JPH07316448A - Production of copper phthalocyanine - Google Patents

Abstract

PURPOSE:To provide a process for producing copper phthalocyanine and/or its deriv. useful for dyes, pigments, and other applications at high purity and yield. CONSTITUTION:Copper phthalocyanine is produced by thermally reacting phthalic acid and/or its deriv., a nitrogen source (e.g. urea), a copper compd., and a catalyst (e.g. a molybdenum compd.) in an inert solvent in the presence of at least one activator. The activator is such a compd. that it acts as a dispersant for those reactants and catalyst in the solvent during the reaction and is decomposed by an acid or alkali in the step of purifying and/or pigment making after the reaction to thereby be removed or deactivated.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing copper phthalocyanine and / or a derivative thereof, which is useful in dyes and pigments and other fields, in high purity and in high yield.

[0002]

2. Description of the Related Art Conventionally, as a method for producing copper phthalocyanines, there has been industrially used a method of synthesizing phthalic anhydride and / or its derivative, a copper compound and urea by heating in an inert solvent in the presence of a catalyst. It is most commonly taken and is known as the urea or Weyler method. The above-mentioned urea method is a method which is widely used in the industry at present, but when the reaction process is examined, the raw material mixture, the reaction intermediate and the product are not completely dissolved and the reaction is heterogeneous throughout. In addition to the above, the viscosity of the system increases at the stage where the reaction intermediate is produced, resulting in poor mixing of the system, non-uniform heat transfer, and adhesion of resin-like reaction intermediate to the vessel wall. It not only causes the above problems, but also reduces the purity and yield of the product. Several proposals have hitherto been made to solve such drawbacks. For example, the stirring state of the system is improved by using a solvent having a high dissolving power,
The use of a solvent as small as twice the amount of phthalic acid gives a better effect on the reaction yield. However, the former is effective but it is not sufficient and there is a difficulty that it is not possible to freely select a solvent that is easy to handle. Also, the latter has a small amount of solvent and the viscosity of the system is high, so it is necessary to increase the stirring power and the strength of the device. There are drawbacks.

Japanese Patent Publication No. 5-5866 discloses that an anion activator is added to the reaction system to lower the viscosity and the solvent. This method certainly shows a great effect in improving the reaction system. However, on the other hand, there arises a problem that the anion activator present in the pigment lowers the interfacial tension of the offset printing ink with water and causes troubles such as plate stains during printing. It is extremely difficult to completely remove the anion activator added to the reaction system in the subsequent purification step and pigmentation step. Is not the solution. Therefore, a method for improving the condition of the reaction system to obtain copper phthalocyanine in high purity and high yield by a method that does not impair the suitability for use and economy is still in strong demand.

[0004]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention As a result of researches to solve the above problems and meet the demands, the present inventor can decompose phthalocyanine by an acid or an alkali in a reaction mixture when producing phthalocyanine by the urea method. When a certain type of activator is added, the viscosity of the reaction system decreases, the homogeneity of the system increases, and the reaction proceeds smoothly. Furthermore, the activator acting in the reaction system is further purified and / or pigmented in the subsequent steps. The present invention has been completed by finding that copper phthalocyanine can be obtained in high purity and in high yield, which can be decomposed and removed by an acid or an alkali or can be inactivated and does not cause a problem in suitability for use.

[0005]

That is, according to the present invention, phthalic acid and / or a derivative thereof, a nitrogen source such as urea, a catalyst such as a copper compound and a molybdenum compound are heated in an inert solvent to produce copper phthalocyanine. In the way
During the reaction, it has dispersibility in the above-mentioned inert solvent such as the above-mentioned raw material, catalyst and reaction product, and after the reaction, it is decomposed by acid or alkali in the purification step and / or the pigmentation step of the reaction product to be removed or inactive. The present invention relates to a method for producing copper phthalocyanine, which comprises adding one of the above activatable activators or a mixture thereof.

Furthermore, the present invention relates to a method for producing the above copper phthalocyanine, wherein the activator is a compound represented by the general formula (1). Formula (1) _{^{(R 1 -B) k -A (}} X m, Y n) ( wherein, R ¹ is a saturated or unsaturated aliphatic containing carbon atoms 1 to 20, B is -COO -, - OCO -, -CO-, A
Is a direct bond, a saturated or unsaturated aliphatic group which may be branched, a sorbitan residue, X is a hydrogen atom, a hydroxyl group, -C
OO ^- M ⁺ , Y is a hydrogen atom, a hydroxyl group,-(OCH ₂ CH
_{2) p -Z, -D-SO} 3 - M +, k is 1 or 2, m
And n represent 0 to 3, and p represents 1 to 20. Also here Z
Is ^{-OH, - (OCOR 2),} D is -O- or a direct bond, R ² is a saturated or unsaturated aliphatic radical containing carbon atoms 1 to 20, M represents K or Na. However, B is -OC
In the case of O- and -CO-, B is combined with A or Y to form -COO-. )

The present invention will be described in more detail. The phthalic acid and its derivative used in the present invention are phthalic acid and its alkali metal, ammonium and organic amine salts, phthalic anhydride, phthalimide, phthalic acid diamide, and phthalic acid. Rhodonitrile and 1,3-diiminoisoindoline and their benzene nuclei substituted with 1 to 4 halogen atoms and mixtures thereof. As the nitrogen source such as urea used in the present invention, 3 mol or more of urea is generally used for 1 mol of phthalic acid, but substituted urea such as biuret can also be used. When nitrogen-free phthalic acid such as phthalic acid or phthalic anhydride is used as a raw material, part of urea can be replaced with ammonia or ammonium compound in the first-stage imidization reaction. As the copper source used in the present invention, copper chloride is the most common, but copper salts such as metallic copper powder, copper oxide, copper sulfate, copper acetate and other copper salts such as copper chloride and ammonia, urea, and amines. It is also possible to use a complex compound of.

As the catalyst used in the present invention, ammonium molybdate is generally used, but molybdenum (VI) oxide, molybdic acid and the like can also be used. These catalysts are used in a ratio of 0.001 to 0.02 part as molybdenum content to 1 part of phthalic acid.
Further, as the inert solvent used in the present invention, nitrobenzene, trichlorobenzene, chloronaphthalene,
The solvent conventionally used for the production of copper phthalocyanine such as alkylbenzenes, alkylnaphthalenes and kerosenes can be used without limitation, and the amount used is 1 to 5 times that of phthalic acids, preferably 1.5 to 2 When the amount is 0.5 times the amount, the stirring becomes easy when the amount is large, but the yield of copper phthalocyanine tends to decrease, and when the amount is small, the viscosity increases and the stirring becomes difficult.

The activator which characterizes the present invention is obtained by a suitable hydrolysis condition such that only the activator is decomposed without decomposition of the reaction product in the reaction step of purifying copper phthalocyanine or the pigmentation step. It is a compound that loses its activity. As such an activator, anionic, nonionic, cationic and amphoteric activators having a structure that can be hydrolyzed by an acid or an alkali can be used. Particularly, in the molecule represented by the general formula (1), Those having at least one ester group such as an aliphatic ester group or a sorbitan ester group are preferred. The following can be given as examples.

Aliphatic polyhydric alcohol sulfate ester salt In the general formula (1), B is -CO- and A is-(OCH₂CH₂)
_p-, Y is -D-SO₃ ^-M⁺(D is -O-), k and
A compound characterized in that n is 1 and m is 0. Sulfoethanol fatty acid ester salt In the general formula (1), B is —COO—, A is a saturated aliphatic residue,
Y is -D-SO₃M⁺(D is a direct bond), n is 1, m is
Compound represented by 0 Alkyl sulfoacetate In the general formula (1), B is -OCO-, A is a saturated aliphatic group, Y
Is -D-SO₃M⁺(D is a direct bond), n is 1, m is 0
Compound represented by dialkyl sulfosuccinate R in the general formula (1)¹Is an alkyl group having 6 to 18 carbon atoms, B
Is -OCO-, A is an ethane residue, for example -CH₂-CH
= Group, Y is -SO₃Na group, k is 2, m is 0, n is 1
A compound

Monoalkyl sulfosuccinate R ¹ is an alkyl group having 6 to 18 carbon atoms in the general formula (1), B
Is -OCO-, A is an ethylene group, X is -COO ^- M ⁺ ,
Compound in which Y is a —SO ₃ ^— Na ⁺ group, k is 1, m and n are each 1 Polyoxyethylene monofatty acid ester R ¹ is an alkyl group having 5 to 17 carbon atoms in the general formula (1), B
There -CO-, A is a direct bond, Y is - (OCH ₂ -C
H _{2) p} -OH, k is the 1, m is 0, n 1, p is 1-2
Compound which is 0 Polyoxyethylene propylene glycol fatty acid ester R ¹ is an alkyl group having 5 to 17 carbon atoms in the general formula (1), B
There -COO-, A is propyl residue, Y is - (OCH ₂ -
CH ₂ ) _p —OH, a compound in which m is 0 and n is 1 Polyoxyethylene sorbitan monofatty acid ester R ^{1 in the} general formula (1) is an alkyl group having 5 to 17 carbon atoms, B
There -OCO-, A is sorbitan residue, X is -OH, Y is _{- (OCH 2 CH 2) p} -OH, k is the 1, m 0 to 3,
A compound in which n is 3 to 0 and p is 1 to 20, and these activators are preferably used in an amount of about 0.005 to 0.15 parts by weight with respect to 1 part of phthalic acids.

Conventionally known conditions can be applied to the production conditions such as temperature, time and pressure, and post-treatment conditions such as solvent removal and purification in the method for producing copper phthalocyanines according to the method of the present invention. The temperature is 160 to 220 ° C. and the time is 2-8 hours, pressure is normal pressure
It takes about 5 kilograms / square centimeter,
In particular, when these activators are used, the reaction system maintains a stable dispersed state throughout the course of the reaction, and the reaction proceeds smoothly, as compared with the case where these activators are not used. After completion of the reaction, the product is freed from the solvent by a conventional method, and then heated in an acid or alkali environment to hydrolyze and purify the activator used, whereby copper phthalocyanine having excellent suitability can be obtained. The operating conditions for hydrolysis with an acid or alkali are 0.5 to several hours at 70 to 100 ° C. in a 1 to 5 wt% solution. The amount of the acid or alkali solution is 5 to 100 parts by weight based on 1 part by weight of copper phthalocyanine.

[0013]

EXAMPLES Next, the present invention will be described with reference to examples. Parts and% in the text are based on weight unless otherwise specified. Example 1 59.2 parts phthalic anhydride, 78 parts urea, cuprous chloride 9.
7 parts, ammonium molybdate 0.592 parts, and Hisol P (Nippon Petrochemical's alkylbenzene solvent)
108 parts, in the general formula (1), R ¹ is an octyl group,
B is -OCO-, A is -CH ₂ -CH = group, Y is -SO
1. An activator having ₃ ^- Na ⁺ , k = 2, m = 0, and n = 1.
37 parts was reacted at 190 to 200 ° C. under normal pressure for 4 hours.
During this period, the system maintained a good mixed state and the reaction proceeded smoothly. After completion of the reaction, the solvent was removed by evaporation under reduced pressure, 1 part of the residual product was added with 10 parts of a 1% sodium hydroxide aqueous solution, the mixture was heated at 90 ° C. for 1 hour, filtered, washed with water and dried.
0 part (purity 98.2%, yield 95.5%) of crude copper phthalocyanine (crude-1) was obtained. Further, Crude-1 was pigmented by a conventional method to obtain β-type copper phthalocyanine pigment (Pigment-1). 5.0 g of Pigment-1 was moistened with 5 ml of methanol, dispersed in 200 ml of pure water, and stirred at 80 ° C. for 60 minutes. Then, the mixture was cooled to room temperature, pure water was added to adjust to 300 grams, and filtration was performed. When the surface tension of the obtained filtrate was measured, 68.
A value of 7 millinewtons / meter was obtained. This value is similar to the surface tension shown in Comparative Example 2, and it is shown that the use of this activator at the time of synthesis does not lower the surface tension and does not adversely affect the emulsifying property in the offset ink. Was there.

Example 2 59.2 parts phthalic anhydride, 90 parts urea, cuprous chloride 9.
9 parts, ammonium molybdate 0.179 parts, and kerosene 118 parts, in the general formula (1), R ¹ is a C ₁₁ straight-chain saturated alkyl group, B is —COO—, A is a sorbitan residue, and X is —. 55 was used in the same manner as in Example 1 except that 3.55 parts of an activator having OH, k = 1, m = 3, and n = 0 was used and a pressure of 2.5 kg / cm <2> was applied. 2.8 parts (purity 98.0%, yield 95.0
%) Of crude copper phthalocyanine (Crude-2).
The state of the reaction system was as good as in Example 1. Crude-2 was pigmented in the same manner as in Example 1 to obtain a β-type copper phthalocyanine pigment (Pigment-2). The surface tension of the water-extracted filtrate of Pigment-2 was 68.0 millinewtons / meter. This value shows that the emulsifiability is not adversely affected even when this activator is used as in Example 1.

Example 3 58.8 parts phthalimide, 66 parts urea, 1 cuprous chloride
0.1 part, ammonium molybdate 0.237 part, and Hisol P136 part, in the general formula (1), R ¹
Is a C ₁₁ alkyl group, B is —CO—, A is a direct bond, Y
There _{- (OC 2 H 4) 4} -OH, k is the 1, m is 0, n 1
Was synthesized and post-treated in the same manner as in Example 1 using 1.76 parts of the dispersant, which was 55.4 parts (purity: 97.6%,
Yield 94.0% of crude copper phthalocyanine (crude-
3) was obtained. The state of the reaction system was as good as in Example 1. Crude-3 was pigmented in the same manner as in Example 1 to obtain a β-type copper phthalocyanine pigment (Pigment-3). The surface tension of the water-extracted filtrate of Pigment-3 was 68.1 millinewtons / meter. This value shows that the emulsifiability is not adversely affected even when this activator is used as in Example 1.

Example 4 50.1 parts of phthalic anhydride, 14.3 parts of monochlorophthalic acid sodium salt, 108 parts of urea, 9.9 parts of cuprous chloride,
0.414 parts of ammonium molybdate, and 149 parts of kerosene, in the general formula (1), R ¹ is an alkyl group of C ₁₇ , B is —COO—, A is a propane residue, X is OH,
Y is _{^{-OSO 3 - Na +, k,}} m, n are synthesized in the same manner as in Example with 2.58 parts 1 of the activator, respectively, performs post-processing, 55.8 parts (97.0% pure, Yield 91.0
%) Crude low chlorocopper phthalocyanine (Crude-4)
Got The state of the reaction system was as good as in Example 1.
Crude-4 was pigmented by the acid paste method according to a conventional method to obtain an α-type low chlorocopper phthalocyanine pigment (Pigment-4). Pigment-4 was clear and excellent in dispersibility, and was also excellent in resistance to water squeezing with ink.

Comparative Example 1 59.2 parts phthalic anhydride, 90 parts urea, cuprous chloride 9.
9 parts, ammonium molybdate 0.178 parts, Hisol-P 112 parts, and sodium dodecylbenzenesulfonate 3.55 parts were synthesized in the same manner as in Example 1 and post-treated to obtain 56.8 parts (purity 97.0). %, Yield 93.0
%) Of crude copper phthalocyanine (Crude-5).
The state of the reaction system was as good as in Example 1. Crude-5 was pigmented by the same method as in Example 1 to obtain a β-type copper phthalocyanine pigment (Pigment-5). The surface tension of the water extraction filtrate of Pigment-5 was 37.5 millinewtons / meter. This value shows that this additive significantly reduces the surface tension of the pigment and impairs the emulsifying property in the offset ink. Further, after repeatedly washing Pigment-5 with a 1% aqueous sodium hydroxide solution, the surface tension of the water extraction filtrate was measured, and was 45.3 millinewtons / meter.
Insufficient value, indicating that the additive was not completely removed.

Comparative Example 2 59.2 parts of phthalic anhydride, 90 parts of urea, cuprous chloride 9.
9 parts, 0.178 parts of ammonium molybdate, and 112 parts of Hisol P were used for the synthesis in the same manner as in Example 1 without using an activator to obtain 55.3 parts (purity: 96.9).
%, Yield 93.0%) of crude copper phthalocyanine (Crude-6) was obtained. In the reaction system, a good state could not be obtained in which the Harz-shaped reaction intermediate and the solvent were separated and adhered to the vessel wall. For Crude-6, a β-type copper phthalocyanine pigment (Pigment-6) was obtained in the same manner as in Example 1. The surface tension of the water extract filtrate of Pigment-6 was 69.2 millinewtons / meter. This value shows that the surface tension is sufficiently high when no additive is used, and this is an index showing the good emulsifiability.

[0019]

INDUSTRIAL APPLICABILITY In the production of phthalocyanine by the urea method, the viscosity of the reaction system decreases during the reaction, the uniformity of the system increases, and the reaction proceeds smoothly, so that copper phthalocyanine can be obtained in high purity and high yield. . Since the activator added during the reaction can be decomposed and removed or deactivated by acid or alkali after the reaction, it lowers the interfacial tension between the offset printing ink and water, and causes problems such as problems such as plate stains during printing. It has the effect of not causing.

Claims (6)

[Claims] 1. A method for producing a copper phthalocyanine by heating a phthalic acid and / or a derivative thereof, a nitrogen source such as urea, a catalyst such as a copper compound and a molybdenum compound in an inert solvent to produce copper phthalocyanine, the above raw materials during the reaction, The above-mentioned activator having dispersibility in the above-mentioned inert solvent in the catalyst and the reaction product and capable of being decomposed and removed or inactivated by acid or alkali in the purification step and / or pigmentation step of the reaction product after the reaction. 1. A method for producing copper phthalocyanine, which comprises adding one of the above or a mixture thereof. 2. The method for producing copper phthalocyanine according to claim 1, wherein the activator is a compound represented by the general formula (1). Formula (1) _{^{(R 1 -B) k -A (}} X m, Y n) ( wherein, R ¹ is a saturated or unsaturated aliphatic containing carbon atoms 1 to 20, B is -COO -, - OCO -, -CO-, A
Is a direct bond, a saturated or unsaturated aliphatic group which may be branched, a sorbitan residue, X is a hydrogen atom, a hydroxyl group, -C
OO ^- M ⁺ , Y is a hydrogen atom, a hydroxyl group,-(OCH ₂ CH
_{2) p -Z, -D-SO} 3 - M +, k is 1 or 2, m
And n represent 0 to 3, and p represents 1 to 20. Also here Z
Is ^{-OH, - (OCOR 2),} D is -O- or a direct bond, R ² is a saturated or unsaturated aliphatic radical containing carbon atoms 1 to 20, M represents K or Na. However, B is -OC
In the case of O- and -CO-, B is combined with A or Y to form -COO-. ) 3. In the general formula (1), R ¹ has 6 to 18 carbon atoms.
_{3. The} method for producing copper phthalocyanine according to claim 2, wherein the alkyl group is B, -OCO-, A is an ethane residue, Y is a -SO3Na group, k is 2, m is 0, and n is 1. . 4. In the general formula (1), R ¹ has 5 to 17 carbon atoms.
Alkyl group, B is -COO-, A is a sorbitan residue,
X is -OH, Y is _{- (OCH 2 CH 2) p} -OH, copper k is 1, m is 0 to 3, n is 3-0, according to claim 2, wherein p is a compound is 1 to 20 Method for producing phthalocyanine. 5. In the general formula (1), R ¹ has 5 to 17 carbon atoms.
Alkyl group, B is -COO-, A is a propyl residue, X
The method for producing copper phthalocyanine according to claim 2, wherein is a compound in which --OH, Y is --SO ₃ Na, k, m and n are each 1. 6. In the general formula (1), R ¹ has 5 to 17 carbon atoms.
Alkyl group, B is -CO-, A is a direct bond, Y is-
The method for producing copper phthalocyanine according to claim _{2, wherein} (OCH ₂ —CH ₂ ) _p —OH, k is 1, m is 0, n is 1 and p is 1 to 20.