JPS6314016B2 - - Google Patents

Description

[Detailed description of the invention]

"Industrial Application Field" The present invention is a graft copolymer resin obtained by copolymerizing an ethylene-α-olefin rubbery polymer with a monomer mixture consisting of an aromatic vinyl compound and a vinyl cyanide compound. A copolymer obtained by polymerizing a composition and a monomer mixture consisting of a methacrylic acid ester compound, an aromatic vinyl compound, and a vinyl cyanide compound, and has improved weather resistance, impact resistance, and molding processability. The present invention relates to a thermoplastic resin composition having excellent properties. "Prior art" A copolymer obtained by graft copolymerizing a monomer mixture consisting of an aromatic vinyl compound and a vinyl cyanide compound to an ethylene-α-olefin rubber polymer, such as an ethylene-propylene rubber, or , and a resin composition (A) consisting of a copolymer of an aromatic vinyl compound and a vinyl cyanide compound (AES
Resin) has moldability, molded appearance, impact resistance, heat resistance,
This resin has excellent mechanical strength and chemical resistance, making it suitable for injection molding and extrusion molding. Furthermore, since there are no double bonds in the main chain of the rubbery polymer, it has excellent weather resistance. However, conventional methods have had the problem of poor coloring properties. The method for coloring the molding material is to blend the resin with a coloring agent such as an organic or inorganic pigment or dye, a dispersant, a lubricant, etc. as necessary, melt and knead it into colored pellets, and then mold the pellets. The method is common. Regarding colorability in these methods, there is a tendency for colors to be easily colored and colors to be difficult to color depending on the color and transparency of the material itself. Colorability is an important criterion for material selection. However, rubber-modified resins such as ABS resins are said to have slightly inferior coloring properties in certain color tones compared to homogeneous resins. The inventors have investigated that, even among the same rubber-modified resins, AES resin has particularly bright colors, deep colors, and
The jet black tone system lacked sharpness and depth, and a large amount of coloring agent was required to achieve the same level of color depth. "Problems to be Solved by the Invention" As a result of intensive studies on these points, we found that a monomer mixture consisting of the resin composition (A), a methacrylic acid ester compound, an aromatic vinyl compound, and a vinyl cyanide compound was polymerized. Obtained copolymer (B)
The present invention was developed based on the recognition that colorability can be improved by blending the following in a specific ratio. ``Means for Solving the Problems'' That is, the present invention provides a method for copolymerizing a monomer mixture consisting of an aromatic vinyl compound and a vinyl cyanide compound in the presence of an ethylene-α-olefin rubbery polymer. Graft copolymer resin composition (A) 80~
20 parts by weight and 35 to 90 parts of methacrylic acid ester compound
Copolymer (B) 20-80% by weight, obtained by polymerizing a monomer mixture consisting of 5-60% by weight of an aromatic vinyl compound and 5-60% by weight of a vinyl cyanide compound.
Parts by weight of thermoplastic resin compositions. The resin composition of the present invention has superior coloring properties compared to conventional AES resins, and can produce vivid colors that are difficult to express with conventional AES resins. Pigment requirements are reduced. Furthermore, the resin composition of the present invention has excellent weather resistance and molded appearance, and has a good balance of physical properties between impact resistance and moldability, further enhancing the characteristics of AES resins. AES resin, ethylene-propylene copolymer or ethylene-propylene used in the present invention
Ethylene-α- such as non-conjugated diene copolymers
A graft copolymer obtained by copolymerizing a monomer mixture consisting of an aromatic vinyl compound and a vinyl cyanide compound in the presence of an olefinic rubbery polymer, or a copolymer of the same and the monomer mixture. It is a resin composition consisting of AES resins can be produced by various methods in which vinyl monomers are radically polymerized in the presence of rubber, such as emulsion polymerization, bulk polymerization, suspension polymerization, and solution polymerization.
Intrinsic viscosity [η] of the matrix resin (solvent soluble content) in the resin composition (A) (methyl ethyl ketone, 30
C) is preferably in the range of 0.3 to 0.8. Aromatic vinyl compounds used as monomers include styrene-α-methylstyrene and p-methylstyrene. Further, the vinyl cyanide compound is selected from acrylonitrile, methacrylonitrile, and the like. Furthermore, a small amount of vinyl compounds copolymerizable with these, such as alkyl acrylates such as methyl acrylate and methyl methacrylate, and alkyl methacrylates, may be used in combination. The rubber content in the AES resin used in the present invention is 10
A suitable range is 60% by weight, more preferably 15% to 50% by weight. Copolymer (B) used in combination with AES resin
As the methacrylic acid ester compound used in
Weight%. If the amount is less than this range, the colorability cannot be improved, and if it is more than this range, the balance between moldability and impact resistance will be poor. As the aromatic vinyl compound, styrene, α-methylstyrene, or a mixture thereof is preferably used in an amount of 5 to 60% by weight.
It is appropriate to use it, preferably 10 to 50% by weight; if the amount exceeds this range, coloring properties cannot be improved;
If the amount is too low, the balance between impact resistance and moldability will be poor. As the vinyl cyanide compound, acrylonitrile is preferred, and it is appropriate to use 5 to 60% by weight, preferably 10 to 50% by weight; if it exceeds this range, a large amount of pigment will be required to match the hue after coloring. Become. Moreover, if it is less than this range, impact resistance will decrease. The manufacturing method may be any of emulsion polymerization, suspension polymerization, bulk polymerization, and the like. The blending ratio of AES resin (A) and copolymer (B) is in the range of 80:20 to 20:80 by weight. Preferably 70:
30-30:80. If the amount of AES resin exceeds this range, the colorability, which is one of the characteristics of the present invention, will hardly be improved. On the other hand, if the amount of AES resin is less than this range, the impact resistance will be lowered, which is not preferable. The mixture of AES resin and copolymer may be mixed in a solution-solution or solution-latex state after the weight is finished, and then the resin composition may be recovered, or the resin composition may be recovered from both. Powder - powder, powder -
They may be mixed in the form of pellets, pellet-pellets, etc. During mixing or pelletizing, commonly used antioxidants, lubricants, etc. can also be added. "Example" Next, the present invention will be specifically explained by referring to an example. Note that the AES resin and copolymer used in the examples were manufactured by the following method. Manufacture of AES resin <AES resin No. 1> Iodine value 15, Mooney viscosity 42, and 5-ethylidene-2-norbornene as the diene component were made into a homogeneous solution in advance in a stainless steel autoclave with an internal volume of 50 and equipped with a ribbon-type stirring blade. Contains 20 parts by weight of EPDM (JSR EP22 manufactured by Japan Synthetic Rubber Co., Ltd.), styrene
56 parts by weight, 120 parts by weight of toluene, and 0.1 part by weight of tertiary decyl mercaptan were charged, the temperature was raised while stirring, and at 50°C, 24 parts by weight of acrylonitrile, 0.5 parts by weight of benzoyl peroxide, and 0.1 part by weight of dicumyl peroxide were added. Then, the temperature is further increased and after reaching 80°C, the polymerization reaction is carried out at a stirring rotation speed of 100 rpm while controlling the temperature to be constant at 80°C. It took 1 hour from 6 hours after the start of the reaction to 120
The temperature was raised to .degree. C., and the reaction was continued for an additional 2 hours to complete the reaction. The polymerization rate was 97%. After cooling to 100℃, 2,2'-methylene-bis(4-methyl-6-
After adding 0.2 parts by weight of t-butylphenol,
The reaction mixture was extracted from the autoclave, most of the unreacted monomers and solvent were distilled off by steam distillation, and after finely pulverized, volatile components were substantially distilled off using a 40 mmφ vented extruder (220°C > 700 mmHg vacuum). The polymer was recovered as pellets. <AES Resin No. 2> Same method as above <AES Resin No. 1> except that 35 parts by weight of EPDM, 45.5 parts by weight of styrene, 19.5 parts by weight of acrylonitrile, 180 parts by weight of toluene, and 0.05 parts by weight of tertiary decyl mercaptan were used. A polymer was obtained. Production of copolymer (B) <Polymer No. 1> 55 parts by weight of methyl methacrylate, 20 parts by weight of styrene, 25 parts by weight of acrylonitrile, which were uniformly dissolved in a stainless steel autoclave with an internal volume of 50 mm equipped with a ribbon-type stirring blade, Add 30 parts by weight of toluene and 0.3 parts by weight of tertiary decyl mercaptan, raise the temperature while stirring, add 0.1 part by weight of dicumyl peroxide at 50°C, and further raise the temperature to 120°C.
After reaching this temperature, the reaction was carried out for 10 hours at a stirring speed of 100 rpm while controlling the temperature to be constant at 120°C. The polymerization yield was 90%. The subsequent treatments were performed in the same manner as <Manufacture of AES resin> to obtain a polymer. <Polymer No. 2> After sufficiently replacing the inside of a stainless steel reactor with a stirrer with nitrogen, add 200 parts by weight of ion-exchanged water in a nitrogen stream,
Add 2 parts by weight of potassium rosinate, and while stirring, add 70 parts by weight of methyl methacrylate, 5 parts by weight of styrene, 15 parts by weight of acrylonitrile, 10 parts by weight of α-methylstyrene, 0.2 parts by weight of tertiarydecyl mercaptan, and sodium formaldehyde sulfonate. Water salt 0.4 parts by weight, sodium ethylenediaminetetraacetate 0.2 parts by weight, ferrous sulfate 0.005 parts by weight
parts by weight, and 0.3 parts by weight of cumene hydroperoxide are added. The polymerization reaction was carried out at 70° C. for 4 hours while stirring was continued. The polymerization yield at this time was 96%. After coagulating using water-soluble sulfuric acid, dehydration and drying were performed to obtain a polymer. <Polymer No. 3> Except for 45 parts by weight of methyl methacrylate, 15 parts by weight of styrene, and 40 parts by weight of acrylonitrile,
A polymer was obtained in the same manner as the above <Polymer No. 2>. <Polymer No. 4> A polymer was obtained in the same manner as for <Polymer No. 2> above, except that 45 parts by weight of methyl methacrylate, 40 parts by weight of styrene, and 15 parts of acrylonitrile were used. <Polymer No. 5> 60 parts by weight of methyl methacrylate, 40 parts by weight of styrene, 30 parts by weight of toluene, and 0.2 parts by weight of tertiary decyl mercaptan were charged, the temperature was raised, and after reaching 140°C, the temperature was kept constant at 140°C. A polymer was obtained in the same manner as the above <Polymer No. 1>. <Polymer No. 6> The above <Polymer No. 1> except that 65 parts by weight of methyl methacrylate and 35 parts by weight of acrylonitrile were used.
A polymer was obtained in the same manner as above. <Polymer No. 7> A polymer was obtained in the same manner as for <Polymer No. 2> above, except that 25 parts by weight of methyl methacrylate, 50 parts by weight of styrene, and 25 parts by weight of acrylonitrile were used. Examples Examples 1 to 5, Comparative Examples 1 to 7 The AES resin pellets and copolymer (B) pellets obtained by the above method were heated in a 40 mmφ extruder (220°C).
The resin compositions shown in the table were obtained by melt-kneading.
Test pieces were molded using a 90TON injection molding machine (220°C) and their physical properties were measured. The resulting resin composition was passed through an extruder in the following formulation to obtain colored pellets, which were molded to obtain a color tone evaluation plate. Regarding the colorability of the black blend, the lightness was measured using a color difference meter and expressed as a Munsell color table value (the larger the value, the worse the colorability). For other coloring formulations, saturation was determined visually. Black compound resin 100 Carbon black 0.5 Ca stearate 0.3 Red compound resin 100 Red red 1.0 Ca stearate 0.5 Blue compound resin 100 Ultramarine blue 1.0 Ca stearate 0.5 Regarding weather resistance, Izot impact value after 1000 hours irradiation with Sunshine Weatherometer was measured. The results are shown in the table.

【table】

[Table] In the formulations of Examples 1 to 5, the
The same level of blackness and color saturation as ABS resin was obtained.
On the other hand, in Comparative Examples 1 and 2, examples of AES resin alone were given, but in this case, compared to the ABS resin mentioned in the reference example, the black blend has lower blackness, and the red and blue blends have different color impressions, but Munsell Compared to the color chart, the chroma was inferior. In addition, Comparative Example 3 uses a copolymer (B) that does not use vinyl cyanide, and Comparative Example 4 uses a copolymer (B) that does not use aromatic vinyl. In Comparative Example 3, the colorability can be improved. However, the balance between moldability and impact resistance becomes poor. On the other hand, in Comparative Example 4, both colorability and impact resistance are poor.
In addition, in Comparative Examples 5 and 6, examples were given in which the amount of methyl methacrylate in the copolymer (B) exceeded the range, but when the amount of methyl methacrylate was small, no improvement in coloring property was observed; If there is a large amount, the balance between moldability and impact resistance is poor, and the impact resistance is particularly poor. In Comparative Example 7, an example was given in which the amount of AES was above the range of the present invention, but if the amount of AES was large, no improvement in coloring property was observed. Examples 6 to 8, Comparative Examples 8 to 12 Using No. (1) used in Example 1 as the AES resin,
The physical properties of the composition were determined in the same manner as in Example 1, except that the copolymer (B) was manufactured in the same manner as copolymer No. (2) with each composition shown in the following table. was measured. The results are shown in the table below.

[Table] "Effects of the Invention" As is clear from the above, according to the present invention, a monomer mixture consisting of an aromatic vinyl compound and a vinyl cyanide compound is co-produced in the presence of an ethylene-α-olefin rubbery polymer. By blending a graft copolymer composition obtained by polymerization and a copolymer obtained by polymerizing a monomer mixture consisting of a methacrylic acid ester compound, an aromatic vinyl compound, and a vinyl cyanide compound in a specific ratio. As a result, a thermoplastic resin composition with improved colorability and an excellent balance between moldability and impact resistance can be obtained.

Claims (1)

[Claims] 1 Graft copolymer resin composition (A) 80 to 20 obtained by copolymerizing a monomer mixture consisting of an aromatic vinyl compound and a vinyl cyanide compound in the presence of an ethylene-α-olefin rubbery polymer weight part,
Copolymer (B) 20-80 obtained by polymerizing a monomer mixture consisting of 35-80% by weight of a methacrylic acid ester compound, 5-60% by weight of an aromatic vinyl compound and 5-60% by weight of a vinyl cyanide compound A thermoplastic resin composition comprising parts by weight.