JPH01152141A - How to color thermoplastic resin - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention provides a method for coloring a thermoplastic resin by using a high-concentration ε-type copper phthalocyanine pigment with a bright red hue and a specific copper phthalocyanine derivative. <Prior art> Copper phthalocyanine exists in many homogeneous quantities, of which the reddish α type (unstable type) and the greenish β type (stable type) are well known as pigments and are often used industrially. has been done. On the other hand, the ε-type copper phthalocyanine pigment is a pigment that has attracted attention in recent years because of its bright red color and high concentration. This ε-type copper phthalocyanine pigment was
No. 0, Special Publication No. 52-6300, Special Publication No. 52-6301
No., JP-A-53-39325, JP-A-57-1414
No. 53 and JP-A No. 57-149358 describe the manufacturing method, its properties, performance, etc., but as a coloring agent for thermoplastic resin, it is not always satisfactory in terms of economy, performance, such as heat resistance, etc. isn't it. When coloring thermoplastic resins, treatment and processing are carried out at high temperatures, so the copper phthalocyanine pigments used must also have heat resistance. For this purpose, an expensive low-chlorinated copper phthalocyanine with a hue intermediate between the α-type and β-type is used. <Problems to be Solved by the Invention> Coloring processing of thermoplastic resins generally tends to raise the processing temperature from the viewpoint of productivity, workability, etc., and is usually carried out at a temperature of 200° C. or higher. For example, in polyolefin resin, 2
High-temperature processing such as 80 to 300°C, and 260 to 280°C for ABS resin, is also being performed. Under such conditions, even β-type copper phthalocyanine has insufficient heat resistance, and therefore, at present, 1. There is nothing that can be used other than expensive low chloride copper phthalocyanine. Thus, at present, an inexpensive copper phthalocyanine pigment that has heat resistance comparable to low-chloride steel phthalocyanine and has a reddish hue and high concentration has not yet been found. Means for Solving the Problems In order to solve these problems, the present inventors have conducted various studies and found that an ε-type copper phthalocyanine pigment (I), preferably an ε-type copper phthalocyanine obtained by a specific manufacturing method. By coloring a thermoplastic resin using a pigment and a specific imidomethyl copper phthalocyanine derivative (II), it is possible to color a thermoplastic resin with excellent economic efficiency, a high concentration of redness, and good heat resistance. This discovery led to the completion of the present invention. That is, the present invention uses an ε-type copper phthalocyanine pigment and the general formula (
II) CuPc +CL-X)m (II)(C
uPc is a copper phthalocyanine residue, X is (in the formula, m is
This is a method for coloring a thermoplastic resin, characterized in that it is used in combination with an imidomethyl copper phthalocyanine derivative represented by 0.5 to 2.0. In the present invention, as the ε-type copper phthalocyanine pigment (1), a compound capable of forming a phthalocyanine ring, urea, a copper compound, and a catalyst are mixed in a sulfolane solvent with the following formula (A) CuPc +5OJ) n (A ) (CuP
c- is a copper phthalocyanine residue, M is H, or alkali metal n is 0.2 to 3) Preferably used. In particular, the ε-type copper phthalocyanine pigment produced by this method has even higher industrial utility value in that it can be used without undergoing the usual pigmentation treatment. The method of the present invention will be explained in more detail below. First, a method for producing ε-type copper phthalocyanine (1), which is preferably used in the present invention, will be described. Examples of the compound capable of forming a phthalocyanine ring to be used include phthalic acid, phthalic anhydride, phthalimide, phthalamic acid and its salts or esters, phthalic acid esters, phthalonitrile, and the like. Particularly preferred are phthalic acid, phthalic anhydride, and phthalimide. Examples of the copper compounds used include metallic copper, cupric or cupric halides, copper oxide, copper sulfate, copper acetate, copper cyanide, copper nitrate, copper sulfide, copper hydroxide, etc. It will be done. The amount of the copper compound used is about 1 to 1.2 mol per 4 mol of the phthalocyanine ring-forming compound. The amount of urea used in the reaction is phthalocyanine! The amount is about 4 to 30 moles per 4 moles of the forming compound. Any conventionally known reaction catalyst can be used, but examples include molybdenum compounds such as ammonium molybdate and molybdenum oxide, and titanium compounds such as titanium tetrachloride and titanate esters. The amount used is 0.0 per 4 moles of phthalocyanine ring-forming compound.
It is about 1 to 1.0 mol. Furthermore, it is important to use sulfolane as a solvent, and specific examples of sulfolane solvents used here are:
Examples include sulfolane, methylsulfolane, dimethylsulfolane, etc., and the amount used may be at least 3.0 times the weight of the compound capable of forming a phthalocyanine ring, but preferably 4.5 to 10.0 times the weight of the compound capable of forming a phthalocyanine ring. Good condition. Here, the sulfolane solvent alone can be used, but other solvents such as dimethyl sulfoxide (DMSO) can also be used in combination as necessary. The copper phthalocyanine sulfonic acids to be allowed to coexist are preferably the following - Tsuzuriyo (A) (wherein M represents a hydrogen atom or an alkali metal atom,
n represents 0.2 to 3. ) is a compound represented by Specific examples include and. The compound represented by (A) above includes both a single compound and a mixture, and n in the formula A represents the total number of sulfonic acid groups with respect to the gold copper phthalocyanine nucleus in the single compound or mixture. It is something. n is 0.2-3
．． 0, particularly preferably 0.5 to 2.0. Further, the amount of the compound represented by (A) is not particularly limited, but is generally preferably 1 to 20% by weight, particularly 1 to 10% by weight, based on the phthalocyanine ring-forming compound. As the reaction temperature, a range of 150 to 250°C is sufficient. Further, the compound represented by the above-mentioned term "-" may be added at any time before the phthalocyanine ring is formed. The obtained copper phthalocyanine can be recovered by distilling off the solvent under reduced pressure from the reaction mass, then washing the powder with warm water or a mineral acid solution, and filtering it, or by diluting the reaction mass with warm water, etc., and then filtering it. There is a way to do it. It is noteworthy that the ε-type steel phthalocyanine obtained by the above method does not require a product production process such as a mechanical atomization process, and can be obtained with pigment suitability only by a synthesis reaction. Imidomethyl copper phthalocyanine derivative (
Specifically, as IF), a compound represented by the following formula is preferably used. or (in the formula, ffi and ffi' represent numbers from 0.5 to 2.0) these imidomethyl copper phthalocyanine derivatives (
The method for producing II) includes, for example, reacting 1 mole of copper phthalocyanine with 0.5 to 2.0 moles of phthalimide or tetrahydrobutalimide and paraformaldehyde in sulfuric acid, and then pouring into ice water and separating. It can be easily obtained by As the thermoplastic resin referred to in the present invention, polyolefin resins such as polyethylene and polypropylene, or ABS resins are particularly suitable for coloring.
These resins are usually colored and molded at 200°C or higher. In the coloring method of the present invention, ε-type copper phthalocyanine II
The mixing ratio of IF-1 (I) and imidomethyl copper phthalocyanine derivative (II) is (1): (
II) =98:2-7Q:3Q, more preferably (
I): (II)=97:3~85:1
It is preferable that it is 5. The method for coloring a thermoplastic resin according to the present invention can be carried out by a conventionally known method. For example, the ε-type copper phthalocyanine pigment (I), copper phthalocyanine derivative (■), resin, and various additives of the present invention are mixed in a mixer such as a tumbler or mixer, and then processed using an extruder, injection molding machine, roll mill, etc. Depending on the machine, desired coloring can be achieved. ε-type copper phthalocyanine pigment of the present invention for resin (1)
The amount of addition of phthalocyanine derivative (II) and phthalocyanine derivative (II) is not particularly limited, but it is usually appropriate that the total amount of both is about 0.01 to 2% by weight based on the resin. <Effects of the Invention> According to the method of the present invention, it is possible to produce a reddish color at low cost in coloring thermoplastic resins at high temperatures, which has conventionally been considered difficult to use for anything other than expensive low-chlorinated copper phthalocyanine. It is now possible to color thermoplastic resins with a vivid taste and high concentration. Further, the ε-type pigment used in the present invention does not require a post-synthesis pigmentation process (for example, mechanical atomization) that is normally applied to copper phthalocyanine pigments, and is an excellently economical pigment. In addition, the effect of adding the phthalocyanine derivative (ilP-Blue) is the α-type (Stn, Cy, Blue He-2
) is still insufficient, but it is surprising that it is extremely remarkable and specific for the ε-type pigment of the present invention. <Examples> The present invention will be described in more detail below by giving Examples, Comparative Examples, and Reference Examples. In addition, parts and % in the examples are based on weight, and specific surface area values are BET.
The N2 gas phase adsorption method was adopted. Example-1

[Synthesis of ε-type copper phthalocyanine pigment-1] 592 parts of phthalic anhydride, 960 parts of urea, 105 parts of cuprous chloride, 80 parts of titanium tetrachloride, and copper phthalocyanine sulfonic acid (n=o in - Tsuzuriyo (A), 9) 30 parts were added to 4500 parts of sulfolane, the temperature was raised to 180 to 190°C with stirring, and the mixture was heated at the same temperature for 5 hours. Next, the mixture was cooled to 100°C, and 5000 parts of warm water previously kept at 60°C was added. Then, the reaction mass is filtered, and after the filtration is completed, it is washed with 5000 parts of 80° C. warm water. Thereafter, the wet cake taken out was added to 10,000 parts of 2% hydrochloric acid, stirred at 60°C for 1 hour, and then filtered. Next, 80℃ hot water too
By washing with oo part and drying, 590 parts of the desired copper phthalocyanine pigment were obtained. The purity of the obtained compound was 95%, and the specific surface area was 65 m'/g. Moreover, the crystal type showed ε type.

[Synthesis of copper phthalocyanine derivative (II)] 20 parts of copper phthalocyanine is dissolved in 200 parts of concentrated sulfuric acid, 1005 parts of phthalimide and 3.7 parts of paraformaldehyde are added, and the mixture is stirred at 80°C for 3 hours. Thereafter, by pouring into 1000 parts of water, filtering, washing with water, and drying, phthalimidomethyl copper phthalocyanine (hereinafter referred to as MP-Blue l) containing 1.1 substituents represented by the formula for copper phthalocyanine was obtained. I got 2.4 copies.

[Performance in polyolefin resin coloring]

After mixing 20.5 parts of Tie with a mixer, the mixture was kneaded and dispersed using an extrotor at 220°C to produce colored pellets. The colored pellets were molded using a 3.5 oz injection molding machine at 220°C to 300°C, and the hue and heat resistance were evaluated. The mixed product of the ε-type copper phthalocyanine pigment and the phthalocyanine derivative (MP-Blue) produced by the method of the present invention has the following distinctive and excellent performance: ■ Excellent heat resistance compared to the α-type, ε-type, and β-type. Monochlorophthalocyanine (Stn, Cy, Blue BH3
) has a heat resistance close to or higher than. ■Of course, it has a bright red color and high concentration for the α type as well. Example 2 In Example 1, injection molding was performed at 230 to 280°C using Talalastic M) I Natural (manufactured by Sumitomo Chemical, ABS resin) instead of Noblen AH-661V (PP resin), and performance evaluation was performed. . As in Example 1, the coloring of the ε-type pigment of the present invention by the phthalocyanine derivative has a bright reddish hue and high concentration, and has heat resistance similar to that of monochlorocopper phthalocyanine. Example-3

[Synthesis of ε-type steel phthalocyanine pigment-2] 592 parts of phthalic anhydride, 960 parts of urea, 105 parts of cuprous chloride, 50 parts of titanium tetrachloride, and sodium copper phthalocyanine sulfonate (
- Binding allowance (I) 30 parts of n=1.9) was added to 4,500 parts of sulfolane, the temperature was raised to 180 to 190°C with stirring, and the mixture was heated at the same temperature for 5 hours. Next, the mixture was cooled to 100°C, and 5000 parts of warm water previously kept at 60°C was added. Next, the reaction mass was filtered, and after the filtration was completed, it was heated to 80°C.
Wash with 5000 parts of warm water. After that, the removed wet cake was added to 10,000 parts of 2% hydrochloric acid and heated to 60℃ for 1 hour.
After stirring for an hour, it was filtered. Next, the mixture was washed with 10,000 parts of 80°C warm water and dried to obtain 585 parts of copper phthalocyanine pigment. The purity of the obtained compound was 96%, and the specific surface area was 70 m'/g.
Met. The crystal type was ε type.

[Performance in polyolefin resin coloring]

Using the ε-type copper phthalocyanine pigment-2 obtained above, the performance was evaluated in the same manner as in Example-1.
Coloring with type pigment and phthalocyanine derivative, Example-
Similar to 1, good results were obtained. Example-4 In the synthesis of the copper phthalocyanine derivative of Example-1,
The following derivative-2 was obtained by using tetrahydrophthalimide in place of phthalimide. Using this, performance evaluation with ABS resin was performed in the same manner as in Example-2, and as a result, good results were obtained as in Example-2.

Claims (4)

[Claims] (1) ε-type copper phthalocyanine pigment (I) and general formula (II)
) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (CuPc is a copper phthalocyanine residue, 1. A method for coloring a thermoplastic resin, characterized in that it is used in combination with an imidomethyl copper phthalocyanine derivative represented by the formula (m represents 0.5 to 2.0). (2) ε-type copper phthalocyanine pigment (I) contains a compound capable of forming a phthalocyanine ring, urea, a copper compound, and a catalyst in a sulfolane solvent using the following general formula (A) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (A ) (CuP is a copper phthalocyanine residue, M is H or an alkali metal, and n is 0.2 to 3) It is an ε-type copper phthalocyanine pigment obtained by reacting in the coexistence of copper phthalocyanine sulfonic acids. A method according to claim 1, characterized in that: (3) The usage ratio of ε-type copper phthalocyanine pigment (I) and imidomethyl copper phthalocyanine derivative (II) is (I)
:(II)=98:2 to 70:30 (weight ratio). (4) Thermoplastic resin is polyolefin resin or ABS
The method according to any one of claims 1 to 3, characterized in that the material is a resin.