CN112638882A - Alkylene compounds, quinophthalone compounds and quinophthalone mixtures - Google Patents
Alkylene compounds, quinophthalone compounds and quinophthalone mixtures Download PDFInfo
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- CN112638882A CN112638882A CN201980055609.XA CN201980055609A CN112638882A CN 112638882 A CN112638882 A CN 112638882A CN 201980055609 A CN201980055609 A CN 201980055609A CN 112638882 A CN112638882 A CN 112638882A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/38—Nitrogen atoms
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B25/00—Quinophthalones
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Abstract
An alkylene compound represented by the following formula (1). [ formula 1]
[ in the formula (1), X1And X2Each independently represents a hydrogen atom or a halogen atom, and Z represents an alkylene group having 1 to 3 carbon atoms.]。
Description
Technical Field
The present invention relates to an alkylene compound, a process for producing a quinophthalone compound, and a quinophthalone mixture.
Background
Conventionally, coloring compositions have been used in various fields, and specific applications of the coloring compositions include printing inks, paints, coloring agents for resins, coloring agents for fibers, coloring materials for IT information recording (color filters, toners, inkjet printers), and the like. The coloring matter used in the coloring composition is required to have color characteristics (coloring power, vividness), resistance (weather resistance, light resistance, heat resistance, solvent resistance), and the like. The coloring matter is mainly classified into a pigment and a dye, and the pigment develops color in a particle state (aggregate of primary particles) unlike a dye that develops color in a molecular state. Therefore, in general, a pigment is superior in resistance to a dye, but is inferior in tinting strength and chroma (vividness).
Under such circumstances, pigments having high coloring power and high chroma are required, and organic pigments having an advantage in coloring power are particularly attracting attention. For example, patent document 1 discloses a coloring composition containing a predetermined quinophthalone compound.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2012 and 247587
Disclosure of Invention
Problems to be solved by the invention
However, the conventional quinophthalone compound-containing coloring composition is not necessarily excellent in coloring power, and is never sufficient particularly for applications requiring high color reproducibility such as a color filter. Further, since the quinophthalone compound is obtained by a condensation reaction between a quinaldine (2-methylquinoline) compound and phthalic anhydride, the development of a novel quinaldine compound is important in order to find a quinophthalone compound having excellent coloring power.
Accordingly, an object of the present invention is to provide a novel quinaldine compound for producing a quinophthalone compound having excellent coloring power as a pigment. Further, an object of the present invention is to provide a method for producing a quinophthalone compound having excellent coloring power as a pigment. Further, an object of the present invention is to provide a novel quinophthalone compound and a quinophthalone mixture containing the quinophthalone compound.
Means for solving the problems
One aspect of the present invention is an alkylene compound represented by formula (1).
[ solution 1]
[ in the formula (1), X1And X2Each independently represents a hydrogen atom or a halogen atom, and Z represents an alkylene group having 1 to 3 carbon atoms.]
The above Z may be a methylene group.
Another aspect of the present invention is a method for producing a quinophthalone compound, comprising the steps of: condensing an alkylene compound represented by formula (1) with an acid anhydride represented by formula (2) to obtain at least one selected from the group consisting of a first quinophthalone compound represented by formula (3) and a second quinophthalone compound represented by formula (4).
[ solution 2]
[ in the formula (1), X1And X2Each independently represents a hydrogen atom or a halogen atom, and Z represents an alkylene group having 1 to 3 carbon atoms.]
[ solution 3]
[ in the formula (2), X3、X4、X5And X6Each independently represents a hydrogen atom or a halogen atom.]
[ solution 4]
[ in the formula (3), X1、X2、X3、X4、X5And X6Each independently represents a hydrogen atom or a halogen atom, and Z represents an alkylene group having 1 to 3 carbon atoms.]
[ solution 5]
[ in the formula (4), X1、X2、X3、X4、X5And X6Each independently represents a hydrogen atom or a halogen atom, and Z represents an alkylene group having 1 to 3 carbon atoms.]
In one embodiment, the step may be a step of condensing the alkylene compound with the acid anhydride in the presence of an acid catalyst.
A further aspect of the present invention is a quinophthalone compound represented by formula (4).
A further aspect of the present invention is a quinophthalone mixture containing a first quinophthalone compound represented by formula (3) and a second quinophthalone compound represented by formula (4).
Effects of the invention
According to the present invention, a novel quinaldine compound for producing a quinophthalone compound having excellent tinting strength as a pigment is provided. Further, the present invention provides a method for producing a quinophthalone compound having excellent coloring power as a pigment. In addition, according to the present invention, there are provided a novel quinophthalone compound, and a quinophthalone mixture containing the quinophthalone compound.
Detailed Description
Hereinafter, preferred embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments.
(alkylene compound)
The alkylene compound according to the present embodiment is a compound represented by the following formula (1).
[ solution 6]
In the formula (1), X1And X2Each independently represents a hydrogen atom or a halogen atom, and Z represents an alkylene group having 1 to 3 carbon atoms.
The halogen atom in the formula (1) may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom, a chlorine atom or a bromine atom, more preferably a chlorine atom.
Specific examples of the alkylene group having 1 to 3 carbon atoms in formula (1) include, for example, a methylene group, an ethylene group (1, 1-ethanediyl or 1, 2-ethanediyl), a propylene group (1, 1-propanediyl, 2-propanediyl, 1, 2-propanediyl or 1, 3-propanediyl), more preferably a methylene group, a 1, 1-ethanediyl group, 1-propanediyl or 2, 2-propanediyl, and still more preferably a methylene group.
One embodiment of the method for producing the above-mentioned alkylene compound is described below, but the production method is not limited thereto.
The alkylene compound according to the present embodiment can be obtained, for example, by a method including the following step I, step II, and step III. In the formulae (1-i) and (1-ii), a plurality of X's are present1Each other and a plurality of X2May be the same or different from each other.
< Process I >
First, a compound of the following formula (1-i) is synthesized by adding 2 to 3 equivalents of crotonaldehyde to 1 equivalent of a bisaniline compound and reacting the mixture in a strong acid in the presence of an oxidizing agent by the method described in j.heterocyclic, Chem,30,17 (1993).
[ solution 7]
In the formula (1-i), X1、X2And Z is as described above.
Here, examples of the strong acid include hydrochloric acid, sulfuric acid, and nitric acid. Examples of the oxidizing agent include sodium iodide, tetrachlorop-benzoquinone, and nitrobenzene.
In the step I, the reaction temperature may be from 80 to 100 ℃ and preferably from 90 to 100 ℃ and the reaction time may be from 1 to 6 hours and preferably from 3 to 6 hours.
< Process II >
Further, the compound of formula (1-ii) can be obtained by reacting the obtained compound of formula (1-i) with nitric acid or fuming nitric acid in the presence of concentrated sulfuric acid.
[ solution 8]
In the formula (1-ii), X1、X2And Z is as described above.
In the step II, the reaction temperature may be from-20 ℃ to 70 ℃, preferably from 0 ℃ to 50 ℃, and the reaction time may be from 1 hour to 4 hours, preferably from 1 hour to 3 hours.
< step III >
Further, by reduction of the resulting compound of formula (1-ii), a nitro group (-NO) is converted into a nitro group (-NO)2) Conversion to amino (-NH)2) Thereby, an alkylene compound represented by the above formula (1) can be obtained.
In the step (III), the compound of formula (1-ii) is subjected to reduction treatment with reduced iron, for example, to obtain an alkylene compound represented by formula (1). In this case, the amount of reduced iron may be 6 to 8 equivalents based on 1 equivalent of the compound of formula (1-ii), the reaction temperature may be 60 to 80 ℃, preferably 70 to 80 ℃, and the reaction time may be 1 to 3 hours, preferably 2 to 3 hours.
In the step (III), the compound of the formula (1-ii) is subjected to a reduction treatment with a metal catalyst such as palladium-carbon (Pd-C), platinum-carbon (Pt-C), or Raney nickel to obtain an alkylene compound represented by the formula (1). In this case, the amount of the metal catalyst may be, for example, 0.4 to 5% by mass of the compound of the formula (1-ii), the reaction temperature may be, for example, 30 to 100 ℃ and the reaction time may be, for example, 1 to 10 hours, as the amount of the metal. As the hydrogen source for the reaction, hydrogen gas, hydrazine, ammonium formate, or the like can be used.
(Process for producing quinophthalone Compound)
The method for producing a quinophthalone compound according to the present embodiment includes the steps of: at least one selected from the group consisting of a first quinophthalone compound represented by the following formula (3) and a second quinophthalone compound represented by the following formula (4) is obtained by condensing an alkylene compound represented by the following formula (1) with an acid anhydride represented by the following formula (2) (hereinafter referred to as process IV). In the formulae (3) and (4), a plurality of X's are present3Each other, a plurality of X4Each other, a plurality of X5Each other and a plurality of X6May be the same or different from each other.
[ solution 9]
[ solution 10]
[ solution 11]
[ solution 12]
In the formula (1), X1、X2And Z is as described above.
In the formula (2), X3、X4、X5And X6Each independently represents a hydrogen atom or a halogen atom. The halogen atom in the formula (2) may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom, a chlorine atom or a bromine atom, more preferably a chlorine atom.
In the acid anhydride represented by the formula (2), X3、X4、X5And X6In (3), at least 1 is preferably a halogen atom, and more preferably 2 or more are halogen atoms. In addition, X4And X5In (3), preferably at least 1 is a halogen atom, more preferably X4And X5Are all halogen atoms. By reaction at X3、X4、X5Or X6Introduction of a halogen atom tends to further improve the dispersibility and durability of the quinophthalone compound produced using the anhydride, and the above effects can be more remarkably obtained.
Examples of the acid anhydride represented by the formula (2) include terephthalic anhydride and halogen-substituted phthalic anhydride, and specific examples of the halogen-substituted phthalic anhydride include tetrafluorophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, 4, 5-dichlorophthalic anhydride, 4-chlorophthalic anhydride, 4, 5-dibromophthalic anhydride, and the like.
The acid anhydride represented by the formula (2) may be used singly or in combination of two or more. By using two or more acid anhydrides represented by formula (2), a plurality of X's can be obtained3Each other, a plurality of X4Each other, a plurality of X5Each other and a plurality of X6The aforementioned quinophthalone compounds are different from each other.
In the formulae (3) and (4), X1、X2、X3、X4、X5And X6Each independently represents a hydrogen atom or a halogen atom. The halogen atom in the formulae (3) and (4) may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom, a chlorine atom or a bromine atom, more preferably a chlorine atom.
In the quinophthalone compounds represented by the formulae (3) and (4), X3、X4、X5And X6In (3), at least 1 is preferably a halogen atom, and more preferably 2 or more are halogen atoms. In addition, X4And X5In (3), preferably at least 1 is a halogen atom, more preferably X4And X5Are all halogen atoms. By reaction at X1、X2、X3、X4、X5Or X6Introduction of a halogen atom tends to further improve the dispersibility and durability of the quinophthalone compound, and the above effects can be more remarkably obtained.
In the structure of formula (3), structural tautomers such as the following formulae (3-i) and (3-ii) exist, and the quinophthalone compound may have any of these structures. In addition, in the structure of formula (4), a plurality of tautomers exist similarly, and the quinophthalone compound may have any of these structures.
[ solution 13]
In the formulae (3-i) and (3-ii), X1、X2、X3、X4、X5、X6And Z is as described above.
Specific examples of the quinophthalone compound are given below, but the quinophthalone compound is not limited thereto.
[ solution 14]
[ solution 15]
[ solution 16]
[ solution 17]
[ solution 18]
[ solution 19]
The quinophthalone compound exhibits selective absorption and transmission due to dimerization of a heterocyclic skeleton centered on a quinoline ring. In addition, the quinophthalone compound is inhibited from excessively reddening by cleaving conjugation by dimerizing the heterocyclic skeleton with an alkylene group as a linker as a spacer. Further, the quinophthalone compound has improved dispersibility due to the introduction of an imide structure. Thus, according to the quinophthalone compound, a pigment having excellent brilliance and tinting strength can be obtained. Specifically, for example, a yellow pigment composed of the quinophthalone compound has better luminance than a yellow pigment (c.i. pigment yellow 150) generally used at present, and has better excellent tinting strength.
The step IV may be, for example, the following steps: by the method described in Japanese patent application laid-open No. 2013-61622, for example, 3 to 6 equivalents of an acid anhydride represented by the formula (2) is reacted with 1 equivalent of an alkylene compound represented by the formula (1) in the presence of an acid catalyst, thereby condensing the alkylene compound represented by the formula (1) and the acid anhydride represented by the formula (2).
The reaction temperature for the condensation may be 180 ℃ to 250 ℃, preferably 200 ℃ to 250 ℃. The reaction time for the condensation may be 1 to 8 hours, preferably 3 to 8 hours.
Examples of the acid catalyst include a bronsted acid such as benzoic acid, p-toluenesulfonic acid, zinc chloride, and ferric chloride, and a lewis acid.
The step IV may be a step of obtaining the first quinophthalone compound represented by the formula (3) or the second quinophthalone compound represented by the formula (4), or may be a step of obtaining a mixture of the first quinophthalone compound and the second quinophthalone compound (quinophthalone mixture).
The quinophthalone compound (or quinophthalone mixture) obtained by the production method according to the present embodiment has excellent coloring power as a pigment. The quinophthalone compound may be pigmented by a known and conventional method.
The pigment (yellow pigment) composed of the quinophthalone compound can be micronized, for example, by salt milling. The yellow pigment may be surface-treated by a method such as rosin treatment, surfactant treatment, solvent treatment, or resin treatment.
Examples
(example A-1)
5.00g (56.1mmol) of 4, 4' -methylenebis (2-chloroaniline), 27.6g (112mmol) of tetrachlorop-benzoquinone, 150ml of water, 150ml of concentrated hydrochloric acid, and 100ml of n-butanol were added to a flask, and the mixture was stirred at 95 ℃ for 30 minutes. To the mixture, 11.8g (168mmol) of crotonaldehyde dissolved in 12ml of n-butanol was added dropwise, followed by stirring for further 1 hour. The temperature was lowered to 80 ℃ and 15.3g (112mmol) of zinc chloride was added in small portions, followed by addition of THF200ml and stirring at 80 ℃ for 1 hour. After standing and cooling to room temperature, the yellow soil powder was recovered by filtration under reduced pressure. The resulting yellow-earth powder was washed with 200ml of THF, and recovered again by filtration under reduced pressure. Further, the obtained loess powder was transferred to a flask, 200ml of water and 40ml of 28% aqueous ammonia were added, and stirred at room temperature for 2 hours. The powder was recovered by filtration under reduced pressure to give 20.3g of a crude product. The resulting crude product was dissolved in toluene, and insoluble matter was removed by filtration, followed by recrystallization to obtain 12.6g of intermediate (i). (yield: 61%)
[ solution 20]
1H-NMR(CDCl3)δppm：2.81(s，6H)，4.24(s，2H)，7.34(d，J＝8.0Hz，2H)，7.49(s，2H)，7.67(s，2H)，7.99(d，J＝8.8Hz，2H)
13C-NMR(CDCl3)δppm：25.8，41.1，123.2，126.2，127.8，130.9，133.1，136.3，137.6，143.1，160.0
FT-IR cm-1：3054，3030，2915，1603，1487，1206
FD-MS：366M+
Next, 4.15g (11.3mmol) of intermediate (i) and 7.55mL of concentrated sulfuric acid were charged into the flask, and stirred at 45 ℃ for 20 minutes. Then, 1.62mL of fuming nitric acid was added dropwise, and stirring was continued for 1 hour while maintaining the temperature. After the mixture was left to cool, 250mL of ice water was slowly poured into the system. Further, a 10 wt% aqueous solution of sodium hydroxide is used to adjust the pH to 8 to 9. The precipitated powder was collected by filtration under reduced pressure, and washed with 200mL of distilled water and 100mL of ethanol to obtain 4.86g (10.6mmol) of intermediate (ii) (yield: 94%).
[ solution 21]
1H-NMR(CDCl3)δppm：2.86(s，6H)，4.27(s，2H)，7.56(d，J＝8.8Hz，2H)，7.62(s，2H)，8.08(d，J＝8.8Hz，2H)
13C-NMR(CDCl3)δppm：25.7，32.4，119.9，125.6，127.5，130.1，131.1，137.3，143.1，145.9，162.2
FT-IR cm-1：1604，1530，1487，1362
LC-MS：457[MH]+
7.36g (132mmol) of reduced iron and 125ml of acetic acid were charged into the flask, and the flask was heated to 60 ℃ with stirring. Then, 7.36g (16.1mmol) of the intermediate (ii) was added in several portions, and stirred at 60 to 70 ℃ for 1 hour. The reaction mixture was cooled to 35 ℃ or lower, and then poured into 500ml of ice water, which was then adjusted to pH9 with 20% NaOH water. The resulting precipitate was filtered and washed with water. After the obtained solid was air-dried at 70 ℃, it was added to 200ml of N, N-Dimethylformamide (DMF), stirred at 30 ℃ for 2 hours, insoluble matter was removed by filtration, and the obtained filtrate was added dropwise to 1.2L of water and stirred at room temperature for 40 minutes. The resulting precipitate was filtered, washed with water, and then dried by air blowing at 70 ℃ to obtain 5.52g (13.9mmol) of the objective alkylene compound. (yield 86%)
1H-NMR(CDCl3)δppm:2.65(s，6H),3.97(s，2H),5.91(s，4H),7.32(s，2H),7.37(d，J＝8.8Hz，2H)，8.58(d，J＝8.8Hz，2H)
13C-NMR(CDCl3)δppm：24.8，31.3，116.2，117.1，117.4，120.4，131.3，131.7，141.5，142.6，158.3
FT-IR cm-1：3476，3373，1627，1605，1409，1359，1250
LC-MS：397[MH]+
The results of the analysis showed that the resulting compound was of the formula (1-1).
[ solution 22]
(example A-2)
55.0g of concentrated sulfuric acid was charged in a flask, and 7.00g (23.5mmol) of 6, 6' -methylenebisquinaldine obtained by the method described in the literature (Polymer, volume39, No.20(1998), p4949) was added under ice-cooling with stirring. While keeping the temperature below 10 ℃, 6.1g of 60% nitric acid is added dropwise, and stirring is continued for 1 hour at 10 ℃ to 20 ℃. The reaction mixture was poured into 150ml of ice water, and adjusted to pH3 with a 20 wt% aqueous solution of sodium hydroxide. The precipitated powder was recovered by filtration under reduced pressure and washed with water until neutral. After the resulting solid was air-dried at 70 ℃ and the crude product was filtered by washing with 100ml of hot ethyl acetate and then 60ml of hot toluene to obtain 6.52g (16.8mmol) of intermediate (iii). (yield: 72%)
[ solution 23]
1H-NMR(DMSO-d6)δppm：2.70(s，6H)，4.42(s，2H)，7.58(d，J＝8.8Hz，2H)，7.63(d，J＝8.8Hz，2H)，8.09(d，J＝8.8Hz，2H)，8.13(d，J＝8.8Hz，2H)
13C-NMR(DMSO-d6)δppm：24.5，32.0，117.7，124.8，127.5，129.8，130.5，131.9，145.8，146.2，160.7
FT-IR(KBr disk)cm-1：3048，1602，1520，1494，1363
LC-MS：389[MH]+
A flask was charged with 5.30g of reduced iron and 135ml of acetic acid, and heated to 50 ℃ with stirring. Next, 4.50g (11.6mmol) of intermediate (iii) was added while keeping the temperature at 70 ℃ or lower. After the completion of the addition, the reaction mixture was stirred at 60 ℃ for 1hr, cooled to 35 ℃ or lower, poured into 500ml of ice water, and adjusted to pH9 with 20% NaOH water. The resulting precipitate was filtered under reduced pressure over ceria. The solid was recovered, air-dried at 70 ℃ and then added to a mixed solvent of 100ml of dimethyl sulfoxide (DMSO) and 100ml of N, N-Dimethylformamide (DMF), and the mixture was stirred at 90 ℃ for 1 hr. The mixture was filtered under reduced pressure over ceria to remove insoluble matter, and the obtained filtrate was added to 1L of water with stirring. The resulting precipitate was collected by vacuum filtration, washed with water, and dried by air blowing at 70 ℃ to obtain 3.80g (11.6mmol) of the objective alkylene compound. (yield 100%)
1H-NMR(DMSO-d6)δppm：2.57(s，6H)，3.95(s，2H)，5.66(s，4H)，7.06(d，J＝8.2Hz，2H)，7.16(d，J＝8.2Hz，2H)，7.23(d，J＝8.2Hz，2H)，8.49(d，J＝8.2Hz，2H)
13C-NMR(DMSO-d6)δppm：24.6，32.1，115.8，116.2，119.5，130.9，131.8，141.5，147.4，157.0
FT-IR(KBr disk)cm-1：3464，3363，3315，3192，1640，1591，1573，1415，1365，801
LC-MS：329[MH]+
The results of the analysis showed that the resulting compound was of the formula (1-2).
[ solution 24]
(example A-3)
To a flask, 10.0g (25.8mmol) of intermediate (iii), 10% Pd-C1.00g, 50ml of ethanol, and 100ml of Tetrahydrofuran (THF) were added under a nitrogen atmosphere, and the mixture was stirred at room temperature. Then, 12.9g (257mmol) of hydrazine monohydrate dissolved in a mixed solution of ethanol 20ml and THF40ml was added dropwise. After the dropwise addition, the mixture is stirred at 60-65 ℃ for 3 hours. After dissolving the precipitate by adding 140ml of N-methylpyrrolidone (NMP) to the reaction mixture, Pd-C was removed by filtration, and the obtained filtrate was poured into 1800g of 10% NaCl water and stirred at room temperature for 1 hr. The resulting precipitate was collected by vacuum filtration, washed with water, and dried by air blowing at 70 ℃ to obtain 8.40g (25.6mmol) of the objective alkylene compound. (yield 99%)
1H-NMR、13The results of C-NMR, FT-IR and LC-MS were in accordance with those of example A-2. That is, the results of the analysis showed that the resulting compound was of the formula (1-2).
[ solution 25]
(example B-1)
In a flask, 14.1g (116mmol) of benzoic acid was weighed out under a nitrogen atmosphere, and melted at 140 ℃. 1.44g (3.62mmol) of the alkylene compound obtained in example (A-1) and 5.53g (19.3mmol) of tetrachlorophthalic anhydride were added thereto, and the mixture was stirred at 220 ℃ for 4 hours. After leaving to cool, 300mL of acetone was added to the reaction solution, and after stirring for 1 hour, 4.41g (3.00mmol) of quinophthalone compound B-1 was obtained as a yellow powder by filtration under reduced pressure (yield: 83%).
FT-IR cm-1：3449，1727，1622，1536，1410，1363，1308，1192，1112，737
FD-MS：1467M+
The results of the analysis showed that the resulting compound was of the formula (3-1-i).
[ solution 26]
(example B-2)
135g (1.11mol) of benzoic acid was weighed out into a flask under a nitrogen atmosphere, and melted at 140 ℃. 3.80g (11.6mmol) of the alkylene compound obtained in example A-2, 18.0g (62.9mmol) of tetrachlorophthalic anhydride, and 0.490g (3.60mmol) of anhydrous zinc chloride were added thereto, and the mixture was stirred at 220 ℃ for 6 hours. After the reaction mixture was cooled to 120 ℃, 300mL of chlorobenzene was added and stirred for 1 hour, followed by filtration under reduced pressure. The obtained solid was washed with chlorobenzene, acetone and methanol in this order to obtain 10.5g (7.5mmol) of quinophthalone compound B-2 as a yellow powder. (yield: 65%)
FT-IR cm-1：1788，1729，1688，1638，1607，1537，1420，1310，732
FD-MS：1400M+
The results of the analysis showed that the resulting compound was of the formula (3-2-i).
[ solution 27]
Example C-1
58.0g (475mmol) of benzoic acid was weighed into a flask under nitrogen atmosphere and melted at 140 ℃. 2.00g (5.03mmol) of the alkylene compound obtained in example (A-1) and 5.04g (17.6mmol) of tetrachlorophthalic anhydride were added thereto, and the mixture was stirred at 220 ℃ for 4 hours. After leaving to cool, 500mL of acetone was added to the reaction solution, and after stirring for 1 hour, 6.00g of quinophthalone compound C-1 was obtained as a yellow powder by filtration under reduced pressure.
As a result of MALDI-MS, it was found that the obtained C-1 was a mixture of the compound of the above formula (3-1-i) and the compound of the formula (4-1-i).
[ solution 28]
(example C-2)
58.0g (475mmol) of benzoic acid was weighed into a flask under nitrogen atmosphere and melted at 140 ℃. 2.00g (6.09mmol) of the alkylene compound obtained in example A-2, 6.09g (21.3mmol) of tetrachlorophthalic anhydride, and 0.205g (1.50mmol) of anhydrous zinc chloride were added thereto, and the mixture was stirred at 220 ℃ for 6 hours. After the reaction mixture was cooled to 120 ℃, 500mL of chlorobenzene was added and stirred for 1 hour, followed by filtration under reduced pressure. The obtained solid was washed with chlorobenzene, acetone, and methanol in this order to obtain 7.00g of quinophthalone compound C-2 as a yellow powder.
As a result of MALDI-MS, it was found that the obtained C-2 was a mixture of the compound of the above formula (3-2-i) and the compound of the formula (4-2-i).
[ solution 29]
(pigmentation example 1)
0.500 parts by mass of the quinophthalone compound represented by the formula (3-1-i) obtained in example B-1 was ground together with 1.50 parts by mass of sodium chloride and 0.750 part by mass of diethylene glycol. Then, the mixture was put into 600 parts by mass of warm water and stirred for 1 hour. The water-insoluble fraction was separated by filtration, washed thoroughly with warm water, and dried by blowing air at 90 ℃ to obtain a quinophthalone pigment. The obtained pigment particles have an average aspect ratio of less than 3.00 and an average primary particle diameter of 100nm or less.
(pigmentation example 2)
A quinophthalone pigment was obtained by pigmenting in the same manner as in pigmenting example 1 except that the quinophthalone compound represented by the formula (3-2-i) obtained in example B-2 was used in place of the quinophthalone compound represented by the formula (3-1-i) obtained in example B-1. The obtained pigment particles have an average aspect ratio of less than 3.00 and an average primary particle diameter of 100nm or less.
(example D-1)
0.660 part by mass of the quinophthalone pigment obtained in pigmenting example 1 was placed in a glass bottle, and 0.040 part by mass of the sulfonic acid derivative (5) synthesized by the method described in Japanese patent application laid-open No. 2013-54200, 12.60 parts by mass of propylene glycol monomethyl ether acetate, 1.400 parts by mass of BYK LPN-21116(BYK corporation),
22.0 parts by mass of beads were dispersed with a paint shaker (Toyo Seiki Kagaku K.K.) for 2.5 hours to obtain a pigment dispersion. The sulfonic acid group in formula (5) represents a substitution at any hydrogen atom on the quinoline ring.
[ solution 30]
Subsequently, 4.00 parts by mass of the pigment dispersion, 0.600 parts by mass of UNIDIC (registered trademark) ZL-295 (manufactured by DIC corporation) as an acrylic resin solution, and 0.220 parts by mass of propylene glycol monomethyl ether acetate were put in a glass bottle and shaken to prepare a yellow toning composition.
(example D-2)
A yellow toner composition was obtained in the same manner as in example D-1, except that the quinophthalone pigment obtained in pigmenting example 2 was used in place of the quinophthalone pigment obtained in pigmenting example 1.
Comparative example d-1
1.14 parts by mass of C.I. pigment yellow 150 (manufactured by SHANYANG PIGMENT Co., Ltd.) was placed in a glass bottle, and 12.0 parts by mass of propylene glycol monomethyl ether acetate, 2.84 parts by mass of BYK LPN-21116 (manufactured by BYK corporation) were added thereto,
38.0 parts by mass of the beads were dispersed with a paint conditioner (manufactured by Toyo Seiki Seisaku-Sho Ltd.) for 4 hours to obtain a pigment dispersion. Further, 2.00 parts by mass of the obtained pigment dispersion, 0.490 parts by mass of UNIDIC (registered trade name) ZL-295 (manufactured by DIC corporation) as an acrylic resin solution, and 0.110 parts by mass of propylene glycol monomethyl ether acetate were put in a glass bottle and shaken to prepare a yellow toning composition.
Production example 1
2.48 parts by mass of C.I. pigment Green 59 (produced by DIC) was put in a glass bottle, and 10.9 parts by mass of propylene glycol monomethyl ether acetate, 1.24 parts by mass of BYK LPN-6919 (produced by BYK corporation), 1.86 parts by mass of acrylic resin solution UNIDIC (registered trademark) ZL-295 (produced by DIC corporation), and the mixture were added thereto,
The beads were dispersed for 2 hours with a paint shaker (manufactured by Toyo Seiki Seisaku-Sho Co., Ltd.) to obtain a pigment dispersion. Further, 4.00 parts by mass of the obtained pigment dispersion, 0.980 parts by mass of UNIDIC (registered trademark) ZL-295 (manufactured by DIC Co., Ltd.) as an acrylic resin solution, and 0.220 parts by mass of propylene glycol monomethyl ether acetate were put in a glass bottle and shaken to prepare a green toning composition.
(example E-1)
The yellow tinting composition obtained in example D-1 was mixed with the green tinting composition obtained in production example 1 at a ratio of 39: 61 to obtain a green toning composition.
(example E-2)
The yellow tinting composition obtained in example D-2 and the green tinting composition obtained in production example 1 were mixed at a ratio of 40: 60 to obtain a green toning composition.
Comparative example e-1
The yellow tinting composition obtained in comparative example d-1 was mixed with the green tinting composition obtained in production example 1 at a ratio of 66: 34 to obtain a green toning composition.
The characteristics of the color filters formed from the green toning compositions obtained in examples E-1 and E-2 and comparative example E-1 were measured by the following methods. The results are shown in Table 1.
< color Filter characteristics test >
The green toning compositions obtained in examples and comparative examples were applied to a glass substrate by a spin coater, dried, and heated at 230 ℃ for 1 hour to obtain a sample for evaluation which exhibited a predetermined green hue when a C light source was used. The chromaticity of the sample for evaluation was determined by a spectrophotometer (model U3900/3900H, manufactured by Hitachi Kagaku K.K.) and the green chromaticity used in Japanese patent application laid-open No. 2015-191208 (0.224, 0.669) was used. The luminance Y of the obtained evaluation sample was measured with a spectrophotometer (model U3900/3900H, manufactured by Hitachi Kagaku K.K.). The thickness of the colored film formed on the glass substrate was measured with respect to the obtained evaluation sample by using a film thickness meter (VS 1330 scanning white interference microscope, hitachi height new technology, ltd.). The thinner the film thickness is, the higher the coloring power is. The results are shown in Table 1.
[ Table 1]
Industrial applicability
The quinaldine compound according to the present invention is useful as a raw material compound for producing a quinophthalone compound having excellent coloring power as a pigment.
Claims (6)
1. An alkylene compound represented by the following formula (1),
[ solution 1]
In the formula (1), X1And X2Each independently represents a hydrogen atom or a halogen atom, and Z represents an alkylene group having 1 to 3 carbon atoms.
2. The alkylene compound of claim 1, wherein Z is methylene.
3. A process for producing a quinophthalone compound, comprising the steps of: condensing an alkylene compound represented by the following formula (1) with an acid anhydride represented by the following formula (2) to obtain at least one selected from the group consisting of a first quinophthalone compound represented by the following formula (3) and a second quinophthalone compound represented by the following formula (4),
[ solution 2]
In the formula (1), X1And X2Each independently represents a hydrogen atom or a halogen atom, Z represents an alkylene group having 1 to 3 carbon atoms,
[ solution 3]
In the formula (2), X3、X4、X5And X6Each independently represents a hydrogen atom or a halogen atom,
[ solution 4]
In the formula (3), X1、X2、X3、X4、X5And X6Each independently represents a hydrogen atom or a halogen atom, Z represents an alkylene group having 1 to 3 carbon atoms,
[ solution 5]
In the formula (4), X1、X2、X3、X4、X5And X6Each independently represents a hydrogen atom or a halogen atom, and Z represents an alkylene group having 1 to 3 carbon atoms.
4. The production method according to claim 3, wherein the alkylene compound is condensed with the acid anhydride in the presence of an acid catalyst.
5. A quinophthalone compound represented by the following formula (4),
[ solution 6]
In the formula (4), X1、X2、X3、X4、X5And X6Each independently represents a hydrogen atom or a halogen atom, and Z represents an alkylene group having 1 to 3 carbon atoms.
6. A quinophthalone mixture comprising a first quinophthalone compound represented by the following formula (3) and a second quinophthalone compound represented by the following formula (4),
[ solution 7]
In the formula (3), X1、X2、X3、X4、X5And X6Each independently represents a hydrogen atom or a halogen atom, Z represents an alkylene group having 1 to 3 carbon atoms,
[ solution 8]
In the formula (4), X1、X2、X3、X4、X5And X6Each independently represents a hydrogen atom or a halogen atom, and Z represents an alkylene group having 1 to 3 carbon atoms.
Applications Claiming Priority (3)
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| JP2018-163802 | 2018-08-31 | ||
| JP2018163802 | 2018-08-31 | ||
| PCT/JP2019/032705 WO2020045200A1 (en) | 2018-08-31 | 2019-08-21 | Alkylene compound, quinophthalone compound, and quinophthalone mixture |
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| US9062206B2 (en) * | 2011-10-24 | 2015-06-23 | Keki Hormusji Gharda | Bis-quinophthalone pigment and a process for preparing the same |
| EP2771323B1 (en) * | 2011-10-24 | 2017-08-30 | Keki Hormusji Gharda | A bis-quinaldine compound and a process for preparing the same |
| JP6891442B2 (en) * | 2016-10-13 | 2021-06-18 | Dic株式会社 | New quinophthalone compound |
| CN110291158B (en) * | 2017-03-01 | 2021-02-09 | Dic株式会社 | Quinophthalone compounds |
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