JP2002194243A - Coloring composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition excellent in coloring concentration, transparency, light resistance, weatherability (resistance to environmental gases) and bleed resistance. SOLUTION: The coloring composition comprises at least one of compounds represented by general formula 1 [wherein A and B are each independently an optionally substituted phenyl group or an optionally 3-substituted, 4,5- dicyano-2-imidazolyl group; P is H or an alkyl group; Q is an alkyl group or a phenyl group; and a, b and d are each 0 or 1, provided that a+b+d=2] or general formula 2 [wherein X is a benzoyl or benzotriazolyl group substituted with a hydroxyl group or an alkoxy group; E and G are each independently a 2-hydroxyphenyl group or a 4,5-dicyano-2-imidazolyl group; R is hydrogen or an alkyl group; and m and n are each 0 or 1] and metal complex coloring matters formed from these compounds and a Cu, Co, Ni or Fe salt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a coloring composition. More specifically, the present invention relates to a colored plastic, a toner for electrophotography, a color ribbon for a sublimation transfer printer, a water-based ink, particularly a water-based ink for inkjet or an oil-based ink, particularly a oil-based ink for a color filter.

[0002]

2. Description of the Related Art Oil-soluble pigments or pigments have been used as colorants for plastic members of toner, household appliances, automobiles and the like or toners. Pigments are excellent in durability, but are dull in color tone and lack transparency. Further, the dispersibility in the plastic is poor, which may cause crystallization of the plastic. On the other hand, the oil-soluble dye has a clear color tone and excellent transparency, but does not have sufficient durability, especially light resistance and bleed resistance. Although an oil-soluble dye is used for a color ribbon for a sublimation transfer type printer, there is a problem that light resistance, heat resistance or bleed resistance is poor.
Water-soluble dyes are usually used in aqueous inks for inkjet, but light resistance and water resistance are not sufficient.
For this reason, various oil-soluble dyes have been proposed. Above all, azo-based metal complex dyes are said to have high durability, and are described in, for example, JP-A-56-155,263 and JP-A-57-30,77.
No. 3, JP-A-59-193,962, JP-A-62-1
No. 90273, JP-A-63-46260, JP-A-Hei3
A number of patents have been proposed, such as Japanese Patent Application Laid-Open Nos. 97-772, 8-156,399 and 10-259,331, but have not yet sufficiently satisfied the market requirements. In addition, anthraquinone-based or quinacridone-based pigments are used as pigments for color filters that are frequently used in personal computers, TVs, portable terminals, and the like.

[0003]

The present invention provides a clear and transparent color tone as a colorant for plastic members, toners, color ribbons for sublimation transfer printers, aqueous inks for ink jet printers, or color filters. It is an object of the present invention to provide an oil-soluble dye and a pigment which are excellent in durability and especially excellent in light resistance, bleed resistance and heat resistance.

[0004]

Means for Solving the Problems The present inventors have ensured a clear color tone and transparency when using an azo metal complex dye having a specific structure among the azo metal complex dyes proposed so far. In addition, the inventors have found that the durability, especially the light resistance, the heat resistance, and the bleed resistance are simultaneously satisfied, and have achieved the present invention. That is, the gist of the present invention is to provide a compound represented by the following general formula (1) or a metal complex dye formed from the compound and a salt of Cu, Co, Ni or Fe or a compound represented by the following general formula (2) or Compound and Cu, C
o, Ni or Fe, which is present in a coloring composition containing one or more metal complex dyes formed from salts thereof.

[0005]

Embedded image [Wherein A and B each independently represent a phenyl group which may have a substituent or a 4,5-dicyano-2-imidazolyl group which may have a substituent at the 3-position;
P represents a hydrogen atom or an alkyl group, Q represents an alkyl group or a phenyl group which may have a substituent, and a, b, and d represent 0 or 1. Where a + b + d =
2. ]

[0006]

Embedded image [In the formula, X represents a benzoyl group substituted with a hydroxy group or an alkoxy group or a benzotriazolyl group which may have a substituent, and E and G each independently have a substituent. Represents a 2-hydroxy-phenyl group or a 4,5-dicyano-2-imidazolyl group optionally having a substituent at the 3-position, R represents a hydrogen atom or an alkyl group, and m and n represent 0 or Represents 1. ]

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The dyes for plastics, electrophotographic toners, aqueous inks for ink jet printers or oily inks for color filters used in the present invention include the compound represented by the general formula (1) and Cu, Co, Ni or A metal complex dye formed from a salt of Fe or a metal complex dye formed from a compound represented by the general formula (2) and a salt of Cu, Co, Ni or Fe. For the color ribbon of a sublimation transfer type printer, the above-mentioned metal complex dyes can also be used, but the compound represented by the general formula (1) or the compound represented by the general formula (2) can be used as a transfer medium. It is preferable to include a salt of Cu, Co, Ni or Fe in a so-called image receiving medium for receiving the compound to be transferred and to form a metal complex in the image receiving medium.

In the general formula (1), A or B
Are individually represented by 2- (4,5-dicyano) -imidazolyl group, 2- (4,5-dicyano-3-methoxycarbonylmethyl) -imidazolyl group 2-
Imidazolyl group such as (4,5-dicyano-3-cyanomethyl) -imidazolyl group or 1- (2-hydroxy) -phenyl group, 1- (2-hydroxy-4-nitro) -phenyl group, 1- (2-hydroxy- 2-hydroxyphenyl groups such as 5-nitro) -phenyl group, 1- (2-hydroxy-4-chloro) -phenyl group, 1- (2-hydroxy-4-methyl) -phenyl group,
Alternatively, a substituted phenyl group such as a nitrophenyl group, a chlorophenyl group, a methylphenyl group, and a methoxyphenyl group can be mentioned.

In the general formula (1), examples of the group represented by P include a hydrogen atom and an alkyl group such as a methyl group and an ethyl group.

In the general formula (1), the group represented by Q is an alkyl group such as a methyl group, an ethyl group, an octyl group, a dodecyl group, or a phenyl group, a toluyl group, an octylphenyl group, a chlorophenyl group, an anisyl group. And a phenyl group which may be substituted, such as a phenethyl group.

In the general formula (2), the group represented by X is a benzoyl group, a hydroxybenzoyl group,
Examples include a benzoyl group such as a dihydroxybenzoyl group and a hydroxy-methoxy-benzoyl group, or a benzotriazolyl group such as a benzotriazolyl group, a tolyltriazolyl group and a chlorobenzotriazolyl group.

In the general formula (2), examples of the group represented by R include a hydrogen atom and an alkyl group such as a methyl group and an ethyl group.

In the general formula (2), E or G
Are individually represented by 2- (4,5-dicyano) -imidazolyl group, 2- (4,5-dicyano-3-methoxycarbonylmethyl) -imidazolyl group 2-
Imidazolyl group such as (4,5-dicyano-3-cyanomethyl) -imidazolyl group or 1- (2-hydroxy) -phenyl group, 1- (2-hydroxy-4-nitro) -phenyl group, 1- (2-hydroxy- 2-hydroxyphenyl groups such as 5-nitro) -phenyl group, 1- (2-hydroxy-4-chloro) -phenyl group and 1- (2-hydroxy-4-methyl) -phenyl group.

Specific examples of the dye used in the present invention are described below. The complexed metal is indicated in parentheses next to the dye number.

[0015]

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[0016]

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[0017]

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[0018]

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The dye represented by the general formula (1) or (2) can be prepared by the following known method (for example,
Yutaka Hosoda, Gihodo Shuppan, 412 pages, 14 to 19
, Or Industrial Chemistry Magazine Vol. 73, No. 5, 143-1
53 pages, or Dyes and Pigment
s No. 18, pages 125 to 136). For example, the dye (1) -4 is obtained by diazotizing 2-amino-4,5-dicyanoimidazole by a conventional method, and adding 2-phenyl-4-methyl-imidazole and pH7.
To 9 to obtain a monoazo compound. After that, the pigment of (1) -4 can be obtained by containing copper using copper sulfate. The dye of the general formula (2) can be obtained in the same manner.

The content of the dye of the general formula (1) or (2) in the coloring composition is preferably 0.01 to 5% by weight based on the total weight of the composition in the case of coloring a plastic member. In the case of a photographic toner, the amount is preferably 1 to 10% by weight based on the total weight of the composition. In the case of an aqueous ink for an inkjet printer or an oily ink for a color filter, 0.5 to 8% by weight based on the total weight of the composition. In the case of a color ribbon for a sublimation transfer type printer, it is preferably 10 to 50 with respect to the total weight of the binder resin composition.
% By weight is preferred.

The resins used in the coloring composition of the present invention include polystyrene resins, polyacrylonitrile resins,
Acrylonitrile butadiene-styrene copolymer resin,
Examples thereof include poly (meth) acrylate resin, polyamide resin, epoxy resin, polysulfone resin, polycarbonate resin, polyvinyl acetal resin, polysulfone resin, nitrocellulose resin, ethylcellulose resin, polyester resin, and polyvinyl chloride resin.

These resins may be used alone or in combination.
More than one type may be used in combination.

To mix the dye of the present invention with the resin,
A method in which the resin and the dye are kneaded with heat by a roll mill or the like and dissolved and mixed in a solvent may be used.

The colored resin composition of the present invention may contain additives such as a resin stabilizer, if necessary.

When the dye of the present invention is used in an aqueous ink for an ink jet printer, water and an aqueous medium such as ethylene glycol, diethylene glycol, polyethylene glycol and glycerin are used as the medium.
Using a substance having a lipophilic structural part and a hydrophilic structural part such as a styrene-acrylic acid copolymer and a styrene-maleic acid copolymer as a dispersant, using a normal wet grinder such as a sand grinder, Finely pulverized so that the average particle diameter becomes 0.1 μm or less.

The amount of the aqueous medium used is 10 to 50% by weight based on the total weight of the composition.

The amount of the dispersant used is 10 to 100% by weight based on the weight of the dye used.

When the dye of the present invention is used in an oil-based ink for a color filter, an oil-based medium such as toluene, xylene, methyl isobutyl ketone, dimethoxyethane or dioxane is used as a medium, and styrene-acrylate is used as a dispersant. Using a material such as a copolymer or a styrene-maleic acid ester copolymer, finely pulverize using an ordinary wet pulverizer such as a sand grinder or a ball mill so that the average particle size becomes 0.1 μm or less. Then, it is mixed with a photocurable resin and a photocuring initiator and used.

The amount of the dispersant used is 10 to 100% by weight based on the weight of the dye used.

[0030]

The present invention will be described in more detail with reference to the following Examples, which, however, are not intended to limit the scope of the invention. In addition, a part shall represent the meaning of a weight part.

[Example 1] Coloring of polystyrene member for household appliances 2 parts of the compound (1) -1 was added to 100 parts of polystyrene resin, and the mixture was heated at 180 ° C for 3 hours using a roll mill.
After mixing for 0 minutes, a colored plate was molded by an injection molding machine.

The obtained flat plate was transparent bluish red.
The colored slab was exposed outdoors to sunlight for one month, with little discoloration.

The colored flat plate was heated at 150 ° C. for 1 day between two colorless polystyrene flat plates injection-molded in the same manner as above without the addition of a dye, but no bleed of the dye was observed. (No colorless polystyrene plate was colored)

Example 2 Preparation of Toner Compound 100 of the above (2) -1 was added to 100 parts of a polyester resin.
Parts, 1 part of a charge control agent (Bontron E82, manufactured by Orient Chemical Industries) was added, and the mixture was heated at 150 ° C. using a roll mill.
Mix for 30 minutes. After cooling, the mixture was finely pulverized by a jet mill and classified by an air classifier to obtain a powder having an average particle diameter of 8 μm. 0.4 parts of hydrophobic silica R972 (manufactured by Nippon Aerosil Co., Ltd.) was added to this powder, and the mixture was uniformly mixed with a Henschel mixer to obtain a toner.

A developer prepared by mixing 4 parts of the obtained toner and 96 parts of a silicone resin-coated carrier was subjected to a copying operation using a commercially available copying machine (Leo Dry 7610 manufactured by Toshiba). A copy image was obtained.

This copied image was displayed on the south window glass surface for 4 weeks, but the discoloration was faint.

Example 3 Preparation of Aqueous Ink for Inkjet Printer 80 parts of water, 1 part of SMA1000 (styrene-maleic acid copolymer, manufactured by Arco Chemical Co.) hydrolyzate, 15 parts of diethylene glycol, 15 parts of (1) -2 Four parts of the compound were mixed and pulverized for 24 hours with a sand grinder using 1 mm diameter glass beads to obtain a dispersion having an average particle diameter of 0.08 μm.

The obtained aqueous dispersion was subjected to Jet Wind
When printing was performed on electrophotographic paper using a 500C (ink jet printer manufactured by Fuji Xerox Co., Ltd.), a normal printed matter of bluish red color was obtained.

The printed matter was displayed on the south window glass surface for 4 weeks, but the discoloration was slight.

Example 4 Preparation of Color Ribbon for Sublimation Transfer Printer (1) 5 parts of the compound (4) (not containing gold) and 5 parts of polyvinyl butyral resin were dissolved in 200 ml of methyl ethyl ketone. The solution was applied on a 5-micron-thick polyethylene terephthalate film using a wire bar so that the film thickness after drying was 1 micron, and dried to form a heat-sensitive transfer layer to prepare a heat-sensitive transfer material. .

On the other hand, as an image receiving paper, 100 parts of polyvinyl phenyl acetal resin and 1 part of copper acetate are dissolved in a mixed solvent of 1000 parts of methyl ethyl ketone and 200 parts of toluene, and this is mixed with Yupo FPG150 (polypropylene synthetic paper, Oji Yuka synthetic paper). (Manufactured by Co., Ltd.) using a wire bar so as to have a dry film thickness of 10 μm and dried. Using the obtained thermal transfer material and image receiving paper, a video printer VY100 (thermal printer,
(Hitachi, Ltd.) to perform a thermal transfer to obtain a blue-red image.

The printed matter was posted on the south window glass surface for 4 weeks, but the discoloration was slight.

Example 5 Preparation of Oily Ink for Color Filter Toluene 80 parts, SMA 1540 (Styrene-maleic acid half ester copolymer, manufactured by Arco Chemical Co., Ltd.) 1
And 4 parts of the compound (2) -6, and the mixture was finely pulverized for 24 hours with a sand grinder using glass beads having a diameter of 1 mm to obtain a dispersion having an average particle diameter of 0.08 μm.

A photopolymerizable prepolymer, Diabeam UK6105 (epoxy acrylate resin,
10 parts of Mitsubishi Rayon Co., Ltd.), 20 parts of a photopolymerizable monomer, acryloylmorpholine, 1 part of a photopolymerization initiator and 1 part of Irgacure 1700 (manufactured by Ciba Specialty Chemicals) were added to prepare a photopolymerizable ink.

After the obtained ink was spin-coated on a glass substrate, ultraviolet light was applied at an irradiation intensity of 300 mW / cm 2.
Irradiation was performed with an integrated light amount of 1500 mJ / cm2, and the mixture was cured to obtain a red film.

[0046]

The coloring composition of the present invention is used for coloring plastic members, toner for electrophotography, sublimation transfer type thermal recording, ink jet recording or for color filters, and provides coloring density, light resistance, weather resistance (environmental gas). ) Excellent bleeding resistance.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G02B 5/20 101 G03F 7/004 505 4J039 G03F 7/004 505 B41M 5/26 101K G03G 9/09 G03G 9 / 08 361 F-term (reference) 2H005 AA21 CA22 2H025 AB13 CC12 2H048 BA57 BA64 2H086 BA55 2H111 BA38 BA39 BA44 CA03 CA31 4J039 AB02 AD03 AD05 AD10 AD11 AD15 AE05 AE06 AE08 AE10 AF07 BA37 BA38 BC12 BC29 BC51 BC41 BC44 BC44 EA33 EA35 EA37 GA05 GA24

Claims (6)

[Claims] 1. A compound represented by the following general formula (1) or a metal complex dye formed from the compound and a salt of Cu, Co, Ni or Fe or a compound represented by the following general formula (2): And Cu, Co, Ni or F
a coloring composition comprising one or more metal complex dyes formed from a salt of e. Embedded image [Wherein A and B each independently represent a phenyl group which may have a substituent or a 4,5-dicyano-2-imidazolyl group which may have a substituent at the 3-position;
P represents a hydrogen atom or an alkyl group, Q represents an alkyl group or a phenyl group which may have a substituent, and a, b, and d represent 0 or 1. Where a + b + d =
2. ] [In the formula, X represents a benzoyl group substituted with a hydroxy group or an alkoxy group or a benzotriazolyl group which may have a substituent, and E and G each independently have a substituent. Represents a 2-hydroxy-phenyl group or a 4,5-dicyano-2-imidazolyl group optionally having a substituent at the 3-position, R represents a hydrogen atom or an alkyl group, and m and n represent 0 or Represents 1. ] 2. A compound represented by the following general formula (1):
a metal complex dye formed from a salt of u, Co, Ni or Fe or a compound represented by the following general formula (2) with C
A colored composition containing at least one metal complex dye formed from a salt of u, Co, Ni or Fe. Embedded image [Wherein A and B each independently represent a phenyl group which may have a substituent or a 4,5-dicyano-2-imidazolyl group which may have a substituent at the 3-position;
P represents a hydrogen atom or an alkyl group, Q represents an alkyl group or a phenyl group which may have a substituent, and a, b, and d represent 0 or 1. Where a + b + d =
2. ] [In the formula, X represents a benzoyl group substituted with a hydroxy group or an alkoxy group or a benzotriazolyl group which may have a substituent, and E and G each independently have a substituent. Represents a 2-hydroxy-phenyl group or a 4,5-dicyano-2-imidazolyl group optionally having a substituent at the 3-position, R represents a hydrogen atom or an alkyl group, and m and n represent 0 or Represents 1. ] 3. A compound represented by the following general formula (1):
a metal complex dye formed from a salt of u, Co, Ni or Fe or a compound represented by the following general formula (2) with C
An electrophotographic toner containing at least one metal complex dye formed from a salt of u, Co, Ni or Fe and a binder resin. Embedded image [Wherein A and B each independently represent a phenyl group which may have a substituent or a 4,5-dicyano-2-imidazolyl group which may have a substituent at the 3-position;
P represents a hydrogen atom or an alkyl group, Q represents an alkyl group or a phenyl group which may have a substituent, and a, b, and d represent 0 or 1. Where a + b + d =
2. ] [In the formula, X represents a benzoyl group substituted with a hydroxy group or an alkoxy group or a benzotriazolyl group which may have a substituent, and E and G each independently have a substituent. Represents a 2-hydroxy-phenyl group or a 4,5-dicyano-2-imidazolyl group optionally having a substituent at the 3-position, R represents a hydrogen atom or an alkyl group, and m and n represent 0 or Represents 1. ] 4. A color ribbon for a sublimation transfer printer comprising a compound represented by the following general formula (1) or a compound represented by the following general formula (2) and a binder resin. Embedded image [Wherein A and B each independently represent a phenyl group which may have a substituent or a 4,5-dicyano-2-imidazolyl group which may have a substituent at the 3-position;
P represents a hydrogen atom or an alkyl group, Q represents an alkyl group or a phenyl group which may have a substituent, and a, b, and d represent 0 or 1. Where a + b + d =
2. Embedded image [In the formula, X represents a benzoyl group substituted with a hydroxy group or an alkoxy group or a benzotriazolyl group which may have a substituent, and E and G each independently have a substituent. Represents a 2-hydroxy-phenyl group or a 4,5-dicyano-2-imidazolyl group optionally having a substituent at the 3-position, R represents a hydrogen atom or an alkyl group, and m and n represent 0 or Represents 1. ] 5. A compound represented by the following general formula (1):
a metal complex dye formed from a salt of u, Co, Ni or Fe or a compound represented by the following general formula (2) with C
An aqueous coloring composition containing at least one metal complex dye formed from a salt of u, Co, Ni or Fe. Embedded image [Wherein A and B each independently represent a phenyl group which may have a substituent or a 4,5-dicyano-2-imidazolyl group which may have a substituent at the 3-position;
P represents a hydrogen atom or an alkyl group, Q represents an alkyl group or a phenyl group which may have a substituent, and a, b, and d represent 0 or 1. Where a + b + d =
2. ] [In the formula, X represents a benzoyl group substituted with a hydroxy group or an alkoxy group or a benzotriazolyl group which may have a substituent, and E and G each independently have a substituent. Represents a 2-hydroxy-phenyl group or a 4,5-dicyano-2-imidazolyl group optionally having a substituent at the 3-position, R represents a hydrogen atom or an alkyl group, and m and n represent 0 or Represents 1. ] 6. A compound represented by the following general formula (1):
a metal complex dye formed from a salt of u, Co, Ni or Fe or a compound represented by the following general formula (2) with C
An oil-based coloring composition containing at least one metal complex dye formed from a salt of u, Co, Ni or Fe. Embedded image [Wherein A and B each independently represent a phenyl group which may have a substituent or a 4,5-dicyano-2-imidazolyl group which may have a substituent at the 3-position;
P represents a hydrogen atom or an alkyl group, Q represents an alkyl group or a phenyl group which may have a substituent, and a, b, and d represent 0 or 1. Where a + b + d =
2. ] [In the formula, X represents a benzoyl group substituted with a hydroxy group or an alkoxy group or a benzotriazolyl group which may have a substituent, and E and G each independently have a substituent. Represents a 2-hydroxy-phenyl group or a 4,5-dicyano-2-imidazolyl group optionally having a substituent at the 3-position, R represents a hydrogen atom or an alkyl group, and m and n represent 0 or Represents 1. ]