JPS5941461B2 - How to color ABS resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for coloring an acrylonitrile-butadiene-styrene copolymer resin (hereinafter referred to as "ABS resin") using an organic solvent-stable or unstable copper phthalocyanine pigment.

More specifically, the present invention uses a copper phthalocyanine pigment and a phthalimidomethyl copper phthalocyanine pigment (weight ratio 100:0).
．． This is a method for coloring ABS resin, which is characterized in that the ABS resin is colored using a mixture of 5 to 50).

The colorant for ABS resin has the properties required for other thermoplastic resins, such as coloring strength, weather resistance, migration resistance,
It must have excellent chemical resistance, etc., and at the same time
It is necessary to withstand the severe conditions peculiar to S resins, that is, high molding temperatures and the discoloration and fading effect of the colorant due to the butadiene component in the resin.

For this reason, the number of colorants suitable for ABS resin is extremely small compared to other thermoplastic resins, and in some cases, the amount of colorant used is increased even though the colorant is known to be inadequate. is the current situation. Conventionally, to color ABS resin blue, oil-soluble dyes (e.g., C, I, s
solventBlue35, C, I, solventB
blue 36, C, I, solvent Blue 87) or inorganic pigments (for example, ultramarine), but the former has relatively good tinting strength, heat resistance, and weather resistance, but has the drawback of poor migration resistance. On the other hand, the latter has good heat resistance, weather resistance, and migration resistance, but has the drawbacks of extremely low tinting strength and extremely poor chemical resistance (particularly acid resistance).

Here, low tinting strength means that a large amount of coloring agent is required for a given coloring, and along with this, ABS
This is not preferable because it results in a decrease in impact resistance, which is a major feature of the resin. Copper phthalocyan blue is relatively used as an organic pigment.

This copper phthalocyanine pigment has excellent fastness,
Because it has a clear hue and high tinting power, it is widely used as a useful coloring agent for various purposes, but when coloring thermoplastic resins, there are generally differences in thermal stability between types. Naturally, different copper phthalocyanine pigments are used depending on the molding processing conditions. For example, a more reddish-blue organic solvent-stable copper phthalocyanine pigment can be colored and molded at temperatures up to 200°C, while a greenish-blue organic solvent-stable copper phthalocyanine pigment can be processed up to 250-260°C. , and a low chlorinated copper phthalocyanine pigment that exhibits a blue color between them is 300
If the temperature is up to ℃, the situation is as follows. Therefore, in terms of molding temperature, organic solvent-stable copper phthalocyanine and low-chlorinated copper phthalocyanine can be used for coloring ABS resin.

However, from the viewpoint of discoloration and fading due to the action of the butadiene component, which is another condition specific to the coloring of ABS resin, the former is inappropriate, and in the end, the coloring of ABS resin with copper phthalocyanine blue requires less chlorinated copper phthalocyanine. The only option was to use pigments. However, the use of low chlorinated copper phthalocyanine pigments has the problem that it is considerably more expensive than other copper phthalocyanine pigments and that the hue is limited to intermediate blue.

The present inventors have finally arrived at the present invention as a result of intensive studies to solve the above problems.

That is, the present inventors have discovered that the high-temperature coloring molding process of ABS resin can be carried out without any of the above limitations by mixing phthalimidomethyl copper phthalocyanine, which is easy to produce and inexpensive, with a copper phthalocyanine pigment. It was.

This is presumed to be because phthalimidomethyl copper phthalocyanine contributes to preventing crystal growth of the copper phthalocyanine pigment due to heat and suppressing the influence on discoloration and fading due to the butadiene component in the ABS resin. Therefore, according to the method of the present invention, even if stable or unstable copper phthalocyanine is used for coloring and molding at high temperatures, the hue hardly changes and there is no deterioration due to high heat, making it suitable for industrial use. ABS resin can be colored at low cost.

The molded product thus obtained has no practical problems in terms of performance such as weather resistance, migration resistance, chemical resistance, and dispersibility. The ABS resin targeted by the present invention is
Unlike general thermoplastic resins such as polyolefin resins, polystyrene resins, or polymethyl methacrylate resins, it is impossible to discuss suitability based solely on the influence of temperature, and the influence of the butadiene component of ABS resin described above must be taken into account. There is a need.

For example, organic solvent-stable copper phthalocyanine pigments, polycondensed azo pigments, perylene pigments, anthraquinone pigments such as brominated andanthrone and indanthrone, and dioxazine pigments can withstand high temperatures and are compatible with polyolefin resins or polystyrene resins. However, it shows significant discoloration and fading when used with ABS resins, making it unsuitable for practical use. From these facts, it is extremely noteworthy that ABS resin can be well colored by the method of the present invention. In the present invention, the copper phthalocyanine pigment refers to an organic solvent-stable copper phthalocyanine pigment, an unstable copper phthalocyanine pigment, or a mixture thereof, which is produced and pigmented by a known method.

In the present invention, the phthalimidomethyl copper phthalocyanine pigment is represented by the following formula (wherein CuPC represents a copper phthalocyanine residue, and n is 0.5 to 8, preferably 1 to 3).

), which can be obtained easily and inexpensively by, for example, reacting 1 mole of copper phthalocyanine, 0.2 to 8 moles of phthalimide, and paraformaldehyde in concentrated sulfuric acid, then pouring into ice water and separating. It will be done. The amount used is 0.5 to 50% of the copper phthalocyanine pigment.
% by weight, preferably from 1 to 20% by weight.

Here, if it is less than 0.5% by weight, no effect can be expected, and if it is more than 50% by weight, migration becomes significant, which is not preferable. Since the phthalimidomethyl copper phthalocyanine pigment itself has low coloring power, its blending has little effect on the overall hue.

For coloring, first, a stable or unstable copper phthalocyanine pigment or a mixture of both pigments and the phthalimidomethyl copper phthalocyanine pigment obtained by the above method are mixed in a dry or wet state to form a coloring agent. .

In order to improve the dispersion state of the obtained colorant in the resin,
It is advantageous to use conventionally known dry colors or so-called processed pigments such as masterbatches. Coloring of ABS resin can be carried out by conventionally known methods. For example, the colorant and resin of the present invention, and if necessary, other pigments, oil-soluble dyes, and various additives are mixed in a mixer such as a drum tumbler or a high-speed mixer, and then an extruder, an injection molding machine, or a mill mill is used. The desired colored molded product can be obtained using processing machines such as the following. The amount of the coloring agent of the present invention added to the resin is not particularly limited, but is usually 0.01 to 2% by weight based on the resin.

As described above, the method of the present invention makes it possible to significantly expand the field of use of stable and unstable copper phthalocyanine pigments, and has great industrial value. Examples of the present invention are as follows.
This will be explained in detail with reference examples.

In the examples, parts mean parts by weight. Production Example 1 [Production of phthalimidomethyl copper phthalocyanine pigment] 20 parts of copper phthalocyanine is dissolved in 200 parts of concentrated sulfuric acid, 13 parts of phthalimide and 4 parts of paraformaldehyde are added, and the mixture is stirred at 80°C for 3 hours.

Thereafter, it was poured into cold water, washed with water, and dried to obtain phthalimidomethyl copper phthalocyanine. Example 12 4 parts of the finely powdered phthalimidomethyl copper phthalocyanine pigment obtained in Production Example 1, 36 parts of the finely powdered unstable copper phthalocyanine pigment, and 60 parts of zinc stearate were premixed and pulverized and mixed using a pulverizer. 40% dry color 2.5
1 part, 5 parts of titanium oxide (Product name: Taipeku R-820 manufactured by Ishihara Sangyo) and ABS resin (Product name: Clarastic M)
H Natural (manufactured by Sumitomo Naugatatsu)) were thoroughly mixed in a square mixer, and then heated at 230°C for 3 minutes using an in-line screw injection molding machine (manufactured by Nissei Plastics).
Test pieces were prepared for 10 minutes at °C and their heat resistance was compared.

As a result, almost no discoloration or fading was observed, and good heat resistance was obtained. Moreover, the chemical resistance of the colorant obtained by mixing and the migration resistance of the colored molded product were good. J Example 2 Production example 1
4 parts of the finely powdered phthalimidomethyl copper phthalocyanine pigment obtained in . , 36 parts of stable copper phthalocyanine pigment in fine powder, 60 parts of zinc stearate were premixed, and 2.5 parts of 40% dry color obtained by grinding and mixing in a pulverizer, 5 parts of titanium oxide, and 1000 parts of ABS resin. The mixture was thoroughly mixed with a square mixer, and a test piece was prepared in exactly the same manner as in Example 1 using an in-line starille complete injection molding machine, and the heat resistance was compared.

As a result, almost no discoloration or fading was observed, and good heat resistance was obtained. Moreover, the chemical resistance of the colorant obtained by mixing and the migration resistance of the colored molded product were good. Example 3 Wet cake of the phthalimidomethyl copper phthalocyanine pigment of Production Example 1 (purity 28.2% by weight)
) and 280.5 parts of a wet cake of unstable copper phthalocyanine pigment (purity 30.3% by weight) were placed in a glass beaker, and an appropriate amount of water was added to make the contents into a slurry. Mix for an hour.

Thereafter, a mixture of 40 parts of cake obtained by over-drying, 60 parts of zinc stearate, 25 parts of 40% by weight dry color obtained by pulverizing and mixing, 15 parts of titanium oxide and AB
S resin (product name JSR-35 manufactured by Japan Synthetic Rubber) 1000
The components were thoroughly mixed in a super mixer, and test pieces were prepared for 3 minutes at 230°C, 10 minutes at 270°C, and the heat resistance was compared in the same manner as in Example 1. As a result, almost no discoloration or fading was observed, and good heat resistance was obtained. Furthermore, the chemical resistance of the colorant obtained by drying and the migration resistance of the colored molded product were good. Example 4 6 parts of the finely powdered phthalimidomethyl copper phthalocyanine pigment obtained in Production Example 1, 17 parts of the finely powdered unstable copper phthalocyanine pigment, 17 parts of the finely powdered stable copper phthalocyanine pigment, 42 parts of zinc stearate, and calcium stearate. 1
40% by weight obtained by crushing and mixing 8 parts with a 1 horsepower crusher
2.5 parts of dry color, 10 parts of Titanium Eroichi (trade name Taipeku Eroichi TY-70 manufactured by Ishihara Sangyo) and 1000 parts of ABS resin were thoroughly mixed in a square mixer, and colored pellets were formed using a 30mmφ extruder at 220°C. I got the trick.

Using an in-line screw type injection molding machine, test pieces were made from these colored pellets at 230°C for 3 minutes and 270°C for 10 minutes, and the heat resistance was compared. Almost no discoloration or fading was observed, indicating good heat resistance. Obtained. Moreover, the chemical resistance of the colorant obtained by mixing and the migration resistance of the colored molded product were good. Reference Example 1 Tested in exactly the same manner as in Example 1 except that 40 parts of finely powdered unstable copper phthalocyanine pigment was used instead of 4 parts of phthalimidomethyl copper phthalocyanine pigment and 36 parts of unstable copper phthalocyanine pigment in Example 1. When we made pieces and compared their heat resistance, we found that the 270 and C10 test pieces were significantly discolored compared to the 230 and C3 test pieces.
It could not withstand conditions of 70°C.

Reference Example 2 Tested in exactly the same manner as in Example 2, except that 40 parts of finely powdered stable copper phthalocyanine pigment was used instead of 4 parts of phthalimidomethyl copper phthalocyanine pigment and 36 parts of stable copper phthalocyanine pigment in Example 2. When I made a piece and compared the heat resistance, it was 27 compared to the 230 method C3 test piece.
The test piece for 10 minutes at 270°C showed considerable discoloration.
I couldn't stand the 0 minute condition.

Claims (1)

[Claims] 1 AB characterized in that ABS resin is colored using a mixture of copper phthalocyanine pigment and phthalimidomethyl copper phthalocyanine pigment (weight ratio 100:0.5-50)
How to color S resin.