JPH0420022B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a thermoplastic resin composition suitable for use as an unpainted exterior material, which has excellent impact resistance and weather resistance, and has an extremely excellent injection molded appearance. (Prior Art and Problems to be Solved by the Invention) Conventionally, hard resins have been generally reinforced with elastic bodies to impart impact resistance. ABS resin is typical of this type of resin, but because it uses diene rubber as an elastic component, it has poor weather resistance, which limits its use outdoors, which is a major drawback. For this reason, the current situation is to improve the weather resistance and allow outdoor use by plating or painting the ABS resin surface. However, such formulas for ABS resin surfaces require many steps and are prone to environmental pollution, so even if used outdoors for a long time without the above-mentioned plating or painting, it will still have excellent appearance, impact resistance, and weather resistance. The emergence of thermoplastic resin compositions that can maintain their properties is particularly desired in fields of use outdoors, such as automobiles and home appliances. Various proposals have been made to use saturated rubber as the elastic body to meet these demands. The use of acrylic ester rubber is one example of this, and many studies have been made to date. However, acrylic ester rubber has the disadvantage that elastic recovery is slower than diene rubber, so when a resin composition consisting of such rubber and a hard resin is injection molded, the orientation of the rubber particles is significantly affected by the gate of the molded product. There was a problem in that a pearl pattern appeared mainly in the vicinity, which was unfavorable in appearance and reduced the commercial value. It has become clear that the degree of occurrence of this pearl pattern depends on the rubber particle size of the acrylic ester rubber, and is reduced as the particle size is made smaller than the wavelength of visible light. However, on the other hand, when rubber particles with such small particle diameters are used, the impact resistance is greatly reduced, making it difficult to say that the resin is well-balanced. In view of the current situation, it is an object of the present invention to provide a weather-resistant resin composition that has excellent molded appearance and impact resistance. (Means for Solving the Problems) As a result of intensive studies to achieve the above object, the present inventors found that cross-linked acrylic ester-based rubber particles having a small particle size within a specific range are used. By coexisting a graft polymer and a graft polymer obtained using large crosslinked acrylic ester rubber particles having a particle size in a specific range, the orientation of rubber particles on the surface of an injection molded product can be disturbed. Therefore, it has been discovered that a resin composition with an injection molded appearance that is far superior to the conventional one can be obtained, and the present invention has been achieved. That is, the present invention involves grafting at least one type of aromatic vinyl monomer with at least one type of vinyl cyanide monomer and unsaturated acid ester monomer in the presence of a crosslinked acrylic ester rubber. A hard material obtained by polymerizing 10 to 70% by weight of the resulting graft polymer (I), at least one type of aromatic vinyl monomer, and at least one type of vinyl cyanide monomer and unsaturated acid ester monomer. The thermoplastic resin () is 90 to 30% by weight and the diene rubber-containing thermoplastic resin () is 0 to 50% by weight, and the total amount of (I), () and () is 100% by weight. In the thermoplastic resin composition, the graft polymer (I) has a monodisperse particle size distribution in which the average particle size of the crosslinked acrylic ester rubber in the emulsion during graft polymerization is in the range of 0.05 to 0.24μ. At least one kind of graft polymer (I-1) obtained using a small particle diameter rubber having 90
~10% by weight and at least 10 to 90% by weight of at least one type of graft polymer (I-2) obtained using a large particle size rubber having a monodisperse particle size distribution with an average particle size in the range of 0.25 to 0.50μ This is a thermoplastic resin composition characterized by being composed of a blend of 100% and 30%, and having extremely excellent impact resistance and weather resistance and an injection molded appearance. The most significant feature of the thermoplastic resin composition of the present invention is that the average particle diameter of the crosslinked acrylic ester rubber in the emulsion during graft polymerization as the constituent graft polymer (I) is
Similar to 90 to 10% by weight of graft polymer (I-1) obtained using a small particle size rubber having a monodisperse particle size distribution in the range of 0.05 to 0.24μ, the amount of crosslinked acrylic ester rubber in the emulsion was Composed of a blend with 10 to 90% by weight of graft polymer (-2) obtained using a large particle diameter rubber having a monodisperse particle diameter distribution with an average particle diameter in the range of 0.25 to 0.50μ. is to use. As a result, the molded appearance, impact resistance, and weather resistance of the injection molded product can be significantly improved. That is, a graft polymer (I
The presence of -2) not only provides an excellent molded appearance but also provides effective impact resistance. Further, by the presence of the graft polymer (I-1) containing the above-mentioned small particle size rubber as a constituent component, it is possible to obtain good impact resistance and at the same time to make the appearance of the injection molded product good. The impact resistance of the thermoplastic resin composition of the present invention largely depends on the average rubber particle diameter of the crosslinked acrylic ester rubber constituting the graft polymer,
The effect of whether the rubber particle size distribution is monodisperse or polydisperse is relatively small. On the other hand, when it comes to the appearance of injection molded products, even if the average rubber particle size is the same, polydisperse rubber particle sizes are much better than monodisperse rubber particle sizes, and gates, which were a problem with conventional methods, are much better. The occurrence of pearl patterns in the vicinity is greatly reduced. Such effects are obtained by graft polymers (I) obtained from rubber particle sizes of different sizes.
This is based on the fact that the coexistence of -1) and (I-2) disturbs the orientation of the acrylic ester rubber particle layer in the surface layer of the injection molded product, and is one of the greatest effects of the present invention. It is. In this way, the present invention is achieved by blending graft polymers (I-1) and (I-2) obtained by graft polymerizing resin components onto crosslinked acrylic ester rubber particles having different particle diameters within a specific range. ,
It has become possible to achieve a balance between injection molded appearance and impact resistance, which has been difficult to achieve with conventional resin compositions made of monodisperse crosslinked acrylic ester rubber particles. In particular, it is surprising that the pearl pattern near the gate of the injection molded product and the color development when dyes and pigments are used in combination are greatly improved. The graft polymer (I-1) constituting the graft polymer (I) used in the present invention is a crosslinked acrylic ester rubber having a monodisperse particle size distribution with an average rubber particle size in the range of 0.05 to 0.24μ. It is obtained by graft polymerizing an aromatic vinyl monomer and at least one of a vinyl cyanide monomer and an unsaturated acid ester monomer in the presence of the monomer. The structure of the crosslinked acrylic ester rubber used here is not particularly limited,
It may be a so-called multilayered crosslinked acrylic ester rubber having a hard resin crosslinked inside the crosslinked acrylic ester rubber particles, or acrylic ester rubber having different degrees of crosslinking.
Furthermore, it may be a crosslinked acrylic ester rubber having a homogeneous structure. The same holds true for the graft polymer (I-2) obtained using a large particle size rubber having a monodisperse particle size distribution with an average rubber particle size in the range of 0.25 to 0.50μ. Furthermore, the graft polymer (I) is not limited to being composed of one type each of the above-mentioned graft polymer (I-1) and graft polymer (I-2). It may be composed of two or more different graft polymers (I-1) and graft polymers (I-2). In the present invention, "having a monodisperse particle size distribution"
means that the particle size distribution has only one peak. The degree of spread of the monodisperse particle size distribution changes depending on the polymerization conditions. Moreover, the "average particle size" is the average value of the entire rubber having this monodisperse particle size distribution. Therefore, for example, in a small particle size rubber having an average particle size in the range of 0.05 to 0.24μ, there may be some rubber particles with a particle size exceeding this range. Examples of the acrylic ester which is the main component of the crosslinked acrylic ester rubber constituting the graft polymer (I) used in the present invention include methyl, ethyl, n-propyl, n-butyl, 2-ethylhexyl, n-lauryl, etc. carbon number 1-12
alkyl esters; aromatic esters such as benzyl acrylate or phenethyl; and the like. In order for the crosslinked acrylic ester rubber to be in a rubber state at room temperature or below, it is necessary to use an acrylic ester, preferably an alkyl ester having 1 to 8 carbon atoms, in an amount of 60% by weight or more of the constituent monomers of the crosslinked acrylic ester rubber. Monomers copolymerizable with these acrylic esters include methacrylic esters such as methyl methacrylate and n-butyl methacrylate;
Examples include acrylonitrile and styrene. This acrylic ester rubber is generally required to have a crosslinked network structure, and the present invention also requires that it have a crosslinked structure. In order to form a crosslinked structure, non-conjugated C=C is used as a crosslinking agent.
Crosslinkable monomers having at least two bonds, such as unsaturated acid esters of polyols such as ethylene glycote methacrylate and butanediol diacrylate; polybasic acid esters such as triallyl cyanurate and triallyl isocyanate; Unsaturated alcohol esters; divinyl compounds such as divinylbenzene; unsaturated alcohol esters of unsaturated acids such as allyl methacrylate and diallyl phthalate can be used. The amount of crosslinking agent used is 0.01 to 3% by weight, preferably 0.1 to 2% by weight. If the amount used is less than 0.01% by weight, defects in appearance will appear in the final molded product, and if it exceeds 3% by weight, fluidity and impact strength will decrease, which is not preferable. This crosslinking agent is mixed with the monomer or monomer mixture containing the acrylic ester as a main component and polymerized, or after polymerization, an organic peroxide such as benzoyl peroxide is added and heated in a latex state. . A combination of both is also used. The swelling degree of the crosslinked acrylic ester rubber polymerized in this way is 5 to 15, and the gel content is 85 to 95.
% is preferable in terms of physical properties. Note that the degree of swelling and gel content of the crosslinked acrylic ester rubber were measured as follows. That is, a film is made from latex and immersed in methyl ethyl ketone at 30°C for 48 hours. If the weight of the film before immersion is W ₀ , the weight of the film after swelling is W ₁ , and the weight of the bone dry film after swelling is W ₂ , the swelling degree is W ₁ /W ₂ and the gel content is W ₂ /W ₀ ×
It was calculated using 100. Next, in the presence of 35 to 85% by weight of the crosslinked acrylic ester rubber latex obtained by the above method, 65 to 15% by weight of the following resin-forming monomer mixture was added in the total amount in the presence of a radical generation initiator. is added to the latex all at once, divided into multiple stages, or continuously to carry out graft polymerization to obtain a graft polymer. In this case, the graft ratio and degree of polymerization may be varied to graft-bond the resin parts in multiple stages, or an emulsion suspension method in which the system is transferred from an emulsion system to a suspension system during graft polymerization may be used. do not have. By performing multistage graft polymerization, the impact resistance and fluidity of the resin composition finally obtained can be further improved. The resin-forming monomer used in the graft polymerization is a mixture of at least one type of aromatic vinyl monomer and at least one type of vinyl cyanide monomer and unsaturated acid ester monomer. Styrene, α-methylstyrene, etc. are used as aromatic vinyl monomers, acrylonitrile, methacrinitrile, etc. are used as vinyl cyanide monomers, and alkyl acrylates are used as unsaturated acid ester monomers. , alkyl methacrylate, etc. are used. The grafting ratio of the graft resin portion to the crosslinked acrylic ester rubber is at least 10%.
It is preferable that Here, the grafting rate means that a certain amount of W ₃ of the graft polymer is
Reflux directly at 70°C for 2 hours, centrifuge the insoluble part, and take the weight after absolute drying as W ₄ (W ₄ − W ₅ )/W ₅
It is expressed as ×100. Note that _W5 is the weight of the crosslinked acrylic ester rubber in the graft polymer _W3 . 10 to 70% by weight of the graft polymer (I) composed of two or more types of graft polymer (I-1) and graft polymer (I-2) having different average rubber particle diameters obtained in this manner. , and 90 to 30% by weight of a separately manufactured hard thermoplastic resin () to form various molding materials. The hard thermoplastic resin () includes at least one of the aromatic vinyl monomers listed as the resin-forming monomer of the graft polymer (I), a vinyl cyanide monomer, and an unsaturated acid ester monomer. Specifically, styrene-acrylonitrile copolymer, α-methylstyrene-acrylonitrile copolymer, methyl methacrylate-styrene copolymer, methyl methacrylate-acrylonitrile-
Examples include styrene copolymers. Although there are no particular restrictions on the polymerization method for this hard thermoplastic resin, it is advantageous in terms of physical properties such as hardness and gloss to use a polymer obtained by suspension polymerization or bulk polymerization. The thermoplastic resin composition of the present invention may be used as it is as a blend of the graft polymer (I) and a specific hard thermoplastic resin (), but if necessary, the content of diene rubber may be adjusted to at least Thermoplastic resin containing diene rubber (10% by weight)
The proportion in the total resin composition is 0 to 50% by weight, and the total amount of (I), () and () is 100% by weight.
They may be blended in such a manner that the amount is % by weight. Examples of the diene rubber include polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, and a typical example of the diene rubber-containing thermoplastic resin is ABS resin. Depending on the purpose, various dyes and pigments, stabilizers against light or heat, inorganic or organic granular, powder or fibrous fillers, blowing agents, etc. can be added to the thermoplastic resin composition of the present invention. The thermoplastic resin composition of the present invention can be molded by various processing methods such as injection molding and extrusion molding, and can be used for various molded products with excellent weather resistance, impact resistance, color tone, etc., particularly for automotive applications, home appliance applications, and outdoor applications. It can be used as an object. It can also be used as a component of other multilayer structures, such as the outermost laminate. The present invention will be specifically explained below using Examples.
In the examples, unless otherwise specified, "%" and "parts" are "% by weight" and "parts by weight", respectively, and the particle size is methyl methacrylate/acrylonitrile/styrene = 20/
A calibration curve was created from the relationship between the particle diameter determined by electron microscopy for an uncrosslinked resin latex consisting of 20/60 (wt%) and the absorbance at a wavelength of 700 mμ of a diluted solution (0.5 g/1) of that latex. It was read from the calibration curve by measuring the absorbance. This calibration curve is shown in FIG. Also, regarding the average particle size when blending two or more types of latex with different particle sizes,
It was measured by this absorbance method. Example 1 Manufacturing method and physical properties of various crosslinked acrylic ester rubber-containing graft polymers. After putting 200 parts of ion-exchanged water into a reaction vessel and replacing it with nitrogen, the temperature is raised to bring the internal temperature to 70°C. Rubber polymerization was carried out by adding 0.15 parts of potassium persulfate into this container and continuously injecting the following mixture over 100 minutes. n-Butyl acrylate (BuA) 45 parts Acrylonitrile (AN) 5 parts Triallyl isocyanurate (TAIC) 0.25 parts Pellex OTP (manufactured by Kao Atlas Co., Ltd., dioctyl sulfosuccinate emulsifier) 5.0 parts The polymerization rate decreased approximately one hour after injection. Reached 99%. Further, the rubber particle diameter was 0.10μ. Subsequently, in the presence of the obtained rubber, the following mixture was continuously injected over 120 minutes to effect graft polymerization. Methyl methacrylate (MMA) 10 parts AN 10 parts Styrene (St) 30 parts n-octyl mercaptan 0.05 parts Benzoyl peroxide 0.25 parts The polymerization rate reached 99% about one hour after injection. The latex thus obtained was poured into twice the amount of calcium chloride aqueous solution (3% by weight) with stirring and coagulated, and then dehydrated, washed and dried to obtain a rubber particle size of 0.10μ. A graft polymer powder (A-1) was obtained. Pellets used in rubber polymerization in the same manner as below.
Graft polymer powders with different rubber particle sizes by changing the amount of OTP (A-2 to A
-8) was obtained. For 50 parts of each of these powders A-1 to A-8, MMA/AN/ST=20/20/60 (% ratio)
50 parts of suspension polymerized particles (MAS pearls) obtained by separately polymerizing the monomer mixture are blended and pelletized using an extruder. At this time, the crosslinked acrylic rubber content in the blended resin composition is 25%. At this time, barium stearate 1 was added to the resin composition.
1 part, and 0.1 part of Tinuvin P (manufactured by Ciba Geigy, ultraviolet absorber). The pellets thus obtained were injection molded to obtain various test pieces and their physical properties were measured. The results are shown in Comparative Examples 1-1 to 1-8 in Table-1. Of the various physical properties in the table, the 1/4 inch notched isot strength is ASTM-
According to D-256. In addition, the appearance of the injection molded plate was examined with the naked eye using a test piece injection molded with a resin composition containing 0.4 parts of carbon black as a coloring agent.
It was measured by the value of Imax/Imin. This Imax/
Imin can be obtained by the following method. That is, the second
As shown in the figure, white light is incident perpendicularly onto the test piece, and while rotating the test piece around the point of incidence,
The scattered light intensity in the 45° direction was measured. This intensity curve is shown as curves 1 and 2 in FIG. 3 as an example. The ratio of the maximum intensity to the minimum intensity at this time is defined as Imax/Imin. This intensity ratio fairly reflects the anisotropy of the appearance of the molded plate as determined by the naked eye, and the larger this value is, the worse the injection molded appearance becomes. (2) Manufacturing method and physical properties of rubber blend resin compositions with different particle sizes. Two types of powders (a) and (b) were selected from powders A-1 to A-8, and the weight ratios of (a)/(b) were blended as shown in Table 2. Blend 50 parts of the mixture with 50 parts of MAS pearls in the same manner as above to give a crosslinked rubber content of 25%. Various physical properties of this resin composition are measured using the method of Comparative Example 1 described above. These results are shown in Examples 1-1 to 1 in Table-2.
-6. Furthermore, two types of powder (a) and (b) are both 0.24μ
The same study as in Example 1 was conducted for smaller or larger cases, and the results are shown in Comparative Examples 1-9 to 1-10 in Table 2. The following becomes clear from the results in Tables 1 and 2. That is, the resin composition of the present invention, which is a blend of rubbers having different particle sizes, has approximately the same average rubber particle size. Compared to a composition made of monodisperse rubber, although the impact resistance is at the same level, the appearance of the injection molded plate is greatly improved. In this way, the overall resin properties including the molded appearance can be improved by blending rubbers with different particle sizes. However, the particle sizes of the two types of rubber used are
If both are smaller than 0.24μ, the molded appearance is good but the impact resistance is insufficient and it is difficult to obtain a well-balanced resin composition. On the contrary, together
If it is larger than 0.25μ, it is difficult to obtain a composition with a good injection molded appearance even if the difference in rubber particle size is large. The appearance of the injection molded plates in Tables 1 and 2 is as follows. ◎: Very good ○: Good △: Fairly good ×: Poor XX: Very poor The measurement methods for evaluation in Tables 1 and 2 are common to the following Examples and Comparative Examples.

【table】

[Table] Example 2 (1) Manufacturing method and physical properties of crosslinked acrylic ester rubber-containing graft polymers having various multilayer structures. After putting 200 parts of ion-exchanged water into a reaction vessel and replacing it with nitrogen, the temperature is raised to bring the internal temperature to 80°C. 0.06 part of potassium persulfate was added into this container, and the following mixture was continuously injected over 30 minutes. MMA 2 parts AN 2 parts St 6 parts TAIC 0.05 parts Perex OTP 8 parts The exothermic reaction was completed about an hour after injection. The particle size of the obtained crosslinked resin latex was 0.80μ. Subsequently, 0.24 parts of potassium persulfate was further added and the following mixture was continuously injected over a period of 2 hours. BuA 38 parts AN 2 parts TAIC 0.20 parts Perex OTP 0.30 parts The swelling degree of the crosslinked acrylic rubber having the crosslinked resin as the core obtained in this way is 6.7, the gel content is 90%, and the particle size is 0.11μ. It was hot. The following mixture was continuously injected into the thus obtained crosslinked acrylic rubber latex over a period of 2 hours. MMA 10 parts AN 10 parts St 30 parts n-octyl mercaptan 0.05 parts Benzoyl persulfide 0.25 parts The thus obtained latex was poured into twice the amount of calcium chloride aqueous solution with stirring, coagulated, and then deliquified, washed, and dried. by doing
A graft polymer (B-1) having a 0.11 μm multilayer structure crosslinked acrylic rubber was obtained. Graft polymer powders (B-2 to B-5) of multilayered crosslinked acrylic rubber having different particle sizes were obtained in the same manner by changing the amount of Pellex OTP during polymerization of the crosslinked resin latex. Using 50 parts each of graft polymer powders B-1 to B-5 having this multilayer structure crosslinked acrylic rubber, the same method as described in (1) of Example 1 was carried out.
Comparative Example 2-1 in Table 3 shows the results of various evaluations of the resin composition after blending with 50 parts of MAS Pearl.
- Shown in 2-5. (2) Manufacturing method and physical properties of rubber blend resin composition with different particle diameters Two types of powders (a) and (b) were selected from powders B-1 to B-5 and prepared in the same manner as described in (2) of Example 1. We investigated various rubber blend formulations with different particle sizes using this method, and the results are shown in Examples 2-1 to 2-2 in Table 4.
It was shown to. Furthermore, graft polymer powders having different crosslinked acrylic rubber structures were blended, and the results are shown in Example 2-3 in Table 4. Note that these blend formulations are not limited to two types of powders, but can also be applied to three or more types. The results are shown in Examples 2-4 to 2-
5. The following becomes clear from the results in Tables 3 and 4. That is, even when the crosslinked acrylic rubber has a multilayer structure, it is possible to improve the appearance of the injection molded product by blending graft polymer powders with different rubber particle sizes, as shown in Example 1. A similar effect can also be obtained by blending graft polymer powders with different crosslinked acrylic rubber structures. Furthermore, a similar effect can be obtained by blending three or more types of graft polymer powders.

【table】

[Table] Example 3 The effects of the different particle diameter rubber blend formulation shown in Examples 1 and 2 are not only exhibited in blending between powders, but are also effective in blending at the latex stage. For example, the graft polymer latexes A-1 and A-6 obtained in Example 1 are blended in a 50/50 ratio and then coagulated to obtain a blended powder. The same evaluation as in Example 1 was carried out by blending this powder with MAG pearls. As expected, the results were not significantly different from those of Example 1-2. Example 4 As the hard thermoplastic resin (C) to be blended with the graft polymer in Example 1, suspension polymerized particles having various compositions (indicated by weight ratio) as shown in Table 5 were produced. Then, two types of graft polymers A-1 and A-6 having different rubber particle diameters and this hard thermoplastic resin were blended at a weight ratio of 25/25/50, and the same evaluation as in Example 1 was performed.
The results are shown in Examples 4-1 to 4-3 in Table 5. Note that the average rubber particle diameter in the rubber blend with different particle diameters in this example is 0.24μ. Furthermore, the hard thermoplastic resin produced in Example 4 is blended with A-4, whose rubber particle diameter is approximately equal to the average rubber particle diameter of Example 4, at a weight ratio of 50/50,
Its basic physical properties were evaluated. The results are shown in Comparative Examples 4-1 to 4-3 in Table 5. The following becomes clear from Table-5. That is, regardless of the composition of the hard thermoplastic resin, a formulation in which rubbers with different particle sizes are blended has a superior injection molded appearance compared to a formulation in which rubbers with monodisperse particle sizes are blended. Example 5 In the blending operation of Example 1, A-1, A-
In addition to 6 and MAS pearl, ABS resin (butadiene-
Styrene rubber content is 50%) were blended in this order so that the blend weight ratio was 20/20/50/10, and a test piece was prepared in the same manner as in Example 1.
Various physical properties were evaluated. At this time, the notched isot strength was 16 kg·cm/cm ² . Moreover, the injection molded appearance was also at the same level as Example 1-2.

【table】

[Table] Example 6 A crosslinked acrylic ester rubber latex with a rubber particle size of 0.10μ was prepared in the same manner as in Example 1.
Subsequently, in the presence of the resulting rubber, the following mixture
Graft polymerization was carried out by continuous injection over 120 minutes. AN 12.5 parts St 37.5 parts n-octyl mercaptan 0.05 parts Benzoyl persulfide 0.25 parts The polymerization rate reached 99% about one hour after injection. The latex thus obtained was poured into twice the amount of calcium chloride aqueous solution (3% by weight) with stirring and coagulated, and then dehydrated, washed and dried to obtain a rubber particle size of 0.10μ. A graft polymer powder (C-1) was obtained. Pellets used in rubber polymerization in the same manner as below.
Rubber particle size by changing the amount of OTP
A 0.34μ graft polymer powder (C-2) was obtained. 50 parts of suspension polymerized particles (AS Pearl) obtained by separately polymerizing a monomer mixture of AN/St=25/75 (% ratio) to 50 parts each of these C-1 and C-2 powders. parts are blended and pelletized using an extruder. At this time, the crosslinked acrylic rubber content in the blended resin composition is 25%. At this time, 1 part of barium stearate and 0.1 part of Tinuvin P (manufactured by Ciba Geigy, ultraviolet absorber) were blended into the resin composition. The pellets thus obtained were injection molded to obtain various test pieces and their physical properties were measured. These results are shown in Table 6 for Comparative Examples 5-1 and 5-2.
Shown below. 50 parts of a mixture of C-1 and C-2 powders blended in the ratio shown in Table 7 and the above AS
Blend with 50 parts of pearl to make the crosslinked rubber pigment 25%. Various physical properties of this resin composition were measured. The results are shown in Table-7.

【table】

[Table] Example 7 A crosslinked acrylic ester rubber latex with a rubber particle size of 0.10μ was prepared in the same manner as in Example 1.
Subsequently, in the presence of the resulting rubber, the following mixture
Graft polymerization was carried out by continuous injection over 120 minutes. MMA 30 parts St 20 parts n-octyl mercaptan 0.05 parts Benzoyl persulfide 0.25 parts The polymerization rate reached 99% about one hour after injection. The latex thus obtained was poured into twice the amount of calcium chloride aqueous solution (3% by weight) with stirring and coagulated, and then dehydrated, washed and dried to obtain a rubber particle size of 0.10μ. A graft polymer powder (D-1) was obtained. Pellets used in rubber polymerization in the same manner as below.
Rubber particle size by changing the amount of OTP
A 0.34μ graft polymer powder (D-2) was obtained. 50 parts of suspension polymerized particles (MS pearls) obtained by separately polymerizing a monomer mixture of MMA/St = 60/40 (% ratio) to 50 parts each of these D-1 and D-2 powders. and pelletize using an extruder. At this time, the crosslinked acrylic rubber content in the blended resin composition is 25%. At this time, 1 part of barium stearate and 0.1 part of Tinuvin P (manufactured by Ciba Geigy, ultraviolet absorber) were blended into the resin composition. The pellets thus obtained were injection molded to obtain various test pieces and their physical properties were measured. These results are shown in Table 8 for Comparative Examples 6-1 and 6-2.
Shown below. 50 parts of a mixture of D-1 and D-2 powders blended in the ratio shown in Table 9 and the above MS
Blend with 50 parts of pearl to make the crosslinked rubber pigment 25%. Various physical properties of this resin composition were measured. The results are shown in Table-9.

【table】

【table】 [Brief explanation of drawings]

FIG. 1 is a calibration curve showing the relationship between the latex particle diameter determined by electron microscopy and the absorbance of a diluted latex solution at a wavelength of 700 mμ. FIG. 2 is a schematic diagram of a method for measuring scattered light intensity, and FIG. 3 is a scattered light intensity curve.

Claims (1)

[Claims] 1 In the presence of crosslinked acrylic ester rubber,
Graft polymer (I) obtained by graft polymerizing at least one kind of aromatic vinyl monomer and at least one kind of vinyl cyanide monomer and unsaturated acid ester monomer, aromatic Hard thermoplastic resin obtained by polymerizing at least one type of vinyl monomer and at least one type of vinyl cyanide monomer and unsaturated acid ester monomer ()
Thermoplastic resin containing 90 to 30% by weight and diene rubber-containing thermoplastic resin () 0 to 50% by weight, and the total amount of (I), (), and () is 100% by weight. In the composition, when the graft polymer (I) is graft-polymerized, the average particle diameter of the crosslinked acrylic ester rubber in the emulsion is
90 to 10% by weight of at least one type of graft polymer (I-1) obtained using a small particle size rubber having a monodisperse particle size distribution in the range of 0.05 to 0.24μ and the average particle size of 0.25 to 0.50 At least one kind of graft polymer (I-2) obtained using a large particle diameter rubber having a monodisperse particle diameter distribution in the range of 10 to
90% by weight of a thermoplastic resin composition having outstanding impact resistance and weather resistance and an injection molded appearance.