JPS6210266B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing highly chlorinated copper phthalocyanine pigments. Copper phthalocyanine is a blue pigment, but when the benzene ring of the copper phthalocyanine molecule is replaced with chlorine, the hue gradually changes from blue to green. Theoretically, up to 16 chlorine atoms can be substituted into a copper phthalocyanine molecule, but 12 or more substitutions produce a greenish color, and 13 or more is usually considered the practical number of chlorine atoms substituted in a green pigment molecule. In particular, if 14 or more chlorine atoms are substituted, it becomes a bright green pigment with a yellowish tinge. Furthermore, this is a green pigment with extremely excellent light resistance and solvent resistance. Conventionally, the method widely used to produce highly chlorinated copper phthalocyanine, which is an excellent green pigment, is to dissolve copper phthalocyanine in a mixture of anhydrous aluminum chloride and common salt, and then chlorine it at a high temperature of around 200°C. In this method, the chlorinated reaction product is separated by chlorinating the reaction product in a large amount of ice water. However, this method is industrially disadvantageous because it uses a large amount of anhydrous aluminum chloride and the reaction product is thrown into water, making it impossible to recover the anhydrous aluminum chloride and common salt. Since the chlorination reaction is carried out at high temperatures for a long period of time, various by-products are likely to be produced, which inevitably leads to a decline in yield. There is also a method of heating chlorinated phthalic anhydride, chlorinated phthalimide, or their derivatives as raw materials in an organic solvent in the presence of a copper compound, urea, and a catalyst at a temperature of 200 to 300°C, but side reactions occur. It has the disadvantage that it is difficult to obtain a green pigment with a clear hue because it contains impurities even after being purified after the reaction. On the other hand, a method for producing highly chlorinated copper phthalocyanine by dissolving copper phthalocyanine in chlorosulfonic acid and passing chlorine gas in the presence of a catalyst is also known (US Pat. No. 2,662,085, 1958); As a result of further trials by the inventors,
The yield was considerably lower than that of the aluminum chloride-salt method, about 50% (vs. theory). Moreover, the color tone of the produced pigment was indistinct and bluish, and a clear yellowish-green color could not be obtained. Therefore, the present inventors have already proposed a method for producing highly chlorinated copper phthalocyanine having a clear yellowish-green color in a high yield and industrially advantageously, by eliminating the above-mentioned conventional drawbacks, and has already been published in Japanese Patent Application No. 52-148081. In the specification, "acid chloride of a sulfuric acid chloride, using chlorsulfonic acid or pyrosulfuryl chloride as a solvent, adding sulfur and/or sulfur chloride as a catalyst, with or without the addition of other chlorination catalysts" In the production method of highly chlorinated copper phthalocyanine in which copper phthalocyanine is chlorinated using chlorine, 7% to 200% by weight of sulfur for chlorosulfonic acid and 1% by weight of sulfur for pyrosulfuryl chloride. % to 200% by weight, including each sulfur and/or sulfur chloride, 1 to 20Kg/cm ² G
A method for producing highly chlorinated copper phthalocyanine, which is characterized by chlorination under pressure (gauge), and
The distillate obtained by chlorinating copper phthalocyanine and distilling the resulting chlorinated reaction product by the above two methods using chlorsulfonic acid or pyrosulfuryl chloride as the acid chloride solvent of the sulfur oxygen acid. You can use it as it is, add copper phthalocyanine to it and chlorinate it again, and then repeat the operation of distilling the obtained chlorination reaction product and adding copper phthalocyanine to it to chlorinate it. A method for producing highly chlorinated copper phthalocyanine, which is characterized by good properties. ” was clarified and explained in detail. In the above production method, the obtained chlorinated reaction product can be distilled to separate the solvent, as well as when the obtained chlorinated reaction product is poured into a large amount of ice water and then filtered, and even when the solvent is recovered. The wet cake containing highly chlorinated copper phthalocyanine obtained by filtering the residue containing highly chlorinated copper phthalocyanine or the crystals precipitated from the obtained chlorination reaction product is washed with water or dilute sulfuric acid, etc. The crude highly chlorinated copper phthalocyanine was obtained in high yield by carrying out the conventional post-treatment method of washing and filtration, alkali washing and filtration, water washing, and drying. A yellowish-green pigment with excellent clarity is obtained by performing a salt grinding method, etc.).
However, as a result of further intensive research, the present inventors have discovered that the chlorinated reaction product obtained by chlorination using the above production method is distilled to separate the solvent, and then a polymer containing highly chlorinated copper phthalocyanine is produced. A wet cake containing highly chlorinated copper phthalocyanine obtained by filtering the crystals precipitated from the residue or the obtained chlorination reaction product is simplified as described above without any post-treatment such as acid/alkali washing, and chlorine Surprisingly, when pigments are formed by directly grinding them under mechanical force such as salt grinding while still containing the reaction solvent, it is surprising that after the above-mentioned post-treatment, the pigments are formed. The inventors have discovered that a yellowish-green pigment can be obtained which is very clear and has extremely excellent coloring power compared to the conventional method, and has arrived at the present invention. That is, the present invention solves the drawbacks of the conventionally known methods described above, and at the same time provides a method for producing a highly chlorinated copper phthalocyanine pigment that has a yellowish-green color that is more vivid and has better coloring power, which is particularly advantageous from an industrial standpoint. The gist of this is that chlorosulfonic acid or pyrosulfuryl chloride is used as the acid chloride solvent for sulfur oxygen acids, sulfur and/or sulfur chloride is added as a catalyst, and other chlorine In producing a highly chlorinated copper phthalocyanine pigment by chlorinating copper phthalocyanine with chlorine, with or without addition of a catalyst, 7% by weight or more and 200% by weight or less as sulfur with respect to chlorosulfonic acid, For pyrosulfuryl chloride, add sulfur and/or sulfur chloride in amounts corresponding to 1% by weight or more and 200% by weight or less as sulfur,
Chlorinated under pressure of 1 to 20 kg/cm ² G (gauge),
Highly chlorinated copper phthalocyanine obtained by filtering the residue containing highly chlorinated copper phthalocyanine after distilling the obtained chlorinated reaction product and separating the solvent or by filtering the crystals precipitated from the obtained chlorinated reaction product A method for producing a highly chlorinated copper phthalocyanine pigment, which is characterized by grinding a wet cake containing a chlorinated reaction solvent while still containing the chlorinated reaction solvent, and a method for producing a highly chlorinated copper phthalocyanine pigment, which is chlorinated in the same manner as above, and the resulting chlorinated reaction product. Copper phthalocyanine is added to the distillate obtained by distilling the product, using the distillate as it is, adding copper phthalocyanine to it and chlorinating it again, and then distilling the obtained chlorinated reaction product. The chlorinated reaction product obtained each time is distilled to separate the solvent, and the residue containing highly chlorinated copper phthalocyanine is obtained. An operation in which the filtrate obtained by filtering the crystals is used as it is, copper phthalocyanine is added thereto to chlorinate it again, and the resulting chlorinated reaction product is filtered, the filtrate obtained is used and copper phthalocyanine is added thereto for chlorination. The chlorination reaction product obtained each time is filtered and the solvent is separated, and the wet cake containing the highly chlorinated copper phthalocyanine is then ground while the chlorination reaction solvent remains contained. The invention consists in a method for producing a chlorinated copper phthalocyanine pigment. In the method of the present invention, crosssulfonic acid or pyrosulfuryl chloride is generally used as the acid chloride solvent for the sulfur oxygen acid, and sulfuryl chloride,
When thionyl chloride is used, it is preferably used in combination with thionyl chloride. These mixtures can be obtained by recovering the solvent from the chlorination reaction mixture by distillation or the like, and the mixture can be reused as a solvent. The amount of the above-mentioned solvent to be used should basically be within a range that dissolves or suspends the copper phthalocyanine raw material and makes sufficient contact with the chlorine gas, but the reaction solution is usually stirred with a stirrer commonly used in industry. The amount is preferably about 3 times to about 50 times the weight of the raw material copper phthalocyanine, and industrially preferably 4 to 8 times the weight of the raw material copper phthalocyanine. The chlorination reaction in the method of the present invention is first carried out by adding sulfur or chloride of sulfur (hereinafter referred to as catalyst A) as a catalyst. This reaction can be carried out with or without the addition of another chlorination catalyst (hereinafter referred to as B catalyst), but it is usually preferable to use a B catalyst such as iodine in combination with the B catalyst. By adding 0.01 to 10% by weight, a clear yellowish-green pigment can be obtained in high yield. Catalyst B used in combination with catalyst A includes iodine, iodine chlorides such as iodine monochloride, and iodine trichloride, and metal chlorides such as anhydrous aluminum chloride, anhydrous ferric chloride, antimony trichloride, and cupric chloride. etc. The above catalyst A may be sulfur or sulfur chloride alone, but of course may be used in combination. The amount added is preferably 7% by weight or more in terms of sulfur for the chlorsulfonic acid solvent, and 1% by weight or more in terms of sulfur for the pyrosulfuryl chloride solvent. . On the other hand, if the content of catalyst A is too large in both of the above solvents, the relative proportion of the solvent will decrease, and even if the proportion of copper phthalocyanine to the solvent is appropriate, the amount of copper to the total amount of catalyst A and solvent will decrease. Since the proportion of phthalocyanine is undesirably reduced, the proportion of sulfur in the solvent should be 900% by weight or less,
Industrially, it can be said that 8 to 100% by weight is good, but 200%
If it exceeds % by weight, it becomes somewhat difficult to chlorinate. Considering that the practical number of chlorine substitutions for green pigments is 13 or more in one molecule of highly chlorinated copper phthalocyanine, the content of catalyst A is A preferable upper limit is 200% by weight or less of sulfur based on the above solvent. In addition, in the chlorination reaction of the method of the present invention, when chlorosulfonic acid is used as a solvent, chlorosulfonic acid mainly reacts with catalyst A and chlorine as shown in the following formula to form a mixture containing pyrosulfuryl chloride as the main component. It is presumed that the copper phthalocyanine is produced and then the chlorination reaction of the copper phthalocyanine proceeds. 8SO ₂ (OH)Cl+2S+6Cl ₂ →4S ₂ O ₅ Cl ₂ +2SO ₂ Cl ₂ +8HCl 8SO ₂ (OH)Cl+S ₂ Cl ₂ +5Cl ₂ →4S ₂ O ₅ Cl ₂ +2SO ₂ Cl ₂ +8HCl I ₂ +Cl ₂ →2IClorICl ₃ S ₂ Cl ₂ +Cl ₂ →2SCl ₂ That is, as mentioned above, for the chlorosulfonic acid solvent, it is necessary to use catalyst A containing at least 7% by weight, preferably at least 8% by weight of sulfur, but by a known method. When separately prepared pyrosulfuryl chloride (a crude product is sufficient) is used as a solvent, it is sufficient to use catalyst A containing 1% by weight or more of sulfur with respect to the solvent; when using the above-mentioned chlorosulfonic acid solvent The reason why the amount can be reduced by about 6% by weight is presumed to be that catalyst A, which is required to produce pyrosulfuryl chloride according to the above reaction formula, is unnecessary. In the chlorination reaction of the method of the present invention, the reaction pressure is 1 to 20 Kg/cm ² G (gauge), preferably 2 to 8 Kg, which has a remarkable effect in obtaining a bright yellowish-green pigment with a high yield. /cm ² G, more preferably 3~
7Kg/cm ² G is good. At 1 to 2 Kg/cm ² G, the yield of crude highly chlorinated copper phthalocyanine is 96% or more (relative to theory) and a clear pigment can be obtained, but it has a slightly strong bluish tinge. 2
Kg/cm ² G, especially above 3 Kg/cm ² G, it is possible to obtain a clear yellowish green crude highly chlorinated copper phthalocyanine in high yield. Although chlorine can be added in liquid or gaseous form, it is generally added in gaseous form. In other words, 20Kg/cm ² G or more is industrially disadvantageous;
Generally 10Kg/cm ² G or less, usually 8Kg/cm 2 G or less where chlorine does not liquefy at room temperature, especially 7Kg/cm ² G or less.
cm ² G or less is preferable. In addition, the reaction temperature is low at the beginning, for example from room temperature to 100-120℃ as the reaction progresses.
Increase the temperature to. At the highest reaction temperature, it is advantageous to increase the reaction pressure as much as possible. At temperatures above 120°C, the color of the pigment obtained is yellowish-green and sufficiently vivid, but the yield is significantly reduced. To carry out the chlorination reaction in the process of the invention, chlorosulfonic acid or pyrosulfuryl chloride is typically used as the acid chloride solvent for the sulfur oxyacid;
A catalyst, optionally a B catalyst such as iodine, and a predetermined amount of copper phthalocyanine are added and brought into contact with chlorine under a predetermined chlorine pressure, generally gradually starting from room temperature.
Raise the temperature to 100-115℃. Usually, the chlorination reaction is completed after further maintaining the temperature for about 1 to 4 hours. In the method of the present invention, most or a part of the solvent can be recovered from the chlorination reaction product obtained as described above by distillation, usually atmospheric pressure or reduced pressure distillation. Doing so has a greater effect than is generally expected.
That is, the solvent recovered by distillation contains acid chlorides of sulfur oxygen acids such as pyrosulfuryl chloride and sulfuryl chloride, as well as catalyst A and catalyst B such as iodine compounds. A
It is used as it is without adding a catalyst or B catalyst, and a predetermined amount of raw material copper phthalocyanine is added thereto, and it is chlorinated again using chlorine under the pressure and temperature conditions of the method of the present invention, and the obtained chlorination reaction product is further obtained. It is also possible to repeat the operation of adding copper phthalocyanine to the distillate obtained by distilling and chlorinating it, and by this method, similarly excellent highly chlorinated copper phthalocyanine can be obtained in high yield. I can do it. It goes without saying that the recovered solvent can be replenished with an amount of solvent and catalyst corresponding to the losses during reaction and solvent recovery, and then reused as the solvent and catalyst for the chlorination reaction in the method of the present invention. Distillation of the chlorinated reaction product is usually first carried out under normal pressure to remove low boiling point solvent components, and then carried out under reduced pressure. For example, after the process is carried out at 80 to 130°C under normal pressure, the temperature is finally raised to 150°C under reduced pressure at about 30 to 40 Torr, and the process ends when almost no distillate is observed. Moreover, it can also be carried out only under normal pressure. The residue obtained after distillation contains chlorinated reaction solvent components in addition to highly chlorinated copper phthalocyanine, and it is unclear in what form these chlorinated reaction solvent components and highly chlorinated copper phthalocyanine are combined. Although it is not clear, it is thought that this chlorination reaction solvent component brings about the excellent effects described below in the pigmentation step. The content of the solvent component is
It varies depending on the conditions during distillation (degree of vacuum, temperature, etc.), and if it is too high, it will not have much effect on the color tone of the pigment, but the recovery rate of the solvent will decrease and the amount of solvent lost will increase as a result, so it is not suitable for industrial use. On the other hand, if too much is used, the excellent effect will be reduced, which is undesirable. In other words, as the above-mentioned Kama remaining,
The content of the chlorination reaction solvent may be in the range of 20 to 350% by weight based on the crude highly chlorinated copper phthalocyanine, and industrially preferably 30 to 250% by weight. In addition, instead of the above-mentioned residue, a part of the solvent is distilled off and concentrated at the stage of distillation recovery of the chlorination reaction solvent, and then the crystals (highly chlorinated copper phthalocyanine) are precipitated by cooling. A wet cake obtained by filtration can be used. Alternatively, in the chlorination reaction, the amount of copper phthalocyanine used as a raw material is increased to carry out the chlorination reaction at a high concentration, and then after the reaction is completed, crystals are precipitated while being cooled to room temperature, and this is filtered. It is also possible to use the wet cake obtained. It is preferable that these wet cakes contain the same amount of chlorinated reaction solvent as in the case of the above-mentioned kama residue, and it is believed that this solvent component will bring about the same excellent effect as in the case of the above-mentioned kama residue in the pigment formation process. It will be done. The filtrate obtained by filtering the wet cake in the above filtration process (if part of the solvent is distilled off and concentrated, the distillate is combined with the filtrate) contains sulfur oxygen such as pyrosulfuryl chloride and sulfuryl chloride. In addition to the acid chloride, the catalyst A and the catalyst B such as iodine are also included, so the recovered solvent can be used repeatedly as it is without adding a new catalyst A or catalyst B. That is, a predetermined amount of raw material copper phthalocyanine is added to the above filtrate, chlorinated again using chlorine under the pressure and temperature conditions of the method of the present invention, and the resulting chlorinated reaction product is filtered. It is also possible to use the wet cake in the method of the present invention after repeating the operation of adding copper phthalocyanine and chlorinating it, and separating the chlorinated reaction product obtained each time by filtration to separate the solvent. The process also provides excellent highly chlorinated copper phthalocyanines in high yields. Furthermore, it goes without saying that the recovered solvent can be refilled with an amount of solvent and catalyst corresponding to the losses during reaction and solvent recovery, and then reused as the solvent and catalyst for the chlorination reaction in the method of the present invention. Nor. In the method of the present invention, the slag residue or wet cake containing the highly chlorinated copper phthalocyanine obtained as described above is processed without any post-treatment, while containing the chlorination reaction solvent, for example, in a kneader, It is ground into pigment using equipment such as a ball mill, sand mill, or Banbury mixer. At this time, although a grinding aid is not necessarily required, sodium sulfate (anhydrous sodium sulfate), acidic sodium sulfate, common salt, etc. are usually used as the aid. When using a solvent during grinding, use one that is liquid at the temperature during grinding. Specific examples include alcohol-based solvents such as glycerin, polyethylene glycol, and diethylene glycol, cellosolve (ethylene glycol ether)-based solvents, and ketone-based solvents. Generally known solvents and aromatic solvents can be used, but inorganic acids such as sulfuric acid can also be used. However, if the content of the chlorination reaction solvent component relative to the crude highly chlorinated copper phthalocyanine in the kama residue or wet cake is large (for example, 100% by weight or more), the above-mentioned solvent for grinding may not necessarily be used. There's no need. Grinding may be carried out at room temperature, or if heated, it should be carried out at 100°C or less, usually preferably in the range of room temperature to 60°C. After the grinding, a known purification post-processing operation is performed. In other words, water-soluble solvents are removed together with the grinding aid salts when they are removed by washing with water or dilute mineral acids, and water-insoluble solvents are removed by distillation or steam distillation. After that, wash with water or dilute mineral acid. Then, it is washed with dilute alkali, water, and dried. If necessary, coating treatment with a surfactant or the like may be performed prior to drying. As described above, the highly chlorinated copper phthalocyanine pigment obtained by the method of the present invention is very soft and has extremely good dispersibility in a color vehicle, and also has excellent clarity and coloring power. It is a yellowish-green pigment with excellent color. As described in detail above, the method of the present invention involves a post-treatment step of the kama residue or wet cake after solvent recovery from the highly chlorinated reaction product of copper phthalocyanine, which is easily obtained in high yield, i.e., water or dilute sulfuric acid. It is extremely advantageous in industrial operations in that it is possible to omit the steps of pickling and filtration, alkali washing and filtration, water washing, drying, etc. It can produce a yellowish-green pigment of highly chlorinated copper phthalocyanine that has better clarity and coloring power than when it is made into a pigment using the above pigmentation method, which is a special effect that has industrial value. be. Next, the present invention will be specifically explained using examples.
In the Examples and Comparative Examples, % means % by weight, and parts represent parts by weight, respectively. Example 1 Chlorination of copper phthalocyanine: 380 parts of chlorosulfonic acid, 59 parts of sulfur (16% to chlorosulfonic acid) and 3.7 parts of iodine are first placed in a reactor, to which 75 parts of crude copper phthalocyanine (purity
92%) was added and stirred to dissolve. Next, chlorine gas was supplied to the solution while gradually increasing the temperature from room temperature to 100°C. At this time, the pressure in the reactor is 3Kg/in about 20 minutes.
cm ² G, and thereafter the opening degree of the control valve at the outlet of the reactor was adjusted to match the amount of chlorine supplied so as to maintain this pressure. 360 for 5 hours until the color of the solution changes from greenish-black to gradually reddish and deep red.
of chlorine was supplied. As a result, 630 parts of chlorinated reaction product (solution) were obtained, the yield of highly chlorinated copper phthalocyanine was 98%.
(pair theory), the number of chlorine substitutions in the phthalocyanine molecule is
It was 14.5. Example 2 630 parts of the chlorinated reaction product obtained in the same manner as in Example 1 was first heated to 110°C under normal pressure to recover the low-boiling fraction by distillation, and then finally heated to 40 Torr under reduced pressure.
The temperature was raised to 150°C and the solvent was distilled off, yielding 191 parts of residue. The solvent component content in the kama residue was 45% based on the crude highly chlorinated copper phthalocyanine. Pigmentation was then carried out as follows. That is, 100 parts of the residue (69 parts of crude highly chlorinated copper phthalocyanine)
120 parts of polyethylene glycol and 500 parts of anhydrous sodium sulfate were placed in a kneader, ground at 30 to 60°C for 8 hours, and then placed in 4300 parts of a 2% sulfuric acid aqueous solution.
After stirring at 90°C for 1 hour, the mixture was filtered and washed with water. Next, this filter cake was treated in the same manner in a 2% caustic soda aqueous solution and then dried. The obtained pigment was superior to that obtained in Comparative Example 1 both in sharpness and coloring power. Note that the sharpness (NBS) is determined by the National Bureau of
It can also be expressed as an objective numerical value called the dye absolute value measured by the Hunter's Lab method using Standard.
In addition, the coloring power (%) is the coloring power of the pigment in the comparative example.
It is a relative value when taken as 100%. For example, if the coloring power is 120%, the amount of pigment used is 1/1.2 x 100 = 87%
It can be done. Therefore, the measured values of coloring power and sharpness obtained by measuring the pigments of Example 2, Examples 3 to 11 below, and Comparative Examples 1 to 2 using the same method are summarized in Table 1 below. to compare and display. Comparative Example 1 630 parts of the chlorinated reaction product obtained by the reaction in the same manner as in Example 1 was distilled in the same manner as in Example 2 to recover the solvent. 300 parts of a 2% sulfuric acid aqueous solution was added to 191 parts of the resulting cake residue, and the mixture was stirred at 90°C for 1 hour, filtered and washed with water.Then, the filter cake was poured into 3000 parts of a 2% caustic soda aqueous solution and heated at 90°C. After stirring for 1 hour, the mixture was filtered, washed with water, and dried to obtain 132 parts of crude highly chlorinated copper phthalocyanine. Then, the crude highly chlorinated copper phthalocyanine 69
120 parts of polyethylene glycol and anhydrous sodium sulfate
500 parts were charged into a kneader, and the pigment formation and post-treatment operations were performed in exactly the same manner as in Example 2. The obtained pigment was compared to that obtained in Example 2,
Both the clarity and coloring power were somewhat low (see Table 1 below). Example 3 The solvent was recovered from 630 parts of the chlorinated reaction product obtained in the same manner as in Example 1 under reduced pressure at 330 Torr and 150° C. to obtain 238 parts of residue. The solvent component content in the kama residue was 80% of the crude highly chlorinated copper phthalocyanine. Then, the pigmentation and post-treatment operations of the caster residue are as follows:
The same procedure as in Example 2 was carried out. The obtained pigment was almost the same as that obtained in Example 2 (see Part 1 below).
(see table). Example 4 630 parts of the chlorinated reaction product obtained in the same manner as in Example 1 was first heated to 130° C. under normal pressure, and the low-boiling fraction was distilled and recovered, yielding 440 parts of the residue. The content of solvent components in the kama residue was 233% based on the crude highly chlorinated copper phthalocyanine. Next, 350 parts of the residue and 616 parts of acidic sodium sulfate
The sample was placed in a kneader and ground at 30 to 60°C for 7 hours, followed by post-treatment in the same manner as in Example 2. The obtained pigment was almost the same as that obtained in Example 2 (see Table 1 below). Example 5 716 parts of the chlorination reaction product obtained in the same manner as in Example 1 was heated under normal pressure in the same manner as in Example 4 to recover the low boiling fraction, and 500 parts of the residue was obtained. . The content of solvent components in the kama residue was 233% based on the crude highly chlorinated copper phthalocyanine. Next, the remaining 470 parts of the kettle was added to anhydrous sodium sulfate in a kneader.
500 parts and 385 parts of sulfuric acid, 30-60
After milling at ℃ for 7 hours, the same post-treatment operation as in Example 2 was carried out. The obtained pigment was almost equivalent to that obtained in Example 2 (see Table 1 below). Example 6 The chlorination reaction product obtained in the same manner as in Example 1 was distilled in the same manner as in Example 2 to recover the solvent, and the recovered solvent was reused in the chlorination reaction. That is,
After adding 75 parts of crude copper phthalocyanine (purity 92%) to 475 parts of the recovered solvent and stirring to dissolve it, chlorine was supplied while gradually raising the temperature from room temperature to 100°C as in Example 1. The opening degree of the reactor outlet valve was adjusted so that the reaction pressure was maintained at 3.0 Kg/cm ² G. 163 parts of chlorine was supplied to the reaction solution over a period of 4 hours until it turned from brownish-black to gradually reddish and then deep red. The obtained chlorinated reaction product was subjected to vacuum distillation in the same manner as in Example 2, and 187 parts of scum residue was obtained.
The content of solvent components in the kama residue was 42% based on the crude highly chlorinated copper phthalocyanine. Next, the casta residue was converted into a pigment and subjected to post-treatment in the same manner as in Example 2, and as a result, a pigment almost equivalent to that in Example 2 was obtained (see Table 1 below). Example 7 The chlorinated reaction product obtained in the same manner as in Example 1 was distilled in the same manner as in Example 2 to recover the solvent. ), 42 parts of anhydrous mirabilite and steel balls
180 parts were placed in a pot and milled at 30-60°C for 30 hours. Post-treatment of the taken out product was carried out in the same manner as in Example 2. The obtained pigment was superior in sharpness and coloring power to that obtained in Comparative Example 2 (see Table 1 below). Comparative Example 2 4.14 parts of crude highly chlorinated copper phthalocyanine obtained in the same manner as Comparative Example 1, 42 parts of anhydrous sodium sulfate, and 180 parts of steel balls.
was put into a pot and converted into a pigment in the same manner as in Example 7,
Post-processing operations were performed. The obtained pigment had slightly lower clarity and coloring power than that obtained in Example 7 (see Table 1). Example 8 The chlorinated reaction product obtained in the same manner as in Example 1 was distilled in the same manner as in Example 2 to recover the solvent, and 200 parts of Kama residue, 2000 parts of anhydrous sodium sulfate,
3000 parts of steel balls (diameter 2 cm) and 1400 parts of polyethylene glycol were placed in a pot and milled at 30 to 60°C for 30 hours. Post-treatment of the taken out product was carried out in the same manner as in Example 2. The obtained pigment was almost the same as that obtained in Example 7 (see Table 1 below). Example 9 630 parts of the chlorinated reaction product obtained in the same manner as in Example 1 was heated to 130° C. under normal pressure, and the low-boiling fraction was distilled and recovered to obtain 440 parts of the residue. The residue was filtered at room temperature to obtain 266 parts of a wet cake. The solvent component content in this wet cake was 160% based on the crude highly chlorinated copper phthalocyanine. The wet cake was then subjected to pigmentation and post-treatment operations as in Example 4. The obtained pigment was almost the same as that obtained in Example 4 (see Table 1 below). Example 10 In Example 1, crude copper phthalocyanine was
The chlorination reaction was carried out in the same manner as in Example 1, except that the supply time and amount of chlorine were 8 hours and 600 parts, respectively, to obtain 718 parts of a chlorination reaction product (slurry). The obtained chlorination reaction product was filtered at room temperature to obtain 486 parts of wet cake. The solvent component content in this wet cake was 161% based on the crude highly chlorinated copper phthalocyanine. The wet cake was then subjected to pigmentation and post-treatment operations as in Example 4. The pigment obtained was almost the same as that obtained in Example 4. The wet cake containing highly chlorinated copper phthalocyanine was obtained by filtrating the crystals precipitated from the chlorination reaction product obtained by chlorinating crude copper phthalocyanine using the filtrate obtained in this example as it is. ,
Pigmentation and post-treatment operations were carried out in the same manner as in Example 4. The pigment obtained was almost the same as that obtained in Example 4 (see Table 1 below). Example 11 380 parts of chlorosulfonic acid, 26 parts of sulfur (6.8% based on chlorosulfonic acid) and 3.7 parts of iodine were placed in a reactor, and chlorine was passed through at 3 kg/cm ² G at room temperature to 40°C. If unreacted chlorine comes out, stop the chlorine supply. Crude pyrosulfuryl chloride is thus obtained. To the crude pyrosulfuryl chloride, 75 parts of crude copper phthalocyanine and 15 parts of sulfur (to 3.7 parts of crude pyrosulfuryl chloride)
%) and reacted in the same manner as in Example 1 to obtain 600 parts of a chlorinated reaction product. The yield of crude highly chlorinated copper phthalocyanine was 98% (versus theory), and the number of chlorine substitutions in the phthalocyanine molecule was 14.6. The chlorinated reaction product obtained above was distilled to recover the solvent in the same manner as in Example 2, and 190 parts of scum residue was obtained. The solvent component content in the kama residue was 45% of the crude highly chlorinated copper phthalocyanine. Then, the pigmentation and post-treatment operations of the caster residue were carried out in the same manner as in Example 2. The pigment obtained was almost the same as that obtained in Example 2. 【table】

Claims (1)

[Claims] 1. Chlorsulfonic acid or pyrosulfuryl chloride is used as a sulfur oxygen acid chloride solvent, sulfur and/or sulfur chloride is added as a catalyst, and other chlorination catalysts are added or not added. When producing a highly chlorinated copper phthalocyanine pigment by chlorinating copper phthalocyanine with chlorine, 7% to 200% by weight of sulfur for chlorosulfonic acid and 200% by weight or less for pyrosulfuryl chloride. Add an amount of sulfur and/or sulfur chloride equivalent to 1% by weight or more and 200% by weight or less as sulfur, and
The residue containing highly chlorinated copper phthalocyanine after chlorination under a pressure of ~20Kg/cm ² G (gauge) and distilling the obtained chlorination reaction product to separate the solvent or the obtained chlorination reaction A method for producing a highly chlorinated copper phthalocyanine pigment, which comprises grinding a wet cake containing the highly chlorinated copper phthalocyanine obtained by filtering out crystals precipitated from the product, while still containing the chlorination reaction solvent. 2. The method according to claim 1, wherein the kama residue or wet cake containing highly chlorinated copper phthalocyanine is ground while the chlorination reaction solvent remains contained in an amount of 20 to 350% by weight based on the highly chlorinated copper phthalocyanine. . 3. The method according to claim 1, wherein the kama residue or wet cake containing highly chlorinated copper phthalocyanine is ground while the chlorination reaction solvent is still contained in an amount of 30 to 250% by weight based on the highly chlorinated copper phthalocyanine. . 4 Acid chloride of sulfur oxygen acid When producing a highly chlorinated copper phthalocyanine pigment by chlorinating copper phthalocyanine with chlorine using chlorosulfonic acid or pyrosulfuryl chloride as a solvent, sulfur is used for chlorosulfonic acid. 7% to 200% by weight as sulfur for pyrosulfuryl chloride, 1% to 200% by weight as sulfur for pyrosulfuryl chloride, with the corresponding amount of sulfur and/or sulfur chloride added as a catalyst, and other chlorine. Chlorination is carried out under a pressure of 1 to 20 Kg/cm ² G (gauge) with or without addition of a chlorination catalyst, and the distillate recovered by distilling the obtained chlorination reaction product is used as it is and copper is added to it. The chlorination reaction obtained each time is repeated by adding phthalocyanine, chlorinating it again, distilling the obtained chlorination reaction product, using the recovered distillate, adding copper phthalocyanine to it, and chlorinating it. The residue containing highly chlorinated copper phthalocyanine after distilling the product and separating the solvent, or the filtrate obtained by filtering the crystals precipitated from the obtained chlorinated reaction product, is used as it is and copper phthalocyanine is added thereto. The resulting chlorinated reaction product is filtered, the resulting filtrate is used, copper phthalocyanine is added thereto, and chlorination is repeated. The chlorinated reaction product obtained each time is filtered out and the solvent A method for producing a highly chlorinated copper phthalocyanine pigment, which comprises grinding a wet cake containing the highly chlorinated copper phthalocyanine after separating the pigment, while still containing the chlorination reaction solvent. 5. The method according to claim 4, wherein the kama residue or wet cake containing highly chlorinated copper phthalocyanine is ground while the chlorination reaction solvent remains contained in an amount of 20 to 350% by weight based on the highly chlorinated copper phthalocyanine. . 6. The method according to claim 4, wherein the kama residue or wet cake containing highly chlorinated copper phthalocyanine is ground while the chlorination reaction solvent is still contained in an amount of 30 to 250% by weight based on the highly chlorinated copper phthalocyanine. .