I] as the average diameter of the entire particle of the multi-structure polymer A

[0015]

[Equation 4] is 2000 to 6000 Å, and the particle diameter distribution ratio defined in general formula [II] as the particle diameter distribution

00
16]

[Math 5] is 1.0 to 3.0,

[0017]

(Here, ni is the number of particles of the polymer A having a particle diameter Di.) and (a) the degree of swelling in acetone (SwI) of the acetone-insoluble portion is 4 to 9, and ( (b) A multi-structure polymer having a tensile modulus of 1,000 to 10,000 kg/cm2, and the thermoplastic polymer B is (a)
A thermoplastic polymer consisting of 20 to 45% by weight of unsaturated nitrile units, (b) 80 to 55% by weight of aromatic vinyl units, and (c) 0 to 30% by weight of one or more monomer units copolymerizable with these. A weather-resistant and impact-resistant polymer composition is provided.

The present invention will be explained in detail below. The polymer composition of the present invention comprises acrylic acid having (a) (b) a specific copolymer composition, (b) a specific morphology, (c) a specific particle diameter and its distribution, and (d) a specific degree of swelling. By combining a multi-structure polymer made of ester rubber (hereinafter referred to as polymer A) and (b) an AS type polymer having a specific copolymer composition (hereinafter referred to as polymer B). , resulting in amazing benefits. First, polymer A (multi-structure polymer) will be mentioned.

(a) Composition of the multi-structure polymer; The multi-structure polymer in the present invention is composed of (a) methacrylic acid alkyl ester units, (b) acrylic acid alkyl ester units, and (c) unsaturated nitrile. It is a multi-structure polymer composed of (d) aromatic vinyl units and (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) as the polyfunctional crosslinking agent, C
=C A crosslinkable monomer having at least two double bonds, such as esters of triallyl isocyanurate and unsaturated alcohols such as triallyl cyanurate and triallyl isocyanurate; divinyl compounds such as divinylbenzene; diallyl compounds, such as dimethacrylic compounds such as ethylene glycol dimethacrylate,
Although commonly known crosslinking agents can be used, triallylisocyanurate is preferably used.

(b) Composition ratio of the multi-structure polymer: 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 30% by weight.
15% by weight, (b) 5 acrylic acid alkyl ester units
0 to 80% by weight, preferably 55 to 70% by weight, (c)
5-20% by weight of unsaturated nitrile units, preferably 6-1
0% by weight, (d) 5 to 40% by weight, preferably 8 to 35% by weight of aromatic vinyl units, and (e) 0.0 polyfunctional crosslinking agent.
It is necessary that the amount is 5 to 5% by weight. If it deviates from this range, it is unfavorable in terms of impact resistance.

(c) Swelling degree (SwI) of the multi-structure polymer;
From the viewpoint of impact resistance and pearlescent appearance, the swelling degree (S
wI) is 4 to 9, and the tensile modulus is 1,000 to
It is essential that it be 10,000 kg/cm2. When the degree of swelling (SwI) is less than 4, the deformation of the rubber particles is suppressed and the pearl color tone is eliminated, but the impact resistance is greatly reduced. On the other hand, if it exceeds 9, the deformation of the rubber particles becomes noticeable, which not only promotes the pearlescent tone but also reduces the impact resistance (Examples 1, 7, 8, 9 and Comparative Example 8 described later). , 9).

(d) Particle diameter and its distribution of the multi-structure polymer; Furthermore, from the viewpoint of balance between impact resistance and appearance without pearlescent color, the number average particle diameter defined in general formula [I]

[0025]

[Equation 7] is 2000 to 6000 Å, preferably 3000 to 50
00 Å and the particle diameter distribution ratio defined in general formula [II]

[0026]

It is very important that .function..times..times..times..times..times..times..times..times..times..times..times..times..times..times..times..times..times..times..times..times..times..times..times..times..times..times..times..times..times..

[0027]

[Equation 9] (Here, Ni is the number of particles of the polymer A having a particle diameter Di.) Number average particle diameter

[0028]

[Formula 10] However, if the thickness is less than 2000 Å, the pearl tone is eliminated, but
Impact resistance is low, and on the other hand, if it exceeds 6000 Å, the pearlescent color is noticeable (see Examples 1, 2, and 3, and Comparative Examples 4 and 5, which will be described later). In addition, particle diameter distribution rate

[0029]

When [Equation 11] is less than 1.0, the impact resistance is poor; on the other hand, when it is 3.0
If it exceeds this amount, weather resistance, appearance during orientation, and impact resistance will deteriorate. In other words,

[0030]

Impact resistance is achieved only when [Equation 12] is in the range of 1.0 to 3.0. This is probably because the rubber particles enter and form a special close-packed structure, and in addition, a craze interaction between large particles and small particles occurs (Examples 1, 4, 5, 6 and comparison described below). Example 6,
(see 7).

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

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

[0033] Therefore, in the multi-structure polymer of the present invention,
If the α part is not covered with the γ part, a product with poor impact resistance and weather resistance will be obtained, and if the β part is not dispersed in the α part, the surface gloss and resistance will be poor. It is not possible to obtain a product that satisfies impact resistance at the same time. Furthermore, the average diameter of the α part needs to be 1900 to 5900 Å, preferably 3000 to 4000 Å. If it is less than 1900 Å, the impact resistance will decrease, while if it exceeds 5900 Å, the surface gloss will decrease.

[0034] Furthermore, the average thickness of the γ portion surrounding the α portion must be 10 to 1000 Å, preferably 20 Å.
It is 0 to 500 Å. If it is less than 10 Å, the compatibility with polymer B decreases, resulting in poor impact resistance. On the other hand, if it exceeds 1000 Å, the compatibility improves, the two-phase system collapses, and it becomes similar to a single substance, resulting in poor impact resistance. Sexuality decreases. In the multi-structure polymer of the present invention, in order to disperse a plurality of β parts in the α part, it is necessary to make the composition, molecular weight, crosslinking density, and distance between crosslinking points of the α part appropriate. It is.

In the multi-structure polymer of the present invention, the term "β part dispersed in the α part" refers to a state in which a plurality of small particles of the β part are dispersed relatively evenly throughout the α part. Therefore,
If the above-mentioned conventional composite structure contains two regions, the α part has small particles of the β part dispersed therein, and the (independent) spherical part where the β part does not exist at all, it is considered to be dispersed. I can not say. As a mode in which the β part is dispersed in the above α part, α
Although it is preferable that the β portion be dispersed throughout the entire portion, the present invention is not limited thereto. Further, the number of small particles in the β portion is not particularly limited, and may be any number, but it is more preferable that a relatively large number of small particles are uniformly dispersed.

Further, although it is preferable that the small particles in the β portion are relatively uniform in size, there may be some variation. The multi-structure polymer itself of the present invention also has α
The shape of both the part and the β part is essentially spherical, and the γ part exists as a layer surrounding the spherical α part. The shape of these particles is not limited in any way as long as the object of the present invention is achieved.

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

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

<First stage polymerization> A monomer mixture of 2 to 30% by weight of alkyl methacrylate and 1 to 6% by weight of alkyl acrylate is mixed with an emulsifier and a polymerization initiator at a monomer/water ratio of 0.3 to 1. Polymerizes at .0. In addition,
If a crosslinking agent or grafting agent is used at this stage,
Impact resistance decreases.

<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> A monomer solution containing 45 to 70% by weight of an acrylic acid alkyl ester and 0.05 to 5% by weight of a crosslinking agent is emulsion polymerized together with an emulsifier and a polymerization initiator.

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

<Fifth stage polymerization> Acrylic acid alkyl ester 0 to 2% by weight Aromatic vinyl 1 to 16% by weight Unsaturated nitrile 3 to 38% by weight of the monomer liquid is mixed with an emulsifier,
Emulsion polymerization is carried out together with a polymerization initiator.

At this time, when performing the third and subsequent polymerizations, it is necessary to select conditions that suppress the generation of new particles as much as possible, but for this purpose, the amount of emulsifier used must be controlled 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.

[0045] In order to control the particle diameter distribution, which is important for developing impact resistance, within a specific range, the polymers A having different particle diameters produced by the above method are mixed in a latex state or a molten state. It can depend on things such as. Furthermore, the degree of swelling (SwI), which is important for achieving a balance between impact resistance and appearance without pearlescent color, can be controlled within a specific range by changing the amount of crosslinking agent added. That is, when decreasing the degree of swelling, the amount of crosslinking agent is increased, while when increasing the degree of swelling, it is decreased.

The appropriate polymerization temperature for forming the polymer and/or copolymer in each polymerization step is selected in the range of 30 to 120°C, preferably 50 to 100°C. There are no particular restrictions on the emulsifier used in the polymerization, and any emulsifier can be selected from 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 as follows:
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. 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 the acrylic ester cross-linked product sequentially. A rubber-like elastic body may be formed by adding unsaturated nitrile (c), aromatic vinyl (d), etc., without completing the polymerization and leaving unreacted monomers.

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

[0051] The multi-structure polymer having a special structure of the present invention is basically obtained by the polymerization method as explained in (f) above, but the characteristics of the polymer obtained at each polymerization step are as follows:
■ The polymer obtained in the first and second stages of polymerization plays a role in increasing the elastic modulus of the multi-structure polymer, and is also important in sheet polymerization because it determines the final particle size of the multi-structure polymer. It is. In particular, if a grafting agent or crosslinking agent is present during the first stage polymerization, only a multi-structure polymer with low impact resistance can be obtained (the layers formed during the first and second stage polymerizations). (referred to as the first layer) ■ The acrylic acid ester crosslinked product mainly obtained in the third stage polymerization plays the role of imparting impact strength. (The layer formed by this polymerization is called the second layer.) ■ The rubber-like elastic body obtained mainly in the fourth stage polymerization is the hard polymer of the first to second stage polymerization, the third 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
It is called a layer. ) ■ The final polymer obtained in the final stage of polymerization serves to improve compatibility with the thermoplastic resin to be further blended. (The layer formed by this polymerization is called the fourth layer.)

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

As a component of polymer B, one or more monomer components copolymerizable with unsaturated nitrile and aromatic vinyl may be introduced. When it is necessary to further improve the blendability with the 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. Furthermore, when it is necessary to improve the heat resistance of the sheet, monomers such as acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleimide are selected. In the composition of Polymer B, the unsaturated nitrile units are in the range of 20 to 45% by weight, the aromatic vinyl units are in the range of 80 to 55% by weight, and the monomer units copolymerizable with these units are in the range of 0 to 30% by weight. Outside this range, the blendability with Polymer A decreases and the mechanical properties of the molded article decrease. This polymer B is produced by a conventional solution polymerization, suspension polymerization, or emulsion polymerization method.

It is also possible to add to the polymer composition of the present invention a polymer that can make polymers A and B compatible. This allows a special function to be imparted to the molded product. 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.

Polymer A constituting the polymer composition of the present invention
Regarding the weight ratio of polymer B and polymer B, A is 10 to 80% by weight.
, preferably 30 to 50% by weight, B 90 to 20% by weight
, preferably in the range 70-50% by weight. Outside the above range, impact resistance and rigidity cannot be balanced ((see Examples 1, 10, 11, 12 and Comparative Examples 10, 11, described later).

The polymer composition of the present invention can be obtained by melt-kneading the above-mentioned polymers in a commercially available single-screw extruder or twin-screw extruder. Fillers, reinforcing materials, dyes, pigments, etc. can be added as necessary. The composition of the present invention thus obtained is injection molded, or stretched using generally known tenter methods, inflation methods, compression/stretch molding methods (press stretching methods), etc. As a result, injection molded products, stretched sheets and films with extremely excellent weather resistance and impact resistance, and an excellent appearance without pearlescent color, or with a good balance of these properties, can be obtained.

[0057]

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.

[0058] Preparation of sample for electron microscopy: The average diameter of the α layer and the average thickness of the γ layer of the multilayer structure polymer of the present invention are measured as follows. That is, the multilayer structure polymer is PMMA.
(Delpet 80N; manufactured by Asahi Kasei Co., Ltd.) was kneaded 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 with an electron microscope, it has a sea-island structure, and the island parts consist of parts that are stained with ruthenium and parts that are not, and the parts that are not stained with ruthenic acid are called the α layer and the outside of the α layer. The part that surrounds the α layer in a ring shape and is stained with ruthenic acid is the γ layer, and the part of the α layer that is stained with ruthenic acid and is dispersed in multiple small particles is called the β layer.
layer.

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

[0061]

[Equation 13] At this time, if the particle cannot be considered spherical, determine its major axis and minor axis, and calculate the arithmetic average value as the average diameter (particle diameter).

[0062]

[Formula 14] Regarding the thickness, 100 were similarly selected at random.
Each particle was measured and the results were arithmetic averaged to determine the average thickness. At this time, if the thickness is uneven, the maximum thickness and minimum thickness were measured, and the arithmetic average value was taken as the thickness. In addition, the particle diameter distribution is the particle diameter distribution ratio defined by the general formula [II]

[0063]

[Math. 15] was used as the measure.

[0064]

[Formula 16] (Here, ni is the number of particles of the polymer A having a particle diameter Di.)

[0065] Swelling degree: Add 30 ml of acetone to about 0.5 g of pellets, immerse 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, add 30 ml of acetone and shake at 25°C for 1 hour.
Centrifuge at 18,000 rpm for 1 hour at 5°C. The supernatant liquid is removed and the weight is measured (W3). After that, 10
Vacuum dry at 0°C for 2 hours and weigh the residue (W
4). The degree of swelling is calculated using the following formula.

[0066]

[Math. 17]

[0067] Composition analysis: The acetone-soluble portion was obtained by pouring the supernatant liquids (a) and (b) obtained from the acetone separation into a large amount of methanol, and drying the precipitate under vacuum. For the acetone-insoluble portion, a sample obtained by acetone fractionation was used. Compositional analysis of each sample was performed by pyrolysis gas chromatography.

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

■Surface gloss; ASTM-D523-6
Based on 2T, specular gloss was determined at an incident angle of 60 degrees.

■ Weather resistance: Dew panel light control weather meter (DPWL-5 manufactured by Suga Test Instruments Co., Ltd.)
A weather resistance acceleration test was conducted using a cycle of irradiation at 60°C and wet condensation at 40°C using a mold. The percentage of the ratio of the Izod impact strength after 20 days of irradiation to that at the initial stage was defined as the retention rate of Izod impact strength, and was used as an evaluation of weather resistance.

■ Tensile strength, tensile elongation: ASTM-D
It was measured by a method based on 638.

■ Bending strength, bending modulus: ASTM-
It was measured by a method based on D790.

(10) Izod impact strength: AST
Measured in accordance with M-D256 (V notch, 1
/4” test piece).

(11) Evaluation of pearl color tone during orientation: A 2 mm sheet of the polymer composition was prepared using a compression molding machine, and heated in an oven at a temperature (stretching temperature) of 130°C using a tenter method.
, uniaxial stretching was performed at a stretching ratio of 3 times. The appearance of the stretched sheet thus obtained was observed and judged based on the following criteria. ○: Good △: Slightly pearlescent color. ×; Exhibits a remarkable pearl color.

[0075]

[Example 1] (A) Production of a multi-structure polymer (polymer A) (I) Production of a large particle polymer (1) Polymerization of the innermost layer of hard polymer (seed first stage), in the reactor 248.3 parts by weight of ion-exchanged water and 0.05 parts by weight of sodium dihexyl sulfosuccinate as an emulsifier were charged, and after sufficient nitrogen substitution with stirring, the temperature was raised to 75°C. This reactor contains 0 ammonium persulfate.
．． After adding 02 parts by weight, 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. The polymerization rate was 99%.

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

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

(4) Polymerization of rubber-like elastic body (fourth stage polymerization), (third layer) 11 parts by weight of butyl acrylate unreacted in the polymerization of (3),
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 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 added continuously at 75° C. over 90 minutes. The polymerization rate is 9
It was 3%. Further, the amount of residual monomer in the latex was measured by gas chromatography, and the copolymerization composition ratio of the third layer was calculated. As a result, the acrylonitrile/styrene/butyl acrylate ratio was 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. In order to further complete the polymerization, the reaction was continued at 85° C. for 1 hour. 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, and the acrylonitrile/styrene/butyl acrylate ratio was 24/65/11, respectively. . The latex thus obtained is called LTX-(I), and its number average particle diameter is

[0080]

[Math. 18] is 5800 Å, and the particle diameter distribution ratio

[0081]

[Math. 19] was 0.05.

(II) Production of small particle polymer In the production of large particle polymer, small particle polymer was produced by omitting the first stage of seeds and increasing the amount of emulsifier. (1) 248.3 parts by weight of ion-exchanged water and 0.50 parts by weight of sodium dihexylsulfosuccinate as an emulsifier were placed in a polymerization reactor for the innermost layer of hard polymer, and after thorough nitrogen purging with stirring, Warm 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,
A mixture of 2 parts by weight of butyl acrylate was added continuously over 50 minutes. After the addition, the reaction was continued for an additional 45 minutes at 75°C. The polymerization rate was 99%.

(2) Polymerization of acrylic acid ester crosslinked product (
2nd layer) In the presence of the latex of (1), ammonium persulfate 0
．． 01 parts by weight, sodium dihexyl sulfosuccinate 0
．． After adding 20 parts by weight, 63 parts by weight of butyl acrylate,
A mixture of 0.6 parts by weight of triallylisocyanurate as a crosslinking agent was continuously added at 70° C. over 80 minutes. After the addition was completed, the reaction was further continued at 70°C for 20 minutes. The polymerization rate through the first layer and the second layer was 84%.

(3) Polymerization of rubber-like elastic body (4th stage polymerization), (3rd layer) 11.63 parts by weight of butyl acrylate and 0.0 parts by weight of triallyl isocyanurate that were unreacted in the polymerization of (2). After adding 0.045 parts by weight of ammonium persulfate and 0.45 parts by weight of sodium dihexylsulfosuccinate in the presence of 15 parts by weight, 3.8 parts by weight of acrylonitrile, 11.4 parts by weight of styrene, and 0.025 parts by weight of t-dodecylmercaptan. Parts by weight of the mixture were added continuously over 90 minutes at 75°C. The polymerization rate was 94%. 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 third layer, the acrylonitrile/styrene/butyl acrylate ratio was 12/44/44, respectively.
Met.

(4) Polymerization of final polymer (5th stage polymerization) (4th layer) 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 98%. In addition, the amount of residual monomer in the latex was measured by gas chromatography, and the copolymerization composition ratio of the fourth layer was calculated. As a result, the acrylonitrile/styrene/butyl acrylate ratio was 25/64/11, respectively. . The latex thus obtained is called LTX-(II), and its number average particle diameter is

[0086]

[Math. 20] is 3100 Å, and the particle diameter distribution ratio

[0087]

[Formula 21] was 0.17. Said LTX-(I) and LTX-
After mixing (II) in a weight ratio of 50/50, 3% by weight
A warm aqueous solution of aluminum sulfate was added, salted out, solidified, dehydrated and washed repeatedly, and then dried to form Polymer A.
-1 was obtained. Number average particle diameter of this polymer A-1

00
88]

[Math. 22] is 4500 Å, and the particle size distribution ratio

[0089]

[Formula 23] is 1.88, and the degree of swelling with respect to acetone (Sw
I) was 7.2. Table 1 shows the analysis results of other polymers A-1.

(b) Morphology of the multi-structure polymer (polymer A) (i) Staining with ruthenic acid and observation with an electron microscope: In addition, a test piece was prepared by the method described above, and the test piece was stained with ruthenic acid. When ultra-thin sections were prepared and observed with a transmission electron microscope, as shown in the schematic diagram in Figure 2, island phases 2 made of a multi-structure polymer were scattered within a sea phase 1 made of thermoplastic resin. condition is observed. The average particle diameter of α portion 4 that is not stained with ruthenic acid is 4100 Å.
The average particle diameter of the entire island 2 (multi-structure polymer) is 4
γ region 3, 500 Å and stained with ruthenic acid
The average thickness of is 400 Å. A plurality of portions (β portions) 5 stained with ruthenic acid were dispersed almost entirely in the α portion 4 that was not stained with ruthenic acid.

[0091] 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) α part Portion 4 contains butyl acrylate, methyl methacrylate units for the hard polymer from the first and second stage polymerizations, and butyl acrylate, crosslinker or graft for the acrylic ester crosslinked product from the third stage polymerization. It is thought that the main component is the curing agent unit, and (b) the γ part 3 contains butyl acrylate, styrene, and acrylonitrile units for the rubber elastic body in the fourth stage polymerization, and the γ part 3 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) β dispersed in α part 4
It is considered that part 5 is formed by a part of the hard component, mainly styrene, charged in the γ part 3, flowing into the α part 4 and polymerizing.

(c) Preparation and evaluation of composition The above polymer A
-1, and AS resin [(acrylonitrile-styrene copolymer) (acrylonitrile/styrene = 29/71 weight ratio) manufactured by Asahi Kasei Corporation, product name "Stylac"<registeredtrademark> AS- 783KT)] in a Henschel mixer at a weight ratio of 35/65.
After mixing for a minute, pelletization was performed at 260° C. using a 30 mm vented twin-screw extruder (manufactured by Nakatani Kikai Co., Ltd., Model A).

[0093] Using the obtained pellets, a specified test piece was prepared using an in-line screw injection molding machine (manufactured by Toshiba Machine Co., Ltd., model IS-75S) at a molding temperature of 260°C and a mold temperature of 60°C. Physical properties were measured. The results are shown in Table 1. On the other hand, a 2 mm sheet was produced from the pellets using a compression molding machine, and uniaxially stretched using a tenter method at an oven temperature (stretching temperature) of 130° C. and a stretching ratio of 3 times. Table 1 shows the appearance of the stretched sheet. According to Table 1, it can be seen that the polymer composition of the present invention has both weather resistance, impact resistance, and an excellent appearance without pearlescent tone during stretching.

[0094]

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

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

(4) Polymerization of the final polymer (4th stage polymerization) In the presence of the latex of (3), ammonium persulfate 0
．． 045 parts by weight, sodium dihexyl sulfuccinate 0
．． After adding 0.045 parts by weight, a mixture of 6.75 parts by weight of acrylonitrile, 20.25 parts by weight of styrene, and 0.045 parts by weight of t-dodecylmercaptan was continuously added at 75° C. over 160 minutes. 8 to further complete the polymerization.
The reaction continued for 1 hour at 5°C. The polymerization rate was 98%. Further, the amount of residual monomer in the latex was measured by gas chromatography and the copolymerization composition ratio of the fourth layer was calculated, and as a result, the acrylonitrile/styrene/butyl acrylate ratio was 25/75/0. The latex thus obtained is called LTX-(III), and its number average particle diameter is

[0097]

[Math. 24] is 5900 Å, and the particle diameter distribution ratio

[0098]

[Math. 25] was 0.04.

(II) Production of small particle polymer (1) Polymerization of innermost layer hard polymer In the production of LTX-(II) in Example 1, except that 0.19 parts by weight of allyl methacrylate was added. was carried out in the same manner as in Example 1.

(2) Polymerization of acrylic acid ester crosslinked product (
In the presence of the latex of 1), ammonium persulfate 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. The polymerization rate was 99.5% through the polymerization of (1) and (2) above.
Met.

(3) Polymerization of the final polymer In the presence of the latex of (2), ammonium persulfate 0
．． 045 parts by weight, sodium dihexyl sulfuccinate 0
．． After adding 0.045 parts by weight, a mixture of 6.75 parts by weight of acrylonitrile, 20.25 parts by weight of styrene, and 0.045 parts by weight of t-dodecylmercaptan was continuously added at 75° C. over 160 minutes. 8 to further complete the polymerization.
The reaction continued for 1 hour at 5°C. The polymerization rate was 98%.

[0102] Furthermore, 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 25/75/0. The latex thus obtained is called LTX-(IV), and its number average particle diameter is

[0103]

[Math. 26] is 3050 Å, and the particle diameter distribution ratio

[0104]

[Formula 27] was 0.16. The LTX-(III) and LT
After mixing X-(IV) at a weight ratio of 50/50, a polymer a-1 was obtained by the same operation as in Example 1. The analysis results of this polymer a-1 are shown in Table 1.

(b) Morphology of the multi-structure polymer (polymer a-1) As a result of electron microscopy observation, as shown in the schematic diagram of FIG. The island phase 2 consists of two layers, and the average major axis of the inner layer (α part) part 4 inside the particle is 420.
0 Å, the average thickness of the outer layer (γ part) portion 3 surrounding the layered layer is 4
It was 00 Å. Not present in Example 1 in α part 4, not stained with osmic acid, diameter 1100 Å
An independent spherical layer 6 was observed. There was no β part 5 dispersed in this spherical layer 6.

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

[0107]

[Table 1]

[0108] Combining Table 1 and the results of electron microscopy observation, when a grafting agent (crosslinking agent) is introduced during the polymerization of the innermost hard polymer, an independent spherical layer exists, and β It can be seen that the mechanical strength is low because the parts are not dispersed.

[0109]

[Comparative Example 2] (A) Production of multi-structure polymer (I) Production of large particle polymer (1) Polymerization of acrylic acid ester crosslinked product (first stage of seeds), 248.3 ml of ion-exchanged water in the reactor parts by weight, and 0.05 parts by weight of sodium dihexylsulfosuccinate, and after sufficiently purging with nitrogen while stirring, the temperature was raised to 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 (
2nd stage of seeds), 1/4 of the latex obtained in (1) (2.5 in terms of solid content)
186.2 parts by weight of ion-exchanged water and 0.03 parts by weight of sodium dihexylsulfosuccinate were added to the reactor, and after sufficient nitrogen purging with stirring, the internal temperature was brought to 70°C. . After adding 0.01 part by weight of ammonium persulfate to this reactor, 70.5 parts by weight of butyl acrylate and 0.6 parts by weight of triallylisocyanurate as a crosslinking agent.
7 parts by weight of the mixture was added continuously over 80 minutes at 70°C. After the addition was completed, the reaction was further continued at 70°C for 20 minutes. The polymerization rate was 85%.

(3) Polymerization of rubber-like elastomer In the presence of 11 parts by weight of butyl acrylate and 0.18 parts by weight of triallylisocyanurate, which were unreacted in the polymerization of (2), 0.045 parts by weight of ammonium persulfate, After adding 0.45 parts by weight of sodium dihexyl sulfuccinate, 3.0 parts by weight of acrylonitrile was added.
A mixture of 8 parts by weight of styrene, 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%. Further, the amount of residual monomer in the latex was measured by gas chromatography, and the copolymerization composition ratio of the third layer was calculated. As a result, the acrylonitrile/styrene/butyl acrylate ratio was 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%. In addition, the amount of residual monomer in the latex was measured by gas chromatography and the copolymerization composition ratio of the final polymer was calculated, and the acrylonitrile/styrene/butyl acrylate ratio was 25/64/11, respectively. . The latex thus obtained is called LTX-(V), and its number average particle diameter is

[0113]

[Math. 28] is 5600 Å, and the particle diameter distribution ratio

[0114]

[Math. 29] was 0.05.

(II) Production of small particle polymer (1) Add 24 liters of ion-exchanged water into the polymerization reactor for crosslinked acrylic acid ester.
8.3 parts by weight, 0 sodium dihexyl sulfosuccinate
．． After charging 50 parts by weight and thoroughly purging with nitrogen while stirring, the temperature was raised to 75°C. After adding 0.02 parts by weight of ammonium persulfate to this reactor, a mixture of 10 parts by weight of butyl acrylate and 0.1 parts by weight of triallylisocyanurate as a crosslinking agent was continuously added over 50 minutes. After the addition, 0.01 part by weight of ammonium persulfate was further added, and the reaction was continued at 75° C. for 45 minutes. Polymerization rate is 99
%Met.

(2) Polymerization of rubber-like elastomer In the presence of 10.7 parts by weight of butyl acrylate and 0.18 parts by weight of triallylisocyanurate, which were unreacted in the polymerization of (1), 0.045 parts by weight of ammonium persulfate was added. After adding 0.45 parts by weight of sodium dihexylsulfuccinate, 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 heated at 75°C to 90% by weight.
Additions were made continuously over a period of minutes. The polymerization rate was 92%. Further, the amount of residual monomer in the latex was measured by gas chromatography, and the copolymerization composition ratio of the third layer was calculated, and the acrylonitrile/styrene/butyl acrylate ratio was 12/41/47, respectively.

(3) Polymerization of the final polymer In the presence of the latex of (2), 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 98%. In addition, the amount of residual monomer in the latex was measured by gas chromatography and the copolymerization composition ratio of the final polymer was calculated, and the acrylonitrile/styrene/butyl acrylate ratio was 24/65/11, respectively. . The latex thus obtained is called LTX-(VI), and its number average particle diameter is

[0118]

[Math. 30] is 3000 Å, and the particle diameter distribution ratio

[0119]

[Formula 31] was 0.16. The LTX-(V) and LTX-
After mixing (VI) in a weight ratio of 50/50, Example 1
Polymer a-2 was obtained by the same operation as above. This polymer a
The analysis results of -2 are shown in Table 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 polymer composition using a multi-structure polymer without a hard polymer in the innermost layer consisting of an alkyl methacrylate ester and an alkyl acrylate ester has poor impact resistance and gloss.

[0121]

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

[0122]

[Examples 1, 2, 3 and Comparative Examples 4, 5] (Effect of particle diameter of polymer A) In the production of polymer A-1 of Example 1, the particle diameter distribution was the same as that of A-1. Polymers A having different particle diameters were obtained. In order to do this, it is necessary to reduce the amount of latex obtained by the first stage polymerization of the seed of the innermost layer hard polymer and continue the seed polymerization to make the particles larger than A-1, or By increasing the amount of sodium dihexyl sulfosuccinate in the first stage and continuing seed polymerization, particles were made smaller than A-1. The latex thus obtained was subjected to the same treatment as in Example 1 to prepare a polymer composition and evaluated. The results are shown in Table 2.

[0123]

[Table 2] According to Table 2, the number average particle diameter

[0124]

When [Equation 32] is less than 2000 Å, the gloss and appearance of the stretched sheet are excellent, but the impact resistance is low;
It can be seen that when the thickness exceeds Å, the appearance of the stretched sheet deteriorates significantly.

[0125]

[Examples 1, 4, 5, 6 and Comparative Examples 6, 7] (Effect of particle diameter distribution of polymer A) In the production of polymer A-1 of Example 1, A-1 and particle diameter were Polymer A, which was identical but had a different distribution, was obtained. To achieve this, large-particle polymer A obtained by continuing seed polymerization by reducing the amount of latex obtained in the seed first stage polymerization of the hard polymer in the innermost layer, and This is achieved by optionally mixing small particle polymer A obtained by increasing the amount of sodium dihexyl sulfosuccinate and continuing seed polymerization and/or polymer A having an intermediate particle diameter. The latex thus obtained was subjected to the same treatment as in Example 1 to prepare a polymer composition and evaluated. The results are shown in Table 3.

[0126]

[Table 3] According to Table 3, particle diameter distribution ratio

[0127]

If [Equation 33] is less than 1.0, the impact resistance will be significantly reduced;
It can be seen that when it exceeds 0, the weather resistance, impact resistance, and appearance of the stretched sheet deteriorate.

[0128]

[Examples 1, 7, 8, 9 and Comparative Examples 8 and 9] (Effect of swelling degree of polymer A) In the production of polymer A-1 of Example 1, the particle diameter and its distribution were the same. Polymers A having different degrees of swelling in acetone were obtained. To this end, the degree of swelling can be increased by increasing the amount of triallyl isocyanurate as a crosslinking agent, or increasing the degree of swelling by decreasing it. The latex thus obtained was subjected to the same treatment as in Example 1 to prepare a polymer composition and evaluated. The results are shown in Table 4.

[0129]

[Table 4] According to Table 4, if the degree of swelling is less than 4.0, the impact resistance will be low, while if it exceeds 9.0, the pearl color tone of the stretched sheet will become noticeable and the commercial value will be impaired. .

[0130]

[Examples 1, 10, 11, 12 and Comparative Examples 10, 11
(Effect of the composition ratio of Polymer A and Polymer B) Polymer A-1 and Polymer B-1 of Example 1 were arbitrarily mixed to prepare a polymer composition and evaluated. The results are shown in Table 5.

[0131]

[Table 5] According to Table 5, it can be seen that when the polymer A content is less than 10% by weight, the impact resistance is low, while when it exceeds 80% by weight, the rigidity is decreased.

[0132]

[Comparative Example 12] (a) Production of ABS resin 70 parts by weight of polybutadiene rubber, 0.05 parts by weight of dihexylsuccinic acid ester, 0.02 parts by weight of ammonium persulfate
An aqueous emulsion liquid consisting of parts by weight 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. Further, according to electron microscopic observation, the average rubber particle diameter was 0.4 μm.

(b) 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 6. According to Table 6, it can be seen that ABS resin has poor weather resistance.

[0134]

[Table 6]

[0135]

Effects of the Invention As explained above, the polymer composition of the present invention has improved weather resistance compared to ABS resin, and has excellent impact resistance and an excellent appearance that does not exhibit a pearl color tone during orientation. This is a novel polymer composition that has the following properties. Injection molded products of this composition can be used for a wide range of applications including automobile parts and electronic parts, especially for conventional metal materials or AB
It can be used without painting for outdoor applications that previously used painted products such as S resin.

[0136] Furthermore, this composition can be heat-melted and extruded into a sheet or cylindrical shape and given an appropriate orientation, so that it can be used in the sheet field, electronic equipment fields such as office automation housings and radomes for planar antennas, and water heaters. Suitable for housing equipment such as exterior and cooling tower parts, civil engineering and construction parts such as traffic signals, road mirrors, and anti-glare panels, interior and exterior parts for transportation equipment, industrial parts, and unpainted exterior materials for vending machines. In the field of film, it is also suitable for packaging materials and films for laminating other molded products, and plays a large role in industry.

[Brief explanation of drawings]

FIG. 1 is a diagram illustrating the mechanism by which a pearl tone appears in stretched sheets and films.

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

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

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

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

[Explanation of symbols]

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

Claims (1)

[Claims] [Claim 1] Multi-structure polymer A (polymer A) 10-8
0% by weight and 90 to 20% by weight of thermoplastic polymer B (polymer B), wherein the multi-structure polymer A is essentially a spherical crosslinked rubber body, (a) A mixture of an acrylic ester crosslinked polymer and a copolymer consisting of methacrylic ester units and acrylic ester units, which has the following form and composition, and has a glass transition temperature of -30°C or lower. (b) a copolymer dispersed within the α portion, which is composed of an aromatic vinyl unit and an unsaturated nitrile unit; /or aromatic vinyl unit and unsaturated nitrile unit and α
(c) a copolymer consisting of acrylic acid ester units constituting the part (β part), and (c) a polymer surrounding the outside of the α part in a layered manner,
A copolymer consisting of an aromatic vinyl unit and an unsaturated nitrile unit and/or a copolymer consisting of an aromatic vinyl unit, an unsaturated nitrile unit, and an acrylic ester unit constituting the α part (γ part), The copolymerization composition is (a)
2 to 30% by weight of methacrylic ester units, (b) 50 to 80% of acrylic ester units, and (c) 5 to 20 unsaturated nitrile units.
Weight% and (d) aromatic vinyl units
A multi-structure polymer A consisting of 5 to 40% by weight,
Essentially, the average diameter of the spherical α portion is 1900 to 590
0 Å, and the average layer thickness of the γ part surrounding this α part is 10~
1000 Å, and the number average particle diameter [Equation 1] defined in general formula [I] as the average diameter of the entire particles of the multi-structure polymer A is 2000 to 6000 Å, and the particle diameter distribution is generally Particle diameter distribution ratio defined in formula [II] [Equation 2
] is 1.0 to 3.0, [Equation 3] (where ni is the number of particles of the polymer A having a particle diameter Di), and (a) the acetone-insoluble portion is resistant to acetone. It is a multi-structure polymer having a degree of swelling (SwI) of 4 to 9 and (b) a tensile modulus of 1,000 to 10,000 kg/cm2, and the thermoplastic polymer B is (a)
A thermoplastic polymer consisting of 20 to 45% by weight of unsaturated nitrile units, (b) 80 to 55% by weight of aromatic vinyl units, and (c) 0 to 30% by weight of one or more monomer units copolymerizable with these. CLAIMS 1. A weatherable, impact-resistant polymer composition, characterized in that it is a polymer composition.