JP2673114B2 - Colorant composition - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to coloring of thermoplastic resins,
Styrene-based thermoplastics such as polystyrene resin (PS resin), acrylonitrile-butadiene-styrene copolymer resin (ABS resin), acrylonitrile-styrene copolymer resin (AS resin), acrylonitrile-EPDM-styrene copolymer resin (AES resin), among others. The present invention relates to a colorant composition (masterbatch) suitable for coloring a resin. Conventionally, colored pellets having the same composition as the final colored molded article have been used for coloring and molding thermoplastic resins, but in recent years, coloring agents have been used for the purpose of reducing coloring costs. In order to reduce the amount of the pigment added, a masterbatch, which is a colorant composition containing a high concentration of pigment, has been favorably used. As such a masterbatch, a masterbatch of the same kind as the thermoplastic resin whose base resin is colored was used. However, these masterbatches have the drawback of (1) lacking versatility. Furthermore, JP-A-52-53955, JP-A-52-53956, and JP-A-59-18750.
In the case where a masterbatch for coloring an ABS resin or AS resin, such as that disclosed in Japanese Patent Publication No. JP-A-2003-264, uses an ABS resin or AS resin as a base resin, (2) a master containing a high concentration of pigment. Batch production is difficult. Even if such a masterbatch can be produced, (3) ABS resin and AS resin have low transparency, and therefore, when colored with such a masterbatch, uneven coloring or weld marks on the surface of the colored molded product obtained can be obtained. However, there is a problem in that the tendency tends to occur, especially when the amount of the masterbatch added is small, the tendency is remarkable. In addition, since AS resin, ABS resin, and AES resin place great importance on mechanical properties, the strength reduction due to addition of the masterbatch is extremely small. The AS resin, ABS resin, and AES resin are dried and mixed with the masterbatch immediately afterwards. Or, after being mixed with the masterbatch and then dried and molded, the masterbatch or the resin pellets to be colored with the masterbatch are not fused to each other, and are not fused to the inner wall of the drying device. Is required. It was extremely difficult to satisfy these requirements and solve the above problems. DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention solves the above problems, contains a high concentration of dyes and pigments, has excellent pigment dispersibility, and has PS resin, AS resin, ABS resin and AES. Even when used for coloring styrenic thermoplastic resins such as resins,
There is no fusion of master batches between master batches during drying or pellets of resin to be colored with the master batch, and even if the addition amount is small, coloring unevenness and weld marks do not occur on the surface of the obtained colored molded product, The present invention provides a colorant composition (masterbatch) capable of coloring various thermoplastic resins without adversely affecting the mechanical properties of the colored molded article. The present invention mainly comprises the following (a), (b) and (c):
The ratio of (a), (b) and (c) is (a), (b)
And (c) are in the ranges of 10 to 40% by weight, 10 to 60% by weight and 10 to 80% by weight with respect to the sum total, respectively, and a colorant composition for coloring a thermoplastic resin. (A) a block copolymer of a conjugated diene compound and an aromatic monovinyl compound, or a thermoplastic elastomer obtained by using a hydrogenated derivative of the block copolymer in combination therewith (b) a low molecular weight styrene polymer, One or more kinds of one or more kinds of dispersant (c) pigments and dyes selected from polyethylene wax, polypropylene wax, and their derivatives, and ethylenebisamides. In the present invention, as the thermoplastic elastomer (a), a block copolymer of a conjugated diene compound and an aromatic monovinyl compound is used. Examples of the conjugated diene compound include 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene and isoprene, and examples of the aromatic monovinyl compound include styrene, α-methylstyrene and vinyltoluene. As such a block copolymer, one having an aromatic monovinyl compound content of 15 to 80% by weight and a molecular weight of 30,000 to 3 are used.
It is preferably 0,000, especially 50,000 to 200,000, and as such, "Clearene" (trade name, manufactured by Denki Kagaku Kogyo Co., Ltd.) series, "Califlex TR"
(Shell Chemical Co., Ltd., trade name) series, "JIS
SBR ”(product name of Nippon Synthetic Rubber Co., Ltd.) series,
"Toughprene" (Asahi Kasei Kogyo Co., Ltd. product name) series is available. When the content of the aromatic monovinyl compound in such a block copolymer is less than 15% by weight,
At the time of masterbatch production, pellets are likely to adhere to each other and defective cutting is likely to occur. When it exceeds 80% by weight, the obtained colored molded product tends to have uneven coloring or deterioration of mechanical properties. If the molecular weight of the block copolymer is less than 30,000 or more than 300,000, the processability during masterbatch production and the mechanical properties of the resulting colored molded article tend to be poor. In the present invention, it is preferable to use the hydrogenated derivative of the above block copolymer in combination from the viewpoint of heat resistance and weather resistance. As such hydrogenated derivative, "Kraton" (shell Made by Kagaku Co., Ltd.
Product name) series, "Elastomer AR" (product name of Aron Kasei Co., Ltd.) series, "Lavalon" using hydrogenated SBS (product name of Mitsubishi Yuka Co., Ltd.) series,
"Sumitomo TPE-SB" (Sumitomo Chemical Co., Ltd., trade name) series is available. In the present invention, if the content of the conjugated diene compound in (a) is high, it may be difficult to uniformly mix the resulting masterbatch with the thermoplastic resin to be colored. It is preferable to plasticize with a plasticizer, oil, etc., or to complex with a small amount of polyolefin-based resin, styrene-based resin, or the like. In the present invention, as the dispersant (b), low molecular weight styrenic polymers are essential and are selected from the group consisting of polyethylene wax, polypropylene wax and their derivatives, and ethylene bisamides.
One kind or two or more kinds are used in combination. Low-molecular-weight styrene polymers are low-molecular-weight polystyrene, low-molecular-weight styrene and other monomers 1
It is a copolymer of two or more species, and its molecular weight is 5
It is preferable to use 000 to 100,000, and typical examples of such low molecular weight styrenic polymers are "Haimer SB" and "Regit S" (both are trade names manufactured by Sanyo Chemical Industry Co., Ltd.) Each series, "Elaststyrene"
(Dainippon Ink and Chemicals, Inc., trade name) and "Picolastic D" (both manufactured by Shell Chemical Co., Ltd., trade name) series. When the molecular weight of the low molecular weight styrene-based polymer is less than 5,000, the dispersion stability of the pigment is low, and the resulting colored molded product tends to have poor pigment dispersion. However, the viscosity of the dispersant becomes high, a large amount of energy is required to disperse the pigment during the production of the masterbatch and during the coloring and molding, and the loosening of the masterbatch and the resulting colored molded article tend to be uneven. Examples of polyethylene wax, polypropylene wax, and derivatives thereof include polyethylene wax and polypropylene wax, and those obtained by modifying these with unsaturated acids or unsaturated acid anhydrides such as maleic acid, acrylic acid, and maleic anhydride. There are such metal salts and those treated with oxidation, and among these, it is preferable to use those having a molecular weight of 500 to 30,000. As typical examples of such polyethylene wax, polypropylene wax, and derivatives thereof, there are "AC polyethylene" (trade name of Allied Chemical Co., Ltd.) series, "high wax" (manufactured by Mitsui Petrochemical Industry Co., Ltd., Product name) There is a series. In the present invention, (c) one of pigments and dyes
As the kind or two or more kinds, organic pigments and dyes such as azo type, anthraquinone type, phthalocyanine type, quinacridone type, isoindolinone type, dioxazine type, perylene type, quinophthalone type, perinone type, cadmium sulfide, selenium Inorganic pigments such as cadmium chloride, ultramarine blue, titanium white, red iron oxide, lead oxide chromate, and carbon black. Colorant composition of the present invention (masterbatch)
Is mainly composed of (a), (b) and (c) above, and the proportion of (a), (b) and (c) is (a),
10 to 4 for the sum of (b) and (c), respectively.
It is characterized by being in the range of 0% by weight, 10 to 60% by weight and 10 to 80% by weight. When the content of (a) is less than 10% by weight, the manufacturing process of the masterbatch becomes difficult, and the mechanical strength, drying resistance and heat resistance of the obtained masterbatch become low, and the content of (a) is If the amount exceeds 40% by weight, the mechanical strength and heat resistance of the obtained colored molded product will be low. The compounding amount of (b) is 10
If it is less than 10% by weight, the dispersion of the pigment during the production of the masterbatch and at the time of coloring and molding will be poor, and coloring unevenness will easily occur on the surface of the obtained colored molded product, and the compounding amount of (b) will be 60% by weight. If it exceeds, the mechanical strength and heat resistance of the obtained colored molded article will be low. In addition, when the content of (c) is less than 10% by weight, the addition amount must be increased in order to achieve sufficient coloring, the coloring cost increases, and the mechanical properties of the obtained colored molded product are increased. When the strength and heat resistance become low and the content of (c) exceeds 80% by weight,
The fluidity and the dispersibility of the pigment become low, the production of the masterbatch becomes difficult, and uneven coloring of the obtained colored molded product easily occurs. The colorant composition of the present invention contains (d) a plasticizer, an antioxidant, an ultraviolet absorber, an antistatic agent, an extender pigment, a flame retardant, and a pigment dispersion, if necessary, within a range that does not impair its performance. Additives such as surfactants can be added in order to save the heat. The colorant composition of the present invention is usually used in the form of pellets, but the method for producing the pelletized form is not limited, and includes (a), (b), (c) and if necessary. A method of kneading (d) with a kneader such as a kneader or a Banbury mixer, and then pelletizing with a two-roll or extruder, (a), (b), (c) and (d) if necessary 2. A method of kneading and repelletizing by a shaft extruder,
There is a method in which (b) and (c) are uniformly mixed and kneaded by a heated three-roll mill or the like, (c) is predispersed in (b), and then the remaining components are added to form a pellet. As the thermoplastic resin colored with the colorant composition of the present invention, various resins including styrene type thermoplastic resins such as AS resin, ABS resin, AES resin and PS resin, which have been difficult to be colored in the past, are included. The thermoplastic resin can be mentioned. EXAMPLES The present invention will be described below with reference to examples. In the examples, “parts” means “parts by weight”. Example 1 "Clearene 750L" (styrene content 70% by weight) 30 parts "AC polyethylene 6A" (molecular weight 4800) 10 parts "Legetto S-120" (molecular weight 8400) 17 parts Titanium white "Taipeque CR-50" (Ishihara) Sangyo Co., Ltd., trade name 42 parts Carbon Black "Mitsubishi Carbon MA-100" (Mitsubishi Kasei Kogyo Co., Ltd., trade name) 1 part After kneading the mixture of the above composition with a kneader, pelletizing with an extruder , Got a masterbatch. 3 parts of the obtained masterbatch and 100 parts of ABS resin "Clarastic MH" (trade name, manufactured by Sumitomo Nogatac Co., Ltd.) were mixed,
After drying at 90 ° C. for 3 hours, a colored molded product was manufactured by an injection molding machine. Drying resistance of the masterbatch at this time, the state of uneven coloring of the obtained colored molded article, and the mechanical properties of the molded article obtained by molding the colored thermoplastic resin in the uncolored state (tensile strength, The retention rate of mechanical properties of the obtained colored molded article was evaluated when the bending elastic modulus, bending strength and Izod impact value) were set to 100%. Table 2 shows the results of the evaluation. The evaluation method and the display of the results are as follows. Drying resistance of masterbatch: The presence or absence of fusion during drying is visually evaluated. ◯: No fusion, Δ: Some fusion was present. Colored state of the colored molded product: visual evaluation. ○: No coloring unevenness, ×: Significant coloring unevenness. Retention of mechanical properties of colored molded products: Tensile strength is JIS
Bending elastic modulus and bending strength are JIS
K-7203, Izod impact value is JIS K-711
Measured according to 0. ◯: 96% or more, Δ: 90% or more and less than 96%, ×: 90
%Less than. Comparative Examples 1 to 8 and Example 2 In the same manner as in Example 1 except that the mixture having the composition shown in Table 1 was used, a masterbatch was prepared and a colored molded product was produced and evaluated. The evaluation results are also shown in Table 2. [Table 1] [Table 2] [0021] Conventionally, sufficient coloring could not be achieved unless a large amount of a master batch of 5 to 10 parts by weight was added to 100 parts by weight of the thermoplastic resin to be colored, but the coloring agent of the present invention was used. In the composition, since the pigment concentration is extremely high, 2 to 3 parts by weight relative to 100 parts by weight of the thermoplastic resin to be colored,
Depending on the conditions, by adding 1 to 3 parts by weight, sufficient coloring can be performed without adversely affecting the mechanical properties of the obtained colored molded article,
The cost required for coloring can be reduced. Further, particularly in injection molding, since the mixing ability is inferior to that in extrusion molding, coloring unevenness was remarkable when the conventional master batch was used, but when the colorant composition of the present invention was used, it was Even when a colored molded article is manufactured, it is possible to obtain a colored molded article having no color unevenness with a small amount of addition. The colorant composition of the present invention is applicable to coloring of various thermoplastic resins and has high versatility. The conventional masterbatch could not achieve uniform coloring and high drying resistance without adversely affecting the mechanical properties of the obtained colored molded article.
Uniform coloring of styrene-based thermoplastic resins such as resins, ABS resins, AES resins, and PS resins is also achieved by using the colorant composition of the present invention, without adversely affecting the mechanical properties of the obtained colored molded article. can do. When the mechanical properties of the molded product made of non-colored resin is 100%,
The retention rate of mechanical properties of the molded article colored with the colorant composition of the present invention reaches 96% or more. Further, even when the colorant composition of the present invention is applied to a resin such as an AS resin, an ABS resin, or an AES resin that needs to be dried and dried at 80 to 90 ° C., the masterbatch between the master batches has a high drying resistance. of,
Alternatively, the masterbatch and the thermoplastic resin pellets to be colored are not fused to each other, and since they are not fused to the inner wall of the drying device, the drying device is not contaminated.

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Claims (1)

(57) [Claims] It mainly consists of the following (a), (b) and (c), and the ratio of (a), (b) and (c) is (a),
10 to 4 for the sum of (b) and (c), respectively.
A coloring agent composition for coloring a thermoplastic resin, which is in the range of 0% by weight, 10 to 60% by weight and 10 to 80% by weight. (A) a block copolymer of a conjugated diene compound and an aromatic monovinyl compound, or a thermoplastic elastomer in which a hydrogenated derivative of the block copolymer is used in combination therewith (b) a low molecular weight styrene polymer , Polyethylene wax, polypropylene wax and their derivatives, and one or more dispersants (c), which are used in combination with one or more selected from the group consisting of ethylene bisamides.