JPS5853670B2 - Manufacturing method of isoindolinone pigment - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing isoindolinone pigments.

More specifically, it is an isoindolinone-based product that has excellent purity, clarity, saturation, coloring power, gloss, and various resistances such as light resistance, weather resistance, and chemical resistance, and has excellent transparency and extremely fine particle shape. This invention relates to a method for producing pigments.

It is well known that isoindolinone pigments are useful as yellow high-grade organic pigments.

Also, the manufacturing method is described in Japanese Patent Publication No. 34-4488, No. 36-
It is disclosed in detail in the specifications related to No. 3826, No. 51-42610, etc.

However, pigments produced by the methods disclosed in these publications often contain trace amounts of unreacted raw materials and reaction by-products, resulting in poor clarity, chroma, light resistance, weather resistance, and chemical resistance. etc., and it is not possible to obtain products that are fully satisfactory for uses such as paints, printing inks, and colorants for plastics.

In addition, organic pigments including isoindolinone pigments generally have the disadvantage of poor dimensional stability of plastic molded products when used as colorants for plastics, and it is known that this effect is particularly large in polyolefin resins. ing.

Various studies have been conducted to improve the dimensional accuracy of plastic molded products, and the shape of pigment particles is also considered to be a factor in dimensional stability.

As colorants for plastics, there is a strong demand for fine pigments with uniform particle shapes that are in a stable dispersion state.

Means for improving various physical properties of isoindolinone pigments are known, and methods for obtaining fine pigments include the following.

(1) An isoindolinone pigment is suspended in a hydrophilic organic solvent, a base capable of forming a salt is added thereto, an alkali salt of the pigment is formed, and the amount of hydrophilicity is such that the pigment salt is considerably dissolved. A method of hydrolysis using acid or water in the presence of an organic solvent (Japanese Patent Publication No. 47-39565).

(2) Dissolve the indolinone pigment in concentrated sulfuric acid, dilute it with water and reprecipitate it to form a fine pigment (60-100?
7Z2/P), the resulting fine pigment is dissolved in an alkaline aqueous solution to form an alkali salt, and this is hydrolyzed using acid or water (JP-A-52-124022).

However, in method (1) above, the alkali salt of the isoindolinone pigment dissolves well in a hydrophilic organic solvent, so if the pigment salt is to be separated, the hydrophilic organic solvent used must be concentrated to dryness. It is necessary to perform operations such as
The pigment salt obtained in this manner reintroduces impurities contained in the crude pigment.

Therefore, it cannot be purified at this pigment salt stage.
After liberating the fine pigments, hydrophilic solvent separation and washing must be performed to remove impurities.

Therefore, in order to fully demonstrate its refining effect,
Solvents that are expensive and have high boiling points and are difficult to recover must be used.

Furthermore, since the hydrophilic organic solvent used in method (1) freely mixes with water, complicated equipment and complicated operations are required for its recovery and wastewater treatment.

Furthermore, when crude pigments are produced in a hydrophobic solvent (Japanese Patent Publication No. 3
4-4488. When using crude pigments such as Japanese Patent Publication No. 51-42610), it has drawbacks such as the necessity of replacing the solvent with a hydrophilic organic solvent.

In addition, the method (2) above requires that the crude pigment must be dried, that a large amount of concentrated sulfuric acid must be used, and that the fine pigment must be filtered and thoroughly washed. This is disadvantageous in terms of equipment and wastewater treatment.When dissolving in sulfuric acid or diluting sulfuric acid, heat is generated, so the pigment itself is partially hydrolyzed and its purity decreases. Water-alkali systems have drawbacks such as insufficient formation of alkali salts of pigments.

Generally, as a method for refining pigments, there is a mechanical pulverization method using a ball mill or the like.

However, since isoindolinone pigments are hydrophobic, foaming phenomenon is observed when mechanically pulverized in an aqueous wet system, resulting in poor pulverization efficiency.For this reason, it takes a lot of time to make pigments into fine particles. It is economically disadvantageous.

In addition, it is difficult to crush the pigment uniformly, and wear materials from the equipment are mixed into the crushed pigment, which impairs the quality of the resulting pigment.

Further, this pulverization cannot be performed with a dispersing machine such as a high-speed stirrer.

In view of the above-mentioned circumstances, the inventors of the present invention conducted extensive research in search of a method for producing highly pure and fine isoindolinone pigments. When reacted with a base in the presence of alcohol or alcohol and water, the formation of the pigment salt of the inindolinone pigment goes through an intermediate step of dissolution in the aromatic hydrocarbon solvent and is therefore extremely highly reactive. The fact that a pigment salt of high purity is precipitated, that this pigment salt is very easily micronized by mechanical means under water dispersion, and that this fine pigment salt is hydrolyzed produces fine grains with a well-defined particle shape. The present invention was completed based on the knowledge that a pigment with a unique color can be obtained.

That is, in the present invention, a crude isoindolinone pigment is dispersed in an aromatic hydrocarbon solvent, and an alkali metal or alkaline earth metal alcoholade or hydroxide and alcohol or alcohol and water are added to the pigment. forming an alkali salt, which is then separated, dispersed in water in the presence or absence of a dispersant, micronized by mechanical means, and then hydrolyzed with water or an acid. The present invention provides a method for producing fine isoindolinone pigments.

In the present invention, the crude isoindolinone pigment can be used regardless of its manufacturing method.

In particular, the present invention is advantageously applied to crude isoindolinone pigments produced by condensing 3,3,4,5,6,7-hexachloroisoindolin-1-one and diamines in an aromatic hydrocarbon solvent. Ru.

Without separating the crude isoindolinone pigment,
This is because the present invention can be applied immediately.

In addition, as the isoindolinone pigment used as a starting material in the present invention, bis-(4,5,6,7-tetrachloroisoindoline-1
-one-3-ylidene)-toluylenediamine (2,6
), bis-(4,5,6,7-tetrachloroisoindolin-1-one-3-ylidene)phenylenediamine (
1, 4), etc.

Examples of the aromatic hydrocarbon solvent include benzene, halogenated benzene, nitrobenzene, and alkylbenzene.

Monochlorobenzene, 0-dichlorobenzene, and 1,2.3-1-lichlor are completely dissolved as intermediates for forming pigment salts and have excellent ability to dissolve impurities in crude pigments. Benzene, nitrobenzene and the like are preferred.

These solvents can be used alone or as a mixture.

The amount of these solvents to be used does not need to be strictly limited, but in consideration of ease of operation and economic efficiency, they are usually used in an amount of about 3 to 20 times the weight of the crude isoindolinone pigment.

The base is not limited as long as it reacts with the isoindolinone pigment to form a pigment salt, but from the viewpoint of reactivity and availability, alkali metal alcoholades or hydroxides, particularly sodium methylate, sodium chloride, etc. Preferred are dium ethylate, caustic potash, caustic soda, and the like.

The amount of these bases used is 2 mol or more, preferably 2 to 2.5 mol, per 1 mol of the isoindolinone pigment.

Lower alcohols include methanol, ethanol, n
-propertool, 1so-propertool, n-butanol, 5ec-butanol, ethylene glycol, etc. are used.

Among these, it is preferable to use a combination of the sodium methylate or sodium ethylate and methanol or ethanol in terms of solvent management.

Further, instead of these alcohols, alcohols with a portion of water added thereto can also be used.

The amount of the alcohol or the mixture of alcohol and water to be used varies depending on the crude isoindolinone pigment used, the type and amount of aromatic hydrocarbon, or the type and amount of the base, but is usually 0.00% of the crude isoindolinone pigment used. 1 times the weight or more is sufficient.

However, if the amount is larger than necessary, some of the generated pigment salt may dissolve and the pigment salt may be lost when separating the pigment salt from the solvent, so some of the alcohol used may be It is necessary to distill it off.

In order to omit such a distillation operation, a ratio of 0.1 to 0.5 times by weight is appropriate.

When a crude isoindolinone pigment is dispersed in an aromatic hydrocarbon at the above-mentioned mixing ratio, and an alkali metal alcoholade or hydroxide and water or alcohol are added, the pigment salt formation reaction proceeds rapidly.

At this time, before the pigment salt precipitates, a state in which the pigment salt intermediate is dissolved in the solvent used is observed as an intermediate step, and the pigment salt precipitates immediately thereafter.

This reaction proceeds even at room temperature, but when heated to 40 to 70°C, the reaction proceeds more quickly.

The pigment salt thus produced is separated, optionally washed with a low-boiling solvent in which the pigment salt is insoluble, and dried in an atmosphere inert to the pigment salt.

The dried pigment salt is then dispersed in water in the presence or absence of a dispersant and micronized by mechanical means.

When dispersing the pigment salt in water, it is further advantageous to add a dispersant in order to improve the dispersibility of the resulting pigment.

Such a dispersant may be an anionic surfactant, a nonionic surfactant, or an anionic surfactant, but
In particular, alkali metal salts of higher fatty acids, alkylbenzene sulfonates, higher aliphatic sulfonates, higher alcohol surfactants, and the like are advantageously used.

It is very easy to make pigment salts fine, and any machine that uses impact force, shearing force, etc. to make particles fine or finely disperse them can be used, including a crusher such as a ball mill. , a disperser such as a high-speed stirrer.

Furthermore, the refinement can be carried out in an extremely short time, and a few minutes to about one hour is sufficient.

The fine pigment salt thus obtained is treated with a large amount of water or acid to be hydrolyzed and liberate the isoindolinone pigment.

The acid used at this time may be a mineral acid such as sulfuric acid or hydrochloric acid, or an organic acid such as acetic acid, but mineral acids are preferred from the viewpoint of subsequent treatment, especially waste water treatment.

The amount of these acids used may be any amount sufficient to neutralize the alkali.

According to the present invention, the aromatic hydrocarbon solvent used has a high solubility in raw material unreacted substances and reaction by-products contained in the crude isoindolinone pigment, and therefore brings about a great purification effect.

Furthermore, since the intermediate is once dissolved prior to the precipitation of the pigment salt, impurities inherent in the crude isoindolinone pigment particles are also transferred into the solvent used, further increasing the purification effect.

The precipitated pigment salt is insoluble in aromatic hydrocarbon solvents,
The separation operation is also easy.

Further, according to the present invention, since the pigment salt is very easily micronized by mechanical means under water dispersion, the processing time may be short and the quality of the resulting pigment is not impaired.

Further, since the pigment salt is finely divided by mechanical means and a portion is gradually released into the pigment, the pigment obtained after hydrolysis has an extremely well-defined particle shape.

Such fine and well-shaped pigments are particularly useful as colorants for plastics that require dimensional stability during molding.

Pigments as fine and well-shaped as those of the present invention cannot be obtained by mechanically grinding pigments using a conventional ball mill or the like.

In the present invention, there is no mixing of organic solvent with water, and there is no need for complicated solvent recovery or waste water treatment in known methods, which is very economically advantageous.

Furthermore, the aromatic hydrocarbon solvent used in the present invention is
Because it is the same type of solvent as the one used when producing crude isoindolinone pigments by reacting 3,3,4,5,6.7-hexachloroisoindolin-1-one and diamine, It is economically very advantageous because the present invention can be carried out by immediately adding an alkali metal alcoholade or hydroxide and water or alcohol to the isoindolinone pigment without once separating it. .

The isoindolinone pigment thus obtained has excellent purity, saturation, sharpness, coloring power, gloss, as well as light resistance, weather resistance, chemical resistance, etc., as is clear from the examples described below. It is a fine particle with good transparency and a regular shape.

The present invention will be explained in detail below with reference to examples.

In Examples and Reference Examples, all parts and subtractions indicate parts by weight and weight φ.

Example 1 To 800 parts of 0-dichlorobenzene, 3, 3, 4,
5゜6.7-hexachloroisoindolin-1-one 1
A solution of 19 parts of 2,6-dolyl diamine dissolved in 800 parts of 0-dichlorobenzene was added thereto, and the mixture was heated to 125°C for 2 hours.

The product was then filtered hot and washed sequentially with methanol and water to give bis-(4,5,6,7-tetrachloroisoindolin-1-one-3-ylidene)-tolylenediamine (2,6 103 parts of crude pigment of ) was obtained.

As shown in the electron micrograph in Figure 1, this pigment is columnar and coarse particles, with a surface area of 22?7Z2/ff (BE
T method).

100 parts of the obtained crude pigment and 22 parts of sodium methylate.
Disperse 5 parts in 1,500 parts of 0-dichlorobenzene to obtain about 4
Warmed to 5°C.

Next, 7 parts of methanol was added to the solution, which turned into a yellow homogeneous solution, and then a yellowish brown pigment salt precipitated.

After further stirring while heating to about 45° C., the precipitated pigment salt was filtered off, washed successively with O-dichlorobenzene and n-hexane, and dried under reduced pressure.

Next, pour the obtained pigment salt into a 2.6 ton pot with 1 ton of water.
, and glass spheres O and Sl- with diameters of 5 and 5, and micronized for 30 minutes in a vibrating mill (manufactured by Chuo Kakoki Co., Ltd.).

In the water slurry of the fine pigment salts thus obtained, 20%
100 parts of sulfuric acid water was added to neutralize and hydrolyze the pigment, which was then filtered, washed, and dried to obtain 95 parts of yellow powder.

As shown in the electron micrograph in Figure 2, this pigment is fine with a well-shaped particle, and has a specific surface area of 66d/7 (BE
T method).

A paint was prepared using the pigment obtained in this way, a coating film was created, and when compared with the coating film of the crude pigment, the pigment of this example was found to be superior in saturation, sharpness, tinting power, gloss, and transparency. , and was also excellent in various properties such as light resistance, heat resistance, and weather resistance.

Even when the pigment salt was hydrolyzed using 30% hydrochloric acid or water instead of the 20% sulfuric acid water of this example, a pigment having the same quality as the pigment of this example was obtained.

In addition, when refining the pigment salt, adding 1 part of Neogen-R (manufactured by Daiichi Kogyo Seiyaku) as a dispersant not only makes the dispersion of the pigment salt in the aqueous system more rapid, but also the resulting pigment The dispersibility into the vehicle was improved without any loss in quality. Even if a mixer (MX-830G manufactured by National) was used in place of the vibrating mill in this example, the same quality as in this example could be obtained. An excellent pigment was obtained.

Example 2 Bis-(4,5,6,7-tetrachloroisoindolin-1-one-3-ylidene)-phenylenediamine (1
, 4) 100 parts of pigment [specific surface area 25 gutter cooling (BET method)]
and 27.5 parts of sodium ethylate were dispersed in 1500 parts of 0-dichlorobenzene, and 40 parts of ethanol was added.
It was heated to 50°C.

The reaction proceeded immediately, and after the color of the reaction liquid changed from orange to reddish brown, it became a highly viscous slurry with the precipitation of the pigment soda salt.

After stirring while heating at the same temperature for 30 minutes, the reddish brown pigment salt was filtered, washed successively with 0-dichlorobenzene and n-hexane, and dried under reduced pressure.

Next, the obtained pigment salt was pulverized together with 1 t of water using a high-speed stirrer (manufactured by Tokushu Kika Kogyo) for 1 hour.

Thereafter, 96 parts of pigment were obtained in the same manner as in Example 1.

This pigment is a fine particle with a regular particle shape [specific surface area: 6
2rr? /ff (BET method)], the sharpness, chroma, coloring power, gloss and transparency were very excellent compared to pigments not subjected to this treatment.

Even when 25 parts of sodium methylate was used in place of the 27.5 parts of sodium ethylyl h used in this example, and the same amount of methanol was used in place of ethanol, a pigment of excellent quality was obtained in the same manner as in this example.

Example 3 When 75 parts of a 28% methanol solution of caustic potash was used in place of sodium methylate and methanol in Example 1, a pale yellow pigmented potassium salt was obtained. This pigmented salt was prepared in the same manner as in Example 1. When treated through the following steps, a pigment of excellent quality as in Example 1 was obtained.

In place of the pigment used in this example, if the pigment shown in Table 1 having the following structural formula is used and treated in the same manner as in this example, a high-quality product with the color tone shown in Table 1 will be produced. A pigment was obtained.

Example 8 32.5 parts of a 48% caustic soda aqueous solution and 40 parts of methanol were used instead of sodium methylate and methanol in Example 1.
A pale yellow pigment salt was obtained.

When this pigment salt was treated in the same manner as in Example 1, a pigment of the same excellent quality was obtained.

Example 9 O-dichlorobenzene, the crude pigment obtained by the reaction of 3,3,4,5,6,7-hexachloroisoindolin-1-one and 2,6-tolylenediamine in Example 1 Sura I
J-1500 parts (pigment content 96 parts) was maintained at 50'C,
When 27 parts of sodium methylate and 43 parts of methanol were added, a yellowish brown pigment salt was obtained once dissolved.

When this pigment salt is treated in the same manner as in Example 1, yellow pigment 93
part was obtained.

Compared to the pigment obtained by immediately removing F from the slurry and sequentially washing with 0-dichlorobenzene, methanol, and acetone, this pigment has a finer particle shape, and has better clarity, chroma, and The gloss, tinting power, transparency, etc. were far superior, and the heat resistance, etc. were also improved.

The same results as in this example were obtained even when monochlorobenzene or 1,2.3-1-lichlorobenzene was used in place of 0-dichlorobenzene in this example.

Reference Example 1 100 parts of the crude pigment obtained in Example 1 was dispersed in 1 t of water, and micronized under the same conditions as Example 1.

After pulverization for 10 hours, the mixture was washed with running water and dried.

The surface area of the obtained pigment is 2777Z2/f (BET method)
Met.

A coating film was prepared using the pigment obtained by this method in the same manner as described in Example 1, and when compared with the coating film of the pigment obtained in Example 1, the saturation, sharpness, coloring power, gloss, The transparency, weather resistance, and heat resistance were poor.

A mixer (manufactured by National) is used instead of the vibrating mill in this reference example.
MX-830G), no pigment pulverization was observed at all.

Resin coloring example The crude pigment of Example 2 and the obtained pigment were each added at 0.1% to high-density polyethylene, and molded using an injection molding machine at a molding temperature of 240°C and an injection pressure of 1000 Kg/cfr.
A flat plate was formed using L.

One week after molding, the length of the flat plate in the flow direction of the resin and in the direction perpendicular to the flow was measured, and the shrinkage rate was determined according to the following formula.

When the shrinkage rate of the resin in the direction of flow is A and the shrinkage rate of the resin in the direction perpendicular to the flow is B, the results were as follows.

A (%) B (rice) Shrinkage ratio (A/B) Crude pigment 3.03 1.23 2.46 Obtained pigment
1.90 1.80 1.0 It can be seen that the pigment obtained by the present invention has excellent dimensional stability during molding.

[Brief explanation of the drawing]

Figure 1 shows an electron micrograph (15,000x magnification) of the crude pigment obtained in Example 1, and Figure 2 shows an electron micrograph (45,000x magnification) of the pigment of Example 1 of the present invention. .

Claims (1)

[Scope of Claims] 1 A crude isoindolinone pigment is dispersed in an aromatic hydrocarbon solvent, and an alkali metal or alkaline earth metal alcoholade or hydroxide and alcohol or alcohol and water are added thereto. Isolation characterized in that an alkaline salt of the pigment is formed, which is then separated, dispersed in water in the presence or absence of a dispersant, micronized by mechanical means and hydrolyzed with water or with an acid. A method for producing indolinone pigments. 2. The method for producing an isoindolinone pigment according to claim 1, wherein an aromatic halogenated hydrocarbon is used as the aromatic hydrocarbon solvent. 3. The method for producing an isoindolinone pigment according to claim 2, using monochlorobenzene, 0-dichlorobenzene, or 1,2,3-trichlorobenzene as the aromatic halogenated hydrocarbon. 4 Claim 1 using sodium methylate or sodium ethylate as the alkali metal alcoholade
A method for producing an isoindolinone pigment according to any one of items 3 to 3. 5. The method for producing an isoindolinone pigment according to any one of claims 1 to 3, using caustic soda or caustic potash as the alkali metal hydroxide. 6. The method for producing an isoindolinone pigment according to any one of claims 1 to 5, in which 0.1 to 0.5 parts by weight of alcohol is used per 1 part by weight of the crude isoindolinone pigment. 7. The method for producing an isoindolinone pigment according to any one of claims 1 to 6, wherein methanol or ethanol is used as the alcohol. 8. The method for producing an isoindolinone pigment according to any one of claims 1 to 7, wherein a mineral acid is used as the acid. 9 Claim 1 in which an alkali metal salt of a higher fatty acid, an alkylbenzene sulfonate, a higher aliphatic sulfonate, or a higher alcohol surfactant is used as a dispersant.
A method for producing an isoindolinone pigment according to any one of items 8 to 8.