JP2000160075A - Colorant and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve color purity and durability of a colorant by comprising a phthalocyanine compound compatible with a resin, and the resin, wherein both the colorant and the resin are each specific in view of a maximum adsorption wavelength and a heat decomposition starting temperature. SOLUTION: This colorant comprises a phthalocyanine compound compatible with a resin, desirably dissolving at least 1 wt.% in the resin or dissolving at least 1 wt.% in a solvent, having a maximum adsorption wavelength of 600-700 nm and a heat decomposition starting temperature of at least 300 deg.C, desirably 350-600 deg.C, and the resin (e.g. a styrene-acrylate copolymer). The colorant is further produced in a benzonitrile solvent, and particularly preferably comprises a phthalocyanine compound obtained by a phthalonitrile method. Furthermore, the colorant comprises a phthalocyanine compound represented by the formula, wherein R1-R16 are: at least two are each a 1-20C straight alkyl, branched alkyl or cyclic alkyl and the others are H; M is a divalent metal (e.g. Zn).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phthalocyanine compound compatible with a resin, a colorant containing the resin, and a color toner composition for electrophotography and an ink jet ink composition containing the phthalocyanine compound. It is.

The phthalocyanine compound contained in the colorant of the present invention has an absorption at 600 to 700 nm and is excellent in solvent solubility, light resistance, and heat resistance, and therefore exhibits excellent effects when used as a colorant. I do.

Further, the present invention provides a blue colorant having excellent solubility and high fastness, for example, dyeing of fibers, paints for automobiles, paints for building materials, colorants for printing plates, inks for writing implements,
Excellent effect when used as a colorant for glass flakes, a colorant for eyeglass lenses, and the like. The present invention exhibits a very excellent effect particularly when used for a cyan colorant.

[0004]

2. Description of the Related Art In recent years, organic dyes have been
In the information recording field, as the colorization of information display images or their hard copies progresses, their functions are paid attention to, and as display materials or recording materials, for example, dyes for sublimation transfer, ink for ink jet, color separation used for imaging tubes Absorbs in the visible region of filters, color filters for liquid crystal displays, color filters for optics, color toners, barcode inks for preventing tampering and counterfeiting, dichroic dyes for guest-host type liquid crystal displays, dichroic dyes for polarizing plates, etc. There is an increasing demand for the development of so-called visible light absorbing functional dyes.

In recent years, in particular, the use of electronic images including computer graphics has been rapidly increasing. Accordingly, it has been required to record electronic images such as video movies and television images of electronic still cameras as color hard copies. ing.

In electrophotography, an electrostatic latent image is generally formed on a photoconductive photoreceptor by charging and exposure.
Then, the electric latent image is developed with toner, and the obtained toner image is transferred to a transfer paper or the like as necessary, and is fixed by heating, pressing, or the like to form a visible image. As the toner for this purpose, a toner in which a black colorant such as carbon black is dispersed in a binder resin is often used. However, in recent years, the use of electronic images, including computer graphics, has been rapidly increasing, and colorization has also been promoted in electrophotographic systems, and yellow, magenta, and cyan color dyes are contained in a binder resin. And / or a color toner prepared by melting or dispersing a pigment.

Conventionally, as a method for producing a full-color toner, a binder resin and a colorant are melted and kneaded.
Generally, a method of pulverizing and then classifying to obtain a particle having a predetermined particle size distribution is used. At this time, a pigment is usually used as a coloring agent, but there is a problem that transparency is inferior in coloring with a pigment because the coloring agent is merely dispersed in a binder resin. In particular, when an image is formed on a transparent sheet or the like for an overhead projector, the projected image becomes dim and the color tone becomes cloudy. The problem of transparency can be improved to some extent by reducing the particle size of the pigment particles to about submicron, but it is difficult to pulverize the pigment to about submicron, and the pigment is finely dispersed uniformly in the binder resin. But it is very difficult to disperse them.

For this reason, the use of a dye soluble in a binder resin has been studied in many cases, but the use of a dye as a coloring agent has a problem that light resistance is mainly deteriorated.
Therefore, the use of a dye having high miscibility and high light resistance in a binder resin has been studied. For example, an anthraquinone cyan dye is disclosed in
JP-A-1-284865, JP-A-2-47668
JP-A-2-110573, JP-A-2-13246
No. 2, JP-A-3-87754, JP-A-5-10781
No. 2 and the like are disclosed. However, at present, there is nothing satisfying all of transparency, color tone and light resistance.

[0009] Also, ink-jet inks often provide critical printing characteristics. That is,
Aqueous inkjet inks generally do not conform to paper and have poor permeability and drying properties to paper. On the other hand, oil-based ink is easy to adjust to paper, but has a drawback that since the surface tension is poor, an excessively large ink dot is generated, and the print quality is deteriorated. On the other hand, solid or semi-solid type inks have the feature that prints with good contrast can be obtained, and are expected to have future prospects. At present, there is no one that satisfies both properties and color tones at the same time.

[0010]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a phthalocyanine compound compatible with a resin, a colorant containing the resin, and a color toner composition for electrophotography containing the phthalocyanine compound and an ink jet printer. An object of the present invention is to provide an ink composition.

Another object of the present invention is to provide a colorant having excellent solubility and high fastness.

Another object of the present invention is to provide a color toner for electrophotography which satisfies all of transparency, color tone and light fastness as a cyan color toner by using a dye which is soluble or miscible in a binder resin. It is to provide a composition.

Still another object of the present invention is to provide an ink-jet ink composition which can provide a print having good contrast and can provide a recorded image excellent in light fastness and color tone.

[0014]

That is, the above objects of the present invention are achieved by the following (1) to (4).

(1) The maximum absorption wavelength is 600 to 700 n
m, and a thermal decomposition initiation temperature of 300 ° C. or higher, and a phthalocyanine compound compatible with the resin and a resin.

(2) The following general formula (1)

[0017]

Embedded image

[In the formula, at least two of R ^{1 to} R ¹⁶ are a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, the other represents a hydrogen atom, and M is a divalent metal. Represents ]
A colorant comprising a phthalocyanine compound represented by the formula: and a resin.

(3) An electrophotographic color toner composition comprising the phthalocyanine compound according to (1) or (2).

(4) An ink-jet ink composition comprising the phthalocyanine compound according to (1) or (2).

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The colorant according to the present invention has a maximum absorption wavelength of 600 to 700 nm and a thermal decomposition onset temperature of 30.
It is characterized by comprising a phthalocyanine compound having a temperature of 0 ° C. or higher, preferably 350 to 600 ° C., which is compatible with the resin, preferably 1% by weight or more in the resin. In particular, the maximum absorption wavelength in a diethylene glycol dimethyl ether solvent is 600 to 700 n.
m, and the thermal decomposition onset temperature is 300 ° C. or higher, preferably 3 ° C.
50-600 ° C, solubility of 2% by weight in resin
Those characterized by containing the phthalocyanine compound described above are more preferable.

The pyrolysis onset temperature referred to herein is measured by a differential thermal-thermogravimetric simultaneous measuring device (DAT-TGA),
It was defined as the temperature at which the degree of thermogravimetric loss per ° C became 0.3% by weight / ° C or more.

The maximum absorption wavelength of the phthalocyanine compound contained in the coloring agent is from 600 to 700 nm. When the maximum absorption wavelength is out of the range of 600 to 700 nm, the color when used as a colorant or the like is deviated from the cyan type, so that the colorant containing the phthalocyanine compound has high color purity characteristics. Is not preferred.
On the other hand, when the maximum absorption wavelength in the diethylene glycol dimethyl ether solvent is in the range of 600 to 700 nm, it can be said that it is particularly preferable because the color when used as a colorant or the like conforms to cyan.

The thermal decomposition onset temperature of the phthalocyanine compound contained in the coloring agent is 300 ° C. or higher, preferably 350 to 600 ° C. When the temperature is lower than 300 ° C., the colorant containing the phthalocyanine compound can have sufficient robustness, for example, when used as a colorant or the like, fading due to heat applied during processing may occur. Not preferred. On the other hand, the thermal decomposition starting temperature is 350-
In the case of 600 ° C., the above-mentioned effects are more remarkable, so that it is particularly desirable.

The phthalocyanine compound contained in the colorant is compatible with the resin, preferably, at least 1% by weight of the resin. If not compatible with the resin, the versatility of the colorant containing the phthalocyanine compound is narrowed,
It is not preferable because the usage is restricted. On the other hand, a colorant having a high color purity can be obtained, so that it is preferably soluble in a resin at 1% by weight or more. Further, a colorant having a higher color purity can be obtained, and the solubility in the resin is 2% by weight.
The above is particularly preferable.

As used herein, the term "compatible with a resin" means that the resin may be slightly dissolved in the resin, and the solubility may be small or small. Further, the resin is not limited to a specific resin, and various types of conventionally known resins can be used as the resin. Examples thereof include polystyrene, polyvinyl toluene, poly α-methyl styrene, poly p-chlorostyrene, and amino styrene. Such as styrene and its derivatives or styrene-vinyl naphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer,
Styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene- Acrylonitrile copolymer, styrene-
Vinyl methyl ether copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-
Styrene-based copolymers such as acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer, and methacrylic acid esters such as methacrylic acid and methyl methacrylate, ethyl methacrylate, and butyl methacrylate. Or a copolymer, acrylic acid and methyl acrylate, ethyl acrylate, butyl acrylate, homo- or copolymers of acrylates such as 2-ethylhexyl acrylate, butadiene, dienes such as isoprene, acrylonitrile, vinyl ethers, maleic acid and Maleic esters, maleic anhydride, vinyl chloride, vinyl acetate and other vinyl monomers alone or copolymers with other monomers, and olefin compounds such as ethylene and propylene alone The copolymers, polyesters, polyamides, polyurethanes, rosin, modified rosin, terpene resins, phenol resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffin, and paraffin wax. Of these, homo- or copolymers of styrene-based compounds, homo- or copolymers of olefin-based compounds, homo- or copolymers of acrylates, waxes, and homo- or copolymers of styrene-based compounds, Waxes are particularly preferred. That is, it can be said that the phthalocyanine compound contained in the colorant of the present invention only needs to be compatible with at least one kind of resin, and does not have to be compatible with other resins.

The phthalocyanine compound contained in the colorant is soluble in a solvent, preferably 1% by weight in the solvent.
What dissolves above is preferable. It is not preferable that the colorant containing the phthalocyanine compound is insoluble in a solvent, because the versatility of the colorant containing the phthalocyanine compound is narrowed, and the usage is restricted. The term "soluble in a solvent" as used herein means that the solvent may be dissolved in the solvent even if it is a little, and the solubility is not limited, whether it is hardly soluble or easily soluble. The solvent is not limited to a specific solvent, and various types of conventionally known solvents can be used as the solvent. Examples thereof include a hydrocarbon-based solvent, a halogen-based hydrocarbon-based solvent, an alcohol-based solvent, and an ether-based solvent. , Ketone solvents, ester solvents, nitrogen-containing solvents, sulfur-containing solvents, water and the like.

The colorant of the present invention also preferably comprises a phthalocyanine compound produced in a benzonitrile solvent. It is preferable to produce the phthalocyanine compound in a benzonitrile solvent because the purity is high and as a result, a phthalocyanine compound having high solubility in a solvent or a resin is obtained.
As a method for producing a phthalocyanine compound in a benzonitrile solvent, a known general method can be used. That is, there are a Weyler method produced by reacting urea and a metal salt in the presence of a condensed acid using phthalic anhydride or phthalic anhydride as a raw material, a phthalonitrile method produced by reacting phthalonitrile with a metal salt, and the like. In addition, it can also be produced using phthalic acid, phthalic diamide, 1,3-diiminoisoindoline and derivatives thereof as raw materials. Of these, the phthalonitrile method using phthalonitrile as a raw material is preferred. When manufacturing by a phthalonitrile method, a metal compound and phthalonitrile are reacted at a reaction temperature of 30 to 300 in a benzonitrile solvent.
C., preferably at 80-200.degree.

The coloring agent according to the present invention further has the following general formula (1):

[0030]

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[Wherein at least two of R ^{1 to} R ¹⁶ are a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms (these are independent of each other and may be the same or different) And the other represents a hydrogen atom, and M is 2
Represents a valent metal. ] The phthalocyanine compound represented by the formula: The phthalocyanine compound having such a chemical structural formula has an absorption at 600 to 700 nm due to its unique chemical structure, and has excellent solvent solubility, light resistance, and heat resistance. It has excellent effects. In particular, it exerts a very excellent effect when used as a cyan colorant.

In the general formula (1), at least two, preferably 3 to 6, of R ^{1 to} R ¹⁶ are a straight-chain or branched chain having 1 to 20, preferably 3 to 8 carbon atoms. , A cyclic alkyl group. Specifically, for example, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, iso-butyl, tert-butyl, cyclobutyl, n-pentyl, sec-pentyl, iso-pentyl, tert-pentyl , N
eo-pentyl, 3-pentyl, cyclopentyl, 2-methylbutyl, n-hexyl, iso-hexyl, sec-hexyl, 3-hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, tert-octyl, and the like. Can be.

In the general formula (1), M is a divalent metal, specifically, iron, magnesium, nickel,
Cobalt, copper, palladium, zinc and the like can be mentioned. Preferred are cobalt, copper, zinc and nickel, and particularly preferred is zinc.

The phthalocyanine represented by the general formula (1)
Preferably, R¹, R^Four, R^Five, R⁸,
R⁹, R¹², R¹³, R¹⁶Is a hydrogen atom, and R^TwoWhen
R^Three, R ⁶And R⁷, R^TenAnd R¹¹, R¹⁴And R¹⁵Combination of
At least one has 1 to 20 carbon atoms, preferably
Is a linear, branched or cyclic alkyl group having 3 to 8 carbon atoms (this
They are independent of each other, they can be the same or different
May be. ) Is a phthalocyanine compound, especially
Preferably, the following general formula (2)

[0035]

Embedded image

[Wherein, R represents a linear, branched or cyclic alkyl group having 3 to 8 carbon atoms, and M represents a divalent metal. ]. Specifically, for example, phthalocyanine compounds (1) to (2)
0).

[0037]

[Table 1]

Specific production examples of the phthalocyanine compounds shown in Table 1 above are shown below for the phthalocyanine compounds (1) and (2). Production Example of Phthalocyanine Compound (1) In a 100 ml four-necked flask, 15.00 g (50 mmol) of 4-t-butylphthalonitrile and zinc iodide 7.
80 g (24 mmol) and benzonitrile 60 m
and then reacted under reflux for 8 hours. After completion of the reaction, benzonitrile was distilled off, and the residue was washed twice with 500 ml of methanol to obtain 12.54 g of a target blue cake (yield: 76.8%).

Visible absorption spectrum Maximum absorption wavelength 674 nm (ε = 2.42 × 10 ⁵ ) in ethylene glycol methyl ether Thin film 682 nm Solubility 9 wt% based on ethylene glycol methyl ether Thermal decomposition onset temperature 516 ° C.

Production Example of Phthalocyanine Compound (2) In a 100 ml four-necked flask, 15.00 g (50 mmol) of 4-t-butylphthalonitrile, copper (I) chloride
2.42 g (24 mmol) and benzonitrile 6
0 ml was charged and reacted under reflux for 8 hours. After the completion of the reaction, benzonitrile was distilled off, and the resultant was washed twice with 500 ml of methanol to obtain a blue cake (11.78).
g was obtained (72.3% yield).

Visible absorption spectrum Maximum absorption wavelength 674 nm (ε = 1.87 × 10 ⁵ ) in polyethylene glycol dimethyl ether Thin film 631 nm Solubility 2.5% by weight based on polyethylene glycol dimethyl ether Thermal decomposition onset temperature 517 ° C.

The coloring agent of the present invention is not particularly limited as long as it is used for coloring metals, wood, concrete, plastic, glass, leather, fibers, clothes, and the like.
For example, colorants for plastics include pellets,
There are flakes, masterbatch colors in plate form, dry colors in granular form, liquid paste colors, and the like. In the case of a colorant for plastics, the constituent components of the colorant include the phthalocyanine compound, other dyes, pigments, metal salts of fatty acids, esters, amides, plastics, monomers, and the like.

That is, the constituents of the colorant of the present invention include:
What is necessary is just to contain the above-mentioned phthalocyanine compound, and in addition, it may have various dyes, pigments and other additives according to the usage form and the like. Of these, the amount of the phthalocyanine compound used as an essential component is not uniquely defined because the optimum range greatly varies depending on the use form and application, but is preferably defined with respect to the entire colorant. Is 5 to 80% by weight. When the use amount of the phthalocyanine compound is less than 5% by weight, the coloring power to the object to be colored is insufficient, and the excellent properties of the phthalocyanine compound cannot be effectively exhibited, which is not preferable. on the other hand,
If it exceeds 80% by weight, there is a disadvantage that coloring of the object to be colored is difficult to be uniform, which is not preferable.

Further, the present invention provides an electrophotographic color toner composition comprising the phthalocyanine compound (ie, the phthalocyanine compound contained in the colorant of the present invention), preferably comprising the phthalocyanine compound and a binder resin. And a color toner composition for electrophotography.

The binder resin applied to the color toner composition for electrophotography of the present invention is not particularly limited, and all known resins can be used. For example, styrene such as polystyrene, polyvinyl toluene, poly α-methyl styrene, poly p-chlorostyrene, amino styrene and derivatives thereof, styrene-vinyl naphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate Copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene -Α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, Sushi Styrene-based copolymers such as len-maleic acid copolymer and styrene-maleic acid ester copolymer, methacrylic acid and homo- or copolymers of methacrylic acid esters such as methyl methacrylate, ethyl methacrylate and butyl methacrylate, acrylic acid And methyl acrylate, ethyl acrylate, butyl acrylate,
Homo- or copolymers of acrylic esters such as 2-ethylhexyl acrylate, dienes such as butadiene and isoprene, acrylonitrile, vinyl ethers, maleic acid and maleic esters, maleic anhydride, vinyl chloride and vinyl acetate A single monomer or a copolymer with another monomer, ethylene or a single or copolymer of an olefin compound such as propylene,
Polyester, polyamide, polyurethane, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like can be used alone or in combination.

The ratio between the binder resin and the phthalocyanine compound depends on the type used, but the ratio of the phthalocyanine compound is 0.1 to 100 parts by weight of the binder resin.
10 to 10 parts by weight, preferably 1 to 6 parts by weight. When the ratio is less than 0.1 part by weight of the phthalocyanine compound with respect to 100 parts by weight of the binder resin, the coloring power of the color toner composition is insufficient and the excellent phthalocyanine compound has an excellent specific wavelength range. Various properties such as absorptivity, solvent solubility, light resistance, heat resistance, etc. cannot be effectively exhibited, and excellent transparency, color tone, and light resistance as a cyan color toner desired for an electrophotographic color toner composition. Is not preferred because it is not possible to have all of the above.
If the ratio exceeds 10 parts by weight of the phthalocyanine compound with respect to 100 parts by weight of the binder resin, the fixability of the color toner composition becomes insufficient, which is not preferable.

One of the important properties of the electrophotographic color toner composition of the present invention is chargeability. The charge control of the electrophotographic color toner composition of the present invention is performed by using a binder resin and a phthalocyanine compound. (Coloring agent) It may be carried out by itself, but if necessary, a charge controlling agent which does not change the color tone may be added. The charge control agent applied to the electrophotographic color toner composition of the present invention is not particularly limited and includes all known ones. For example, salicylic acid metal complexes, organic boron salts, quaternary ammonium salts , Aluminum compounds, silicone derivatives, zinc compounds, imidazole metal complexes,
Pyridinium salts and the like can be used alone or in combination of two or more.

The amount of the charge control agent to be added depends on the binder resin 1
A suitable amount is 0.05 to 15 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight. If the addition amount of the charge control agent is less than 0.05 part by weight with respect to 100 parts by weight of the binder resin, the desired charge performance cannot be exhibited effectively and sufficiently, which is not preferable. On the other hand, when the added amount of the charge controlling agent exceeds 15 parts by weight with respect to 100 parts by weight of the binder resin, the desired charging performance has already been exhibited effectively and sufficiently, and an effect commensurate with further addition is obtained. Is relatively expensive and uneconomical. These charge control agents can be used by being mixed and added to a binder resin, and can also be used in such a form as to adhere to the surface of the electrophotographic color toner composition particles by various methods.

In addition, the electrophotographic color toner composition of the present invention contains a metal electrolyte such as a solid electrolyte, a polymer electrolyte, a charge transfer complex, and tin oxide for the purpose of controlling the electrical characteristics of the electrophotographic color toner composition. Conductors such as oxides, semiconductors or ferroelectrics, magnetic substances, etc. can be added in appropriate amounts.Addition of various plasticizers and release agents for the purpose of adjusting various physical properties such as thermal properties An appropriate amount of the agent can be added. Furthermore, TiO ₂ , Al ₂
An appropriate amount of fine particles such as O ₃ or SiO ₂ or inorganic fine particles such as colloidal silica or organic fine particles such as resin fine particles may be added to improve the fluidity and aggregation resistance of the toner.

As the method for producing the color toner composition for electrophotography of the present invention, general methods or various methods conventionally used can be applied. For example, as a general method, a binder resin, a phthalocyanine compound and other colorants such as other various dyes and pigments as needed, and optionally various additives are uniformly mixed using a ball mill or various mixers, and then, This mixture was melted and kneaded using a pressure kneader, extruder, roll mill, etc., and then the kneaded material was coarsely pulverized with a hammer mill and the like, and further pulverized with a pulverizer using an air jet method. A method of classifying the fine powder into a color toner composition for electrophotography can be used. In addition, as another method, a polymerizable monomer is polymerized by a polymerization method such as an emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method, or a seed polymerization method in the presence of a coloring agent, and a predetermined average particle diameter is obtained. A method for obtaining a color toner composition for electrophotography by obtaining impregnated colored resin fine particles can be used. Further, as another method, a polymerizable monomer is polymerized by a pulverization and classification method similar to a normal toner production method, or an emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method, a polymerization method such as a seed polymerization method,
It is also possible to use a method in which resin fine particles having a predetermined average particle diameter are synthesized in advance, and the particles are colored or dyed with a colorant to obtain a color toner composition for electrophotography.

Further, the electrophotographic color toner composition of the present invention can be mixed with a carrier at an appropriate mixing ratio and used as an electrophotographic developer. As a carrier at this time, in addition to known iron powder, nickel powder, glass beads, and ferrite powder, a styrene-acrylate copolymer, a styrene-methacrylate copolymer acrylic Those coated with an ester polymer, a methacrylate polymer, a silicone resin, a polyamide resin, an ionomer resin, a polyphenylene, a sulfide resin, or a mixture thereof can be used.

Further, the present invention is an ink-jet ink composition comprising the phthalocyanine compound (that is, the phthalocyanine compound contained in the coloring agent of the present invention). Preferably, it is an ink-jet ink composition containing the phthalocyanine compound and a vehicle.

Ink jet recording depends on the system.
There are continuous jet type, intermittent jet type, on-demand type, ink mist type, and water-based, water-solvent-based, solvent-based, and solid type ink jet inks have been developed.
Generally, water-based ones are the mainstream. Among them, solid-type inks are usually solid or semi-solid at room temperature, and are heated by an inkjet apparatus.
It is liquid and is ejected, and the heated ink liquid contacts the target and solidifies and is recorded.However, printing from OHP film to tissue paper is possible, and a print with good contrast is obtained. Although there are some prospects for the future, there is no dye for solid ink that satisfies both light resistance and color tone at the same time.

Since the phthalocyanine compound contained in the ink composition for ink jet of the present invention has high solvent solubility, very high light fastness and excellent hue, it can be used in any of the ink compositions for ink jet ink. Although excellent effects are also exhibited in the method of use (type), among them, it is suitable as a dye for a solvent-based, solid or semi-solid type ink, particularly a solid or semi-solid type ink.

The amount of the phthalocyanine compound to be used cannot be unambiguously defined because the optimum range varies depending on the method of use and the like, but it is usually 0.1 to 25% by weight with respect to the ink composition for ink jet. %, Preferably 0.5 to 20% by weight. The content of the phthalocyanine compound is 0.1 to the ink composition for inkjet.
If the amount is less than 10% by weight, the color density is insufficient and the phthalocyanine compound effectively exhibits various properties such as excellent absorption capacity in a specific wavelength region, solvent solubility, light resistance, heat resistance and the like. Therefore, printing with good contrast can be performed as an ink composition for an ink jet, and a recorded image excellent in color tone and light fastness cannot be obtained. On the other hand, when the content of the phthalocyanine compound is more than 25% by weight based on the whole ink composition for ink jet, the storage stability of the ink composition is deteriorated, and the viscosity increases or precipitates due to ink evaporation near the nozzle tip. It is not preferable because non-discharge is easily caused.

As a vehicle which can be used in the ink composition for ink jet of the present invention, for example, in the case of a drying oil type ink composition for ink jet, rosin-modified phenol resin, petroleum resin, alkyd resin, etc. As the drying oil, linseed oil, cutting oil and synthetic drying oil can be used, and as the solvent, a petroleum-based solvent can be used. Further, in the case of an organic solvent-based inkjet ink composition, a resin such as a polyamide resin, a vinyl-based nitrocellulose resin, or an acrylic resin can be used as the resin, and the solvent can be toluene, an ester-based solvent, a ketone-based solvent, or an alcohol-based solvent. . Further, in the case of water-based, water-solvent-based inkjet ink compositions, the resin is maleic acid-based resin, acrylic resin, etc., the solvent is water,
Alcohol solvents, glycol solvents and the like can be used.
In addition, in the case of a solid or semi-solid type ink-jet ink composition, a wax is used as an additive to a fatty acid such as oleic acid such as oleic acid or a fatty acid such as oleic acid containing benzyl ether as a vehicle. Raw materials or wax can be used as a main component.

Examples of the wax used as a vehicle component of the solid or semi-solid type ink-jet ink composition include all known waxes, such as wood wax, candelilla wax, carnauba wax, and microcrystalline wax. , Paraffin wax, Fischer-Tropsch wax, polyolefin wax, various low molecular weight polyethylenes, beeswax, spermaceti, Ibota wax, wool wax, ceramics wax, candelilla wax, petrolactam, fatty acid ester wax, fatty acid amide wax, long chain acrylate (for example, stearyl) Acrylate, behenyl acrylate, etc.) or long chain acryle such as long chain methacrylate (eg, stearyl methacrylate, behenyl methacrylate, etc.) Or a wax obtained from a polymer of methacrylate or long-chain methacrylate, or an acrylic or methacrylic copolymer containing such a long-chain acrylate or long-chain methacrylate, or a copolymer with another monomer having a vinyl group. Can be used. Also, these waxes may be used in a composite form such as grafting at an appropriate ratio.

Further, the amount of the entire vehicle component to be used cannot be univocally defined because it differs depending on the use method (type) of the ink composition for ink jet. However, it is generally 5 to 99% based on the ink composition for ink jet. %, Preferably 10 to 99% by weight. When the usage amount of the entire vehicle component is less than 5% by weight based on the ink composition for ink jet, the storage stability of the ink composition is insufficient, and sufficient ink spreading performance can be exhibited. Not preferred. On the other hand, when the use amount of the entire vehicle component exceeds 99% by weight based on the ink composition for inkjet, the ratio of the phthalocyanine compound contained is relatively reduced, and a sufficient coloring effect can be exhibited. Not preferred.

The amount of wax used as a vehicle component of the solid or semi-solid type ink-jet ink composition is 0.5 to 99% by weight, preferably 10 to 99% by weight, based on the whole ink-jet ink composition.
99% by weight. When the amount of the wax used is less than 0.5% by weight based on the ink composition for inkjet,
Wettability to the obtained ink-jet ink composition, dispersibility when the ink-jet ink composition is blown out from a fine nozzle, fixability of the wettable ink-jet ink composition to a recording agent (paper, film, etc.), Recording material (paper,
This is not preferable because various properties such as water repellency and water resistance of the inkjet ink composition after fixing and drying onto a film or the like cannot be imparted. On the other hand, when the amount of the wax exceeds 99% by weight with respect to the ink composition for inkjet, the ratio of the phthalocyanine compound relatively contained is reduced, and a sufficient coloring effect cannot be exhibited, which is preferable. Absent.

[0060]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.

Example 1 4 parts of the phthalocyanine compound (1) shown in Table 1 above and 97 of a styrene-acrylate copolymer (trade name, Hymer TB1000F, manufactured by Sanyo Chemical Co., Ltd.)
The portion was melt-kneaded at a temperature of about 150 ° C. with a hot roll, cooled, coarsely pulverized using a hammer mill, and then finely pulverized by an air jet type pulverizer. The obtained fine powder was classified, and 3 to 20 μm was selected to obtain a color toner composition for electrophotography.

Four parts of the electrophotographic color toner composition were uniformly mixed with 100 parts of a carrier (50 to 150 μm ferrite powder coated with a silicon resin) to prepare a developer. Using this developer, copying was performed with a dry plain paper electrophotographic copier [trade name, FT-4060, manufactured by Ricoh Co., Ltd.], and a clear cyan image without fog was obtained. In addition, the light resistance of the copied image was measured using a Xenon lamp light resistance tester (SUNTEST CPS Heraeus).
(Black panel temperature 63 ° C.)
The color density was measured using a densitometer model RD-914 manufactured by Macbeth Co., USA, and the color density after 100 hours was evaluated. When the initial color density was 100%, the color density was 9%.
The color density remaining ratio was 2% or more, and the light resistance was good.

Examples 2 to 4 (1) Preparation of Recording Ink (Inkjet Ink Composition) The components shown in Table 2 below were sufficiently mixed and dissolved under heat and then cooled to record. An ink (ink-jet ink composition) was prepared. (2) Recording Next, the obtained recording ink was inserted by using a partially improved inkjet printer for solid ink, and inkjet recording was performed. As a result, in each case, the contrast was very clear and the contrast was high. A recorded image having high color tone and good color tone was obtained. The light resistance was evaluated by the following method. (3) Evaluation of light fastness The recorded image was evaluated using a Xenon lamp light fastness tester (SUNTE
ST CPS Heraeus Co., Ltd.) (black panel temperature 63 ° C.), a light fastness test, and color density was measured using a densitometer RD-914 manufactured by Macbeth Co., USA.
The evaluation was made based on the residual ratio of the color density after time.
When it was set to 00%, the color density afterimage rate was 90% or more in each case, and the light resistance was good.

Table 2 shows the results.

[0065]

[Table 2]

[0066]

According to the invention of the colorant of the present invention, the maximum absorption wavelength is 600 to 700 nm and the thermal decomposition onset temperature is 300.
° C. or higher, and is characterized by comprising a phthalocyanine compound and a resin compatible with the resin or the phthalocyanine compound and the resin represented by the general formula (1), that is, excellent absorption at 600 to 700 nm. Since it contains a phthalocyanine compound and a resin having excellent solubility and heat resistance in a resin, sufficient dispersibility in the resin and the like is obtained, and has excellent color purity as a colorant and durability. It is also possible to provide a coloring agent having excellent color purity. Further, among the present invention, phthalocyanine having a maximum absorption wavelength in a diethylene glycol dimethyl ether solvent of 600 to 700 nm, a solubility of 2% by weight or more in a resin, and a thermal decomposition onset temperature of 300 ° C. or more. Compound and resin, or R ¹ in the above general formula (1),
R ⁴ , R ⁵ , R ⁸ , R ⁹ , R ¹² , R ¹³ , and R ¹⁶ are hydrogen atoms, and R ² and R ³ , R ⁶ and R ⁷ , R ¹⁰ and R ¹¹ , R ¹⁴ and R ¹⁵ At least one of the combinations has 1 to 1 carbon atoms.
20, a phthalocyanine compound and a resin, preferably a straight-chain, branched-chain or cyclic alkyl group having 3 to 8 carbon atoms (these are independent of each other, and may be the same or different). The phthalocyanine compound containing the phthalocyanine compound represented by the general formula (2) and the resin has a more remarkable action and effect (including a peak effect), and has extremely excellent color purity characteristics, light resistance and heat resistance. . Therefore, when used as a coloring agent for fibers, paints for automobiles, coloring agents for printing plates, inks for writing implements, coloring agents for glass flakes, coloring agents for spectacle lenses, etc., they exert extremely excellent effects.

Since the color toner composition for electrophotography according to the present invention contains the above-mentioned phthalocyanine compound, it is particularly high in transparency, so that an image having a good color tone with excellent color reproducibility in a color image can be obtained. It has good light fastness and always obtains a stable image even in continuous copying.

Further, since the ink composition for inkjet according to the present invention contains the above-mentioned phthalocyanine compound, a print having good contrast can be obtained, and a recorded image excellent in light resistance and color tone can be obtained. is there.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Seiji Masuda 1-25-12 Kannondai, Tsukuba City, Ibaraki Pref. Nippon Shokubai Co., Ltd.

Claims (4)

[Claims] 1. A coloring agent having a maximum absorption wavelength of 600 to 700 nm, a thermal decomposition initiation temperature of 300 ° C. or higher, and comprising a phthalocyanine compound and a resin compatible with the resin. 2. The following general formula (1): [Wherein at least two of R ^{1 to} R ¹⁶ have 1 to 1 carbon atoms.
20 are linear, branched or cyclic alkyl groups, the others represent hydrogen atoms, and M represents a divalent metal. ] The coloring agent characterized by containing the phthalocyanine compound shown by these, and resin. 3. A color toner composition for electrophotography, comprising the phthalocyanine compound according to claim 1. 4. An ink-jet ink composition comprising the phthalocyanine compound according to claim 1. Description: