JP6723205B2 - Pirimidacridone pigment and method for producing the same - Google Patents

Description

The present invention relates to a pyrimidoacridone pigment, a method for producing the same, a pigment colorant using the pyrimidoacridone pigment, a color filter, and an inkjet ink.

Many compounds such as azo compounds having a pyrimidine skeleton, azomethine compounds, and anthrapyrimidine compounds are useful as dyes and pigments (Patent Documents 1 and 2). Also, barbituric acid dyes such as Pigment Yellow 150 and Pigment Yellow 185 are well known.

By the way, quinacridones are widely used in various fields as organic pigments exhibiting a bluish red color. Further, since quinacridones have very excellent pigment properties, many analogs have been investigated. For example, compounds represented by the following formulas (X) and (Y) into which the above-described pyrimidine skeleton is introduced are known (Non-patent documents 1 and 2).

JP, 2007-51098, A JP-A-7-304985

The Chemical Society of Japan, 1977, (3), p. 382-386 The Chemical Society of Japan, 1979, (3), p. 398-402

The compounds disclosed in Non-Patent Documents 1 and 2 were useful as orange to yellowish red pigments having excellent weather resistance. However, these compounds have poor acid resistance and alkali resistance, and further improvement is required.

The present invention has been made in view of such problems of the conventional technology, and the problem is that the coloring power, solvent resistance, acid resistance, alkali resistance, and transparency are excellent. Another object of the present invention is to provide a pyrimidoacridone pigment having a unique pyrimidine skeleton. Another object of the present invention is to provide a method for producing the pyrimidoacridone pigment, a pigment colorant using the pyrimidoacridone pigment, a color filter, and an inkjet ink.

That is, according to the present invention, the following pyrimidoacridone pigments are provided.
[1] A pyrimidoacridone pigment represented by the following general formula (1).

（前記一般式（１）中、Ｒ₁は、置換基を有してもよいアリール基又は置換基を有してもよい複素環基を示し、Ｒ₂は、ハロゲン原子、ヒドロキシ基、アルキル基、アリール基、アルコキシ基、アリールオキシ基、アルキルチオ基、アリールチオ基、アミノ基、又はニトロ基を示し、ｎは、０〜４の数を示す）

(In the general formula (1), R ₁ represents an aryl group which may have a substituent or a heterocyclic group which may have a substituent, and R ₂ represents a halogen atom, a hydroxy group or an alkyl group. , An aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an amino group, or a nitro group, and n represents a number of 0 to 4).

[2] The pyrimidoacridone pigment according to the above [1], wherein in the general formula (1), R ₁ is an aryl group which may have a substituent.

Moreover, according to this invention, the manufacturing method of the pyrimido acridone pigment shown below is provided.
[3] A method for producing the pyrimidoacridone pigment according to the above [1] or [2], which comprises a compound represented by the following general formula (2-1) and a compound represented by the following general formula (2-2). Each of these compounds is subjected to a condensation reaction with a compound represented by the following general formula (3), and an oxidation reaction and a cyclization reaction are performed to form a pyrimidacridone structure. Method for producing don pigment.

（前記一般式（２−１）中、Ｒ₁は、置換基を有してもよいアリール基、又は置換基を有してもよい複素環基を示す。前記一般式（２−２）中、Ｒ₂は、ハロゲン原子、ヒドロキシ基、アルキル基、アリール基、アルコキシ基、アリールオキシ基、アルキルチオ基、アリールチオ基、アミノ基、又はニトロ基を示し、ｎは、０〜４の数を示す。前記一般式（３）中、Ｒ₃及びＲ₄は、それぞれ独立に、水素原子、置換基を有してもよいアルコキシ基、アミノ基、又はハロゲン原子を示す）

(In the general formula (2-1), R ₁ represents an aryl group which may have a substituent or a heterocyclic group which may have a substituent. In the general formula (2-2), , R ₂ represents a halogen atom, a hydroxy group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an amino group, or a nitro group, and n represents a number of 0 to 4. In the general formula (3), R ₃ and R ₄ each independently represent a hydrogen atom, an alkoxy group which may have a substituent, an amino group, or a halogen atom.)

Further, according to the present invention, the following pigment colorant, color filter, and inkjet ink are provided.
[4] A pigment colorant containing the pyrimidoacridone pigment according to [1] or [2].
[5] A color filter comprising a colored layer containing the pyrimido acridone pigment according to the above [1] or [2].
[6] An ink jet ink containing the pyrimidoacridone pigment according to the above [1] or [2].

According to the present invention, it is possible to provide a pyrimidoacridone pigment having a novel pyrimidine skeleton, which is excellent in coloring power, solvent resistance, acid resistance, alkali resistance, and transparency. Further, according to the present invention, it is possible to provide a method for producing the pyrimidoacridone pigment, a pigment colorant using the pyrimidoacridone pigment, a color filter, and an inkjet ink.

<Pirimidacridone pigment>
Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. The pyrimidoacridone pigment of the present invention is a compound having a skeleton (structure) represented by the following general formula (1). Hereinafter, the details of the pyrimidoacridone pigment of the present invention will be described.

（前記一般式（１）中、Ｒ₁は、置換基を有してもよいアリール基又は置換基を有してもよい複素環基を示し、Ｒ₂は、ハロゲン原子、ヒドロキシ基、アルキル基、アリール基、アルコキシ基、アリールオキシ基、アルキルチオ基、アリールチオ基、アミノ基、又はニトロ基を示し、ｎは、０〜４の数を示す）

(In the general formula (1), R ₁ represents an aryl group which may have a substituent or a heterocyclic group which may have a substituent, and R ₂ represents a halogen atom, a hydroxy group or an alkyl group. , An aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an amino group, or a nitro group, and n represents a number of 0 to 4).

One of the important characteristics of the pyrimidacridone pigment of the present invention is that it is a compound having a structure represented by the general formula (1). The compound having the structure represented by the general formula (1) has excellent pigment characteristics such as having a coloring power equal to or higher than that of other condensed polycyclic pigments, and is suitable as a pigment. Furthermore, the pyrimido acridone pigment of the present invention is a pigment excellent in transparency, solvent resistance, acid resistance, and alkali resistance. The pyrimido acridone pigment of the present invention includes not only the compound represented by the general formula (1) but also tautomers of the compound represented by the general formula (1).

The pyrimido acridone pigment of the present invention can form a strong intermolecular/intramolecular hydrogen bond and thus exhibits excellent pigment characteristics. The compound represented by the general formula (1) includes tautomers as shown below.

Specific examples of the pyrimidoacridone pigment of the present invention include compounds represented by the following formula.

One of the features of the pyrimidoacridone pigment of the present invention is excellent acid resistance and alkali resistance. The compounds represented by the following formulas (X) and (Y) disclosed in Non-Patent Documents 1 and 2 have a nitrogen atom (N) shared by two rings in their molecular structures, and are shown below. It is speculated that such an equilibrium exists. Therefore, it is considered that the compounds represented by the following formulas (X) and (Y) have low acid resistance and alkali resistance.

On the other hand, the pyrimido acridone pigment of the present invention does not have a nitrogen atom (N) shared by two rings in its molecular structure, so that the above equilibrium does not exist, and the acid resistance and It is considered to have excellent alkali resistance.

<Production method of pyrimidoacridone pigment>
The method for producing a pyrimidoacridone pigment of the present invention comprises a compound represented by the following general formula (2-1) and a compound represented by the following general formula (2-2), as shown in the following reaction formula. , A step of conducting a condensation reaction with a compound represented by the following general formula (3) (condensation reaction step), and a step of forming a pyrimidoacridone structure by an oxidation reaction and a cyclization reaction (oxidation/cyclization reaction) Process) and.

In the condensation reaction step, the compound represented by the general formula (2-1) and the compound represented by the general formula (2-2) are each subjected to a condensation reaction with the compound represented by the general formula (3). This condensation reaction can be carried out, for example, in a polar solvent. Further, it is preferable to react with a base as a catalyst in order to improve the yield. Specific examples of the base include inorganic bases (inorganic catalysts) such as sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate; organic bases (organic catalysts) such as triethylamine and diazabicycloundecene. it can. It is preferable to use an organic catalyst because the reaction system becomes a homogeneous system.

As shown in the above reaction formula, for example, by subjecting the compound represented by the general formula (2-1) and the compound represented by the general formula (3) to a condensation reaction, the compound represented by the general formula (A) is represented. The compound can be obtained. A compound represented by the general formula (B′) can be obtained by subjecting the obtained compound represented by the general formula (A) to a condensation reaction of the compound represented by the general formula (2-2). .. The compound represented by the general formula (3) may be reacted with the compound represented by the general formula (2-1) first, and the compound represented by the general formula (2-2) may be reacted first. May be reacted with. Whatever compound is reacted first, the compound represented by the general formula (B′) can be obtained.

Specific examples of the compound represented by the general formula (2-1) include 4-fluorobenzamidine, 3,5-difluorobenzamidine, 3-chlorobenzamidine, 4-chlorobenzamidine, 4-bromobenzamidine, 4-methylbenzamidine, 4-methoxybenzamidine, 4-nitrobenzamidine, 2-naphthalenecarbamidine, 1H-pyrrole-3-carbamidine, furan-2-carbamidine, furan-3-carbamidine, thiophene-2. There may be mentioned carboamidine, thiophene-3-carbamidine and the like.

Specific examples of the compound represented by the general formula (2-2) include aniline, toluidine (o-, m-, p-), xylidine (2,3-; 2,6-; 3,4-, etc.). , Anisidine (o-, m-, p-), phenetidine (o-, m-, p-), halogen-substituted aniline, and the like.

In the general formula (3), the compound in which R ₃ and R ₄ are both alkoxy groups is an inexpensive succinyl succinic acid alkyl ester. Therefore, it is industrially advantageous to use a compound in which both R ₃ and R ₄ in the general formula (3) are alkoxy groups.

In the oxidation/cyclization reaction step, first, the compound represented by the general formula (B′) obtained in the above condensation reaction step is oxidized to obtain the compound represented by the general formula (B″). By subjecting the obtained compound represented by the general formula (B″) to cyclization, the desired compound represented by the general formula (1) (pyrimidacridone pigment) can be obtained. The oxidation/cyclization reaction can be carried out with reference to a conventional method for synthesizing an acridone compound.

<Pigment colorant>
The pigment colorant of the present invention contains the above pyrimidoacridone pigment. The pigment colorant of the present invention can be used in a wide range of fields as a colorant for image display, image recording, printing ink, writing ink, plastics, pigment printing, paint, and the like. In particular, the pigment colorant of the present invention is suitable as an image display material for which improvement in the transparency of colored pixels (colored layer) is a problem, and above all, as a colorant for color filters. Further, the pigment colorant of the present invention is also useful as a material for an image recording agent such as an inkjet ink, an electrodeposition recording liquid, and a developer for an electrophotographic system. The materials for these image recording agents are used in image recording methods such as an inkjet recording method, an electrodeposition recording method, and an electrophotographic method. By using the pigment colorant of the present invention, it is possible to prepare a material for an image recording agent which can provide a high quality image by any image recording method.

The pigment colorant of the present invention may further contain a film-forming material, for example. The amount of the pyrimido acridone pigment in the pigment colorant is preferably 5 to 500 parts by mass, and more preferably 50 to 250 parts by mass with respect to 100 parts by mass of the film-forming material. The pigment colorant of the present invention can be prepared, for example, by mixing a finely-divided pyrimidoacridone pigment with a film-forming material such as a resin ((co)polymer), an oligomer, or a monomer.

The pigment colorant of the present invention can also be prepared by mixing a finely divided pyrimidoacridone pigment with a liquid containing the above film-forming material. As the liquid containing the film forming material, a liquid containing a photosensitive film forming material, a liquid containing a non-photosensitive film forming material, or the like can be used. Specific examples of the liquid containing a photosensitive film-forming material include liquids containing a photosensitive film-forming material used for ultraviolet curable ink, electron beam curable ink and the like. Further, specific examples of the liquid containing a non-photosensitive film forming material include varnishes used for printing inks such as letterpress inks, planographic inks, gravure inks and screen inks; varnishes used for room temperature drying or baking paints; Examples include varnishes used for coating and coating; varnishes used for thermal transfer ribbons.

Specific examples of the photosensitive film forming material include photosensitive cyclized rubber-based resin, photosensitive phenol-based resin, photosensitive polyacrylate-based resin, photosensitive polyamide-based resin, photosensitive polyimide-based resin, unsaturated polyester-based resin. Examples thereof include photosensitive resins such as polyester acrylate resin, polyepoxy acrylate resin, polyurethane acrylate resin, polyether acrylate resin, and polyol acrylate resin. Various monomers may be added as a reactive diluent to the liquid containing these photosensitive resins.

To a pigment colorant containing a photosensitive resin as a film-forming material, a photopolymerization initiator such as benzoin ether or benzophenone is added and kneaded by a conventionally known method to obtain a photocurable photosensitive pigment dispersion. be able to. Further, a thermosetting pigment dispersion can be prepared by using a thermal polymerization initiator instead of the above photopolymerization initiator.

Specific examples of the non-photosensitive film forming material include styrene-(meth)acrylic acid ester-based copolymer, soluble polyamide-based resin, soluble polyimide-based resin, soluble polyamide-imide-based resin, soluble polyester-imide-based resin, water-soluble Examples include aminopolyester resins, water-soluble salts thereof, water-soluble salts of styrene-maleic acid ester-based copolymers, water-soluble salts of (meth)acrylic acid ester-(meth)acrylic acid-based copolymers, and the like. it can.

<Color filter>
The color filter of the present invention comprises a colored layer containing the above pyrimidoacridone pigment. For example, when the above-mentioned pigment colorant containing a film forming material is used, a color filter which is an image display material having a colored layer (colored pixel) excellent in coloring power and transparency can be obtained.

Hereinafter, the present invention will be specifically described based on Examples, but the present invention is not limited to these Examples. In addition, "part" and "%" in Examples and Comparative Examples are based on mass unless otherwise specified.

<Production of intermediates>
(Production Example 1)
To 170 parts of methanol, 11 parts of dimethyl succinyl succinate, 8 parts of benzamidine hydrochloride, and 5 parts of triethylamine were added, and heated and refluxed for 2 hours. After cooling, it was filtered and washed with methanol and water. It dried at 80 degreeC and obtained 11 parts of intermediate bodies (A-1) represented by a following formula (A-1).

(Production Example 2)
The intermediate (A-2) represented by the following formula (A-2) was prepared in the same manner as in Production Example 1 described above except that 13 parts of 4-chlorobenzamidine hydrochloride was used instead of 8 parts of benzamidine hydrochloride. -2) 13 parts were obtained.

(Production Example 3)
To 100 parts of methanol, 10 parts of the intermediate (A-1), 3 parts of aniline, and 1 part of 35% hydrochloric acid were added, heated and refluxed for 2 hours. After cooling, 13 parts of sodium 3-nitrobenzenesulfonate, 9 parts of sodium hydroxide, and 45 parts of water were added, and the mixture was heated and refluxed for 5 hours. After cooling, the mixture was filtered, and the obtained filtrate was neutralized to precipitate the precipitate. The filtered precipitate was washed with methanol and water and dried at 80°C to obtain 11 parts of intermediate (B-1) represented by the following formula (B-1).

(Production Example 4)
13 parts of the intermediate (B-2) represented by the following formula (B-2) was prepared in the same manner as in Production Example 3 described above except that 3 parts of 4-methylaniline was used instead of 3 parts of aniline. Got

(Production Example 5)
13 parts of the intermediate (B-3) represented by the following formula (B-3) were prepared in the same manner as in Production Example 3 above, except that 3 parts of 4-chloroaniline was used instead of 3 parts of aniline. Got

(Production Example 4)
It is represented by the following formula (B-4) in the same manner as in Production Example 3 described above except that 10 parts of the intermediate (A-2) was used instead of 10 parts of the intermediate (A-1). 13 parts of intermediate (B-4) were obtained.

<Production of pigment>
(Example 1)
10 parts of the intermediate (B-1) was added to 100 parts of polyphosphoric acid, and heated at 120 to 130°C for 2 hours. The reaction product was poured into ice water and the precipitate was filtered. The precipitate was washed with water until the filtrate became neutral, and then dried at 80°C to obtain 9 parts of pigment (C-1) represented by the following formula (C-1).

(Example 2)
It is represented by the following formula (C-2) in the same manner as in Example 1 described above except that 10 parts of the intermediate (B-2) was used instead of 10 parts of the intermediate (B-1). 9 parts of pigment (C-2) was obtained.

(Example 3)
It is represented by the following formula (C-3) in the same manner as in Example 1 above, except that 10 parts of the intermediate (B-3) was used instead of 10 parts of the intermediate (B-1). 9 parts of pigment (C-3) was obtained.

(Example 4)
It is represented by the following formula (C-4) in the same manner as in Example 1 described above except that 10 parts of the intermediate (B-4) was used instead of 10 parts of the intermediate (B-1). 9 parts of pigment (C-4) was obtained.

When mass spectrometry (MALDI) was performed on each of the obtained pigments, peaks corresponding to the following molecular weights were detected. From the raw materials used and the results of mass spectrometry, it was confirmed that the compound (pigment) having the desired structure was obtained.
-Pigment (C-1): molecular weight 339
-Pigment (C-2): molecular weight 353
-Pigment (C-3): molecular weight 374
Pigment (C-4): molecular weight 374

(Comparative Examples 1 and 2)
The compound represented by the following formula (X) produced by referring to the descriptions of Non-Patent Documents 1 and 2 was used as Pigment (X) of Comparative Example 1. Further, the compound represented by the following formula (Y) produced by referring to the descriptions of Non-Patent Documents 1 and 2 was used as a pigment (Y) of Comparative Example 2.

<Preparation of dark color paint>
The pigments of Examples 1 to 4 and Comparative Examples 1 and 2 were used, respectively, and dispersed for 90 minutes in the following formulation using a paint conditioner to prepare a dark color paint.
-Pigment: 1.5 parts-Product name "Super Beckamine J-820" (*1): 8.5 parts-Product name "Phtalkid 133-60" (*2): 17.0 parts-Xylene/1- Butanol (2/1 mass ratio) mixed solvent: 5.0 parts (*1) Butylated melamine resin (manufactured by Dainippon Ink and Chemicals, Inc.)
(*2) Short oil alkyd resin of palm oil (manufactured by Hitachi Chemical Co., Ltd.)

<Paint test>
(1) Coloring Power A dark color paint was prepared by diluting a dark color paint with a white paint containing titanium white (titanium oxide) so that the pigment:titanium white=1:20 (mass ratio). The light-colored paint was spread on a spreading paper using an applicator (6 mils) and baked at 140° C. for 30 minutes to form a coating film. The formed coating film was visually observed, and the coloring power was evaluated according to the following criteria. The results are shown in Table 1.
◯: Good coloring power Δ: Coloring power ×: No coloring power

(2) Solvent resistance 1 part of the pigment was dispersed in 50 parts of methyl ethyl ketone and then left at room temperature for 1 day. The degree of coloring of the filtrate obtained by filtration was observed, and the solvent resistance was evaluated according to the criteria shown below. The results are shown in Table 1.
◯: Not colored (solvent resistance was good)
X: Remarkably colored (solvent resistance was poor)

(3) Acid resistance 1 part of the pigment was dispersed in 50 parts of a 5% sulfuric acid aqueous solution, and then left at room temperature for 1 day. The change in color was observed, and the acid resistance was evaluated according to the criteria shown below. The results are shown in Table 1.
○: No discoloration ×: Discoloration

(4) Alkali resistance 1 part of the pigment was dispersed in 50 parts of a 5% sodium hydroxide aqueous solution, and then left at room temperature for 1 day. The change in color was observed, and the alkali resistance was evaluated according to the criteria shown below. The results are shown in Table 1.
○: No discoloration ×: Discoloration

(5) Transparency The state of the black band portion on the color-developed paper on which the above-described dark paint was color-developed was visually observed, and the transparency was evaluated according to the following evaluation criteria. The results are shown in Table 1.
○: A black belt on the ground is visible (good transparency)
×: The black band of the background is hidden and the ink color looks strong (poor transparency)

(6) Lightness and hue Regarding the coating film on the color-developed paper on which the dark color paint was color-developed in the evaluation of "(1) Coloring power" described above, a colorimeter (trade name "Karacom System", Dainichi Seika Kogyo Co., Ltd.) Manufactured) was used to measure L ^* , a ^* , and b ^* . The results are shown in Table 2.

The pyrimido acridone pigment of the present invention is used for printing inks (offset inks, gravure inks, etc.), various paints, plastics, pigment printing agents, dry/wet toners for electrophotography, ink jet inks, thermal transfer recording inks, color filters. It is useful as a pigment used in resists, inks for writing instruments, etc.

Claims (6)

A pyrimidoacridone pigment represented by the following general formula (1).

(In the general formula (1), R ₁ represents an aryl group which may have a substituent or a heterocyclic group which may have a substituent, and R ₂ represents a halogen atom, a hydroxy group or an alkyl group. , An aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an amino group, or a nitro group, and n represents a number of 0 to 4). The pyrimidoacridone pigment according to claim 1, wherein in the general formula (1), R ₁ is an aryl group which may have a substituent. A method for producing the pyrimidoacridone pigment according to claim 1 or 2, wherein
A step of subjecting a compound represented by the following general formula (2-1) and a compound represented by the following general formula (2-2) to a condensation reaction with a compound represented by the following general formula (3), respectively;
An oxidation reaction and a cyclization reaction to form a pyrimidoacridone structure;
A method for producing a pyrimidacridone pigment having:

(In the general formula (2-1), R ₁ represents an aryl group which may have a substituent or a heterocyclic group which may have a substituent. In the general formula (2-2), , R ₂ represents a halogen atom, a hydroxy group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an amino group, or a nitro group, and n represents a number of 0 to 4. In the general formula (3), R ₃ and R ₄ each independently represent a hydrogen atom, an alkoxy group which may have a substituent, an amino group, or a halogen atom.) A pigment colorant containing the pyrimidoacridone pigment according to claim 1. A color filter comprising a colored layer containing the pyrimido acridone pigment according to claim 1. An inkjet ink containing the pyrimidoacridone pigment according to claim 1.