JP6200913B2 - Pyrimidoquinazoline pigment and synthesis method thereof - Google Patents

Description

  The present invention relates to a pyrimidoquinazoline pigment, a synthesis method thereof, and a pigment colorant using the pyrimidoquinazoline pigment.

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

  By the way, compounds having a pyrimidoquinazoline skeleton having two pyrimidine rings have been known for a long time. For example, a compound useful as an anticancer agent having a predetermined pyrimidoquinazoline skeleton is known (Patent Document 3). In addition, an organic electroluminescence device having a layer containing a compound having a predetermined pyrimidoquinazoline skeleton has been proposed (Patent Document 4).

JP 2007-51098 A JP-A-7-304985 JP 7-309873 A JP-A-10-294178

  However, a compound having a pyrimidoquinazoline skeleton useful as a coloring material (pigment) excellent in pigment properties such as coloring power, transparency, and weather resistance has not been known so far.

  The present invention has been made in view of such problems of the prior art, and the object of the present invention is to have pigment properties such as coloring power, transparency, and weather resistance having a novel pyrimidine skeleton. An object of the present invention is to provide an excellent pyrimidoquinazoline pigment, a synthesis method thereof, and a pigment colorant using the pyrimidoquinazoline pigment.

That is, according to the present invention, the following pyrimidoquinazoline pigments are provided.
[1] A pyrimidoquinazoline pigment represented by the following general formula (1-1) or (1-2).

（前記一般式（１−１）及び（１−２）中、Ｒ₁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キル基、又はアシル基を示し、Ｒ₂及びＲ₅は、それぞれ独立に、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（１−２）中、Ｒ₃及びＲ₆は、ヒドロキシ基、置換基を有してもよいアルコキシ基、又は置換基を有してもよいアミノ基を示す）

(In the general formula (1-1) and (1-2), R ₁ and R ₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, or an acyl group, R ₂ And R ₅ each independently represents an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, in the general formula (1-2), R ₃ and R ₆ Represents a hydroxy group, an alkoxy group which may have a substituent, or an amino group which may have a substituent)

[2] The pyrimidoquinazoline pigment according to [1], wherein R ₁ and R _{4 in the} general formula (1-1) are hydrogen atoms.

Moreover, according to this invention, the synthesis | combining method of the pyrimidoquinazoline pigment shown below is provided.
[3] A method for synthesizing a pyrimidoquinazoline pigment according to the above [1] or [2], wherein the compound is represented by the following general formula (2-1) and the following general formula (2-2). A method for synthesizing a pyrimidoquinazoline pigment comprising a step of subjecting a compound represented by the following general formula (3) to a condensation reaction in an inert solvent.

（前記一般式（２−１）及び（２−２）中、Ｒ₂及びＲ₅は、それぞれ独立に、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（３）中、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀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 formulas (2-1) and (2-2), R ₂ and R ₅ are each independently an aryl group which may have a substituent or a heterocyclic ring which may have a substituent. In the general formula (3), R ₇ , R ₈ , R ₉ , and R ₁₀ each independently represent a hydrogen atom, an alkoxy group that may have a substituent, an amino group, or a halogen atom. Show)

  [4] The method for synthesizing a pyrimidoquinazoline pigment according to [3], wherein the inert solvent is a hydrophobic solvent.

Furthermore, according to the present invention, the following pigment colorants are provided.
[5] A pigment colorant containing the pyrimidoquinazoline pigment according to [1] or [2].

  The pyrimidoquinazoline pigment of the present invention has a novel pyrimidine skeleton, and is excellent in pigment properties such as coloring power, transparency, and weather resistance.

<Pyrimidoquinazoline pigment>
Embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments. The pyrimidoquinazoline pigment of the present invention is a compound having a skeleton (structure) represented by the following general formula (1-1) or (1-2). Hereinafter, details of the pyrimidoquinazoline pigment of the present invention will be described.

（前記一般式（１−１）及び（１−２）中、Ｒ₁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キル基、又はアシル基を示し、Ｒ₂及びＲ₅は、それぞれ独立に、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（１−２）中、Ｒ₃及びＲ₆は、それぞれ独立に、ヒドロキシ基、置換基を有してもよいアルコキシ基、又は置換基を有してもよいアミノ基を示す）

(In the general formula (1-1) and (1-2), R ₁ and R ₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, or an acyl group, R ₂ And R ₅ each independently represents an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, in the general formula (1-2), R ₃ and R ₆ Each independently represents a hydroxy group, an alkoxy group which may have a substituent, or an amino group which may have a substituent)

In the general formula (1-2), examples of the alkoxy group which may have a substituent represented by R ₃ and R ₆ include an alkoxy group having 1 to 20 carbon atoms and containing one or more oxygen atoms. Can do. Moreover, as an amino group which may have a substituent represented by R < ₃ > and R < ₆ > in general formula (1-2), a C1-C20 amino group containing a 1 or more nitrogen atom is mentioned. Can be mentioned.

  One of the important features of the pyrimidoquinazoline pigment of the present invention is that it is a compound having a structure represented by the above general formula (1-1) or (1-2). The compound having the structure represented by the general formula (1-1) or (1-2) is excellent in pigment properties such as coloring power, transparency, and weather resistance equal to or higher than those of other condensed polycyclic pigments. It can be suitably used as a pigment. In addition, the pyrimidoquinazoline pigment of the present invention includes not only the compound represented by formula (1-1) or (1-2) but also tautomers of these compounds.

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

The pyrimidoquinazoline pigment of the present invention is preferably _one in which R ₁ and R ₄ are hydrogen atoms among the compounds represented by the general formula (1-1). The compound in which R ₁ and R ₄ in the general formula (1-1) are hydrogen atoms can form strong intermolecular / intramolecular hydrogen bonds, and thus exhibits superior pigment characteristics. The compounds in which R ₁ and R ₄ in the general formula (1-1) are hydrogen atoms include tautomers as shown below.

Specific examples of the pyrimidoquinazoline pigment in which R ₁ and R ₄ in the general formula (1-1) are hydrogen atoms include compounds represented by the following formulas.

<Synthesis Method of Pyrimidoquinazoline Pigment>
The pyrimidoquinazoline pigment of the present invention is represented by, for example, a compound represented by the following general formula (2-1), a compound represented by the following general formula (2-2), and the following general formula (3). The compound can be synthesized by a condensation reaction in an inert solvent. If R ₂ in the following general formula (2-1) and R ₅ in the following general formula (2-2) are the same, a symmetrical pyrimidoquinazoline pigment can be obtained. On the other hand, when R ₂ in the following general formula (2-1) and R ₅ in the following general formula (2-2) are non-identical (different), they are represented by the following general formula (2-1). The asymmetric pyrimidoquinazoline pigment can be obtained by subjecting the compound represented by the general formula (2-2) below to a stepwise condensation reaction.

  Specific examples of the compounds represented by the general formulas (2-1) and (2-2) include 4-fluorobenzamidine, 3,5-difluorobenzamidine, 3-chlorobenzamidine, 4-chlorobenzamidine, 4-bromobenzamidine, 4-methylbenzamidine, 4-methoxybenzamidine, 4-nitrobenzamidine, 2-naphthalenecarbomidine, 1H-pyrrole-3-carboamidine, furan-2-carboamidine, furan-3- Carboamidine, thiophene-2-carboamidine, thiophene-3-carboamidine and the like can be mentioned. Since the above compound having an amidine structure is easily hydrolyzed, it is preferable to use a hydrophobic solvent as an inert solvent.

  Specific examples of the hydrophobic solvent include aliphatic hydrocarbons such as n-hexane, n-heptane, cyclohexane, methylcyclohexane, ethylcyclohexane, 2-methylpentane; toluene, xylene, chlorobenzene, dichlorobenzene, nitrobenzene, chloronaphthalene, etc. And aromatic hydrocarbons. In addition, it is preferable to use a solvent having a high solubility and a high boiling point such as chlorobenzene, dichlorobenzene, nitrobenzene, or chloronaphthalene because the reaction proceeds smoothly.

  The reaction temperature is preferably 20 to 200 ° C, more preferably 100 to 140 ° C. When the reaction is carried out at a temperature of less than 100 ° C., a large amount of 1-substituted product is generated, and the yield of the compound having the expected skeleton tends to be reduced. On the other hand, when the reaction is carried out at a temperature higher than 140 ° C., a large amount of by-products are likely to be produced, and the yield tends to decrease.

  In addition, it is preferable to make the reaction coexist as a catalyst because the yield is improved. Specific examples of the base include inorganic bases (inorganic catalyst) such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate; organic bases (organic catalyst) such as triethylamine and diazabicycloundecene. it can. Use of an organic catalyst is preferable because the reaction system becomes a homogeneous system.

A compound in which R ₇ and R ₉ in the general formula (3) are alkoxy groups is preferable because it can be synthesized using an inexpensive succinyl succinate as a raw material. Furthermore, the compound (4) represented by the following formula (4) in which R ₇ and R ₉ in the general formula (3) are methoxy groups and R ₈ and R ₁₀ are chlorine atoms is, for example, a reference document. : Synthesis, 2303-2306 (2008), by L. Hintermann, and K. Suzuki can be synthesized in a high yield by a simple method.

In addition, about the compound represented by general formula (1-2) among the pyrimidoquinazoline pigments of this invention, the compound represented by general formula (1-1) synthesize | combined as mentioned above is made into predetermined reaction. It can be synthesized by attaching. For example, the compound represented by R ₃ and R ₆ in the general formula (1-2) is a hydroxy group, and the compound represented by the general formula (1-1) is tin (Sn) under acidic conditions of hydrochloric acid. It can synthesize | combine by reducing using. Furthermore, if it is modified with an alkylating agent or an acylating agent, a compound in which R ₃ and R ₆ are represented by an alkoxy group can be synthesized.

Moreover, the compound by which R < ₃ > and R < ₆ > in General formula (1-2) are represented by an amino group made the compound represented by General formula (1-1), and the compound which has an amino group condensation-react. Thereafter, it can be synthesized by reduction.

<Pigment colorant>
The pigment colorant of the present invention contains the aforementioned pyrimidoquinazoline 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, plastic, pigment printing, and paint. In particular, the pigment colorant of the present invention is suitable as an image display material in which the transparency of colored pixels is a problem, and particularly as a pigment colorant for color filters. The pigment colorant of the present invention is also useful as a material for an image recording agent such as an ink for ink jet recording, an electrodeposition recording liquid, and a developer for electrophotography. These materials for the image recording agent are used for image recording methods such as an ink jet recording method, an electrodeposition recording method, and an electrophotographic method. By using the pigment colorant of the present invention, a material for an image recording agent capable of providing a high-quality image can be prepared by any image recording method.

  The pigment colorant of the present invention usually further contains a film forming material as a component other than the pyrimidoquinazoline pigment. The amount of the pyrimidoquinazoline 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 refined pyrimidoquinazoline pigment and 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 refined pyrimidoquinazoline pigment and a liquid containing the above film forming material. As the liquid containing the film-forming material, a liquid containing a photosensitive film-forming material or a liquid containing a non-photosensitive film-forming material can be used. Specific examples of the liquid containing the photosensitive film-forming material include liquid containing a photosensitive film-forming material used for ultraviolet curable ink, electron beam curable ink, and the like. Specific examples of liquids containing non-photosensitive film-forming materials include varnishes used for printing inks such as letterpress inks, lithographic inks, gravure inks and screen inks; varnishes used for room temperature drying or baking paints; Examples thereof include varnishes used for coating and varnishes used for thermal transfer ribbons.

  Specific examples of photosensitive film forming materials include photosensitive cyclized rubber resins, photosensitive phenol resins, photosensitive polyacrylate resins, photosensitive polyamide resins, photosensitive polyimide resins, and unsaturated polyester resins. And photosensitive resins such as polyester acrylate resins, polyepoxy acrylate resins, polyurethane acrylate resins, polyether acrylate resins, and polyol acrylate resins. Various monomers may be added as reactive diluents to the liquid containing these photosensitive resins.

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

  Specific examples of non-photosensitive film-forming materials include styrene- (meth) acrylic ester copolymers, soluble polyamide resins, soluble polyimide resins, soluble polyamideimide resins, soluble polyesterimide resins, and water-soluble materials. Examples include aminopolyester resins, water-soluble salts thereof, water-soluble salts of styrene-maleic acid ester copolymers, and water-soluble salts of (meth) acrylic acid ester- (meth) acrylic acid copolymers. it can.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified.

<Preparation of pigment>
Example 1
To 140 parts of nitrobenzene, 16 parts of benzamidine hydrochloride, 7 parts of compound (4) and 10 parts of triethylamine were added and heated at 100 to 110 ° C. for 5 hours. After cooling, the mixture was filtered and washed with methanol and water. It dried at 80 degreeC and obtained 7 parts of pigments (A) represented by a following formula (A).

(Example 2)
8 parts of pigment (B) represented by the following formula (B) in the same manner as in Example 1 except that 17 parts of 4-methylbenzamidine hydrochloride was used instead of 16 parts of benzamidine hydrochloride. Got.

(Example 3)
To 140 parts of nitrobenzene, 16 parts of benzamidine hydrochloride, 7 parts of compound (4) and 10 parts of triethylamine were added and heated at 60 ° C. for 5 hours. Subsequently, 17 parts of 4-methylbenzamidine hydrochloride and 10 parts of triethylamine were added and heated at 100 to 110 ° C. for 5 hours. After cooling, the mixture was filtered and washed with methanol and water. It dried at 80 degreeC and obtained 7 parts of pigments (C) represented by a following formula (C).

Example 4
To 200 parts of 35% hydrochloric acid, 10 parts of pigment (A) and 10 parts of tin powder were added and heated at 80 ° C. for 5 hours. After cooling, the mixture was filtered and washed with methanol and water. It dried at 80 degreeC and obtained 10 parts of pigments (D) represented by a following formula (D).

(Example 5)
To 120 parts of N, N-dimethylformamide, 10 parts of pigment (A), 12 parts of N, N-dimethyl-4-aminopyridine and 5 parts of acetic anhydride were added and heated at 40 ° C. for 24 hours. After cooling, the mixture was filtered and washed with methanol and water. It dried at 80 degreeC and obtained 7 parts of pigments (E) represented by a following formula (E).

When the obtained pigment was subjected to mass spectrometry (MALDI), peaks corresponding to the following molecular weights were detected. From the raw materials used and the results of mass spectrometry, it was confirmed that a compound (pigment) having the target composition was obtained.
Pigment (A): molecular weight 396
Pigment (B): molecular weight 424
Pigment (C): molecular weight 410
Pigment (D): molecular weight 398
Pigment (E): molecular weight 480

(Comparative Examples 1 and 2)
Pigment Orange 13 was used as the pigment of Comparative Example 1. Pigment Orange 34 was used as the pigment of Comparative Example 2.

<Preparation of dark paint>
The pigments obtained in Examples 1 to 5 and the pigments of Comparative Examples 1 and 2 were used and dispersed for 90 minutes using the paint conditioner according to the formulations shown below to prepare dark paints.
-Pigment 1.5 parts-Trade name "Super Becamine J-820" (* 1) 8.5 parts-Trade name "Phthalkid 133-60" (* 2) 17.0 parts-Xylene / 1-butanol (2 / 1 mass ratio) Mixed solvent 5.0 parts (* 1) Butylated melamine resin (Dainippon Ink Chemical Co., Ltd.)
(* 2) Short oil alkyd resin of coconut oil (manufactured by Hitachi Chemical Co., Ltd.)

<Paint test>
(1) Coloring power Pigment: Titanium white = 1: 20 (mass ratio) A dark paint was diluted with a white paint containing titanium white (titanium oxide) to prepare a light-color paint. The light color paint was spread on art paper using an applicator (6 mil) and baked at 140 ° C. for 30 minutes. The formed coating film was observed with the naked eye, and the coloring power was evaluated according to the following criteria. The results are shown in Table 1.
○: Good coloring power △: High coloring power ×: No coloring power

(2) Transparency Using an applicator (6 mil), the dark paint was developed on a glass plate and baked at 140 ° C. for 30 minutes. The formed coating film was observed with the naked eye, and the transparency was evaluated according to the following criteria. The results are shown in Table 1.
○: Excellent transparency △: Transparency ×: No transparency

(3) Weather resistance Dark paint and light paint were diluted to spray viscosity (14 seconds in Ford Cup No. 4) and spray-coated on a steel panel that had been ground-treated using an air spray gun to obtain a colored coated plate . The obtained colored coated plate was baked at 140 ° C. for 30 minutes and then exposed for 500 hours with a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.) to obtain a coated plate after exposure. The color difference between the exposed and unexposed coated plates was observed with the naked eye, and the weather resistance was evaluated according to the following criteria.
○: Almost no color difference △: There is a color difference ×: There is a large color difference

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

Claims (5)

A pyrimidoquinazoline pigment represented by the following general formula (1-1) or (1-2).

(In the general formula (1-1) and (1-2), R ₁ and R ₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, or an acyl group, R ₂ And R ₅ each independently represents an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, in the general formula (1-2), R ₃ and R ₆ Each independently represents a hydroxy group, an alkoxy group which may have a substituent, or an amino group which may have a substituent) The pyrimidoquinazoline pigment according to claim 1, wherein R ₁ and R _{4 in the} general formula (1-1) are hydrogen atoms. A method for synthesizing a pyrimidoquinazoline pigment according to claim 1 or 2,
A condensation reaction of a compound represented by the following general formula (2-1) and a compound represented by the following general formula (2-2) with a compound represented by the following general formula (3) in an inert solvent And a method for synthesizing a pyrimidoquinazoline pigment.

(In the general formulas (2-1) and (2-2), R ₂ and R ₅ are each independently an aryl group which may have a substituent or a heterocyclic ring which may have a substituent. In the general formula (3), R ₇ , R ₈ , R ₉ , and R ₁₀ each independently represent a hydrogen atom, an alkoxy group that may have a substituent, an amino group, or a halogen atom. Show)   The method for synthesizing a pyrimidoquinazoline pigment according to claim 3, wherein the inert solvent is a hydrophobic solvent.   A pigment colorant containing the pyrimidoquinazoline pigment according to claim 1.