JP2003128669A - Quinophtalone sulfonic acid derivative and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a quinophtalone derivative with which, when mixed with an object to be colored such as a resin, a colored object can maintain high liquidity and thermal shrinkage of the colored object during molding can be suppressed. SOLUTION: The quinophtalone sulfonic acid derivative represented by formula (1) is provided (wherein, X is a halogen atom; M is H, a monovalent, divalent or trivalent metal atom, ammonia or an organic amine; and n is 1-3). In the production method of quinophtalone sulfonic acid derivative, quinophtalone compound having halogen atoms within the molecule is reacted with sulfuric acid.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a quinophthalonesulfonic acid derivative useful as a pigment additive for improving the properties of organic pigments, and a method for producing the same.

[0002]

2. Description of the Related Art C. I. Pigment Yellow
A quinophthalone compound represented by 138 belongs to a condensed polycyclic compound and is used as a yellow colorant for plastics and paints because it has much higher heat resistance than an azo compound as a yellow pigment. . As such a quinophthalone compound, quinophthalone monosulfonic acid is known as disclosed in British Patent No. 445201. This compound can be obtained by heating a sulfate of quinophthalone or an adduct of sulfurous acid gas of quinophthalone under reduced pressure, if necessary. The publication discloses the use of quinophthalone monosulfonic acid as a dye, and this method is useful for sulfonation of unsubstituted quinophthalone and quinophthalone having a hydroxyl group. However, this method is not suitable for sulfonation in the case of producing a sulfonic acid derivative of quinophthalone containing a halogen atom as a substituent. That is, in this conventional production method, when an attempt was made to produce a sulfonic acid derivative of quinophthalone containing a halogen atom as a substituent, unreacted raw materials were likely to remain, and the unreacted raw materials were inferior in the original pigment coloring performance. There are times when you want to. Moreover, in order to remove such unreacted raw materials, a separate refining step is required, which is troublesome. C. I. Pigment Yellow 138
The quinophthalone-based compound typified by 1 has a drawback that when it is added alone to a material to be colored, the fluidity of the colored material is lowered due to insufficient dispersibility in the material to be colored. There is.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a sulfonic acid derivative of a quinophthalone compound containing a halogen atom as a substituent, which is not described in the above-mentioned known documents and which is useful as a pigment having higher durability. With the goal. More specifically, C.I. I. Pigment Yel
A quinophthalone-based compound that enhances dispersibility in a material to be colored, consequently improves fluidity of the colored material and makes thermal shrinkage less likely to occur, while maintaining almost the same hue as a yellow pigment such as low 138. It is intended to provide a sulfonic acid derivative of Another object of the present invention is to provide a method for more easily obtaining such a sulfonic acid derivative.
Such a quinophthalone compound, even if it is a pigment, has a drawback that it has insufficient fluidity and that heat shrinkage easily occurs during molding.

[0004]

[Means for Solving the Problems] Then, as a result of intensive studies to solve such a drawback, it was found that a quinophthalone-based sulfonic acid derivative containing a halogen atom as a substituent is a sulfonic acid derivative of an unsubstituted quinophthalone or a hydroxyl group-containing quinophthalone. It was found that the sulfonic acid derivative is excellent in various durability as compared with, and that the sulfonic acid derivative can be easily obtained in a high yield by using sulfuric acid as a solvent / catalyst, and the present invention has been completed. It was found that these characteristics are improved by introducing a sulfonic acid group into a portion of the quinophthalone compound corresponding to the quinaldine skeleton, and the present invention has been completed.

That is, according to the present invention, a quinophthalonesulfonic acid derivative represented by the following general formula (1) and a quinophthalone compound having a halogen atom in the molecule are reacted with 5 to 50 times the equivalent amount of sulfuric acid in terms of mass. Provided is a method for producing a quinophthalone sulfonic acid derivative.

[0006]

[Chemical 2]

[However, in the formula (1), X is a halogen atom,
M is a hydrogen atom, a monovalent, divalent or trivalent metal atom, ammonia or an organic amine, and n is 1 to 3. ]

[0008]

The present invention will be described in detail below. The quinophthalonesulfonic acid derivative in the present invention is represented by the above general formula (1). Examples of the halogen atom represented by X include a chlorine atom and a bromine atom, and each X may be the same atom or different atoms. M
Are hydrogen atoms, ammonia, monovalent, divalent or trivalent metal atoms, and organic amines. Examples of these metal atoms are potassium atom, sodium atom, lithium atom, calcium atom, magnesium atom, strontium atom, aluminum. The atom, or as an organic amine,
Monoalkylamines such as ethylamine and butylamine,
Examples thereof include dialkylamines such as dimethylamine and diethylamine, trialkylamines such as trimethylamine and triethylamine, and alkanolamines such as monoethanolamine, diethanolamine and triethanolamine.

In the general formula (1), n is 1 to 3 which is the number of atomic groups (SO ₃ ) substituted on the aromatic ring derived from quinaldine described later. When n ≧ 2, the individual atomic groups (SO ₃ ) are bonded to different carbon atoms of the aromatic ring derived from quinaldine. Further, the atomic group (SO ₃ ) M corresponding to the sulfonic acid group or the sulfonate is electrically neutral like SO ₃ Na and (SO ₃ ) ₃ Al. Since sulfonic acid (SO ₃ H) is a monovalent acid,
When substituting with an atomic group M other than a hydrogen atom, when n = 1, it is 1/2 mol when M is a divalent metal atom or the like, and 1/3 mol when M is a trivalent metal atom or the like. It will be equivalent.

This quinophthalonesulfonic acid derivative can be obtained by sulfonating a quinophthalone compound by an aromatic electrophilic substitution reaction and, if necessary, substituting a terminal hydrogen atom of the sulfonic acid with a metal atom or the like. I can.

The quinophthalone compound in the present invention is
It is a raw material of a quinophthalone sulfonic acid derivative, and is a compound having a quinophthalone skeleton formed by the reaction of 1 mol of 8-aminoquinaldine and 2 mol of phthalic anhydride having a halogen atom. Examples of the quinophthalone compound as the raw material include compounds represented by the above formula (1) with a structure in which a sulfonic acid group or a sulfonate is removed.
This quinophthalone compound can be used as a raw material for a sulfonic acid derivative produced by reacting as described above, but Paliotol Gelb K0961HD manufactured by BASF (where X in the general formula (1) is a chlorine atom and an atomic group (SO ₃ )
A quinophthalone yellow pigment without M. C. I. Pig
It is also possible to use a commercially available quinophthalone-based pigment such as ment yellow 138).

Examples of the sulfonating agent include concentrated sulfuric acid, fuming sulfuric acid, combined use of concentrated sulfuric acid and fuming sulfuric acid, combined use of sulfuric acid and phosphorus pentoxide, chlorosulfonic acid, sodium hydrogen sulfite,
A combination of sulfuryl chloride and aluminum chloride can be adopted.

The amount of the sulfonating agent used with respect to the raw material quinophthalone compound varies depending on the number of sulfonic acid groups contained in one molecule and the strength of the sulfonating agent.
For example, the amount of the sulfonating agent is 50 to 2000 parts with respect to 100 parts of the raw material quinophthalone compound.

As the sulfonation catalyst, for example, a sulfate metal salt such as calcium sulfate, aluminum sulfate or iron sulfate can be used in combination. The amount of this catalyst used is, for example, 0.05 to 10 parts in terms of mass per 100 parts of the raw material quinophthalone compound.

When the sulfonation reaction is too vigorous, the reaction can be carried out in a solvent such as ethylene glycol, propylene glycol, chloroform, ethylene chloride or carbon tetrachloride.

Such a sulfonation reaction has a reaction temperature of 50.
It can be carried out at a temperature of up to 180 ° C. and a reaction time of 2 to 10 hours.

Since the quinophthalone compound which is a raw material in the present invention has a halogen atom in the molecule, it is not possible to directly adopt the general sulfonation method of unsubstituted quinophthalone which does not have it and the conditions therefor. In the present invention,
Since it is not necessary to remove the organic solvent after the reaction and the reaction rate is excellent, it is preferable to use 5 to 50 times by mass of sulfuric acid as the sulfonating agent / solvent with respect to the raw material quinophthalone compound. . As the sulfuric acid in this case, concentrated sulfuric acid, fuming sulfuric acid or a mixture thereof is preferable.

This reaction can be carried out by mixing the starting quinophthalone compound with the sulfuric acid and stirring at a predetermined temperature. The conditions for this sulfonation depend on the kinds of the raw material quinophthalone compound and sulfuric acid used, but are preferably at a temperature of 100 to 140 ° C. for 1 to 9 hours.

The end point of sulfonation is appropriately adjusted depending on the desired number n of sulfonic acid groups or sulfonates contained in the quinophthalone skeleton. At this end point, the reaction temperature is fixed and the reaction time is changed to obtain respective reaction product samples, and mass spectrometry (mass spectrum; MS) is performed on these samples.
By measuring the infrared absorption spectrum (IR) and the calibration curve in advance, it is possible to control from the next time only by the reaction time. This calibration curve can be created based on the quasi-molecular ion peak value and the presence and intensity of the characteristic infrared absorption peak based on the sulfonic acid group that appears around 1000 to 1100 cm ⁻¹ . That is, according to mass spectrometry,
With the formation of the quinophthalone sulfonic acid derivative corresponding to the number n of sulfonic acid groups or sulfonates, the corresponding pseudo-molecular ion peak appears, and according to the infrared absorption spectrum, the proportion of the derivative is increased. As a result, the intensity of the specific infrared absorption peak of the sulfonic acid group or the sulfonate becomes high.

When the reaction is terminated before the sulfonation rate becomes saturated and constant, the reaction product obtained can be a mixture of a quinophthalone compound and a quinophthalone sulfonic acid derivative except for the sulfonating agent. .

When sulfuric acid is used as the raw material, the infrared absorption peak of the sulfuric acid and that of the sulfonic acid group or sulfonate of the quinophthalone sulfonic acid derivative may be close to each other in terms of wavelength and may be difficult to separate. In this case, sulfuric acid may be removed from the reaction product, washed if necessary, and then a calibration curve may be prepared according to each analysis described above. Of course, elemental analysis can also be used to identify the final product.

By the way, the quinophthalonesulfonic acid derivative is a quinophthalonesulfonic acid derivative in which X in the general formula (1) is a chlorine atom and M is a hydrogen atom, that is,
C. I. In the case of a sulfonic acid derivative of a quinophthalone compound having the same chemical structure as Pigment Yellow 138, in addition to the specific infrared absorption peak based on the quinophthalone compound itself, a specific infrared absorption peak based on a sulfonic acid group is newly added at 1030 ± 5 cm. ^It is expressed in ^-1 .

Further, which position in the quinaldine-derived aromatic ring skeleton the sulfonic acid group or sulfonate in the quinophthalone sulfonic acid derivative is substituted with can be specified by, for example, nuclear magnetic resonance spectrum (NMR). I can.

After the completion of the above reaction, operations such as filtration, drying, pulverization, classification, purification and pigmentation can be carried out, if necessary, so that the intended use form and quality can be obtained.

The reaction mixture thus subjected to the sulfonation reaction can be precipitated as a solid by adding it to water in a large excess of the sulfonating agent used. Here, water can be used in an amount of, for example, 500 to 1200 parts per 100 parts of the reaction mixture in terms of mass.

If necessary, following the above operation, stirring may be further carried out for 10 minutes to 2 hours and aged to complete the precipitation.

The quinophthalonesulfonic acid derivative can be filtered out from the mixture containing water and the quinophthalonesulfonic acid derivative and used as a wet cake.
It can also be dried and used as a dry powder. On the other hand, it is also possible to remove the sulfonating agent from the reaction mixture obtained after the completion of the reaction and obtain a dry powder of the quinophthalonesulfonic acid derivative with a spray dryer or the like.

The quinophthalonesulfonic acid derivative thus precipitated in a large excess of water is filtered and washed with water to obtain
It can be purified. If necessary, the purity of the quinophthalonesulfonic acid derivative can be further increased by washing with a dilute acid such as dilute hydrochloric acid.

In particular, when the use of the quinophthalone sulfonic acid derivative is in the advanced field such as optical materials and electrophotographic materials, it is necessary to sufficiently purify the wet cake and the dry powder so that the concentration of free sulfuric acid and the conductivity can be reduced. It is preferable because it can be reduced to a level at which there is no problem in the required performance in the final use, and the characteristic improvement in the final use can be expected.

If the particle size of the quinophthalonesulfonic acid derivative is relatively large, or if it is desired to further reduce the particle size, it can be crushed before use.

The sulfonic acid group in the quinophthalone sulfonic acid derivative may be in the state as it is, but if necessary, as described above, a metal of a monovalent, divalent or trivalent metal is added to the sulfonic acid group. A compound, ammonia, or an organic amine can be reacted to form a corresponding sulfonic acid salt, for example, a metal salt such as sodium sulfonate, an ammonium salt, an organic amine salt, or the like.

By utilizing the difference in solubility of the quinophthalone sulfonic acid derivative containing a sulfonate as a functional group and the raw material quinophthalone compound in water, the mixture containing the quinophthalone sulfonic acid derivative and the raw material quinophthalone compound can be used to obtain the former It is also possible to reliably separate only. A quinophthalone sulfonic acid derivative containing a sulfonate as a functional group is more likely to migrate to the aqueous phase than a raw material quinophthalone compound having no hydrophilic atomic group. Therefore, by dehydrating and drying an aqueous solution containing the derivative, the sulfonate It is possible to isolate a quinophthalone sulfonic acid derivative which contains as a functional group.
If necessary, the quinophthalone sulfonic acid derivative containing this sulfonate as a functional group can be added to an acid or an aqueous solution thereof to convert it back into a quinophthalone sulfonic acid derivative containing a sulfonic acid group as a functional group.

The quinophthalone sulfonic acid derivative may be composed of only components of n = 1 to 3 as in the above formula (1), but industrially, without purification or the like in the above production method, Included in the entire pigment composition as a composition also containing a quinophthalone compound of n = 0, or as a pigment composition in combination with the above-mentioned derivative of only n = 1 to 3 and an existing quinophthalone-based pigment as described above. Sulfonic acid group or sulfonate content (average number of substituents) 0.3 to
It can also be used as an additive for a pigment described later by setting it to 3.

Since the quinophthalonesulfonic acid derivative of the present invention thus obtained has a halogen atom in the molecule, it is superior in durability to organic solvents and heat resistance as compared with an unsubstituted quinophthalonesulfonic acid derivative which does not have a halogen atom. .

The quinophthalone sulfonic acid derivative of the present invention, by itself, is more fluid dispersible than the corresponding quinophthalone compound having no sulfonic acid group or sulfonate as a substituent when added to a material to be colored such as a resin. Is good, it is possible to further enhance the fluidity of the colored product,
It has the advantage that heat shrinkage is unlikely to occur during molding. Further, according to the production method of the present invention, the quinophthalone sulfonic acid derivative has a sulfonic acid group or a sulfonic acid salt with a decrease in crystallinity due to the inclusion of a sulfonic acid group or a sulfonic acid salt as a substituent in the molecular structure. Can be made finer than the corresponding quinophthalone-based pigment having no as a substituent. When a sulfonic acid group and a sulfonic acid salt are compared (that is, when M in the formula (1) is a hydrogen atom and a metal atom, etc.), a quinophthalone sulfonic acid derivative (M Is a hydrogen atom), it is more excellent in water resistance than a quinophthalonesulfonic acid derivative having only a sulfonate as a functional group (when M is a metal atom or the like), and thus is preferable.

Therefore, the quinophthalonesulfonic acid derivative of the present invention can be used as a pigment additive in C.I. I. Pigment
When added to a quinophthalone-based pigment such as Yellow 138 and used in combination, the fluidity and dispersibility of the pigment itself in the material to be colored can be improved, and the fluidity of the colored material can be further increased, and the heat shrinkability at the time of molding etc. Can be improved to be smaller. The amount of the quinophthalone sulfonic acid derivative of the present invention added to the quinophthalone-based pigment is not particularly limited, but in consideration of the degree of the above-mentioned effect and the change in hue, the quinophthalone-based pigment 10 is converted into mass.
0.5-20 quinophthalone sulfonic acid derivative per 0 part
You can choose from a range of parts.

The mixture containing the quinophthalone compound and the quinophthalone sulfonic acid derivative can be made finer and have a uniform particle size distribution, if necessary, by forming it into a pigment by a known conventional post-treatment such as a solvent method or a solvent salt milling method. A quinophthalone-based pigment composition can be prepared. Rather than adding a quinophthalone sulfonic acid derivative to a quinophthalone-based pigment afterwards to form a pigment composition, a pigment composition obtained by adding a quinophthalone sulfonic acid derivative to a quinophthalone compound to form a pigment is better than a quinophthalone-based pigment particle surface. As a result of adsorption of the derivative in the vicinity, the same effect can be achieved by using a smaller amount of the derivative.

The quinophthalone sulfonic acid derivative thus obtained, a quinophthalone pigment and a pigment composition containing the quinophthalone sulfonic acid derivative are various thermoplastic resins,
Printed products, colored resin molded products, coated products in which the base material is coated with a colored resin film, etc. by mixing and dispersing in a thermosetting resin or active energy ray curable resin, molding or coating on a base material and curing if necessary. Can be obtained.

[0039]

EXAMPLES Next, the present invention will be explained based on examples. The following parts and% are based on mass unless otherwise specified.

Reference Example Paliotol Gelb K0961HD (C.I.
Pigment Yellow 138) 10 parts,
2.5 parts of N, N′-dimethylformamide, Disperbic 161 (dispersing agent manufactured by BYK Chemie) 6.78 parts,
Eucerester EEP (solvent manufactured by Union Carbide Co.) 80.80 parts was added with 0.5 mmφ sepul beads,
1 with paint conditioner (manufactured by Toyo Seiki Co., Ltd.)
It was dispersed for a time to obtain a pigment dispersion.

This dispersion is VIS manufactured by Toki Sangyo Co., Ltd.
It was 44.7 mPa * s when the viscosity was measured using COMETER MODEL RL.

Example 1 Paliotol Gelb K0961HD (C.I.
Pigment Yellow 138) 20 parts and 9
300 parts of 8% sulfuric acid was put in a 500 ml separable flask and reacted at 120 ° C. for 5 hours to sulfonate the quinophthalone compound. After that, the reaction mixture was taken out into 3000 parts of water, and a quinophthalonesulfonic acid sulfonic acid derivative was precipitated, stirred for 30 minutes for aging, and then filtered and washed with water three times.

Then, 1 part of the wet cake obtained above is used.
%, Diluted with 300 parts of hydrochloric acid, filtered, and washed with water until the filtrate became colored. After that, it is dried with a hot air dryer, and 5
4 parts (yield 95.9%) of solid (1) was obtained.

This solid substance (1) was used as a liquid chromatography / mass spectrometer LC / LC manufactured by Hewlett-Packard Company.
MS (Electro Spray Ionizatio)
As a result of mass spectrometric analysis according to n), m / z = which coincides with the pseudo-molecular ion of quinophthalonesulfonic acid in the chart.
733

[MH] -was detected. Moreover, it was confirmed by elemental analysis by a usual method that the composition was as follows.

[0045]

[Table 1] Table 1

Further, the infrared absorption spectrum was measured by the powder KBr method.
It was confirmed that there was specific absorption based on a sulfonic acid group near 030 cm ⁻¹ .

Dilute hydrochloric acid was added to this solid substance (1),
The residual sulfuric acid content was filtered off. The residue was dried and dehydrochlorinated with a hot air drier and subjected to mass spectrometry in the same manner as described above.
Was confirmed to be a derivative having a sulfonic acid group with n = 1 as a functional group.

The solid (1) thus obtained has the formula (1)
Among them, X was a chlorine atom, m was 4, M was a hydrogen atom, and it was found to contain a quinophthalonesulfonic acid derivative with n = 1. The content rate (average number of substituents) of sulfonic acid groups contained in the entire solid (1) was 0.9. Paliotol Gelb K0961HD in place of the solid material (1)
The viscosity of the pigment dispersion liquid, which is a colored product, was measured in the same manner as in Reference Example except that the above was used, and the viscosity was 7.8 mPa · s, which was significantly lower than that in Reference Example and had excellent fluidity. I understood.

[0049]

Since the quinophthalone sulfonic acid derivative of the present invention has a sulfonic acid group or a sulfonic acid salt as a substituent in the quinophthalone compound, it hardly changes the hue when mixed with an object to be colored, A particularly remarkable effect is obtained in that a colored product exhibiting superior fluidity and the like can be obtained as compared with a colored product in which a quinophthalone compound containing no substituents is mixed. According to the manufacturing method of the present invention,
Compared to the conventional sulfonation method that uses sulfuric acid as a catalyst with an organic solvent, no organic solvent is used, so there is no need to remove and recover the organic solvent after the reaction is complete, and the reaction rate is also outstanding. Has a great effect.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Ryo Kimura             3097 Miyanaka, Kashima City, Ibaraki Prefecture (72) Inventor Arata Kudo             3428-1 Chite, Kamisu Town, Kashima District, Ibaraki Prefecture (72) Inventor Junko Sunouchi             3-9809-9 Togo, Hasaki-cho, Kashima-gun, Ibaraki F-term (reference) 4C063 AA01 BB02 CC14 DD07 EE10

Claims (4)

[Claims] 1. A quinophthalonesulfonic acid derivative represented by the following general formula (1). [Chemical 1] [In the formula (1), X is a halogen atom, M is a hydrogen atom, a monovalent, divalent or trivalent metal atom, ammonia or an organic amine, and n is 1 to 3. ] 2. The quinophthalonesulfonic acid derivative according to claim 1, wherein X is a chlorine atom and M is a hydrogen atom. 3. A method for producing a quinophthalonesulfonic acid derivative, which comprises reacting 5 to 50 times by mass of sulfuric acid in terms of mass with a quinophthalone compound having a halogen atom in the molecule. 4. The production method according to claim 3, wherein the reaction is carried out without using any other solvent.