KR20120065389A - Dye derivative, colorant, and coloring method - Google Patents

Abstract

The pigment derivative of the present invention is a pigment in which a water-insoluble pigment (A) molecule and a compound (C) residue are linked through an alkylene group formed by the reaction of the dye (A) and an aldehyde compound (B). By selecting the hydrocarbon compound (C-1) having a methine group (-CH =) which has a bicyclic hydrogen group which is the said compound (C), or the amino compound (C-2) which has a reactive amino group suitably, The color tone of the existing pigments also cause a deeper color effect. Moreover, the pigment derivative which is effective before the crystal | crystallization of a pigment and as an additive for suppressing crystal growth, and also using the said pigment derivative, in addition to the above, the performances, such as the fall of the viscosity of a pigment dispersion liquid, dispersion stability, long-term storage stability, etc. improve. One colorant is realized, whereby a useful coloring method and colored article are provided.

Description

Dye Derivatives, Colorants and Coloring Methods {DYE DERIVATIVE, COLORANT, AND COLORING METHOD}

This invention relates to a pigment derivative, a coloring agent, and a coloring method. More specifically, the present invention relates to a pigment derivative comprising a compound having a methine group or an amino group via an alkylene group in the molecular structure of a water-insoluble dye, a colorant containing the same, a method for coloring articles using the same, and colored articles.

Conventionally, as a pigment | dye used for coloring of an article, the pigment soluble in water or a solvent, and the pigment which is insoluble in these media, and disperse | distributed to fine particle form, are used normally. However, although dye has many pigment | dye as a molecular structure, and color is excellent in transparency and clarity, there existed a problem in fastness, such as light resistance and heat resistance. In addition, pigments have a wider or less clear color tone than dyes, and many of them have a crystalline form. Among them, pigments are unstable in organic solvents and heat, coarse before crystallization and particles change color. There was. Liquid colorants of pigments sometimes have drawbacks such as unstable dispersion in liquid media such as solvents and water, tend to settle or aggregate, and problems with preservation such as agglomeration in the long term even when improved with a dispersing aid. .

Regarding the color tone of the dye, for example, as a color print representation of information recording of a laser print or a color copying machine, an expression in a wider color gamut is desired, and a colorant capable of coping with this is required. . In particular, a more greenish blue pigment is desired than β-type copper phthalocyanine (C.I. pigment blue 15: 3), which is a blue pigment used for cyan color toner. Moreover, as a soluble blue oil-soluble dye, there exists a dye (for example, CI solvent blue 25) which introduce | transduced the alkyl group as a sulfoamide group as a linking group in the molecular structure of copper phthalocyanine, and in patent document 1, it is functional, such as polarity control and redispersibility. Although it is effective in the aspect of the present invention, when it is increased as a flavor component of the color toner, there is a problem in the light resistance of the printed matter.

In addition, red-blue blue ε-type copper phthalocyanine pigment (CI pigment blue 15: 6) is used as a blue pigment used for formation of a blue pixel of an image display material of a color filter, but it is slightly different from a solvent and heat. Unstable Therefore, although monosulfonated copper phthalocyanine is often used as an additive for suppressing the crystal transition of a pigment and suppressing crystal growth, there is a tendency for the color tone to melt | dissolve and to reduce chroma, and it is red blue It is not preferable to the blue pixel in terms of color tone. In other words, there is a demand for a pigment derivative capable of achieving a better color tone without inhibiting the color tone of the original pigment.

Japanese Patent Publication No. 3685863

Conventionally used direct dyes and acid dyes are synthesized for the purpose of dyeing woven fabrics, such as cotton or nylon, and does not sufficiently satisfy the fastness required for the dye including the current information field, light resistance The pigment | dye excellent in fastness, etc. is desired. In addition, in terms of color, in the field of information recording such as digital printing, dyes capable of achieving a wide color gamut, which cannot be obtained with conventional dyes, in particular, sky blue dyes are expected. In addition, the development of pigment derivatives effective before the crystal of the pigment and as an additive for suppressing the crystal growth, the improvement of the dispersibility of the pigment of the organic solvent-based dispersion color, the decrease in the viscosity of the dispersion, dispersion stability, storage stability, etc. There is a need for development of improved dispersing aids.

Therefore, the objective of this invention is to develop as a pigment derivative which used the existing pigment skeleton as a matrix, in order to perform the improvement of the fastness of these pigment | dyes, and the change of a color tone economically and efficiently.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching so that the objective of this invention may be achieved, the present inventors discovered the following and came to this invention in synthesizing a pigment derivative. That is, by reacting a compound (B) for forming an alkylene group with a water-insoluble dye (A), and a compound (C) having a reactive methine group or an amino group, dye molecules such as pigments and alkylene groups are carbon- It was found that a new dye derivative bonded with a carbon bond and linked with the residue of the compound (C) to the other end of this alkylene group can be solved by using these.

That is, this invention is a derivative of the water-insoluble pigment | dye used as a coloring agent, The water-insoluble pigment | dye (A) and the aldehyde compound (B) which can form an alkylene group by reacting with the said water-insoluble pigment | dye (A), and Compound (C) selected from the group consisting of a hydrocarbon compound having a methine group (-CH =) having a cyclic hydrogen group, a derivative thereof (C-1), an amino compound having a reactive amino group, and a derivative thereof (C-2) The water-insoluble dye (A) molecule and the compound (C) moiety formed by reacting a compound) are derivatives of a dye formed by being linked through the alkylene group.

As a preferable aspect of the pigment derivative of this invention, the following are mentioned. The aldehyde compound (B) is at least one selected from the group consisting of paraformaldehyde, trioxane, formaldehyde, formalin, glyoxal and alkyl aldehyde having 1 to 10 carbon atoms. The said compound (C) has a bicyclic hydrogen group chosen from the group which consists of a C6-C20 phenol compound and a C8-C20 N, N-di-substituted aniline compound. Hydrocarbon compounds having a methine group (-CH =) and derivatives (C-1). The said compound (C) is a C1-C10 amino acid compound, a C1-C20 amino compound, a C1-C10 amino triazine compound, a C1-C20 carboamide compound, and a C1-C20 carboy The amino compound which has a reactive amino group chosen from the group which consists of a mid compound (except a phthalimide) and a sulfamic acid compound of C10-10, and these derivatives (C-2).

The number of compound (C) residues couple | bonded with a water-insoluble pigment | dye (A) molecule | numerator through an alkylene group is 1-6. The water-insoluble pigment (A) is at least one selected from the group consisting of organic pigments, bat dyes and disperse dyes. The water-insoluble pigment (A) is a phthalocyanine series, anthraquinone series, perylene series, perinone series, dioxazine series, quinacridone series, diketopyrrolopyrrole series, indigo thioindigo series, quinophthalone series, isoindolinone series At least one member selected from the group consisting of metal complexes, insoluble azo and high molecular weight azo pigments.

Moreover, as another embodiment, this invention is a liquid medium which consists of any one of said pigment derivatives, an organic solvent type | system | group, an aqueous system, or a water-hydrophilic organic solvent mixed solvent system as a dilution medium, or a polymeric oligomer, or The coloring agent which comprises at least any one of the polymeric liquid medium which consists of a polymerizable monomer, or the resin medium which consists of synthetic resins is provided. As a preferable thing of such a coloring agent, the following form is mentioned. Furthermore, what consists of containing a polymeric dispersing agent or a low molecular dispersing adjuvant as a dispersing adjuvant. Any one of a dye, printing, printing, printing ink, stationery, painting tools, resin coloring, electrophotographic developer, electrostatic printing developer or color filter pixel forming ink.

Moreover, this invention is another embodiment when coloring by the coloring method chosen from dyeing, printing, painting, printing, writing, drawing, resin coloring, electrophotographic printing, electrostatic printing, or the color filter pixel formation method. It provides a coloring method of the article, characterized by using any one of the above coloring agent.

Moreover, as another embodiment, when this invention colors on the color filter board by the coloring method of pixel formation according to any one of a photoresist method, the inkjet printing method, the printing method, the transfer method, or the pasting method, Provided is a method of coloring an article characterized by the use of one colorant.

In more detail, this invention is a pigment solution or dispersion liquid (henceforth generically called a "base color") used for a coloring agent, any one of said pigment derivatives, if necessary, a pigment, an oil-soluble dye, or a water-soluble dye further A dilution medium, comprising: a liquid medium comprising an organic solvent system, an aqueous system, or a water-hydrophilic organic solvent mixed solvent system; Polymeric liquid medium which consists of a polymerizable oligomer and a polymerizable monomer; The base color characterized by using the resin medium which consists of a plasticizer, an oligomer, and a synthetic resin, and if necessary, uses a polymeric type dispersing agent and a low molecular weight dispersing aid as a dispersing aid.

In the present invention, the colorant contains any one of the pigment derivatives as the colorant, and optionally, a pigment, an oil-soluble dye or a water-soluble dye, and as a dilution medium, an organic solvent-based, water-based or water-hydrophilic A liquid medium comprising an organic solvent mixed solvent system; Polymeric liquid medium which consists of a polymerizable oligomer and a polymerizable monomer; Using a resin medium consisting of a plasticizer, an oligomer, a synthetic resin, and / or using the base color comprising a pigment derivative, and / or with a thermoplastic polymer, a reactive polymer, a reactive oligomer, a polymerizable monomer and a crosslinking agent as a coating film forming material. It contains the 1 type or more material chosen from the group which consists of, and further provides the coloring agent characterized by containing a hardening catalyst, a polymerization catalyst, etc. as needed.

This invention uses the coloring agent of any one of said invention, and provides the coloring article formed by following a well-known coloring method.

According to the present invention described above, since the carbon atom of the alkylene group is connected to the carbon atom of the water-insoluble dye, a carbon-carbon bond is formed, and in a more preferred form, the hydrophilic group is used. As a dye, pigment derivatives having excellent light resistance as compared with dyes are provided. Moreover, since the pigment derivative of this invention produces a deep color effect by the introduction water of a substituent, a characteristic appears also in color tone, and especially in phthalocyanine type pigment | dye, a lot of introduction water is carried out. It becomes possible to provide sky blue color excellent in the fastness used for the dyeing field, the painting field, the printing / recording field, the resin coloring field, etc., and is useful for various uses.

Moreover, according to this invention, the pigment which is effective as an additive before crystallization or suppression of crystal growth by the property of the various substituents introduce | transduced into the compound (C) residue connected to the water-insoluble pigment | dye (A) molecule. It is possible to provide derivatives. For this reason, according to this invention, the coloring agent containing functional additives, such as dispersing adjuvant which improves the dispersibility of the pigment of the organic-solvent pigment dispersion color, the viscosity of a dispersion liquid, dispersion stability, long-term storage stability, etc. improves, etc. You can get it. Moreover, since these can be obtained from the derivative | guide_body which used the existing pigment skeleton, it can implement economically and efficiently, and is very useful also practically.

Next, the present invention will be described in more detail with reference to preferred embodiments.

The dye derivative of the present invention is made by reacting a water-insoluble dye (A), an aldehyde compound (B), a compound and a derivative thereof (C) which react with the dye (A) to form an alkylene group, A) A molecule | numerator and the said compound (C) residue are a derivative | guide_body of the pigment | dye formed by connecting through the said alkylene group, It is characterized by the above-mentioned. That is, the derivative of the pigment | dye which is a structure which connected the compound (C) residue which can provide various characteristics to the molecular structure of a water-insoluble pigment | dye (A) by the alkylene group (carbon-carbon bond) is provided. And the said compound (C) consists of a hydrocarbon compound which has a methine group (-CH =) which has a disubstituted hydrogen group, its derivative (C-1), an amino compound which has a reactive amino group, and its derivative (C-2) It is characterized in that it is selected from the group. The structure of the said pigment derivative and the compound (C) connected to a dye molecule are the said structures, According to this invention, as mentioned earlier, it is a derivative which used the existing pigment skeleton as a mother, and changes its basic color tone. In particular, it is possible to realize a pigment derivative having excellent deep color effect and characteristics. Hereinafter, the synthesis | combining method of the pigment derivative of this invention and each component to be used are demonstrated.

[Synthesis method]

The dye derivative of the present invention has a structure in which the molecular structure of the water-insoluble dye (A) and the compound (C) residue are bonded via an alkylene group which is a residue of the aldehyde compound (B). As a synthesis | combining method of the said pigment derivative, the following method is mentioned, for example.

(1) A method of dissolving a water-insoluble dye (A), an aldehyde compound (B) which is an alkylene-forming reactive compound, and a compound (C) having an active hydrogen group capable of condensation reaction in a reaction medium, reacting and synthesizing simultaneously.

(2) First, a water-insoluble dye (A) is dissolved in a reaction medium, the aldehyde compound (B) is added to react, and an alkylene group is formed on a dye. Subsequently, the compound (C) which has an active hydrogen group which can condensate-react with it is made to react.

(3) The said aldehyde compound (B) is made to react with the said compound (C), the reactant is isolated in some cases, and an alkylene group is added to the compound (C). Subsequently, a water-insoluble pigment | dye (A) is added, or the solution is mixed, reacted, and synthesize | combined.

(4) In each synthesis method of said (1), (2), and (3), instead of a water-insoluble pigment | dye (A), the pigment | dye intermediate (A ') is used as a precursor, and reaction in each method is carried out. Subsequently, the dye intermediate (A ') may be used as the dye (A).

[Water-insoluble pigment (A)]

The water-insoluble pigment | dye (A) which is a structural material of the pigment derivative of this invention is demonstrated. As said pigment | dye (A), as a pigment | dye molecular structure which forms the pigment | dye main body part in the molecular structure or the produced | generated pigment derivative, what has the water-insoluble pigment | dye molecular structure which is not bonded to a hydrophilic group is used. As a specific example, the molecular structure of the water-insoluble pigment | dye used as well-known organic pigment, bat dye, dispersible dye, etc. is contained. Here, the bat dye, the naphthol dye, and the like are solubilized in water as a precursor at the time of dyeing, and are used. However, the bat dye, naphthol dye, etc. are water-insoluble dyes in the developed state and are included in the dye (A) used in the present invention.

As a thing which has a water-insoluble pigment | dye molecular structure which can be used as a pigment | dye (A) in this invention, specifically, it is a phthalocyanine series, anthraquinone series, a perylene series, a perinone series, a dioxazine system, a quinacridone system, a diketopyrrolopyrrole system And indigo-thioindigo-based, quinophthalone-based, isoindolinone-based, metal complexes, insoluble azo-based and polymeric azo-based pigments.

Generally, the light fastness of a pigment | dye is represented by the division of 8th grade | class 1, or E grade | grade, VG grade, G grade, F grade, P grade. In the present invention, as the water-insoluble dye (A) used as the dye matrix, depending on the use, it is generally 6 or G grade or higher, preferably 7 or VG grade or higher, more preferably 8 or E grade. It is preferable that the above pigment | dye is selected.

Here, in the case of the light resistance of the pigment, the one having high fastness in the molecular structure of the pigment is excellent in light resistance, but in addition, it exhibits a pigment that is solid by the crystal structure formation of the pigment molecule or the fastness by the size of the pigment particle. There is something to indicate. However, as a pigment | dye (A) used by this invention, when the pigment which can be considered that fastness is high in the molecular structure of a pigment comprises the pigment derivative of this invention as a final form, it can be considered that it is excellent in light resistance. For this reason, as a molecular structure of the preferable water-insoluble pigment | dye (A) used in this invention, it has a substitution position which can introduce | transduce the coupling group formed by the aldehyde compound (B) mentioned later among the above, What is necessary is just to select mainly the bat dye which has the chemical structure of the organic pigment classified as a high pigment which has light resistance, and high pigment similarity as a basic skeleton.

As a water-insoluble pigment | dye (A) used by this invention, the following are mentioned, for example. Here, "C.I. Pigment is abbreviated as "P", and blue is abbreviated as "B". Thus, C.I. Pigment Blue is abbreviated as "PB". In addition, green is "G", yellow is "Y", orange is "O", violet is "V", and abbreviate | omits similarly about each color. For example, as a phthalocyanine system, PB15, aluminum phthalocyanine blue, PB16, PG7, PG36, poly (13-16) bromine copper phthalocyanine green, PG58 etc .; As an anthraquinone type, PY123, PY24, PY108, bat yellow 48 (Hereinafter, bat yellow is abbreviated as "VY"), PO40, PR177, PR168, PB60, etc .; As a perylene system, PR189, PR190, PR149, etc .; As perinone series, PO43, PR194, etc .; As a dioxazine system, PV23 etc .; As quinacridone system, PV19, PR122, PR209, etc .; As a diketopyrrolopyrrole system, PR254, PR255, etc .; As indigo thio indigo system, it is PR87, PV36; As a quinophthalone system, PY138 etc .; As an isoindolinone system, PY139, PY109, etc .; PY153 etc. are mentioned as a metal complex system. Furthermore, the pigment compound which has a chemical structure similar to the said higher grade pigment of each said system as a basic skeleton can also be used.

[Aldehyde compound (B)]

The aldehyde compound (B) which is a structural material of the pigment derivative of this invention is demonstrated. The said aldehyde compound (B) can react with the said pigment (A), and can form an alkylene group. Specifically, in the addition reaction in the first step, hydroxyl groups such as a methirol group, an alkoxymethyl group, and a halogenomethyl group or a reactive inducer thereof are formed, followed by dehydration, dealcoholization and dehalogenation in the second step. It is a compound which connects the water-insoluble pigment | dye (A) mentioned above and the compound (C) residue mentioned later through alkylene group by condensation reaction, such as hydrogen. Examples of the aldehyde compound (B) include formaldehyde, trioxane, paraformaldehyde, formalin, glyoxal or alkyl aldehydes having 1 to 10 carbon atoms. Among these, especially paraformaldehyde is preferable.

[Compound (C)]

The compound (C) which is a structural material of the pigment derivative of this invention is demonstrated. In the present invention, the compound (C) is selected from the group consisting of the following compounds and derivatives.

(1) Hydrocarbon compounds having a methine group (-CH =) having a disubstituted hydrogen group and derivatives thereof (C-1)

(2) Amino compounds having a reactive amino group and derivatives thereof (C-2)

Since the methine group of the hydrocarbon compound which has a methine group in said (C-1) has a disubstituted hydrogen group, the aldehyde group which the aldehyde compound (B) demonstrated previously, the metirol group formed from the said aldehyde compound (B), etc. The dehydration reaction can be carried out with a hydroxyl group of to form a bond. As a hydrocarbon compound which has the said methine group, the hydrocarbon group etc. which have a heterocyclic hydrogen atom of an aromatic skeleton are mentioned. Specifically, a phenol compound (carbon number: 6-20) or an N, N-di-substituted aniline compound (carbon number: 8-20), etc. are mentioned, It is used preferably.

As a preferable thing of the amino compound which has a reactive amino group in said (C-2), an amino acid compound (carbon number: 1-10), an amino compound (carbon number: 1-20), an amino triazine compound (carbon number: 0-10) ), A carboamide compound (carbon number: 1-20), a carbodiimide compound (excluding phthalimide) having 1 to 20 carbon atoms, or a sulfamic acid compound (carbon number: 0 to 10). Also with these compounds, a bond can be formed by dehydration reaction similarly to compound (C-1) mentioned above.

(Substituent)

It is preferable that well-known substituent is introduce | transduced into the compound (C) selected from any one of said compound (C-1) or (C-2), and these derivatives. The said substituent becomes a substituent of the compound (C) residue, and it becomes possible to bring the performance of various properties, a function, a physical property, etc. to the pigment derivative of this invention. A substituent is selected from the group of the following hydrophilic groups, the group of lipophilic groups, and the group of reactive groups, for example.

<Group of hydrophilic group>

Any one anionic group selected from a carboxyl group, a sulfonic acid group, a phosphate ester group and a sulfate ester group;

Alkali metal salts, ammonium salts, (mono, di, tri) -alkylamine salts, (mono, di, tri) -alkanolamine salts, (mono, di, tri)-(polyoxyalkylene) of these anionic groups Salts of any one anionic group selected from oxyalkylamine salts;

Any one cationic group selected from tertiary amino groups and quaternary ammonium groups;

Salts of any one cationic group selected from halides, sulfonates, alkyl carboxylates of these cationic groups;

Any nonionic group selected from polyalcohol groups and polyethylene glycol groups;

<Group of lipophilic group>

Any group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, and a halogen group

<Group of reactive groups>

Any group selected from the group which consists of a glycidyl group, a metyrol group, and the alkoxy (C1-C4) methyl group.

(Hydrocarbon Compound (C-1))

Next, about the hydrocarbon compound (C-1) which has a methine group (-CH =) which has said bicyclic hydrogen group, it shows concretely below. As a phenolic compound suitable as a hydrocarbon compound which has a bicyclic hydrogen atom of an aromatic skeleton, the reactive phenolic compound which has an active hydrogen group in the o-position or p-position of a hydroxyl group, or the position equivalent to them is preferable. Specifically, the C6-C20 aromatic hydrocarbon and heterocyclic compound which have a phenolic hydroxyl group are mentioned. For example, phenolic compounds, such as well-known phenol (hydroxybenzene), naphthol, hydroxycarbazole, which have one hydroxyl group (four etc.) in a molecule | numerator, are suitable.

Especially preferable phenolic compounds in the present invention, when reacted with the dye (A) and the aldehyde compound (B), the substituents are active at the o- or p-position of the phenolic hydroxyl group or at positions equivalent to them. The thing introduce | transduced to leave a hydrogen group is mentioned. For example, the following are mentioned. As phenols which have an alkyl group as a substituent, for example, 2-t-butyl-4-methylphenol, 2-t-butyl-6-methylphenol, 2,3,6-trimethylphenol as a non-polar phenolic lipophilic compound , 2-methyl-5-isopropylphenol, 3-methyl-4-isopropylphenol, 5-methyl-2-isopropylphenol and the like; As ionic phenols, o-cresol-4-sulfonic acid, 3-methyl salicylic acid, 4-methyl salicylic acid, 5-methyl salicylic acid, etc. are mentioned. In particular, in order for the reaction to be controlled and to produce a single pigment derivative of the structure, a compound substituted with one active hydrogen group on the o- or p-position is preferable.

In addition, said phenolic hydroxyl group can be etherified by a halogenated alkyl and an epoxy compound subsequently. As an ether group formed at this time, an alkyl ether group, an alkyl (hydroxy) propyl ether group, an alkoxy (hydroxy) propyl ether group, a phenyl ether group, a phenoxy (hydroxy) propyl ether group, etc. are mentioned, for example. Can be.

N, N-di-substituted aniline compounds are mentioned as a hydrocarbon compound which has a bisubstituted hydrogen atom of a suitable aromatic skeleton other than the above-mentioned phenol compound. For example, it is preferable to use N, N-dialkylaniline, N, N-dialkanolaniline, and the like.

(Amino compound (C-2) having a reactive amino group)

About the amino compound (C-2) which has a reactive amino group used by this invention, the specific example which can be used suitably is shown below. As a C1-C10 amino acid compound, glutamic acid, aspartic acid, taurine, N-methyltaurine, etc. are mentioned, for example. Examples of the amino compound having 1 to 20 carbon atoms include N, N-dimethylethylenediamine, N, N-diethyl-1,3-diaminopropane, N, N-diethyl1,4-diaminopentane, Diethanolamine, diisopropanolamine, N, N, N'-trimethylethylenediamine, N, N, N'-triethylethylenediamine, etc. are mentioned. Moreover, as an aminotriazine compound of 0-10 carbon atoms, for example, 2-amino-4,6-dihydroxy-s-triazine, 2-amino-4,6-dipropylamino-s-triazine , 2-amino-4,6-carboxymethylamino-s-triazine, 2-amino-4,6-dicarboxymethylamino-s-triazine, and the like.

Moreover, as a C1-C20 carboamide compound, it is used, for example in acetamide, propioamide, butylamide, octaneamide, stearamide, trimellitic acid monoamide, sulfobacmic acid monoamide, and sulfuric acid. Nitriles to amidate are mentioned, for example, acetonitrile, octenitrile, stearonitrile, benzonitrile and the like. Specific examples of carbodiimide compounds (except phthalimide) suitable for the present invention include trimellitic acid imide, sulfobacmic acid imide, o-sulfobenzimide and the like. Moreover, as a sulfamic acid compound, sulfamic acid etc. are mentioned, for example.

[Reaction medium]

Although the pigment derivative of this invention is made by making the water-insoluble pigment | dye (A), aldehyde compound (B), and compound (C) demonstrated above react, the reaction medium used at that time is demonstrated. As a reaction medium suitable for this invention, it is a medium in which a water-insoluble pigment | dye (A) melt | dissolves. Organic pigments and bat dyes, which are pigments (A) suitable for the present invention, which are mentioned above, are not dissolved in a conventional organic solvent. Therefore, 95% to 100% of high concentration sulfuric acid, fuming sulfuric acid, polyphosphoric acid, etc. Used. The reaction product obtained from the above-mentioned components (A), (B) and (C) is injected into a large amount of water, ice water or ice on a precipitate according to a usual method in a sulfuric acid solution or the like to precipitate, and filtered and washed with water. (水洗) good. At this time, it wash | cleans with weakly acidic hydrochloric acid aqueous solution by the property of a pigment derivative.

In the dye derivative of the present invention, the properties of the compound (C) residues bonded to the molecular structure of the water-insoluble dye (A) via an alkylene group and the number of residues to be introduced change properties such as color tone and affinity. Therefore, it is preferable to determine the setting and the number of introduction of the compound (C) residue through an alkylene group (for example, methylene group) so that the target pigment derivative may be synthesized. The number of bonds (the number) of the residues of the compound (C) is not particularly determined, but is almost one to six. When using as a water-soluble dye, it is necessary to be able to generate water solubility, and it is preferable to introduce at least two, preferably three or more.

When using the pigment derivative of this invention as a water-soluble dye, it is preferable that the substituent of the compound (C) residue which a pigment derivative has is a salt form. For example, when a substituent is an anionic group which consists of a carboxyl group, a sulfonic acid group, a phosphate ester group, and a sulfate ester group, Alkali metal salts, such as the sodium salt and potassium salt of these anionic groups; Ammonium salts; (Mono, di, tri) alkylamine salts such as (mono, di, tri) ethylamine salt and (mono, di, tri) propylamine salt; (Mono, di, tri) alkanolamine salts such as (mono, di, tri) ethanolamine salts and (mono, di, tri) propanolamine salts; It is preferable to use in the form of (mono, di, tri)-(polyoxyalkylene) oxyalkylamine salts, such as a (mono, di, tri) (polyethylene oxyethyl) amine salt. Moreover, when a substituent is a cationic group which consists of a tertiary amino group and a quaternary ammonium group, For example, Halide salts, such as hydrochloride of these cationic groups; Alkyl carboxylates such as acetic acid and propionate; It is preferable that they are hydrophilic groups, such as hydroxyalkyl carboxylates, such as a glycolic acid salt and a lactate.

As mentioned above, the pigment derivative of this invention is comprised by the alkylene group which the compound (C) residue formed with the aldehyde compound (B) and the compound (C) couple | bonded with the molecular structure of the original pigment | dye as a substituent. For this reason, in the color tone, the effect of deepening the original color tone (absorption wavelength shifts to the long wavelength side) of the water-insoluble pigment (A) is recognized in the color tone. For example, in the molecular structure of copper phthalocyanine, the number of the above substituents (the alkylene group to which the compound (C) residue is bonded) shifts particularly to two or more to blue blue, and the characteristics desired in the field of image recording such as inkjet printing You can get cyan and sky blue. In addition, the number of substituents in this invention means the number of the compound (C) residues couple | bonded through an alkylene group.

[coloring agent]

When using the pigment derivative of this invention demonstrated above as a coloring agent, it is set as the following form which diluted the pigment derivative of this invention with the various dilution media suitable for various uses, and can be used more easily in various fields. Done. That is, the colorant of the present invention is a pigment derivative of the present invention and a liquid medium composed of any one of an organic solvent system, an aqueous system, or a water-hydrophilic organic solvent mixed solvent system, or a polymerizable oligomer or polymerizable monomer. It is characterized by containing at least any one of the polymeric liquid medium which consists of, or the resin medium which consists of synthetic resins. For example, the base color (color solution or dispersion) which comprises the coloring agent of this invention contains the pigment derivative of this invention, if necessary, another pigment, oil-soluble dye, or water-soluble dye, and the said liquid medium as a medium , A polymerizable liquid medium and a resin medium may be used, and a polymerizable dispersant or a low molecular dispersant may be further used as a dispersing aid if necessary.

Moreover, when manufacturing a pigment or when using a pigment for uses, such as an organic-solvent dispersion colorant and a coloring agent for plastics, the pigment derivative of this invention is a pigment transition suppression, crystal growth suppression, the improvement of dispersibility, heat resistance It can also add and use for the purpose of improvement. In particular, the pigment derivative of this invention is added to a pigment crude and a granule pigment, and what was considered a pigment composition is effective for the post-processing (pigmentation process) of a pigment. Moreover, the pigment derivative of this invention has the effect excellent in the improvement of the dispersion performance of the liquid dispersion color of a pigment, the improvement of storage stability, etc. When used as a crystal growth inhibitor or dispersion stabilizer of such a pigment, it is preferable that it is insoluble in the organic solvent medium. For this reason, a lipophilic group is introduced as a substituent which the above-mentioned compound (C) residue has, and about 1 or less of the said lipophilic groups, Preferably, it is 0.5 to 0.1 in average number with respect to the whole pigment containing a pigment derivative. The dog lipophilic group introduced is preferably used. On the other hand, in the case of using the color filter pixel forming ink or the solvent-based coloring agent, in addition to the pixel forming pigment, the film forming material and the dilution medium, the dye derivative of the present invention having the above ionic group and the counter ionic group It is preferable to set it as the structure which uses a lipophilic polymer as a dispersing agent of a pigment.

In the pigment derivative-containing composition using the pigment derivative of the present invention as exemplified above, the pigment is contained at a high concentration, and the pigment derivative or other pigments used in combination are dissolved in advance or undispersed to produce a colorant. Can be facilitated. The pigment derivative containing composition using the pigment derivative of this invention contains a pigment derivative and other pigment | dye as needed in accordance with the target coloring agent prescription, and mixes an organic solvent type, water system, or water-hydrophilic organic solvent as a medium. Liquid medium comprising a solvent system; Polymeric liquid medium which consists of a polymerizable oligomer and a polymerizable monomer; The resin medium which consists of a plasticizer, an oligomer, and a synthetic resin is used, and if necessary, it can be prepared by containing a polymeric dispersing agent and a low molecular-dispersion adjuvant as a dispersing aid.

The coloring agent containing the pigment derivative of this invention is a coloring agent used for dyeing agent, printing agent, paint, printing ink, stationery, a paint tool, resin coloring agent, and various information technology related colorants, for example, a color filter manufacture. It can be applied as a liquid colorant such as a colorant for a solvent, a liquid developer for an electrophotographic printer, or a dry developer for an electrophotographic printer. And it is used for the use of well-known coloring methods, such as dyeing, printing, painting, printing, writing, drawing, resin coloring, electrophotographic printing, electrostatic printing, or a color filter pixel formation method, respectively.

The coloring agent of this invention contains the pigment derivative of this invention, uses other pigments, such as a pigment, an oil-soluble dye, and a water-soluble dye, as needed and uses a thermoplastic polymer as a dilution medium or a coating-film forming material according to a compounding prescription. It is prepared by adding one or more materials selected from reactive polymers, reactive oligomers, polymerizable monomers, crosslinking agents and the like. The coloring agent of this invention further adds a curing catalyst, a polymerization catalyst, etc. as needed, or uses the said pigment derivative containing composition, and adds the said material further needed, and melt | dissolves, mixes, disperses, etc. according to a use. It can be prepared by adding necessary processing.

As resin added as a coating film forming material used above, the well-known resin component according to a use is used, respectively. For example, well-known coating film forming materials, such as a synthetic rubber resin, an acrylic resin, a vinyl resin, a chlorinated rubber resin, an alkyd resin, a urethane resin, an epoxy resin, a silicone resin, and a fluororesin, an ultraviolet curable resin system, an electron beam curable resin system, etc. Energy ray curable coating film forming materials; and the like. The coating film forming material may or may not have a reactive group, and examples of the reactive group include a metyrol group, an alkyl methrol group, an isocyanate group, a masked isocyanate group, an epoxy group, and the like. Moreover, an oligomer and a monomer are used depending on a use, and a crosslinking agent, for example, methylol melamine type, an isocyanate type, and an epoxy type crosslinking agent is also used together. In the said coloring agent, although the compounding mass ratio of a pigment | dye (P) and a coating film forming material (V) is arbitrarily determined by a use, required performance, etc., it is P: V = 80: 20 ~ 1: 99, 70:30 10:90 is preferable.

The material or article to be colored by the coloring agent of the present invention is determined by the purpose and use of the coloring itself, and a conventionally known material or article is the object. For example, it is a coloring composition for image recording, such as a digital laser printer and the full color toner for full color copiers, As a coloring object of the said composition, paper, synthetic paper, a nonwoven fabric, a plastic film, etc. are mentioned, for example. Can be.

When the coloring agent of this invention is used for color filter pixel formation, each appropriate coloring agent is used for the formation method, and a pixel is made to adhere on a color filter board according to a well-known photoresist method, the printing method, the transfer method, and the pasting method. Is formed. In the coloring composition for image display, such as a color filter for liquid crystal displays, or an advertisement display, as a coloring object of the said composition, a glass substrate, a plastic plate board, etc. are mentioned, for example.

Example

Next, the present invention will be described in more detail with reference to specific preparation examples and examples. In addition, the part and% of a door are a mass reference | standard unless there is particular limitation.

[Production example 1: synthesis of ε-type copper phthalocyanine pigment for color filters]

(1-1) (Synthesis of Anionic Pigments Containing Sulphonic Acid in Pigments)

120 g of sulfuric anhydride was added to a reactor equipped with a heat transfer heater, a stirrer, a reagent inlet, and a countercurrent cooler as a heating device, and 5.76 g (0.01 mol) of copper phthalocyanine blue pigment (MW (molecular weight): 576) was added thereto while stirring. I was. Then, it heated at 50 degreeC, added 0.60 g (0.02 mol) of paraformaldehyde (MW: 30 (monomer)), stirred for 1 hour and 30 minutes, and made it react, and synthesized the metirol body.

Subsequently, the temperature was raised to 80 ° C., and 3.76 g (0.02 mol) of o-cresol-4-sulfonic acid (MW: 188.2, purity 86%) was added as a pure portion, and the mixture was heated at 80 ° C. to 85 ° C. for 6 hours. The reaction was stirred. After the reaction was completed, the mixture was cooled to room temperature and precipitated in approximately 1,000 ml of ice water. The precipitated reaction product was filtered, washed with water and dried. Thereafter, the mixture was washed with acetone to remove the soluble component, thereby obtaining o-cresol-4-sulfonic acid (-6-) methylated copper phthalocyanine. The number of substitutions is almost 0.5. Hereinafter, this is called "blue pigment derivative-1." Table 1 summarizes the composition.

(1-2) (Preparation of ε-type copper phthalocyanine pigment)

100 parts of α-type copper phthalocyanine, the blue pigment derivative-1 obtained above, 1 part, phthalimide methyl copper phthalocyanine 3 parts, epsilon copper phthalocyanine blue pigment (CI pigment blue 15: 6) 10 parts, salt 300 parts And 110 parts of diethylene glycol were ground in a kneader at a temperature of 100 to 110 ° C. for 20 hours.

The obtained contents were heated in an aqueous solution of 2% diluted sulfuric acid (diluted sulfuric acid) to dissolve soluble salts such as salts, and the treated pigment was filtered and washed with water to obtain a press cake of a pigment composition containing copper phthalocyanine as a main component. The copper phthalocyanine obtained above was confirmed to be ε type by X-ray diffraction.

(1-3) (Preparation of Blue Pigment Composition)

Furthermore, the press cake of the pigment composition containing said epsilon copper phthalocyanine and the press cake of the blue pigment derivative-1 obtained by said (1-1) are mix | blended so that it may be 91: 9 by solid content, water is added, and a homomixer The solution was dissolved into a 5% aqueous suspension. After stirring for 1 hour, the product was filtered, washed with water, dried and pulverized to obtain a red rice blue pigment composition containing? -Type copper phthalocyanine as a main component. Hereinafter, this is called "blue pigment composition-1." Table 2 summarizes the composition.

[Comparative Production Example 1: Preparation of Comparative Blue Pigment Composition]

Except for using the known monosulfonated copper phthalocyanine, instead of the blue pigment derivative-1 used in Production Example 1-3, the comparative example containing the epsilon type copper phthalocyanine pigment as a main component similarly to Production Example 1-3. A blue pigment composition was prepared. Hereinafter, this is called "comparative blue pigment composition-1." Table 2 summarized the composition.

[Production example 2: production of epsilon copper phthalocyanine pigment for color filters]

(2-1) (Synthesis of Anionic Pigments Containing Sulphonic Acid in Pigments)

N-methyl taurine (MW: 139) 2.09 g (0.015 mol) was used in place of the o-cresol-4-sulfonic acid used in Production Example 1-1, and was subjected to the same procedure as in Production Example 1-1. Methyl-N- (sulfoethyl) aminomethylated copper phthalocyanine was obtained. The number of substitutions is almost 0.4. Hereinafter, this is called "blue pigment derivative-2." Table 1 summarizes the composition.

(2-2) (Preparation of Blue Pigment Composition)

In Preparation Example 1-3, in place of the blue pigment derivative-1 used, the production process was similarly carried out using the blue pigment derivative-2 obtained above, and a red rice blue pigment containing ε-type copper phthalocyanine as a main component. A composition was obtained. Hereinafter, this is called "blue pigment composition-2." Table 2 summarizes the composition.

[Production example 3: production of epsilon copper phthalocyanine pigment for color filters]

(3-1) (Synthesis of Anionic Pigments Containing Sulphonic Acid in Pigments)

The sulfoamide methylated copper phthalocyanine was obtained like manufacture example 1-1 except having used 1.46 g (0.015 mol) of sulfamic acid (MW: 97) instead of the o-cresol-4-sulfonic acid used. The number of substitutions is almost 0.4. Hereinafter, this is called "blue pigment derivative-3". Table 1 summarizes the composition.

(3-2) (Preparation of Blue Pigment Composition)

In the manufacture example 1-3, the manufacturing process is similarly performed using the blue pigment derivative-3 obtained above instead of the used blue pigment derivative-1, and the red rice blue pigment composition which contains (epsilon) copper phthalocyanine as a main component Got. Hereinafter, this is called "blue pigment composition-3." Table 2 summarizes the composition.

[Production example 4: synthesis of pigment which improved introduction of hydrophobic group, color]

To 120 g of anhydrous sulfuric acid, 9.20 g (0.06 mol) of caprionitrile (MW: 153.3) and 2.25 g (0.075 mol) of paraformaldehyde are added, dissolved, and reacted to synthesize a methirol body. Next, 6.04 g (0.01 mol) of dimethyl copper phthalocyanine pigments (average molecular weight: 604) which have an average of two methyl groups in a molecule | numerator was added, and it stirred and reacted at 80 degreeC-85 degreeC for 6 hours. It cooled to room temperature, precipitated in about 1,000 ml of ice-water, filtered, washed with water, and dried. It wash | cleaned with acetone, and the soluble component was removed and caprinamide methylation dimethyl copper phthalocyanine was obtained. The number of substitution of the caprinamide methyl group is nearly 3.1. Hereinafter, this is referred to as "blue pigment derivative-4". Table 1 summarizes the composition.

The above results are summarized in Table 1 and Table 2 below.

[Production example 5: hydrophilic group is introduce | transduced into pigment and synthesizes water-soluble pigment | dye]

(5-1) (Preparation of hydrophilic pigments)

In the same manner as in Production Example 1-1, 5.76 g (0.01 mol) of copper phthalocyanine blue pigment was added to 130 g of anhydrous sulfuric acid, dissolved, and then 2.25 g (0.075 mol) of paraformaldehyde was added and stirred for 20 minutes. 11.46 g (0.06 mol) of trimellitic acid imide (MW: 191) was added, it heated, and it reacted by stirring at 80 degreeC-85 degreeC for 6 hours. It cooled to room temperature, precipitated in about 1,000 ml of ice-water, filtered, washed with water, and dried. It wash | cleaned with acetone, the soluble component was removed, and the trimellitic acid imide methylated copper phthalocyanine which is a pigment derivative of this invention was obtained. The number of substitutions is almost 3.2.

(5-2) (Preparation of hydrophilic dye solution: method with sodium hydroxide)

Subsequently, 12.26 g of the trimellitic acid imide-methylated copper phthalocyanine obtained above was stirred in 100 g of water, and dispersed. 12.8g of 20% sodium hydroxide aqueous solution was added, temperature was added at 50 degreeC, stirring was continued for 30 minutes, saponified, and dissolved. Furthermore, pH was adjusted to 8 with 1% sodium hydroxide aqueous solution, the insoluble content was isolate | separated by filtration, water was added, and it adjusted to 10% aqueous solution. To obtain a 10% aqueous solution of trimethylated amide methylated copper phthalocyanine sodium salt. Hereinafter, this is called "blue pigment derivative-5 aqueous solution."

(5-3) (Preparation of red solution and yellow solution)

In the same manner, in place of the copper phthalocyanine blue pigment, a bisaminoanthraquinone-based red pigment (C.I. Pigment Red 177) was reacted to obtain a 10% aqueous solution of the sodium salt of the trimellitic acid monoamidemethyl derivative of bisaminoanthraquinone. Hereinafter, it is called "red pigment derivative-1 aqueous solution."

In the same manner, a flavantron yellow pigment (C.I. Pigment Yellow 24) was reacted to obtain a 10% aqueous solution of the sodium salt of trimellitic acid monoamidemethyl derivative. Hereinafter, this is called "yellow pigment derivative-1 aqueous solution."

(5-4) (Preparation of hydrophilic dye solution: method by ethanolamine)

In the above, each pigment derivative aqueous solution saponified with the sodium hydroxide aqueous solution was made acidic with the diluted hydrochloric acid aqueous solution, the pigment derivative carboxylic acid was precipitated, and it filtered and obtained the mud state thing. 20% ethanolamine aqueous solution was added to this, and it neutralized, and pH was adjusted to 8. Thereafter, the insoluble component was separated by filtration, water was added to adjust to a 10% aqueous solution to obtain a 10% aqueous solution of the ethanolamine salt of trimellitic acid amidemethyl derivative. Hereinafter, "blue pigment derivative-5-2 aqueous solution", "red pigment derivative-1-2 aqueous solution", and "yellow pigment derivative-1-2 aqueous solution" are respectively called. The above result is put together in following Table 3.

[Production example 6] (we introduce hydrophilic group into pigment and synthesize water-soluble dye)

(6-1) (Preparation of hydrophilic dye solution)

In the same manner as in Production Example 5-1, the reaction was carried out using 8.82 g (0.06 mol) of glutamic acid in place of the trimellitic acid imide, and precipitated in ice water. After filtration, washing with water and drying, the solvent was washed with acetone. It removed and obtained glutaric acid-1- iminomethylation copper phthalocyanine. The number of substitutions is almost 3.1. Hereinafter, this is called "blue pigment derivative-6". Table 4 shows the compositions together.

(6-2) (Preparation of hydrophilic dye solution: method with sodium hydroxide)

In the same manner as in Production Example 5-2, the mixture was dispersed in water, neutralized with an aqueous sodium hydroxide solution, the pH was adjusted to 8, the insoluble fraction was filtered off, and water was added to adjust to a 10% aqueous solution. A 10% aqueous solution of the sodium salt of glutaric acid-1-iminomethylated copper phthalocyanine was obtained. Hereinafter, this is called "blue pigment derivative-6 aqueous solution."

[Production example 7] (we introduce hydrophilic group into pigment and synthesize water-soluble dye)

(7-1) (Preparation of hydrophilic dye solution)

In the same manner as in Production Example 5-1, the reaction was carried out using 8.34 g (0.06 mol) of N-methyltaurine in place of the trimellitic acid imide, and precipitated in ice water. After filtration, washing with water and drying, the mixture was washed with acetone. The soluble component was removed to obtain N- (sulfoethyl) -N-methylaminomethylated copper phthalocyanine. The number of substitutions is almost 3.2. Hereinafter, this is called "blue pigment derivative-7". Table 4 shows the compositions together.

(7-2) (Preparation of hydrophilic dye solution: method with sodium hydroxide)

In the same manner as in Production Example 5-2, the mixture was dispersed in water, neutralized with an aqueous sodium hydroxide solution, the pH was adjusted to 8, the insoluble fraction was filtered off, and water was added to adjust to a 10% aqueous solution. A 10% aqueous solution of the sodium salt of N-methyl-N- (sulfoethyl) aminomethylated copper phthalocyanine was obtained. Hereinafter, this is called "blue pigment derivative-7 aqueous solution."

[Production example 8] (we introduce hydrophilic group into pigment and synthesize water-soluble dye)

(8-1) (Preparation of hydrophilic dye solution)

In the same manner as in Production Example 5-1, the reaction was carried out using 5.82 g (0.06 mol) of sulfamic acid (MW: 97) in place of trimellitic acid imide, and precipitated in ice water to remove filtration, water washing, and soluble matter. The sulfoamide methylated copper phthalocyanine was obtained. The number of substitutions is almost 3.3. Hereinafter, this is called "blue pigment derivative-8". Table 4 shows the compositions together.

(8-2) (Preparation of hydrophilic dye solution: method with sodium hydroxide)

In the same manner as in Production Example 5-2, the mixture was dispersed in water, neutralized with an aqueous sodium hydroxide solution, the pH was adjusted to 8, the insoluble fraction was filtered off, and water was added to adjust to a 10% aqueous solution. A 10% aqueous solution of the sodium salt of sulfoamidemethylated copper phthalocyanine was obtained. Hereinafter, this is called "blue pigment derivative-8 aqueous solution."

EXAMPLE 1: Preparation of Dispersion

(1-1) (Preparation of Blue Pigment Dispersion-1)

100 parts of blue pigment composition-1 (red rice blue pigment composition containing an epsilon copper phthalocyanine as a main component) obtained by manufacture example 1-3, benzyl methacrylate- methacrylate 2-hydroxyethyl methacrylate copolymer ( Molar ratio: 60:20:20, weight average molecular weight 30,000) (hereinafter, referred to as "BzMA-MAc-HEMA copolymer") 30 parts, cyclohexanone 100 parts and propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMA) ) 60 parts and 66.7 parts of Disperbyk-163 (manufactured by Byk-Chemie: 45% solids) were premixed with a paint conditioner. Then, 143.3 parts of PGMA were added so that a pigment concentration might be 20%, and it disperse | distributed with the continuous horizontal type media disperser, and the blue pigment dispersion liquid was obtained. Hereinafter, this is called "blue pigment dispersion-1."

(1-2) (Preparation of Comparative Blue Pigment Dispersion-1)

It carried out similarly to Example 1-1 except having used the comparative blue pigment composition-1 obtained by the comparative manufacture example 1 (containing the epsilon type copper phthalocyanine pigment which used the known monosulfonated copper phthalocyanine as a main component). Blue pigment dispersion liquid-1 &quot; was prepared.

<Evaluation: Comparison of color tone of blue pigment dispersion liquid>

The color tone of the blue pigment dispersion liquid-1 and comparative blue pigment dispersion liquid-1 obtained above were compared. Blue pigment dispersion liquid-1 using blue pigment composition-1 was blue of redness more than comparative blue pigment dispersion liquid-1 using comparative blue pigment composition-1 (monosulfonated copper phthalocyanine).

[Example 2: Application to Glass Substrate]

(2-1) (Preparation of Blue Glass Substrate)

The glass substrate was set with a spin coater, and the blue pigment dispersion-1 obtained in Example 1 was added dropwise, and spin-coated at 300 rpm for 5 seconds, and then 1,200 rpm for 5 seconds. Subsequently, it prebaked at 90 degreeC for 2 minutes, post-baking was further performed at 230 degreeC for 30 second, and blue coating glass substrate-1 was prepared. Hereinafter, this is called "blue coating glass substrate-1."

(2-2) (Preparation of blue coated glass substrate for comparison)

Using the blue pigment dispersion liquid -1 for comparison of the epsilon copper phthalocyanine pigment which used the monosulfonated copper phthalocyanine obtained in Example 1, it apply | coats it similarly to said (2-1), and prepares the comparative blue coating glass substrate-1. It was. Hereinafter, it is called "the comparative blue coating glass substrate-1."

<Evaluation: Comparison with evaluation of optical characteristic of blue coated glass substrate>

Optical characteristics were evaluated about the blue coating glass substrate-1 produced above and the comparative blue coating glass substrate-1. The colorimeter used the color analyzer TC-1800MK2 (made by Tokyo Denshoku Co., Ltd.). Light at this time was made into the auxiliary standard illuminant C.

As a result, the blue coating glass substrate-1 using the blue pigment dispersion liquid-1 showed the maximum transmission wavelength of 458 nm, and the Y value of 17.6. On the other hand, the comparative blue coating glass substrate-1 which used the comparative blue pigment dispersion liquid-1 which has monosulfonated copper phthalocyanine showed the maximum transmission wavelength of 461 nm, and the Y value showed 17.0. Since the glass substrate using the dye derivative of the present invention exhibits a reddish blue color than the glass substrate using the monosulfonated copper phthalocyanine in comparison, and the maximum transmission wavelength is on the short wavelength side, the dye derivative of the present invention is more It was reddish blue. Moreover, it was confirmed that the Y value is high in the pigment derivative of this invention.

[Example 3: Application to Color Filters]

(3-1) (Preparation of Blue Pigment Dispersion)

In the same manner as in Example 1-1, 20 parts of the blue pigment composition-1 obtained in Production Example 1-2, 2 parts of BzMA-MAc-HEMA copolymer, 13.3 parts of Disperbyk-163 and 64.7 parts of PGMA were freed with a paint conditioner. After mixing, the dispersion was carried out with a continuous horizontal medium disperser to obtain a blue pigment dispersion using the dye derivative of the present invention. Hereinafter, this is called "blue pigment dispersion liquid-2". The blue pigment microdispersion liquid obtained here was excellent in storage stability, without thickening in 45 degreeC 1 week. The composition is shown in Table 5.

In addition, as shown in Table 5, instead of the blue pigment composition-1 used above, "blue pigment dispersion liquid-3" was produced using the blue pigment composition-2 obtained by the manufacture example 2-2, and the manufacture example 3 "Blue pigment dispersion-4" was prepared using the blue pigment composition-3 obtained at -2, respectively.

(3-2) (Preparation of Green, Red, Yellow, and Purple Pigment Dispersions)

In the same manner as in the above (3-1), green, red, yellow, and purple pigment dispersion liquids used in the resist ink were prepared. Specifically, PG36 (copper phthalocyanine green pigment), PR254 (diketopyrrolopyrrole red pigment), PR177 (aminoanthraquinone red pigment), PY150 (nickel) instead of the blue pigment composition-1 used by (3-1) Complex yellow pigment) and PV23 (dioxazine violet pigment) were used in the respective pigment compositions to which a well-known pigment derivative was added, and it carried out similarly to said (3-1), and obtained the pigment dispersion of 20% of pigment content, respectively. Hereinafter, these are called "green pigment dispersion liquid-1", "red pigment dispersion liquid-1", "red pigment dispersion liquid-2", "yellow pigment dispersion liquid-1", and "purple pigment dispersion liquid-1", respectively.

(3-3) (Preparation of the photosensitive resist ink of each pigment)

In order to form red (R), green (G), and blue (B) pixels on the glass substrate of the color filter, photosensitive blue resist inks-1, 2, 3, and photosensitive green according to the combination of Table 6 below. A resist ink and a photosensitive red resist ink were obtained.

(3-4) (Formation of RGB pixel of color filter)

The glass substrate was set with a spin coater, and the photosensitive red resist ink was spin-coated at 300 rpm for 5 seconds and then 1,200 rpm for 5 seconds. Subsequently, prebaking was performed at 80 degreeC for 10 minutes, and the photomask which has a mosaic pattern was exposed to the application surface of a glass substrate with the light quantity of 100mJ / cm <2> with an ultrahigh pressure mercury lamp using a proximity exposure machine. . Subsequently, development and washing were performed with a dedicated developer and a dedicated rinse to form a red mosaic pattern on the glass substrate.

Subsequently, the green mosaic pattern and the blue mosaic pattern were coated and formed in accordance with the above method using the photosensitive green resist ink and the photosensitive blue resist ink shown in Table 6 to obtain an RGB color filter.

The obtained color filter had excellent spectral curve characteristics, was excellent in fastness such as light resistance and heat resistance, and also had excellent properties in light transmission, and showed excellent properties as a color filter for liquid crystal color display.

[Example 4: Preparation and digital electronic printing of electrophotographic developer for digital printing]

(4-1) (Preparation of pigment high concentration-containing resin composition)

70 parts of polyester resins (average molecular weight: about 15,000) of bisphenol A-bis (propylene glycol ether) and terephthalic acid (hereinafter only referred to as polyester resins), 30 parts of “blue pigment derivative-4” obtained in Production Example 4; It knead | mixed in two rolls and prepared the polyester masterbatch (pigment high concentration containing resin composition) of a blue pigment (henceforth a blue masterbatch).

In the same manner, 30 parts each of PR-122 (dimethylquinacridone pigment) and PY-74 (monoazo yellow pigment) and PBK-7 (carbon black pigment) were kneaded with 70 parts of the above polyester resins, respectively, , Yellow and black polyester masterbatch were obtained. Hereinafter, they are called red master batch, yellow master batch, and black master batch, respectively.

(4-2) (Preparation of coloring composition for image recording and printing of full color electrophotographic)

According to the combination of the following Table 7, the polyester masterbatch of each color obtained above, the said polyester resin, and the chromium complex salt type negative charge control agent were kneaded according to the conventional method. After cooling, it was pulverized, finely pulverized with a jet mill, filtered through a classifier, and the fine powder of the coloring composition for image recording of 5-7 micrometers was obtained. Then, the colloidal silica of the fluidizing agent was added, and it mixed with the magnetic iron powder of a carrier, and it was set as the cyan, magenta, yellow, and black electrophotographic dry developer. Electronic printing was performed with an electrophotographic full color laser printer. A full-color electrophotographic print having a distinct characteristic of cyan to greenish cyan was obtained.

EXAMPLE 5 Aqueous Printing Ink and Printing

(5-1) (Preparation of coating agent for aqueous gravure ink)

50 parts of a polyurethane-based aqueous resin (30% solids) containing a carboxyl group obtained from a carbonate polyol and aliphatic isocyanate, 5 parts of a water dispersion wax (30% solids), 15 parts of a polycarbodiimide crosslinking agent, 1 part of an antifoaming agent, and water 9 parts were mix | blended and the coating vehicle base was prepared. 20 parts of the blue pigment derivative-5 aqueous solution, red pigment derivative-1 aqueous solution, and yellow pigment derivative-1 aqueous solution obtained by the manufacture example 5 were added there as a coloring agent, and it fully mixed, and the blue, red, and yellow coating agent was prepared. In addition, the said polycarbodiimide type crosslinking agent synthesize | combined with toluene diisocyanate, and used the O / W emulsion (20% of solid content) of the mineraltaphene solution which made the terminal of polycarbodiimide the oleyl urethane.

<Evaluation>

Gravure printing or flexographic printing was performed to plastic films and sheets, such as polyvinyl chloride, polyethylene, polyester, and nylon, as aqueous gravure ink using the blue, red, and yellow coating agent obtained above, and obtained the printed matter. All of these printed materials were beautiful and transparent printed materials excellent in physical properties such as weather resistance, water resistance and durability.

(5-2) (Preparation of coating agent for aqueous gravure ink)

Blue pigment derivative-5-2 aqueous solution obtained in manufacture example (5-4) instead of said blue pigment derivative-5 aqueous solution, red pigment derivative-1 aqueous solution, and yellow pigment derivative-1 aqueous solution, red pigment derivative-1- A blue, red and yellow coating agent was prepared using 2 aqueous solutions and yellow pigment derivative-1-2 aqueous solutions, respectively.

<Evaluation>

In the same manner as in Example (5-1), the obtained coating agent was subjected to gravure printing or flexographic printing on the plastic film or sheet described above as an aqueous gravure ink. All the obtained printed matter was a beautiful and transparent printed matter excellent in physical properties, such as weather resistance, water resistance, and durability.

EXAMPLE 6 Preparation, Dyeing, and Painting of a Colored Coating Agent

(6-1) (Preparation of colored coating agent)

Methyl methacrylate-ethyl acrylate-acrylic acid (64: 32: 4) containing carboxyl group 40 parts of copolymerized latex (40% of solid content), 3 parts of mica, 7 parts of talc, 10 parts of 3% hydroxycellulose aqueous solution, propylene glycol 1 part monoethyl ether, 2 parts ethylene glycol, 0.5 part antifoamer, 0.5 part preservative, 10 parts of polycarbodiimide crosslinking agents used in Example 5, and 6 parts of water were mix | blended, and the coating vehicle base was prepared.

20 parts of blue pigment derivative-5 aqueous solution, red pigment derivative-1 aqueous solution, and yellow pigment derivative-1 aqueous solution which are the pigment derivative of this invention are respectively added to the obtained vehicle base as a coloring agent, and it fully mixed, and a blue, red, and a yellow coating agent Was prepared.

<Evaluation: Wood product>

Using the blue, red, and yellow coating agents obtained above, they were used alone or in combination with wood products, and the coating of each color was performed. Since the dye derivative of this invention crosslinks-reacts at normal temperature, the obtained coating film was excellent in the physical properties, such as weather resistance, water resistance, and durability, and the wood product coated with the beautiful each color was obtained.

<Evaluation: other than wooden goods>

In the same manner, the above-mentioned blue, red and yellow coating agents can be used for dyeing textile articles such as woven fabrics, nonwoven fabrics, synthetic leather, artificial leather, etc., . Similarly to wood products, it was possible to obtain a beautiful colored product having excellent physical properties such as weather resistance, water resistance and durability.

(6-2) (Preparation and Evaluation of Blue Coating Agent)

In the same manner as described above, a blue coating agent was obtained using a blue dye derivative-6 aqueous solution, a blue dye derivative-7 aqueous solution, and a blue dye derivative-8 aqueous solution composed of the dye derivative of the present invention, respectively. Evaluation similar to the above was performed using the obtained coating agent. Specifically, with the red and yellow coating agents produced above, the obtained blue coating agent was used for dyeing wood products, paper products, textile products and the like, and coating them with metal products, plastic products and the like. The beautiful coloring product which was excellent in physical properties, such as weather resistance, water resistance, and durability, was obtained.

According to the pigment derivative of the present invention described above, the soluble dye is excellent in light resistance as compared to the dye, and the color tone also causes a deep color effect depending on the number of substitutions, and in particular, sky blue from a phthalocyanine-based dye can be suitably obtained. Moreover, the pigment derivative which is effective as an additive before crystallization of a pigment and suppression of crystal growth by the property of the substituent of the derivative residue connected to the water-insoluble pigment | dye, the improvement of the dispersibility of the pigment of the organic-solvent pigment dispersion color, dispersion liquid The coloring agent containing functional additives, such as a dispersion adjuvant which improves performance, such as the fall of viscosity, dispersion stability, and long-term storage stability, can be obtained. Since these can be obtained from the derivative | guide_body which used the existing pigment | dye frame | skeleton as a mother, it can carry out economically and efficiently.

Claims (13)

As a derivative of the water-insoluble pigment used as a colorant,
A water-insoluble pigment (A),
An aldehyde compound (B) capable of reacting with the water-insoluble dye (A) to form an alkylene group,
Any one compound selected from the group consisting of a hydrocarbon compound having a methine group (-CH =) having a disubstituted hydrogen group, a derivative thereof (C-1), an amino compound having a reactive amino group, and a derivative thereof (C-2) Made by reacting C),
The said water-insoluble pigment | dye (A) molecule and the said compound (C) residue are derivatives of the pigment | dye formed by connecting through the said alkylene group, The pigment derivative characterized by the above-mentioned. The method of claim 1,
The said aldehyde compound (B) is at least 1 sort (s) of pigment derivative which is chosen from the group which consists of a paraformaldehyde, a trioxane, formaldehyde, formalin, glyoxal, and the alkyl aldehyde of C1-C10. The method according to claim 1 or 2,
The methine group (-CH) in which the said compound (C) has a bicyclic hydrogen group selected from the group which consists of a C6-C20 phenol compound and a C8-C20 N, N-di substituted aniline compound Hydrocarbon compounds having =) and pigment derivatives thereof (C-1). The method according to claim 1 or 2,
The said compound (C) is a C1-C10 amino acid compound, a C1-C20 amino compound, a C1-C10 amino triazine compound, a C1-C20 carboamide compound, and a C1-C20 carboy The dye compound which is an amino compound which has a reactive amino group, and these derivatives (C-2) selected from the group which consists of a mid compound (except a phthalimide) and a sulfamic acid compound of C10-C10. The method according to claim 1 or 2,
The pigment derivative whose number of compound (C) residues couple | bonded with a water-insoluble pigment | dye (A) molecule | numerator through an alkylene group is 1-6. The method of claim 1,
Pigment derivatives whose said water-insoluble pigment | dye (A) is at least 1 sort (s) chosen from the group which consists of an organic pigment, a bat dye, and a disperse dye. The method of claim 1,
The water-insoluble pigment (A) is a phthalocyanine series, anthraquinone series, perylene series, perinone series, dioxazine series, quinacridone series, diketopyrrolopyrrole series, indigo thioindigo series, quinophthalone series, isoindolinone series And at least one pigment derivative selected from the group consisting of metal complexes, insoluble azo and high molecular weight azo pigments. The method of claim 1,
The said compound (C) residue has a substituent, The said pigment derivative is any one selected from the group of the following hydrophilic group, the group of a lipophilic group, and the group of a reactive group.
Group of hydrophilic groups;
Any one anionic group selected from carboxyl group, sulfonic acid group, phosphate ester group and sulfate ester group;
Alkali metal salt, ammonium salt, (mono, di, tri) alkylamine salt, (mono, di, tri) alkanolamine salt, (mono, di, tri)-(polyoxyalkylene) oxyalkylamine of these anionic groups Salts of any anionic group selected from salts;
Any one cationic group selected from tertiary amino groups and quaternary ammonium groups;
Salts of any one cationic group selected from halogenated salts, sulfonates, alkyl carboxylates of these cationic groups;
Any one nonionic group selected from polyalcohol groups and polyethylene glycol groups;
Group of lipophilic groups;
Any one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, and a halogen group;
Group of reactive groups;
Any group selected from the group which consists of a glycidyl group, a metyrol group, and the C1-C4 alkoxymethyl group. As a coloring material, the liquid derivative which consists of the pigment derivative as described in any one of Claims 1-8, and any one of an organic solvent type | system | group, an aqueous system, or a water-hydrophilic organic solvent mixed solvent system as a dilution medium, or A colorant comprising at least one of a polymerizable liquid medium made of a polymerizable oligomer or a polymerizable monomer or a resin medium made of a synthetic resin. The method of claim 9,
Furthermore, the coloring agent which contains a polymeric type dispersing agent or a low molecular weight dispersing adjuvant as a dispersing adjuvant. The method of claim 9,
A colorant which is any one of a dyeing agent, a printing agent, a coating material, a printing ink, a stationery, a painting tool, a resin coloring agent, an electrophotographic developer, an electrostatic developer or a color filter pixel forming ink. The coloring agent in any one of Claims 9-11 when coloring by the coloring method chosen from dyeing, printing, painting, printing, writing, drawing, resin coloring, electrophotographic printing, electrostatic printing, or a color filter pixel formation method. The coloring method of the article characterized by using. The method according to any one of claims 9 to 11, when coloring by a coloring method of forming a pixel according to any one of a photoresist method, an inkjet printing method, a printing method, a transfer method or a pasting method on a color filter substrate. The coloring method of the article characterized by using a coloring agent.