JP3151571B2 - Oxidation resistant solvent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrocarbon solvent having a high boiling point and excellent oxidation resistance, and further produces copper phthalocyanine as a pigment by using the oxidation resistant solvent as a reaction medium. It is about the method.

[0002]

2. Description of the Related Art Hydrocarbon solvents are used in various fields such as paints, inks, rubbers, adhesives, adhesives, degreasing and cleaning of metals, and reaction solvents. The solvent is required to have compatibility with the resin and solubility in the resin and the substance causing stains, depending on the purpose of use. It is often used under conditions where it is exposed to high temperatures to increase the efficiency of dissolution, and in addition to safety in practice,
It is important that it is not easily oxidized. Therefore, a stable solvent that can withstand oxidation even when used at a high temperature has been desired.

[0003] Aromatic hydrocarbon solvents have been used in many cases as solvents which have high solubility and can withstand use at high temperatures. Most aromatic hydrocarbon solvents that can withstand oxidation tend to precipitate crystals as they can be used at high temperatures, so even if they remain liquid when used at high temperatures, they crystallize when returned to room temperature. At present, it cannot be used as a solvent. High-boiling aromatic solvents that remain liquid at high or normal temperatures during use are susceptible to oxidation by use at high temperatures, and the solvent itself tends to deteriorate. Therefore, there has been a demand for an inexpensive and efficient method for producing a solvent that can withstand oxidation even at a high temperature in use and maintain a liquid state at room temperature.

Various synthetic methods have been proposed for copper phthalocyanine, which is a useful pigment. However, industrial production methods include (1) reacting phthalonitrile with copper or a copper salt in a reaction medium. A nitrile solvent method and (2) a phthalic acid solvent method of reacting phthalic acid, phthalic anhydride, phthalimide, or the like with urea and copper or a copper salt in a reaction medium are often used.

Conventionally, chlorobenzenes and the like have been used for these reaction media, but improvements have been made from the necessity of protecting the working environment such as odor from halogenated solvents. As one of the improvements, there has been proposed a reaction medium such as alkylbenzene containing no halogen.
-60126, JP-A-49-63735, JP-A-Showa 4
Various reaction media have been proposed in JP-A No. 9-116121, JP-A-50-44224, JP-A-52-38536, and JP-B-44-26372.

[0006]

However, the proposed reaction medium is a solvent having a specific structure in which the color tone of the produced copper phthalocyanine pigment is not clear, and the supply of the solvent is not sufficient. From an industrial point of view, which is carried out on a large scale, etc., an efficient production method of a reaction medium giving a vivid color tone is desired. The present inventor has found that a specific fraction obtained by distillation and that satisfies a specific index can be a solvent having a high boiling point and high oxidation resistance. Furthermore, they have found that a clear color pigment can be obtained by using the oxidation-resistant solvent of the present invention as a reaction medium for producing copper phthalocyanine, thereby completing the present invention.

Further, although the use of a single compound is described in the literature such as the above-mentioned patent gazette, for example, a solvent for producing copper phthalocyanine is expected to be inexpensive and to have a low melting point, for example, in the case of a solvent for producing copper phthalocyanine. In many cases, the solvents that are actually used industrially from the viewpoint of, for example, being in the form of a mixture of multiple components including isomers. All such solvents are used as distillates. On the other hand, components that are not suitable for the target reaction may be mixed in some cases from the fact that they are a multi-component mixture, and thus cannot be said to be necessarily preferable as a solvent for producing copper phthalocyanine. In such a case, since it is a multi-component mixture, component analysis is not easy, and preparation of a solvent must be difficult.

[0008]

That is, the first aspect of the present invention is to provide a fractionated hydrocarbon mixture containing mainly components having a boiling point of 200 ° C to 230 ° C and having an average boiling point of 200 ° C to 220 ° C. The boiling point range is 30 ° C. or less,
Exponent given by the following equation

(Equation 2) (Where n ₂₀ is the refractive index at 20 ° C., D ₂₀ is 20 ° C.)
(G / cc) and Bp are average boiling points (° C.), and the distillation temperatures of 10%, 50%, and 90% obtained by the distillation test were calculated as (10% distillation temperature (° C.) + 2 × 50% distillation). Outlet temperature (℃)
+ 90% distillation temperature (° C.)) / 4. ) Is in the range of 7.0 × 10 ^{−4 to} 7.6 × 10 ⁻⁴ , and the wavelength region 650 of the infrared absorption spectrum is
maximum absorption wavelength λ from cm ⁻¹ to 2000 cm ⁻¹
_The present invention relates to an oxidation-resistant solvent, wherein _max is in a range of 690 cm ^{-1 to} 710 cm ^-1 .

The second aspect of the present invention is to produce copper phthalocyanine by reacting phthalic anhydride or a derivative thereof with urea and copper or a copper salt, or phthalonitrile or a derivative thereof and copper or a copper salt in a reaction medium under heating. In the method, the method for producing copper phthalocyanine, characterized in that the oxidation-resistant solvent is used as a reaction medium,
An object of the present invention is to provide an industrially useful solvent and to enable production of a clear pigment.

Hereinafter, the present invention will be further described. In the present invention, the distillation temperature and the average boiling point are determined according to ASTM test method D86 (corresponding to JIS K22) which is generally applied to petroleum products.
54-1990, ISO 3405-1988 Pet
roleum products-Determina
Tion distilation charact
The values are determined by the distillation test method as defined by the following methods. The boiling point range is a numerical value represented by the difference between the 10% distillation temperature (° C.) and the 90% distillation temperature (° C.). And the average boiling point is 10%, 50% and 90%
% Distillation temperature, (10% distillation temperature (° C) + 2 x 50%
Distillation temperature (° C.) + 90% distillation temperature (° C.)) / 4. However, the term “boiling point” simply means the usual meaning.

When used industrially, it is important in practical use that the solvent has high solubility, is stable when used at high temperatures, is easy to recover after use, and can be handled safely. Element. The oxidation resistant solvent of the present invention has a boiling point of 2
A hydrocarbon-distilled fraction containing mainly components having a temperature of from 00 ° C to 230 ° C and having an average boiling point of 200
The temperature is not lower than 220 ° C and the boiling point is not higher than 30 ° C. When the average boiling point is less than 200 ° C. and the boiling point range exceeds 30 ° C., the oxidation-resistant solvent is easily flammable and requires special measures in handling. If the average boiling point exceeds 220 ° C. and the boiling point range exceeds 30 ° C., the efficiency of recovery of the oxidation-resistant solvent decreases and the solubility of the oxidation-resistant solvent decreases, which is not preferable for use.

[0012] Oxidation solvents of the present invention, in the maximum absorption wavelength lambda _max of the wavelength region 650 cm ^-1 to 2000 cm ^-1 in the infrared absorption spectrum is 690 cm ^-1 or more 71
It exists in a range of 0 cm ^-1 or less. Maximum absorption wavelength λ _max is less than 690 cm ⁻¹ or 710 cm
^If it exceeds ^-1 , the risk of crystal precipitation at low temperatures increases, which is not preferable.

The present inventor has studied the oxidation resistance of aromatic hydrocarbon compounds such as alkylbenzenes, especially the relationship between the performance as a solvent for producing copper phthalocyanine and its chemical structure. It has been found that a more compact molecule is preferable. Then, if the molecular weight is constant, paying attention to the fact that the degree of compactness of the molecule as the molecular shape is proportional to the density or the refractive index, and particularly according to the specific index as a function of the density or the refractive index of the hydrocarbon mixture fraction, It has been found that it is possible to easily correlate the anti-oxidation performance, particularly the performance as a solvent for producing copper phthalocyanine, even without complicated component analysis.

Further, the present inventor has found that the use of the obtained oxidation-resistant solvent as a solvent for producing copper phthalocyanine is a preferable reaction medium for producing copper phthalocyanine which is preferable as a pigment. In the production of the copper phthalocyanine pigment by the nitrile solvent method of the above 1), phthalonitrile or a derivative thereof such as chlorophthalonitrile or phenylphthalonitrile and copper or a copper salt such as copper chloride, copper sulfate or copper acetate are mixed with the solvent of the present invention. In the presence of

1 to 10 moles of phthalonitrile or a derivative thereof is used per gram atom of copper in copper or copper salt. Further, the production of the copper phthalocyanine pigment by the phthalic acid solvent method of the above 2) is a method of producing a phthalic anhydride or a derivative thereof such as phthalic acid, phthalic diamide, phthalamino acid, phthalimide, a halogen nucleus-substituted product, an alkyl nucleus-substituted product,
Urea or a derivative of phthalic anhydride such as buret or triuret is reacted with copper or a copper salt such as copper chloride, copper sulfate or copper acetate in the presence of the solvent of the present invention.

A catalyst is not essential, but molybdenum oxide,
Molybdenum compounds such as ammonium molybdate and molybdenum carbonyl, arsenic compounds such as arsenic oxide, and boric acid can be used as catalysts. The usage ratio of the above raw materials and the like is as follows.
３０30 mol%, urea is 50-500 mol%, the solvent of the present invention is about 1-10 weight times, and the catalyst to be added as needed is about 0.1 weight times.

In any of the methods, the above-mentioned solvent is used as a reaction medium in order to achieve a copper phthalocyanine production reaction efficiently, and the temperature is from 160 ° C. to 250 ° C., preferably 180 ° C.
It is produced at a reaction temperature of at least 230 ° C. Therefore, for industrial copper phthalocyanine pigment production, the boiling point of the reaction medium used is an important factor. The reaction medium used in the method of the present invention is a hydrocarbon mixture mainly containing components having a boiling point of 200 ° C to 230 ° C, and having an average boiling point of 200 ° C to 220 ° C and a boiling point of 30 ° C or less. It is. When the boiling point of mainly contained components is less than 200 ° C or the average boiling point of the solvent is less than 200 ° C,
In order to maintain the above-mentioned reaction temperature, manufacturing equipment capable of withstanding excessive pressurization is required, which is not preferable for industrial practice. If the boiling point of the components mainly exceeds 230 ° C. or the average boiling point of the solvent exceeds 220 ° C., the efficiency of evaporating and separating the reaction medium from the produced pigment decreases, and the reaction medium is evaporated and recovered. This is not preferable because a higher temperature than necessary is required at the time of performing the process, which results in an effect of deteriorating the sharpness of the pigment. Further, in the production of copper phthalocyanine pigments on an industrial scale, it is generally employed to separate the pigment produced after the reaction from the reaction medium by evaporation under reduced pressure. At this time, in the case of a reaction medium having a boiling point range exceeding 30 ° C., in order to stably remove the reaction medium, complicated adjustment is required for the decompression and heating operations, and for industrial practice in which a large amount is used. Not preferred.

The reaction medium used in the method of the present invention is 2
The index derived from the refractive index at 0 ° C., the density at 20 ° C., and the average boiling point is 7.0 × 10 ⁻⁴ or more and 7.6.
× 10 ⁻⁴ or less. The present inventors have found that the boiling point of the reaction medium is a practically important factor in determining the performance of the produced copper phthalocyanine pigment, and this index of the reaction medium plays a very important role. I found something. The index of the reaction medium is 7.0 ×
When it is less than 10 ^-4, the yield of the product pigment with respect to the raw material used is reduced, and it cannot be industrially used for producing a copper phthalocyanine pigment. The index is 7.6 × 10
If it exceeds ^-4 , the stability of the reaction medium itself is not sufficient, which adversely affects the sharpness of the pigment to be produced, and the reaction medium itself has a rather strong odor and is presumed to be used in large quantities. It is not industrially preferable from the viewpoint of maintaining the working environment. The reaction medium used in the method of the present invention is preferably a wavelength region 650c of an infrared absorption spectrum.
Maximum absorption wavelength λ from m ^-1 to 2000 cm ^-1
_max is in the range of 690 cm ^{-1 to} 710 cm ^-1 .

[0019]

According to the above-mentioned specific index, which is a function of the density and the refractive index of the hydrocarbon mixture fraction, it is possible to easily carry out oxidation resistance without using particularly complicated component analysis, and particularly to use it as a solvent for producing copper phthalocyanine. As a result, even with a multi-component hydrocarbon mixture fraction, a solvent having excellent oxidation resistance, particularly excellent performance as a solvent for producing copper phthalocyanine, can be obtained.

[0020]

The method of the present invention will be described in more detail with reference to the following examples. Reference Example 1 "Production of solvent" Using anhydrous aluminum chloride as a catalyst, propylene was reacted with benzene, toluene, orthoxylene or pseudocumene, and a fraction having the following properties was obtained by distillation.

[0021]

[Table 1]

The infrared absorption spectrum of solvent A, solvent B, solvent C and solvent D has a wavelength range of 650 cm ^-1 to 2000 c.
690 cm ^-1 or more and 700 cm at m ^-1
The maximum absorption wavelength λ _max was not shown in the range of ⁻¹ or less.

Reference Example 2 "Preparation of solvent" A mixture of benzene and butene, a mixture of pentene and hexene, and a mixture of butene and a mixture of pentene and methylpentene were reacted with anhydrous aluminum chloride as a catalyst, and a fraction having the following properties was obtained by distillation. Obtained.

[0024]

[Table 2]

The infrared absorption spectrum of the solvent E and the solvent F was the maximum absorption in the range of either 690 cm ^-1 or more 700 cm ^-1 or less at the 2000 cm ^-1 wavelength region 650 cm ^-1.

Reference Example 3 "Production of Solvent" A propylene polymer having an average molecular weight of 217 was reacted with benzene using anhydrous aluminum chloride as a catalyst, and a fraction having the following properties was obtained by distillation.

[0027]

[Table 3]

The infrared absorption spectrum of the solvent G and solvent H is the maximum absorption in the range of either 690 cm ^-1 or more 700 cm ^-1 or less at the 2000 cm ^-1 wavelength region 650 cm ^-1.

Reference Example 4 "Production of Solvent" A fraction having the following properties was obtained by distillation from a fraction obtained by isomerizing a naphtha raw material with a platinum-based catalyst.

[0030]

[Table 4]

The infrared absorption spectrum of solvent I has a wavelength range of 6
690 cm at 50 cm ^-1 to 2000 cm ^-1
The maximum absorption wavelength λm is in the range of ^{-1 to} 700 cm ^-1.
ax was not indicated.

Example 1 "Oxidation resistance of solvent" 200 ml capacity equipped with heating device, thermometer, reflux condenser
Solvent A obtained in the above reference example in a glass round bottom flask
To supply 100 cc of the solvent I, and maintain the reflux temperature.
Wavelength 420 nm to compare the degree of coloring of the solvent itself
The time change of the absorbance at was measured. The vapor of the evaporated fraction was kept in contact with air in the reflux condenser while maintaining the reflux temperature.

[0033]

[Table 5] Numerical values in the table are absorbance at a wavelength of 420 nm × 1000.
Represents

As a result of measuring the absorbance at 420 nm (indicating the degree of yellowing of the solution) at 420 nm for comparing the oxidation resistance of each solvent with the degree of coloring under heating, the solvent according to the method of the present invention was used. Certain solvent F, solvent G and solvent H have higher stability and lower coloration of the solvent itself even when placed in contact with air at a high temperature compared to other solvents, and have excellent oxidation resistance. Was.

Example 2 "Production of copper phthalocyanine" 26.6 g of phthalic anhydride, 45.6 g of urea, 4.4 g of anhydrous cuprous chloride and 0.01 g of ammonium molybdate were obtained in Examples and Comparative Examples as a reaction medium. Each fraction 1
Using 85 g, the mixture was supplied to a 500 ml container equipped with a stirrer, a thermometer, a heater and a reflux condenser, and reacted at the reflux temperature for 2 hours. The vapor of each fraction used as the reaction medium evaporated during the reaction maintained at the reflux temperature was kept in contact with air in the reflux condenser.

After cooling, the reaction product was removed by filtration under reduced pressure.
Washed twice in 00 g of methanol and filtered. After removing the solvent, the mixture was boiled and washed in 4 l of a 2% aqueous solution of caustic soda for 1 hour, filtered, and washed with hot water until the washing water was neutralized.
Further, by using 2 liters of 2% hydrochloric acid in the same manner, washing by boiling, filtration, and washing with hot water to the neutralization point were performed to obtain copper phthalocyanine as a blue powder. The pigment obtained after drying with a reduced-pressure drier at a temperature of 85 to 95 ° C. was used for a sharpness test.

12 g of the obtained pigment, 56 g of a coconut oil-modified alkyd resin (oil length 33%, 60% solution of xylene),
28 g of melamine resin, 10 g of xylene and 2 g of titanium oxide powder were put into a 300 cc ceramic rotary ball mill and kneaded for 5 hours to prepare a pigment-dispersed paint. The obtained paint is applied on a 0.2 m thick white high quality paper with an applicator having a thickness of 10 mil, dried with hot air at 120 ° C. and baked, the reflectance of the paint-coated surface is measured, and the hue of the coated surface is measured. Was measured. The reflectance was measured at a wavelength of 610 nm.

[0038]

[Table 6] The density of the coated surface is represented by a reflectance (%) where the reflectance of the upper blank paper surface is 100%.

As a result of the reflectance (indicating the degree of hue density on the coated surface) for comparison as a reaction medium for pigment production of each fraction used as a reaction medium, the solvent F which is a solvent by the method of the present invention was obtained , Solvent G and Solvent H are superior to other fractions in both the yield of copper phthalocyanine and the rich hue, as compared with other fractions, indicating that they have preferred performance as solvents for synthesis. .

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-2-247296 (JP, A) JP-A-2-247295 (JP, A) JP-A-2-247293 (JP, A) JP-A-2-247 247292 (JP, A) JP-A-2-247291 (JP, A) JP-A-2-247290 (JP, A) JP-A-2-247289 (JP, A) JP-A-2-247288 (JP, A) JP-A-2-247287 (JP, A) JP-A-2-247286 (JP, A) JP-A-53-22524 (JP, A) JP-A-52-38536 (JP, A) JP-A-52-36130 (JP, A) JP-A-50-44224 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C10G 7/00 C09B 47/06 C07C 15/00-15/085 C11D 7 / 50

Claims (2)

(57) [Claims] 1. A distillation-separated hydrocarbon mixture fraction mainly containing components having a boiling point of 200 ° C. or more and 230 ° C. or less, having an average boiling point of 200 ° C. or more and 220 ° C. or less, and a boiling point range of 30 ° C. or less. Exponent shown (Where n ₂₀ is the refractive index at 20 ° C., D ₂₀ is 20 ° C.)
(G / cc) and Bp are average boiling points (° C.), and 10%, 50%, and 90% distillation temperatures obtained by a distillation test were calculated as (10% distillation temperature (° C.) + 2 × 50% distillation). Temperature (℃) +
Numerical values calculated by (90% distillation temperature (° C.)) / 4 are shown. ) Is in the range of 7.0 × 10 ^{−4 to} 7.6 × 10 ⁻⁴ , and the wavelength region 650c of the infrared absorption spectrum
Maximum absorption wavelength λ from m ^-1 to 2000 cm ^-1
An oxidation-resistant solvent, wherein _max is in a range of 690 cm ^{-1 to} 710 cm ^-1 . 2. A method for producing copper phthalocyanine by reacting phthalic anhydride or a derivative thereof with urea and copper or a copper salt, or phthalonitrile or a derivative thereof and copper or a copper salt in a reaction medium under heating. Item 6. A method for producing copper phthalocyanine, comprising using the oxidation-resistant solvent according to Item 1 as a reaction medium.