JP2019014871A - Organic colorant, coloring composition, and inkjet ink - Google Patents

Abstract

To provide an organic colorant capable of forming an image having silver gloss.SOLUTION: An organic colorant is represented by a general formula (1). In the general formula (1), Rand Reach independently represent a C1-20 alkyl group, a C1-20 alkenyl group, a phenyl group, a naphthyl group, or the like. In a preferred embodiment, Rand Rare each either a group represented by a C1-20 linear alkyl group or a group represented by a C1-20 linear alkenyl group.SELECTED DRAWING: None

Description

  The present invention relates to an organic colorant, a coloring composition, and an inkjet ink that can form an image having excellent silver gloss derived from a compound having a specific structure.

  Those with metallic luster have many opportunities to see in every scene of daily life because they give people a glittering impression. Although the design property may be imparted using the metal itself, the design property is often imparted by coating the base material with a colored composition having a metallic luster.

As the coating method, there have been used a method of printing by various printing methods using a printing ink containing a pigment having glitter and a method of transferring foil by an adhesive or heat fusion.
Among metallic lusters, gold is a symbol of wealth, and has been loved by people since ancient times, and is an indispensable color for celebrations such as New Years. On the other hand, silver is also popular because of its calm texture and is often found in various situations. In addition, silver is different from gold, and by mixing with coloring compositions of other colors, various metallic luster colors including gold can be expressed, so it is more versatile than gold and has industrial utility value. high.

Conventionally, pigments used in a coloring composition having a silver metallic luster include aluminum fine particles and silver powder, but aluminum fine particles are widely used due to cost problems. However, since the aluminum fine particles have a high specific gravity, it is difficult to stably exist in the coloring composition, and there is a problem that the aluminum fine particles settle with time, adhere in some cases, and form a hard cake.
In order to reduce the environmental burden, coloring compositions such as printing inks are successively replaced with water-based ones that do not use organic solvents as much as possible. However, aluminum particles react with water to generate hydrogen gas. In addition, since aluminum is changed to alumina, there is a problem that the metallic luster is lost.

  In addition, with the development of inkjet printing technology, there is an increasing demand to obtain printed matter with metallic luster even in inkjet printing. For example, commercially available scaly aluminum pigments or titanium oxide-coated mica pigments are used as bright pigments in inkjet inks. Utilization has been proposed (see, for example, Patent Document 1). In addition, it has been proposed that the scaly aluminum pigment is subjected to a treatment that does not easily settle in ink (see, for example, Patent Document 2). Furthermore, it has been proposed that aluminum particles and water react with each other to suppress generation of hydrogen gas by using a water-resistant aluminum pigment (see, for example, Patent Document 3).

  In recent years, organic pigment materials having a metallic luster have been widely developed (see, for example, Patent Documents 4 to 6). Since the organic pigment material has a very low specific gravity compared to metal, if it can be dispersed appropriately, the risk of sedimentation in the coloring composition can be greatly reduced. In addition, it is possible to stably exist even in an aqueous system by appropriately designing the structure of the organic dye material.

  An object of the present invention is to provide an organic colorant capable of forming an image having silver gloss.

The organic colorant of the present invention as a means for solving the above problems is represented by the following general formula (1).
General formula (1)
However, the general formula (1), _{R 1} and _{R 2} are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, a phenyl group, a naphthyl group, and, - ( _{CH 2) n -COO-R 3} , - (CH 2) n -R 4, - (CH 2) n -CONH-R 5, -CR 6 R 7 -COO-R 8, or - _{(CH 2) n} Represents any of the groups represented by —OCOCH ₃ , R ₃ represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and R ₄ represents a hydroxy group or an alkoxy group having 1 to 2 carbon atoms. , An alkenyloxy group having 2 to 5 carbon atoms, a SO ₃ Na group, an OSO ₃ Na group, a phenyl group, a phenylalkyl group (the alkyl part has 1 to 3 carbon atoms), a naphthyl group, or a naphthylalkyl group (an alkyl part) of carbon atoms represents 1 to 3), _{R 5} , Alkyl group having 1 to 20 carbon atoms, a hydroxy alkyl group of the alkenyl group having 1 to 20 carbon atoms, or carbon atoms 1 to 12, _{R 6} represents a hydrogen atom, or a methyl group, _{R 7} Represents an alkyl group having 1 to 4 carbon atoms, R ₈ represents an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 1 to 12.

  According to the present invention, an organic colorant capable of forming an image having silver gloss can be provided.

(Organic colorant)
The organic colorant of the present invention is represented by the following general formula (1).
General formula (1)
However, the general formula (1), _{R 1} and _{R 2} are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, a phenyl group, a naphthyl group, and, - ( _{CH 2) n -COO-R 3} , - (CH 2) n -R 4, - (CH 2) n -CONH-R 5, -CR 6 R 7 -COO-R 8, or - _{(CH 2) n} Represents any of the groups represented by —OCOCH ₃ , R ₃ represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and R ₄ represents a hydroxy group or an alkoxy group having 1 to 2 carbon atoms. , An alkenyloxy group having 2 to 5 carbon atoms, a SO ₃ Na group, an OSO ₃ Na group, a phenyl group, a phenylalkyl group (the alkyl part has 1 to 3 carbon atoms), a naphthyl group, or a naphthylalkyl group (an alkyl part) of carbon atoms represents 1 to 3), _{R 5} , Alkyl group having 1 to 20 carbon atoms, a hydroxy alkyl group of the alkenyl group having 1 to 20 carbon atoms, or carbon atoms 1 to 12, _{R 6} represents a hydrogen atom, or a methyl group, _{R 7} Represents an alkyl group having 1 to 4 carbon atoms, R ₈ represents an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 1 to 12.

  The organic colorant of the present invention is based on the finding that inks containing conventional metal particles have a problem that nozzles are clogged or glitter pigments settle due to the large pigment of the particles in the ink. In addition, the organic colorant of the present invention has not been proposed as an organic dye material having silver gloss that is the most versatile among conventional organic dye materials, and an ink that has excellent silver gloss has not yet been developed. It is based on the knowledge that there is.

In general, the metallic luster refers to a glossiness or glossiness peculiar to a metal, and includes, for example, a matte metallic luster having low luster. Specifically, the regular reflectance is measured to determine the presence or absence of metallic luster. If the regular reflectance is 10% or more, it is determined that metallic luster is present. If the regular reflectance is less than 10%, the matte color tone becomes stronger and it may be difficult to say that the metallic luster is.
On the other hand, the silver luster in the present invention, there regular reflectance 10% or more, and color values ^{(a *} value, ^{b *} value) in the ^{a *} value, ^{b *} the values are all -3.5 or more 3. The case where it is 5 or less. Outside this range, it is difficult to say silver because it is yellowish or bluish. The regular reflectance of the silver origami paper is 38%, the a ^* value is −1.2, and the b ^* value is −3.2.

<Compound>
In order for the compound represented by the general formula (1) to exhibit silver gloss, a basic skeleton other than R ₁ and R ₂ is important. On the other hand, R ₁ and R ₂ can be variously selected as long as the characteristics of the basic skeleton are not adversely affected.
Further, it is important for the silver gloss to be a trans isomer, and a pure cis isomer does not exhibit a silver gloss. Therefore, although the trans isomer is shown as the general formula (1), even if the cis isomer is mixed to some extent, the silver gloss is not greatly affected. Therefore, the cis isomer may be mixed as long as the silver gloss is not affected. Absent.

R ₁ and R ₂ in the general formula (1) are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, a phenyl group, a naphthyl group, and other groups. Represents any represented.

As the alkyl group having 1 to 20 carbon atoms in R ₁ and R ₂ in the general formula (1) is not particularly limited and may be appropriately selected depending on the purpose, for example, a methyl group, an ethyl group, Examples include propyl group, isopropyl group, butyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, tert-octyl group, cyclohexyl group and the like. As carbon number of the said alkyl group, it is 1-20, 2-20 are preferable, 3-20 are more preferable, 3-11 are still more preferable, and 4 (butyl group) is especially preferable. The lower limit of the carbon number of the alkyl group is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, and particularly preferably 11 or more.
When the number of carbon atoms is 1 to 20, the crystallinity of the compound can be improved and silver luster is easily developed. A linear alkyl group is preferred from the viewpoint of glossiness. These may be used individually by 1 type and may use 2 or more types together.

Examples of the alkenyl group having 1 to 20 carbon atoms in R ₁ and R ₂ in the general formula (1) is not particularly limited and may be appropriately selected depending on the purpose, a plurality in the structure carbon - carbon It may have a double bond, for example, vinyl group, 1-propenyl group, allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group, 2-pentenyl group 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, 1,3-butadienyl group , Cyclohexadienyl group, cyclopentadienyl group and the like. When the number of carbon atoms is 1 to 20, the crystallinity of the compound can be improved and silver luster is easily developed. These may be used individually by 1 type and may use 2 or more types together.

As a phenyl group in R < ₁ > and R < ₂ > in the said General formula (1), you may have a substituent in the range which does not have a bad influence on expression of silver luster, etc. Examples of the substituent include an alkyl group, an alkenyl group, a hydroxyalkyl group, a hydroxy group, an alkoxy group, an alkenyloxy group, a cyano group, a cyanoalkyl group, a carboxy group, an alkoxycarbonyl group, and an amino group. As for carbon number of the alkyl part in the said substituent, 1-6 are preferable. These may be used individually by 1 type and may use 2 or more types together.

As a naphthyl group in R < ₁ > and R < ₂ > in the said General formula (1), you may have a substituent in the range which does not have a bad influence on expression of silver luster etc. Examples of the substituent include an alkyl group, an alkenyl group, a hydroxyalkyl group, a hydroxy group, an alkoxy group, an alkenyloxy group, a cyano group, a cyanoalkyl group, a carboxy group, an alkoxycarbonyl group, and an amino group. As for carbon number of the alkyl part in the said substituent, 1-6 are preferable. These may be used individually by 1 type and may use 2 or more types together.

Examples of other groups in R ₁ and R ₂ in the general formula (1) include — (CH ₂ ) _n —COO—R ₃ , — (CH ₂ ) _n —R ₄ , — (CH ₂ ) _{n. -CONH-R 5, -CR 6 R} 7 -COO-R 8, and _{- (CH} 2) a group represented by any one of n -OCOCH ₃ and the like.
R ₃ represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms.
R ₄ is a hydroxy group, an alkoxy group having 1 to 2 carbon atoms, an alkenyloxy group having 2 to 5 carbon atoms, an SO ₃ Na group, an OSO ₃ Na group, a phenyl group, a phenylalkyl group (carbon in the alkyl moiety). The number is 1 to 3), a naphthyl group, or a naphthylalkyl group (the alkyl portion has 1 to 3 carbon atoms).
R ₅ represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or a hydroxyalkyl group having 1 to 12 carbon atoms.
R ₆ represents a hydrogen atom or a methyl group.
R ₇ represents an alkyl group having 1 to 4 carbon atoms.
R ₈ represents an alkyl group having 1 to 5 carbon atoms. These may be used alone or in combination of two or more.

The alkyl group of indicated number of carbon atoms in R ₃ in the general formula (1) is 1 to 2 is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a methyl group, an ethyl group .

The alkoxy group having a carbon number of 1 to 2 in R ₄ in the general formula (1) is not particularly limited and may be appropriately selected depending on the intended purpose, for example, a methoxy group, an ethoxy group .

The alkenyloxy group having 2 to 5 carbon atoms in R ₄ in the general formula (1) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a vinyl group, a methyl vinyl ether group, an ethyl group And vinyl ether groups.

The phenyl group in R ₄ in the general formula (1) and the phenylalkyl group having 1 to 3 carbon atoms in the alkyl moiety are not particularly limited and may be appropriately selected depending on the intended purpose. You may have a substituent in the part of a phenyl group in the range which does not have a bad influence on expression etc. Examples of the substituent include an alkyl group, an alkenyl group, a hydroxyalkyl group, a hydroxy group, an alkoxy group, an alkenyloxy group, a cyano group, a cyanoalkyl group, a carboxy group, an alkoxycarbonyl group, and an amino group. As for carbon number of the alkyl group part in the said substituent, 1-6 are preferable. These may be used alone or in combination of two.

The naphthyl group in R ₄ in the general formula (1) and the naphthylalkyl group having 1 to 3 carbon atoms in the alkyl portion are not particularly limited and may be appropriately selected depending on the intended purpose. You may have a substituent in the part of a naphthyl group in the range which does not have a bad influence on expression etc. Examples of the substituent include an alkyl group, an alkenyl group, a hydroxyalkyl group, a hydroxy group, an alkoxy group, an alkenyloxy group, a cyano group, a cyanoalkyl group, a carboxy group, an alkoxycarbonyl group, and an amino group. As for carbon number of the alkyl group part in the said substituent, 1-6 are preferable. These may be used alone or in combination of two.

The alkyl group having 1 to 20 carbon atoms of R _{5 in} the general formula (1) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, trifluoromethyl, isopropyl, isobutyl, isopentyl, 2-ethylhexyl, sec-butyl Tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like. When the number of carbon atoms is 1 to 20, the crystallinity of the compound can be improved and silver luster is easily developed.

The alkenyl group having 1 to 20 carbon atoms of R _{5 in} the general formula (1) is not particularly limited and may be appropriately selected depending on the intended purpose. A plurality of carbon-carbon double bonds in the structure You may have. Examples of the alkenyl group include a vinyl group, 1-propenyl group, allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group, 2-pentenyl group and 3-pentenyl group. 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, 1,3-butadienyl group, cyclohexadienyl group And cyclopentadienyl group. When the number of carbon atoms is 1 to 20, the crystallinity of the compound can be improved and silver luster is easily developed.

The hydroxyalkyl group having 1 to 12 carbon atoms of R _{5 in} the general formula (1) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, — (CH ₂ ) ₂ —OH , — (CH ₂ ) ₁₂ —OH and the like.

Examples of R ₆ in the general formula (1) include a hydrogen atom and a methyl group.

The alkyl group having 1 to 4 carbon atoms of R _{7 in} the general formula (1) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a methyl group, an ethyl group, a propyl group, A butyl group, an isopropyl group, an isobutyl group, etc. are mentioned.

The alkyl group having 1 to 5 carbon atoms of R _{8 in} the general formula (1) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a methyl group, an ethyl group, a propyl group, Examples thereof include a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a neo-pentyl group, and a tert-pentyl group.

In R ₁ and R ₂ in the general formula (1), n is an integer of 1 to 12. When the n is 1 to 12, the crystallinity of the compound can be improved, and silver gloss is easily exhibited.

  Specific examples of the compound of the present invention include the following, but are not limited thereto. All of these have a silvery luster.

<< Compound Group a >>

<< Compound Group b >>

<< Compound Group c >>

<< Compound Group d >>

<< Compound Group e >>

<< Compound Group f >>

<< Compound Group g >>

<< Compound Group h >>

<< Compound Group i >>

<< Compound Group j >>

(Coloring composition)
The coloring composition of the present invention includes the organic colorant of the present invention, and further includes an organic solvent, water, a resin, a surfactant, and other components as necessary.

<Organic solvent>
As said organic solvent, the organic solvent used for a normal ink can be used.
Examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, tridecyl alcohol, cyclohexyl alcohol, and 2-methylcyclohexyl alcohol; ethylene glycol, diethylene glycol, Glycols such as ethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, glycerin; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol diethyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, Ethylene glycol monobutyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, Propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether, ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, ethylene glycol monobutyl acetate Tate, diethylene glycol monomethyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monoethyl acetate, diethylene glycol monobutyl acetate, triethylene Glycol ethers such as glycol monobutyl ether; Esters such as ethyl acetate, isopropyl acetate, n-butyl acetate, methyl lactate, ethyl lactate, butyl lactate; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, diacetone alcohol, etc. Ketones; Tetra Hydrofuran (THF); Examples of other organic solvents include hexane, toluene, xylene, acetonitrile, γ-butyrolactone, γ-valerolactone, and the like. From these, various solvents are selected from the viewpoints of compatibility with the characteristics of the head nozzle during printing, safety, and drying properties, and a plurality of solvents can be mixed and used as necessary.
These may be used individually by 1 type and may use 2 or more types together.

In addition, as the organic solvent, a water-soluble organic solvent used in ordinary ink can be used.
Examples of the water-soluble organic solvent include ethers such as polyhydric alcohols and polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, and sulfur-containing compounds.
Specific examples of the water-soluble organic solvent include, for example, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3 -Butanediol, 3-methyl-1,3-butanediol, polypropylene glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 1,5- Pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,3-hexanediol, 2,5-hexanediol, 1,5-hexanediol, glycerin, 1,2,6-hexanetriol, 2 -Ethyl-1,3-hexanediol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, 2,2 Polyhydric alcohols such as 4-trimethyl-1,3-pentanediol and petriol; Polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether; 2-pyrrolidone, N-methyl-2- Nitrogen-containing heterocyclic compounds such as pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ε-caprolactam; formamide, N-methylformamide, N, N-dimethylformamide, 3- Amides such as methoxy-N, N-dimethylpropionamide and 3-butoxy-N, N-dimethylpropionamide; amines such as monoethanolamine, diethanolamine and triethylamine; sulfur-containing compounds such as dimethylsulfoxide, sulfolane and thiodiethanol Compound; propylene carbonate, ethylene carbonate and the like can be mentioned.
These may be used individually by 1 type and may use 2 or more types together.

The content of the organic solvent is a coloring composition from the viewpoints of maintaining the moisturizing property of the coloring composition, improving the solubility and dispersibility of the organic coloring agent, and effectively penetrating the coloring composition into the recording medium. 1 mass% or more and 95 mass% or less are preferable with respect to the whole thing, and 30 mass% or more and 90 mass% or less are more preferable.
In the coloring composition, all components other than the coloring agent and the additive (surfactant and dispersant) may be an organic solvent, or may be used without adding water. Even in this case, the mixed water which cannot be excluded may be included.

<Water>
There is no restriction | limiting in particular as said water, According to the objective, it can select suitably, For example, pure water, such as ion-exchange water, ultrafiltration water, reverse osmosis water, distilled water, ultrapure water, etc. are mentioned. . These may be used individually by 1 type and may use 2 or more types together.

  By dissolving or dispersing the organic colorant, which is a colorant having a silvery luster, in a medium, any of them can be used as a colored composition. The medium to be used is preferably water, a mixed solvent of water and a water-soluble organic solvent, or an organic solvent. As the organic solvent to be used, those having an effect of preventing drying of the colored composition are particularly preferable, and it is preferable to use ion-exchanged water instead of general water containing various ions.

  The water content is not particularly limited and may be appropriately selected according to the purpose. However, the solubility of the organic colorant in the coloring composition, the discharge stability of the coloring composition, and clogging at the nozzle tip From the viewpoint of prevention, the content is preferably 1% by mass or more and 70% by mass or less, and more preferably 3% by mass or more and 50% by mass or less with respect to the total amount of the colored composition.

<Resin>
There is no restriction | limiting in particular as said resin, According to the objective, it can select suitably, For example, a urethane resin, a polyester resin, an acrylic resin, a vinyl acetate resin, a styrene resin, a butadiene resin, a styrene-butadiene type | system | group Examples thereof include resins, vinyl chloride resins, acrylic styrene resins, and acrylic silicone resins.
Further, it is possible to obtain a colored composition by mixing resin particles with a material such as a coloring material or an organic solvent in a resin emulsion state in which water is used as a dispersion medium. As said resin particle, what was synthesize | combined suitably may be used and a commercial item may be used. Moreover, these may be used individually by 1 type and may use 2 or more types together.

  Commercially available products can be used as the resin emulsion, and examples thereof include ACRYT WEM-321U (acrylic urethane aqueous emulsion, manufactured by Taisei Kako Co., Ltd.).

<Dispersant>
In order to disperse the organic colorant of the present invention in an aqueous medium, a dispersant may be used. As the dispersant, a chemically synthesized surfactant such as an ionic surfactant or a nonionic surfactant can be used. In addition, those derived from natural products and those modified with enzymes or the like can also be used.

  A commercially available product can be used as the dispersant, and examples of the commercially available product include DISPERBYK-190 (manufactured by Big Chemie).

  The content of the dispersant is preferably 0.5% by mass or more and 20% by mass or less with respect to the total amount of the colored composition for the purpose of maintaining good dispersion stability of the organic colorant.

<Surfactant>
As the surfactant, any of silicone surfactants, fluorine surfactants, amphoteric surfactants, nonionic surfactants and anionic surfactants can be used.

  Examples of the fluorosurfactant include Polyfox PF-156A (Omnova).

<Other ingredients>
In addition to the above-mentioned components, the coloring composition of the present invention is an ink having a desired physical property value. In the range not impairing the effects of the present invention, a pH adjuster, a preservative, Various additives such as antifungal agents may be contained.

<PH adjuster>
The pH adjuster is not particularly limited as long as the pH can be adjusted to 7 or more, and examples thereof include amines such as diethanolamine and triethanolamine.

<Antiseptic and antifungal agent>
The antiseptic / antifungal agent is not particularly limited, and examples thereof include 1,2-benzisothiazolin-3-one.

Examples of uses of the coloring composition include paints, printing inks, plastic colorants, and color toners. Examples of the printing ink include offset printing ink, gravure printing ink, flexographic printing ink, and inkjet ink.
The colored composition can be produced by dispersing it with a dispersion medium or the like using a known disperser. The dispersion medium here is water or a solvent that is being dispersed by a disperser. That is, even in the same water or solvent as in the mixing, it is referred to as a “dispersion medium” for the convenience of dispersion treatment.
Moreover, you may use various adjuvants and stabilizers, such as a dispersion | distribution wetting agent, an anti-skinning agent, a ultraviolet absorber, and antioxidant, as needed.

  The varnish used for the offset printing ink is a polymer resin component, for example, rosin-modified phenol resin, petroleum resin, alkyd resin, or resins such as these dry oil-modified resins, and if necessary, linseed oil, It consists of vegetable oils such as tung oil and soybean oil, and solvents such as n-paraffin, isoparaffin, aromatech, naphthene, and α-olefin. The resin, the vegetable oil, and the solvent are contained in a mass ratio of resin: vegetable oil. : Solvent = 20 to 50: 0 to 30:10 to 60 is preferable. The varnish may contain an acrylate ester as the resin. In addition to the organic colorant and the varnish, the offset printing ink may optionally contain known additives such as the organic solvent, a dryer, a leveling improver, and a thickener as necessary. Good.

The gravure printing ink and the vehicle used for the flexographic printing ink mean those containing a plurality of additives such as resins, solvents and plasticizers.
Examples of the resin include acrylic resins, nitrocellulose resins, polyamide resins, urethane resins, vinyl acetate resins, and rosin resins. These may be used alone or in combination of two or more.
Examples of the solvent include aromatic hydrocarbons, esters, ketones, alcohols, and the like. Specific examples include toluene, xylene, ethyl acetate, butyl acetate, methyl butyl ketone, methyl ethyl ketone, isopropyl alcohol, methanol, ethanol, and the like. These may be used alone or in combination of two or more.

The vehicle used for the paint means one containing a plurality of solvents, resins, additives and the like.
Examples of the resin include alkyd resin, modified alkyd resin, acrylic resin, alkyd-melamine resin, acrylic-melamine resin, phenol resin, polyamide resin An epoxy resin, a urethane resin, a vinyl acetate resin, etc. are mentioned.
Examples of the solvent include aromatic hydrocarbons, esters, ketones, alcohols, and the like. Specific examples include water, toluene, xylene, ethyl acetate, butyl acetate, methyl butyl ketone, methyl ethyl ketone, isobutyl alcohol, normal butanol, and cyclohexanone. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as resin used for the said colorant for plastics, According to the objective, it can select suitably, For example, polyolefin, such as poly (meth) acrylate, polystyrene, ABS resin, AS resin, polyethylene, a polypropylene, etc. , Polyamides, polyacetals, polycarbonates, polyesters such as PET and PBT, and thermoplastic resins such as modified polyphenylene ether.

  Examples of the resin used in the color toner include styrene such as styrene, vinyl toluene, α-methyl styrene, and amino styrene, and derivatives thereof; methacrylic acid esters such as methacrylic acid, methyl methacrylate, ethyl methacrylate, and butyl methacrylate; acrylic Acrylic acid esters such as acid, methyl acrylate, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate; dienes such as butadiene and isoprene; acrylonitriles; maleic acid, maleic anhydride, maleic esters; vinyl ether, vinyl acetate, etc. Examples of the vinyl compounds include homopolymers and copolymers of olefins such as ethylene and propylene, and polyesters, polyamides, and polyurethanes. These may be used alone or in combination of two or more. If necessary, add known materials such as charge control agents such as salicylic acid metal salts, metal-containing azo compounds, niglycine, quaternary ammonium salts, and offset inhibitors such as low molecular weight polypropylene, low molecular weight polyethylene, and wax. May be.

As content of the said organic coloring agent, 70.0 mass% or less is preferable with respect to coloring composition whole quantity, 0.01 mass% or more and 50.0 mass% or less are more preferable, 0.5 mass% or more and 15 mass% % Or less is more preferable. The balance is preferably a dispersion medium.
Since the dispersion conditions vary depending on the dispersion medium and the disperser, the dispersion temperature and dispersion time cannot be specified, but the dispersion temperature is preferably room temperature to 240 ° C., more preferably room temperature to 150 ° C., and the dispersion time is 120 Within 5 hours is preferable, and within 5 hours is more preferable.
The coloring composition can be mixed with other additives, pigments, dyes, and the like, if necessary, and used as a final paint, printing ink, plastic colorant, color toner, inkjet ink, or the like.
The disperser for dispersing the pigment in producing the pigment dispersion is not particularly limited, and a known disperser can be appropriately selected according to the purpose. For example, a disper, a homomixer, a bead mill, a ball mill, two Examples thereof include a roll, a triple roll, a pressure kneader, and an ultrasonic disperser.

(Inkjet ink)
The inkjet ink of the present invention includes the organic colorant of the present invention, and further includes an organic solvent, water, a resin, a surfactant, and other components as necessary.

  The content of the organic colorant is preferably 1.0% by mass or more and 30.0% by mass or less, and more preferably 5.0% by mass or more and 25.0% by mass or less with respect to the total amount of the inkjet ink. When the content is 1.0% by mass or more and 30.0% by mass or less, an image having excellent silver gloss can be obtained.

  As the organic solvent, water, resin, surfactant, and other components in the inkjet ink, the matters described in the coloring composition can be appropriately employed.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not restrict | limited by a following example.

[Example 1 (Synthesis of Compound a1)]
(Reaction Formula 1)

  Under a nitrogen atmosphere, p-aminophenol (2.19 g, 20.1 mmol), 4-hydroxybenzoic acid (2.77 g, 20.1 mmol), 1-ethyl-3- (3-dimethyl) was added to a two-necked eggplant flask. Aminopropyl) carbodiimide hydrochloride (EDC) (3.75 g, 24.2 mmol) was added, 50 mL of acetone (dehydrated) was added, and the mixture was heated to reflux for 12 hours. Thereafter, the solvent was removed under reduced pressure, and the residue was washed once with 40 mL of ethyl acetate, once with 40 mL of diluted hydrochloric acid, and subjected to suction filtration to obtain an intermediate of compound a1. The yield was 72%.

The result of the NMR measurement of the intermediate of compound a1 is as follows.
¹ H NMR (400 MHz; CH ₃ OD): δ 7.79 (doublet (d), 4H), 7.40 (d, 4H), 6.85 (d, 4H), 6.77 (d, 4H)

  Next, the synthesized compound a1 intermediate (3.30 g, 14.4 mmol), 1-bromobutane (19.74 g, 144.1 mmol), potassium carbonate (13.9 g, 100.9 mmol) were placed in a two-necked eggplant flask. After adding 300 mL of acetone, the mixture was heated to reflux for 72 hours. Thereafter, the solvent was removed under reduced pressure, and the residue was washed twice with 100 mL of hexane (100 mL × 2 times). Furthermore, the residue after washing with hexane was recrystallized with acetone to obtain the target compound a1. The yield was 55%.

NMR measurement values of the compound a1 are as follows.
¹ H NMR (400 MHz; CDCl 3): δ 7.82 (d, 4H), 7.60 (singlet (s), 1H), 7.97 (d, 4H), 7.91 (d, 4H), 4 .03 (triplet (t), 2H), 3.97 (t, 2H), 1.80 (multitilt (m), 4H), 1.50 (m, 4H), 0.99 (m, 6H)

  Next, 2.0 g of compound a1 and 1,200 mL of methanol were added to a 30 mL sample bottle, and the mixture was heated to 80 ° C. to completely dissolve the solid. Thereafter, the solution was allowed to stand at room temperature for 24 hours. The precipitated crystals were laminated on a circular filter paper (diameter 21 mm) by suction filtration to obtain a silvery glossy crystal thin film of compound a1.

Example 2 (Synthesis of Compound a2)
(Reaction Formula 2)

  A silvery shiny crystalline thin film of compound a2 was obtained in the same manner as in Example 1 except that 1-bromobutane was changed to 33.89 g (144.1 mmol) of 1-bromoundecane in Example 1. In the same manner as in Example 1, it was measured by NMR, and it was identified that compound a2 was obtained.

[Example 3 (synthesis of compound a3)]
(Reaction Formula 3)

  A silvery shiny crystalline thin film of compound a3 was obtained in the same manner as in Example 1 except that 1-bromobutane was changed to 48.04 g (144.1 mmol) of 1-bromooctadecane in Example 1. In the same manner as in Example 1, it was measured by NMR, and it was identified that compound a3 was obtained.

Example 4 (Synthesis of Compound a4)
(Reaction Formula 4)

  In Example 1, except that 1-bromobutane was changed to 31.87 g (144.1 mmol) of 1-bromo-3,7-dimethyloctane, a silvery shiny crystalline thin film of compound a4 was obtained in the same manner as in Example 1. It was. In the same manner as in Example 1, it was measured by NMR, and it was identified that compound a4 was obtained.

[Example 5 (synthesis of compound a8)]
(Reaction Formula 5)

  A silvery shiny crystalline thin film of Compound a8 was obtained in the same manner as in Example 1 except that 1-bromobutane was changed to 23.79 g (144.1 mmol) of 1-bromo-4-methylpentane in Example 1. In the same manner as in Example 1, it was measured by NMR, and it was identified that compound a8 was obtained.

Example 6 (Synthesis of Compound b2)
(Reaction Formula 6)

  In Example 1, except that 1-bromobutane was changed to 21.47 g (144.1 mmol) of 1-bromo-3-methyl-2-butene, a silvery glossy crystalline thin film of Compound b2 was prepared in the same manner as in Example 1. Obtained. In the same manner as in Example 1, it was measured by NMR, and it was identified that compound b2 was obtained.

[Example 7 (synthesis of compound b3)]
(Reaction Formula 7)

  A silvery glossy crystal thin film of Compound b3 was obtained in the same manner as in Example 1 except that 1-bromobutane was changed to 47.75 g (144.1 mmol) of 18-bromo-1-octadecene in Example 1. In the same manner as in Example 1, it was measured by NMR, and it was identified that compound b3 was obtained.

[Example 8 (synthesis of compound c1)]
(Reaction Formula 8)

  In Example 1, except that 1-bromobutane was changed to 22.62 g (144.1 mmol) of bromobenzene, a silvery glossy crystal thin film of compound c1 was obtained in the same manner as in Example 1. In the same manner as in Example 1, it was measured by NMR, and it was identified that compound c1 was obtained.

[Example 9 (synthesis of compound c3)]
(Reaction Formula 9)

  A silvery shiny crystalline thin film of compound c3 was obtained in the same manner as in Example 1 except that 1-bromobutane was changed to 28.97 g (144.1 mmol) of 4-bromobenzoic acid in Example 1. In the same manner as in Example 1, it was measured by NMR, and it was identified that compound c3 was obtained.

Example 10 (Synthesis of Compound d1)
(Reaction Formula 10)

  A silvery shiny crystalline thin film of the compound (d1) was obtained in the same manner as in Example 1 except that 1-bromobutane was changed to 29.84 g (144.1 mmol) of 2-bromonaphthalene in Example 1. In the same manner as in Example 1, it was measured by NMR, and it was identified that compound d1 was obtained.

[Example 11 (synthesis of compound d7)]
(Scheme 11)

  A silvery shiny crystalline thin film of compound d7 was obtained in the same manner as in Example 1 except that 1-bromobutane was changed to 36.18 g (144.1 mmol) of 6-bromo-2-naphthoic acid in Example 1. In the same manner as in Example 1, it was measured by NMR, and it was identified that compound d7 was obtained.

[Example 12 (synthesis of compound e1)]
(Scheme 12)

  A silvery shiny crystalline thin film of compound e1 was obtained in the same manner as in Example 1 except that 1-bromobutane was changed to 22.04 g (144.1 mmol) of 3-bromopropionic acid in Example 1. In the same manner as in Example 1, it was measured by NMR, and it was identified that compound e1 was obtained.

Example 13 (Synthesis of Compound e2)
(Scheme 13)

  A silvery shiny crystalline thin film of compound e2 was obtained in the same manner as in Example 1 except that 1-bromobutane was changed to 24.07 g (144.1 mmol) of methyl 3-bromopropionate in Example 1. In the same manner as in Example 1, it was measured by NMR, and it was identified that compound e2 was obtained.

Example 14 (Synthesis of Compound e3)
(Scheme 14)

  A silvery shiny crystalline thin film of compound e3 was obtained in the same manner as in Example 1 except that 1-bromobutane was changed to 26.08 g (144.1 mmol) of ethyl 3-bromopropionate in Example 1. In the same manner as in Example 1, it was measured by NMR, and it was identified that compound e3 was obtained.

Example 15 (Synthesis of Compound e5)
(Scheme 15)

  A silvery shiny crystalline thin film of compound e5 was obtained in the same manner as in Example 1 except that 1-bromobutane was changed to 38.21 g (144.1 mmol) of 11-bromoundecanoic acid in Example 1. In the same manner as in Example 1, it was measured by NMR, and it was identified that compound e5 was obtained.

[Example 16 (synthesis of compound f1)]
(Scheme 16)

  In Example 1, except that 1-bromobutane was changed to 2-bromoethanol 18.01 g (144.1 mmol), a silvery glossy crystal thin film of compound f1 was obtained in the same manner as in Example 1. In the same manner as in Example 1, it was measured by NMR, and it was identified that compound f1 was obtained.

[Example 17 (synthesis of compound f2)]
(Reaction Scheme 17)

  A silvery shiny crystalline thin film of Compound f2 was obtained in the same manner as in Example 1 except that 1-bromobutane was changed to 20.03 g (144.1 mmol) of 2-bromoethyl methyl ether in Example 1. In the same manner as in Example 1, it was measured by NMR, and it was identified that the compound f2 was obtained.

[Example 18 (synthesis of compound f4)]
(Scheme 18)

  A silvery shiny crystalline thin film of compound f4 was obtained in the same manner as in Example 1 except that 1-bromobutane was changed to 22.05 g (144.1 mmol) of 2-bromoethyl ethyl ether in Example 1. In the same manner as in Example 1, it was measured by NMR, and it was identified that the compound f4 was obtained.

[Example 19 (synthesis of compound f5)]
(Scheme 19)

  A silvery shiny crystalline thin film of compound f5 was obtained in the same manner as in Example 1 except that 1-bromobutane was changed to 30.41 g (144.1 mmol) of sodium 2-bromoethanesulfonate in Example 1. In the same manner as in Example 1, it was measured by NMR, and it was identified that the compound f5 was obtained.

[Example 20 (synthesis of compound f6)]
(Scheme 20)

  A reaction mixture of the compound f1 (2.04 g, 7 mmol), sulfur trioxide / pyridine complex (2.38 g, 15.0 mmol), and pyridine 20 mL was stirred at 50 ° C. for 24 hours, and then sodium hydroxide (1.2 g , 30 mmol) was added, and the mixture was stirred for 10 minutes. After removing pyridine and water under reduced pressure, methanol was added to the residue to extract the product with methanol. Subsequently, hexane was added to methanol to precipitate product crystals, which were filtered by suction and laminated on a circular filter paper (diameter 21 mm) to obtain a silvery glossy crystal thin film of compound f6. In the same manner as in Example 1, it was measured by NMR, and it was identified that compound f6 was obtained.

[Example 21 (synthesis of compound f8)]
(Scheme 21)

  A silvery shiny crystalline thin film of compound f8 was obtained in the same manner as in Example 1 except that 1-bromobutane was changed to 24.65 g (144.1 mmol) of benzyl bromide in Example 1. In the same manner as in Example 1, it was measured by NMR, and it was identified that the compound f8 was obtained.

[Example 22 (synthesis of compound f9)]
(Scheme 22)

  A silvery shiny crystalline thin film of compound f9 was obtained in the same manner as in Example 1 except that 1-bromobutane was changed to 26.67 g (144.1 mmol) of 4-methylbenzyl bromide in Example 1. In the same manner as in Example 1, it was measured by NMR, and it was identified that the compound f9 was obtained.

[Example 23 (synthesis of compound f12)]
(Scheme 23)

  In Example 1, except that 1-bromobutane was changed to 31.86 g (144.1 mmol) of 1- (bromomethyl) naphthalene, a silvery shiny crystalline thin film of compound f12 was obtained in the same manner as in Example 1. In the same manner as in Example 1, it was measured by NMR, and it was identified that compound f12 was obtained.

[Example 24 (synthesis of compound f14)]
(Reaction Scheme 24)

  A silvery shiny crystalline thin film of compound f14 was obtained in the same manner as in Example 1 except that 1-bromobutane was changed to 38.19 g (144.1 mmol) of 12-bromo-1-dodecanol in Example 1. In the same manner as in Example 1, it was measured by NMR, and it was identified that the compound f14 was obtained.

[Example 25 (synthesis of compound f15)]
(Scheme 25)

  A silvery glossy crystal thin film of compound f1 was obtained in the same manner as in Example 1 except that 1-bromobutane was changed to 20.00 g (144.1 mmol) of 3-bromopropanol in Example 1. In the same manner as in Example 1, it was measured by NMR, and it was identified that compound f15 was obtained.

[Example 26 (synthesis of compound g1)]
(Scheme 26)

Under a nitrogen atmosphere, an intermediate of compound a1 (0.233 g, 0.8 mmol) and potassium carbonate (0.17 g, 1.2 mmol) were placed in a two-necked eggplant flask, and then 10 mL of acetone was added. The resulting solution was stirred at room temperature for 30 minutes and ethyl bromoacetate (0.14 g, 0.8 mmol) was added dropwise. The reaction system was refluxed for 4 hours and then suction filtered to remove potassium carbonate. The solvent was removed from the filtrate under reduced pressure, and the residue was washed with water. Finally, the product was purified by column chromatography to obtain the product (Intermediate 1 of compound g1).
Next, Intermediate 1 (1.049 g, 2.60 mmol) of Compound g1 and dehydrated THF (30 mL) were placed in a two-necked eggplant flask and started to reflux at 70 ° C. 50 mL of aqueous solution was added. After the reaction system was refluxed for 2 hours, the solvent was removed by distillation under reduced pressure, and 100 mL of water was added to the residue. After removing unnecessary water by suction filtration, dilute hydrochloric acid was added dropwise until the filtrate became acidic to precipitate a crude product. The crude product was washed with 30 mL of acetone to obtain Intermediate 2 of Compound g1.
Next, 8 mL of thionyl chloride was added to a two-necked eggplant flask containing Intermediate 2 (0.528 g, 1.52 mmol) of Compound g1 under a nitrogen atmosphere. After the reaction system was refluxed at 80 ° C. for 5 hours, unreacted thionyl chloride was removed under reduced pressure to obtain Intermediate 3 of Compound g1.
Next, 10 mL of chloroform was added to Intermediate 3 of Compound g1, cooled to 0 ° C. with an ice bath, 5 mL of a 2.4 mass% sodium hydroxide aqueous solution at 0 ° C. and isopropylamine (0.89 g, 15.1 mmol). ) Was added. The obtained solution was stirred for 90 minutes, and then filtered by suction, laminated on a circular filter paper (diameter 21 mm), and finally washed with 30 mL of methanol to obtain a silvery glossy crystal thin film of compound g1. In the same manner as in Example 1, it was measured by NMR, and it was identified that compound g1 was obtained.

Example 27 (Synthesis of Compound g2)
(Scheme 27)

  Chloroform 10 mL was added to intermediate 3 (2.97 g, 7.5 mmol) of compound g1 obtained in Example 26, cooled to 0 ° C. in an ice bath, and then a 2.4 mass% aqueous sodium hydroxide solution at 0 ° C. 5 mL and heptadecylamine (3.83 g, 15.0 mmol) were added. The resulting solution was stirred for 90 minutes, then suction filtered and laminated on a circular filter paper (diameter 21 mm), and finally washed with 30 mL of methanol to obtain a silvery glossy crystal thin film of compound g2. In the same manner as in Example 1, it was measured by NMR, and it was identified that compound g2 was obtained.

[Example 28 (synthesis of compound g3)]
(Scheme 28)

  Chloroform 10 mL was added to intermediate 3 (2.97 g, 7.5 mmol) of compound g1 obtained in Example 26, cooled to 0 ° C. in an ice bath, and then a 2.4 mass% aqueous sodium hydroxide solution at 0 ° C. 5 mL and oleylamine (4.01 g, 15.0 mmol) were added. The resulting solution was stirred for 90 minutes, then suction filtered, laminated on a circular filter paper (diameter 21 mm), and finally washed with 30 mL of methanol to obtain a silvery glossy crystal thin film of compound g3. In the same manner as in Example 1, it was measured by NMR, and it was identified that compound g3 was obtained.

[Example 29 (synthesis of compound g4)]
(Scheme 29)

  Chloroform 10 mL was added to intermediate 3 (2.97 g, 7.5 mmol) of compound g1 obtained in Example 26, cooled to 0 ° C. in an ice bath, and then a 2.4 mass% aqueous sodium hydroxide solution at 0 ° C. 5 mL and 2-aminoethanol (0.92 g, 15.0 mmol) were added. The resulting solution was stirred for 90 minutes, then suction filtered and laminated on a circular filter paper (diameter 21 mm), and finally washed with 30 mL of methanol to obtain a silvery glossy crystal thin film of compound g4. In the same manner as in Example 1, it was measured by NMR, and it was identified that compound g4 was obtained.

[Example 30 (synthesis of compound g6)]
(Reaction Scheme 30)

  Chloroform 10 mL was added to intermediate 3 (2.97 g, 7.5 mmol) of compound g1 obtained in Example 26, cooled to 0 ° C. in an ice bath, and then a 2.4 mass% aqueous sodium hydroxide solution at 0 ° C. 5 mL and 12-amino-1-dodecanol (3.02 g, 15.0 mmol) were added. The obtained solution was stirred for 90 minutes, and then filtered by suction, laminated on a circular filter paper (diameter 21 mm), and finally washed with 30 mL of methanol to obtain a silvery glossy crystal thin film of compound g6. In the same manner as in Example 1, it was measured by NMR, and it was identified that compound g6 was obtained.

[Example 31 (synthesis of compound g7)]
(Scheme 31)

  Chloroform 10 mL was added to intermediate 3 (2.97 g, 7.5 mmol) of compound g1 obtained in Example 26, cooled to 0 ° C. in an ice bath, and then a 2.4 mass% aqueous sodium hydroxide solution at 0 ° C. 5 mL and 3-aminopropylene (0.86 g, 15.0 mmol) were added. The resulting solution was stirred for 90 minutes, then suction filtered, laminated on a circular filter paper (diameter 21 mm), and finally washed with 30 mL of methanol to obtain a silvery glossy crystal thin film of compound g7. In the same manner as in Example 1, it was measured by NMR, and it was identified that compound g7 was obtained.

Example 32 (Synthesis of Compound h2)
(Scheme 32)

  A silvery shiny crystalline thin film of compound h2 was obtained in the same manner as in Example 1 except that 1-bromobutane was changed to 26.09 g (144.1 mmol) of ethyl 2-bromopropionate in Example 1. In the same manner as in Example 1, it was measured by NMR, and it was identified that Compound h2 was obtained.

Example 33 (Synthesis of Compound i1)]
(Scheme 33)

  In Example 1, except that 1-bromobutane was changed to 26.09 g (144.1 mmol) of 2-bromoethyl acetate, a silvery glossy crystalline thin film of Compound i1 was obtained in the same manner as in Example 1. In the same manner as in Example 1, measurement by NMR confirmed that compound i1 was obtained.

Example 34 (Synthesis of Compound j2)
(Scheme 34)

Under a nitrogen atmosphere, in a two-necked eggplant flask, 4-hydroxybenzoic acid (3.98 g, 28.8 mmol), 2-bromoethyl methyl ether (40.06 g, 288.2 mmol), potassium carbonate (27.9 g, 201.8 mmol), 300 mL of acetone was added, and the mixture was heated to reflux for 72 hours. Thereafter, the solvent was removed under reduced pressure, and the residue was washed twice with 100 mL of hexane (200 mL × 2 times) to obtain an intermediate 1 of compound j2.
Next, under a nitrogen atmosphere, p-aminophenol (2.19 g, 20.1 mmol), intermediate 1 of compound j2 (5.82 g, 20.1 mmol), 1-ethyl-3- (3-Dimethylaminopropyl) carbodiimide hydrochloride (EDC) (3.75 g, 24.2 mmol) was added, 50 mL of acetone (dehydrated) was added, and the mixture was heated to reflux for 12 hours. Thereafter, the solvent was removed under reduced pressure, and the residue was washed once with 40 mL of ethyl acetate, once with 40 mL of diluted hydrochloric acid, and subjected to suction filtration to obtain an intermediate 2 of compound j2.
Next, intermediate 2 (2.92 g, 10.1 mmol), ethyl bromoacetate (1.69 g, 10.1 mmol) and potassium carbonate (13.9 g, 100.9 mmol) of compound j2 were placed in a two-necked eggplant flask. After the addition, 300 mL of acetone was added and heated to reflux for 72 hours. Then, the solvent was removed under reduced pressure, the residue was washed twice with 100 mL of hexane (100 mL × 2 times), and the residue after washing with hexane was recrystallized with acetone to obtain the target compound j2.
Next, 2.0 g of compound j2 and 1,200 mL of methanol were added to a 30 mL sample bottle, and the mixture was heated to 80 ° C. to completely dissolve the solid. Thereafter, the solution was allowed to stand at room temperature for 24 hours. The precipitated crystals were stacked on a circular filter paper (diameter 21 mm) by suction filtration to obtain a silvery glossy crystal thin film of compound j2. In the same manner as in Example 1, it was measured by NMR, and it was identified that compound j2 was obtained.

[Comparative Example 1 (Synthesis of Compound k1)]
(Scheme 35)

Under a nitrogen atmosphere, p-aminophenol (2.19 g, 20.1 mmol), 4-hydroxy-3,5-dimethylbenzoic acid (3.34 g, 20.1 mmol), 1-ethyl- 3- (3-Dimethylaminopropyl) carbodiimide hydrochloride (EDC) (3.75 g, 24.2 mmol) was added, 50 mL of acetone (dehydrated) was added, and the mixture was heated to reflux for 12 hours. Thereafter, the solvent was removed under reduced pressure, and the residue was washed once with 40 mL of ethyl acetate, once with 40 mL of dilute hydrochloric acid, and subjected to suction filtration to obtain an intermediate of compound k1.
Next, an intermediate (3.73 g, 14.4 mmol), 1-bromobutane (19.74 g, 144.1 mmol), potassium carbonate (13. 9 g, 100.9 mmol) was added, 300 mL of acetone was added, and the mixture was heated to reflux for 72 hours. Thereafter, the solvent was removed under reduced pressure, and the residue was washed twice with 100 mL of hexane (100 mL × 2 times). Furthermore, the residue after washing with hexane was recrystallized with acetone to obtain the target compound k1.
Next, 2.0 g of compound k1 and 1,200 mL of methanol were added to a 30 mL sample bottle, and the mixture was heated to 80 ° C. to completely dissolve the solid. Thereafter, the solution was allowed to stand at room temperature for 24 hours. The precipitated crystals were stacked on a circular filter paper (diameter 21 mm) by suction filtration to obtain a crystal thin film of compound k1. In the same manner as in Example 1, it was measured by NMR, and it was identified that compound k1 was obtained.

<Silver gloss evaluation of compounds>
About each compound synthesize | combined, the regular reflectance and the color value were measured, and silvery glossiness was evaluated.
That is, a large integrating sphere apparatus (JASCO ILN-472 large integrating sphere apparatus color diagnosis program, manufactured by JASCO) is attached to an ultraviolet-visible spectrophotometer (JASCO V-570 UV / VIS / NIR Spectrophotometer, manufactured by JASCO). With the optical trap reflector removed, the diffuse reflectance of each compound crystal set in the sample holder was measured. Next, an optical trap reflector was inserted to measure the total reflectance, and the regular reflectance was calculated by the formula “regular reflectance = total reflectance−diffuse reflectance”. Further, each color value was calculated from the measurement result of total reflectance.
About the obtained regular reflectance and color value, the result judged on the following reference | standard is shown in Table 1-4.
If the regular reflectance and the color value (a value, b value) are both rank 1 or higher, it can be said that the organic colorant has a practical silvery gloss.
[Regular reflectance: Evaluation criteria]
Rank 3: 20% ≤ Regular reflectance Rank 2: 15% ≤ Regular reflectance <20%
Rank 1: 10% ≦ regular reflectance <15%
Rank 0: Regular reflectance <10%
[Color value (a ^* value): Evaluation criteria]
Rank 3: -1.5 ≦ a ^* ≦ 1.5
Rank 2: −2.5 ≦ a ^* <− 1.5 or 1.5 <a ^* ≦ 2.5
Rank 1: −3.5 ≦ a ^* <− 2.5 or 2.5 <a ^* ≦ 3.5
[Color value (b ^* value): Evaluation criteria]
Rank 3: −1.5 ≦ b ^* ≦ 1.5
Rank 2: −2.5 ≦ b ^* <− 1.5 or 1.5 <b ^* ≦ 2.5
Rank 1: −3.5 ≦ b ^* <− 2.5 or 2.5 <b ^* ≦ 3.5

Incidentally, * mark described in Table 1-4 shows the point of attachment to the oxygen atom in the general formula (1) in which R ₁ and R ₂ are bonded. However, the compound k1 further has two methyl groups in the general formula (1).

  From the results of Tables 1 to 4, it can be seen that any of the compounds according to the present invention is an organic colorant having a practical silvery luster. Moreover, from the result of Table 4, in the compound k1 of the comparative example 1 which attached | subjected the substituent to the basic skeleton of the said General formula (1), a regular reflectance is less than 10%, silver gloss is not expressed, but it is practical. It turns out that it is not suitable for.

(Example 35)
-Preparation of coloring composition 1-
Using a vial, the materials of the following formulation are mixed uniformly, irradiated with ultrasonic waves (600 W) at room temperature for 1 hour, and then filtered through a filter having an average pore size of 5.0 μm to give the colored composition 1 Obtained.
-Silver glossy crystal thin film of Compound a1 5.0 parts by mass-5.0 parts by mass of ion-exchanged water-89.8 parts by mass of dehydrated THF-0.2 parts by mass of dispersant (DISPERBYK-190, manufactured by Big Chemie)

(Examples 36 to 68 and Comparative Example 2)
-Preparation of colored compositions 2-35-
In Example 35, except that the compound a1 of Example 1 was changed to the compounds shown in Tables 5 to 8 below, in the same manner as in Example 35, the colored compositions 2 to 34 of Examples 36 to 68 and the comparison The coloring composition 35 of Example 2 was obtained.

<Silver Gloss Evaluation of Colored Composition>
The obtained colored compositions 1 to 35 were applied to glass media and color paper as described below, and the silver gloss of the printed matter was measured and evaluated. The results are shown in Tables 5-8. Here, if both the regular reflectance and the color value (a value, b value) are rank 1 or more, it can be said that it is a coloring composition having a practical silver gloss.

<< Glass medium >>
Using a bar coater (No. 22, manufactured by Daiichi Rika Co., Ltd.), each colored composition was applied to a 25 mm × 75 mm glass substrate having a plate thickness of 1.0 mm so as to have an average thickness of 50 μm. A printed material was obtained. Next, the silver glossiness of the printed material was evaluated in the same manner as in <Evaluation of Silver Glossiness of Compound> in Example 1.

<< Color Paper >>
Using a bar coater (No. 22, manufactured by Daiichi Rika Co., Ltd.), each colored composition is applied to color paper (color paper A4, Nakatsuchiguchi, manufactured by Nagatoya Shoten Co., Ltd.) so as to have an average thickness of 50 μm. Coating was obtained to obtain a printed matter. Next, the silver glossiness of the printed material was evaluated in the same manner as in <Evaluation of Silver Glossiness of Compound> in Example 1.

Incidentally, * mark described in Table 5-8 shows the point of attachment to the oxygen atom in the general formula (1) in which R ₁ and R ₂ are bonded. However, the compound k1 further has two methyl groups in the general formula (1).

  From the results of Tables 5 to 8, it can be seen that when the colored compositions 1 to 34 of the present invention are used, a printed matter having a practical silvery gloss can be obtained. Moreover, from the result of Table 8, in the compound k1 of the comparative example 2 which attached | subjected the substituent to the basic skeleton of the said General formula (1), regular reflectance is less than 10%, silver gloss is not expressed, but it is practical. It turns out that it is not suitable for.

(Example 69)
-Preparation of inkjet ink 1-
After mixing the following mixture uniformly into a vial (product name: SV-50A, manufactured by Nidec Rika Glass Co., Ltd.), 6 parts by mass of a silvery glossy crystal thin film of compound a1 was added, and an ultrasonic homogenizer ( Device name: US-300T: chip diameter 7 mm, manufactured by Nippon Seiki Seisakusho Co., Ltd., irradiated with ultrasonic waves (120 μA) at room temperature for 1 minute, and then a filter having an average pore diameter of 5.0 μm (trade name: Minisalt 17594 -K, manufactured by Sartorius Stedim Japan) to prepare a dispersion.
・ Ion-exchanged water 11.4 mass parts ・ 3-Methyl-1,3-butanediol 12.0 mass parts ・ Dispersant (DISPERBYK-190, manufactured by Big Chemie) 0.6 mass parts

On the other hand, the following raw materials were mixed to prepare a vehicle.
・ 12.3 parts by mass of ACRYT WEM-321U (acrylic urethane aqueous emulsion, manufactured by Taisei Kako Co., Ltd.)
・ Glycerin 11.7 parts by mass ・ 1,3-butanediol 35.2 parts by mass ・ 2-ethyl-1,3-hexanediol 6.3 parts by mass ・ Polyfox PF-156A 5.2 parts by mass (anionic fluorine) Surfactant, manufactured by OMMNOVA SOLUTIONS)
Proxel LV 0.3 part by mass (antiseptic / antifungal agent, 1,2-benzisothiazolin-3-one, manufactured by Avicia)
・ 0.2 parts by mass of triethanolamine ・ 28.9 parts by mass of ion exchange water

  The dispersion and the vehicle prepared above were mixed in equal amounts in a vial to obtain inkjet ink 1.

(Examples 70 to 102 and Comparative Example 3)
-Preparation of inkjet ink 2-35-
In Example 69, except that the compound a1 was changed to the compounds shown in Tables 9 to 12 below, the inkjet inks 2 to 34 of Examples 70 to 102 and the inkjet ink of Comparative Example 3 were the same as Example 69. 35 was obtained.

<Formation method of recorded matter>
Ink cartridge containing the obtained compound was filled into an ink cartridge, and using an inkjet printer (device name: IPSiO GX3000, manufactured by Ricoh Co., Ltd.), it was confirmed that all nozzles were filled with ink and no abnormal image appeared, After adjusting the discharge amount so that the amount of ink attached to the recording medium (product name: Color Paper A4, Nakatsuchiguchi, manufactured by Nagatoya Shoten Co., Ltd.) is 100 g / m ² , a solid image of 50 mm × 50 mm is obtained. It was. Next, the silver glossiness of the obtained solid image was evaluated in the same manner as in <Evaluation of Silver Glossiness of Compound> in Example 1.

Incidentally, * mark described in Table 9-12 shows the point of attachment to the oxygen atom in the general formula (1) in which R ₁ and R ₂ are bonded. However, the compound k1 further has two methyl groups in the general formula (1).

  From the results of Tables 9 to 12, it can be seen that by using the ink-jet inks 1 to 34 containing the compound according to the present invention, an image having a practical silvery gloss can be obtained. Moreover, from the result of Table 12, in the compound k1 of the comparative example 3 which attached | subjected the substituent to the basic skeleton of the said General formula (1), a regular reflectance is less than 10%, silver gloss is not expressed, but it is practical. It turns out that it is not suitable for.

The aspect of the present invention is as follows.
<1> An organic colorant represented by the following general formula (1).
General formula (1)
However, the general formula (1), _{R 1} and _{R 2} are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, a phenyl group, a naphthyl group, and, - ( _{CH 2) n -COO-R 3} , - (CH 2) n -R 4, - (CH 2) n -CONH-R 5, -CR 6 R 7 -COO-R 8, or - _{(CH 2) n} Represents any of the groups represented by —OCOCH ₃ , R ₃ represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and R ₄ represents a hydroxy group or an alkoxy group having 1 to 2 carbon atoms. , An alkenyloxy group having 2 to 5 carbon atoms, a SO ₃ Na group, an OSO ₃ Na group, a phenyl group, a phenylalkyl group (the alkyl part has 1 to 3 carbon atoms), a naphthyl group, or a naphthylalkyl group (an alkyl part) of carbon atoms represents 1 to 3), _{R 5} , Alkyl group having 1 to 20 carbon atoms, a hydroxy alkyl group of the alkenyl group having 1 to 20 carbon atoms, or carbon atoms 1 to 12, _{R 6} represents a hydrogen atom, or a methyl group, _{R 7} Represents an alkyl group having 1 to 4 carbon atoms, R ₈ represents an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 1 to 12.
<2> The phenyl group and the naphthyl group of R ₁ and R ₂ , and the phenylalkyl group and the naphthylalkyl group of R ₄ have a substituent,
The substituent is at least one selected from an alkyl group, an alkenyl group, a hydroxyalkyl group, a hydroxy group, an alkoxy group, an alkenyloxy group, a cyano group, a cyanoalkyl group, a carboxy group, an alkoxycarbonyl group, and an amino group. The organic colorant according to <1>.
<3> The R ₁ and the R ₂ are each independently a group represented by a linear alkyl group having 1 to 20 carbon atoms or a linear alkenyl group having 1 to 20 carbon atoms. <1> An organic colorant according to the above.
<4> The organic colorant according to <1>, wherein R ₁ and R ₂ are — (CH ₂ ) ₂ —OH.
<5> The organic colorant according to any one of <1> to <4>, wherein R ₁ and R ₂ are sodium ethyl sulfonate.
<6> The organic colorant according to any one of <1> to <4>, wherein R ₁ and R ₂ are sodium ethyl ether sulfonate.
<7> The organic colorant according to any one of <1> to <4>, wherein R ₁ and R ₂ are 2-methylbutane.
<8> The organic colorant according to any one of <1> to <4>, wherein R ₁ and R ₂ are propionic acid.
<9> The organic colorant according to any one of <1> to <4>, wherein R ₁ and R ₂ are methyl propionate.
<10> The organic colorant according to any one of <1> to <4>, wherein R ₁ and R ₂ are ethyl propionate.
<11> A colored composition comprising the organic colorant according to any one of <1> to <10>.
<12> The colored composition according to <11>, further including an organic solvent.
<13> The colored composition according to any one of <11> to <12>, further including water.
<14> The colored composition according to any one of <11> to <13>, further including a resin.
<15> The colored composition according to any one of <11> to <14>, further including a surfactant.
<16> The colored composition according to any one of <11> to <15>, wherein the content of the organic colorant is 0.01% by mass to 50.0% by mass.
<17> An inkjet ink comprising the organic colorant according to any one of <1> to <10>.
<18> The inkjet ink according to <17>, further including an organic solvent.
<19> The inkjet ink according to any one of <17> to <18>, further including water.
<20> The inkjet ink according to any one of <17> to <19>, further including a resin.
<21> The inkjet ink according to any one of <17> to <20>, further including a surfactant.
<22> The inkjet ink according to any one of <17> to <21>, wherein the content of the organic colorant is 0.1% by mass to 30.0% by mass.

  The organic colorant according to any one of <1> to <10>, the colored composition according to any one of <11> to <16>, and any one of <17> to <22>. According to the inkjet ink, the above-described problems can be solved and the object of the present invention can be achieved.

Japanese Patent Laying-Open No. 2005-036079 JP 2011-52041 A JP, 2014-074127, A JP 2013-203785 A JP 2009-132641 A International Publication No. 2014/021405 Pamphlet

Claims (6)

An organic colorant represented by the following general formula (1).
General formula (1)
However, the general formula (1), _{R 1} and _{R 2} are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, a phenyl group, a naphthyl group, and, - ( _{CH 2) n -COO-R 3} , - (CH 2) n -R 4, - (CH 2) n -CONH-R 5, -CR 6 R 7 -COO-R 8, or - _{(CH 2) n} Represents any of the groups represented by —OCOCH ₃ , R ₃ represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and R ₄ represents a hydroxy group or an alkoxy group having 1 to 2 carbon atoms. , An alkenyloxy group having 2 to 5 carbon atoms, a SO ₃ Na group, an OSO ₃ Na group, a phenyl group, a phenylalkyl group (the alkyl part has 1 to 3 carbon atoms), a naphthyl group, or a naphthylalkyl group (an alkyl part) of carbon atoms represents 1 to 3), _{R 5} , Alkyl group having 1 to 20 carbon atoms, a hydroxy alkyl group of the alkenyl group having 1 to 20 carbon atoms, or carbon atoms 1 to 12, _{R 6} represents a hydrogen atom, or a methyl group, _{R 7} Represents an alkyl group having 1 to 4 carbon atoms, R ₈ represents an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 1 to 12. The phenyl group and the naphthyl group of R ₁ and R ₂ , and the phenylalkyl group and the naphthylalkyl group of R ₄ have a substituent,
The substituent is at least one selected from an alkyl group, an alkenyl group, a hydroxyalkyl group, a hydroxy group, an alkoxy group, an alkenyloxy group, a cyano group, a cyanoalkyl group, a carboxy group, an alkoxycarbonyl group, and an amino group. The organic colorant according to claim 1. The R ₁ and the R ₂ are each independently any of a group represented by a linear alkyl group having 1 to 20 carbon atoms and a linear alkenyl group having 1 to 20 carbon atoms. The organic colorant described. The organic colorant according to claim 1, wherein R ₁ and R ₂ are — (CH ₂ ) ₂ —OH.   A coloring composition comprising the organic coloring agent according to claim 1.   An ink-jet ink comprising the organic colorant according to claim 1.