WO2011122427A1 - Water-soluble azo compound or salt thereof, ink composition and colored body - Google Patents
Water-soluble azo compound or salt thereof, ink composition and colored body Download PDFInfo
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- WO2011122427A1 WO2011122427A1 PCT/JP2011/057112 JP2011057112W WO2011122427A1 WO 2011122427 A1 WO2011122427 A1 WO 2011122427A1 JP 2011057112 W JP2011057112 W JP 2011057112W WO 2011122427 A1 WO2011122427 A1 WO 2011122427A1
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- water
- formula
- ink
- salt
- ink composition
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- 0 C*c(c(N)c1)ccc1N Chemical compound C*c(c(N)c1)ccc1N 0.000 description 3
- ASWMXOVRFWWJGK-MSUUIHNZSA-N Nc(c(/N=N\c(cc1S(O)(=O)=O)ccc1Cl)c1)cc(N)c1O Chemical compound Nc(c(/N=N\c(cc1S(O)(=O)=O)ccc1Cl)c1)cc(N)c1O ASWMXOVRFWWJGK-MSUUIHNZSA-N 0.000 description 1
- VPXCXBHLKDPWQV-UHFFFAOYSA-N Nc(cc1)cc(S(O)(=O)=O)c1Cl Chemical compound Nc(cc1)cc(S(O)(=O)=O)c1Cl VPXCXBHLKDPWQV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B43/00—Preparation of azo dyes from other azo compounds
- C09B43/12—Preparation of azo dyes from other azo compounds by acylation of amino groups
- C09B43/136—Preparation of azo dyes from other azo compounds by acylation of amino groups with polyfunctional acylating agents
- C09B43/16—Preparation of azo dyes from other azo compounds by acylation of amino groups with polyfunctional acylating agents linking amino-azo or cyanuric acid residues
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/70—Other substituted melamines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/0003—Monoazo dyes prepared by diazotising and coupling from diazotized anilines
- C09B29/0007—Monoazo dyes prepared by diazotising and coupling from diazotized anilines containing acid groups, e.g. CO2H, SO3H, PO3H2, OSO3H, OPO2H2; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
- C09B29/08—Amino benzenes
- C09B29/0801—Amino benzenes containing acid groups, e.g. COOH, SO3H, PO3H2, OSO3H, OPO3H2; SO2NHSO2R or salts thereof, R being hydrocarbonyls
- C09B29/0803—Amino benzenes containing acid groups, e.g. COOH, SO3H, PO3H2, OSO3H, OPO3H2; SO2NHSO2R or salts thereof, R being hydrocarbonyls containing SO3H, OSO3H
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B33/00—Disazo and polyazo dyes of the types A->K<-B, A->B->K<-C, or the like, prepared by diazotising and coupling
- C09B33/02—Disazo dyes
- C09B33/16—Disazo dyes from other coupling components
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
- C09B35/02—Disazo dyes
- C09B35/021—Disazo dyes characterised by two coupling components of the same type
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
- C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
- C09B62/08—Azo dyes
- C09B62/09—Disazo or polyazo dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/322—Pigment inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
Definitions
- the present invention relates to a water-soluble disazo compound or a salt thereof, an ink composition containing the same, and a colored body colored with these.
- ink ejection methods have been developed as recording methods using an ink jet printer, which is one of the representative methods. These all generate ink droplets and attach them to various recording materials (paper, film, fabric, etc.) for recording. In this method, since the recording head and the recording material are not in direct contact with each other, no noise is generated and the method is quiet. In addition, since it has the features that it is easy to downsize, speed up, and colorize, it has been spreading rapidly in recent years and is expected to grow greatly in the future. Conventionally, inks such as fountain pens and felt pens, and inks for ink-jet recording have been used in which water-soluble pigments (dyes) are dissolved in an aqueous medium.
- inks such as fountain pens and felt pens, and inks for ink-jet recording have been used in which water-soluble pigments (dyes) are dissolved in an aqueous medium.
- a water-soluble organic solvent is added to these water-based inks in order to prevent clogging of ink at a pen tip or an ink discharge nozzle.
- These inks give a recorded image of sufficient density, do not cause clogging of the pen tip and nozzles, have good drying properties on the recording material, have little bleeding, and have excellent storage stability. Such performance is required.
- Ink jet nozzle clogging occurs when the water in the ink evaporates in the vicinity of the nozzle before other solvents and additives, and the pigment solidifies and precipitates when the composition state is low in water and high in solvents and additives.
- the very important required performances is that solids are not easily deposited even when the moisture content in the ink is low. For this reason, high solubility in solvents and additives is one of the properties required for pigments.
- a method for eliminating nozzle clogging a method using a dye having a high printing density is known. By using a pigment having a high printing density, the pigment content in the ink can be reduced while maintaining the conventional printing density. This not only makes it difficult to precipitate the dye, but is also advantageous in terms of cost, and development of a dye having a high printing density is desired.
- the color area that can be expressed in a single color or mixed color becomes narrow, and the range of the color area that is desired to be expressed may be insufficient. For this reason, development of highly saturated pigments and inks containing them is desired.
- the ink performance is required to be stable for long-term storage, high in recorded image density, and excellent in fastness such as water resistance, moisture resistance, light resistance and gas resistance. It is done.
- the gas resistance means that a gas having an oxidizing action (also referred to as an oxidizing gas) existing in the air reacts with a dye (dye) of a recorded image on the recording material or in the recording material to record.
- ozone gas is considered to be a main causative substance that promotes the discoloration and fading phenomenon of ink jet recorded images. Since this discoloration phenomenon is characteristic of ink jet recorded images, improvement of ozone gas resistance is an important technical problem in this field.
- inkjet printers have the advantage that the type of recording paper is not limited, and the price of the printer itself is low, and the spread is particularly widespread in small to medium-sized office environments such as small offices and home offices (SOHO).
- SOHO small offices and home offices
- pigment ink does not dissolve in water-based ink, it does not enter a solution state, but is a dispersed ink. Therefore, when this is used for ink jet recording, there are problems with the stability of the ink itself and the nozzles of the recording head. Problems such as clogging occur.
- pigment ink when pigment ink is used, there is often a problem in abrasion resistance. In the case of a dye ink, such a problem is considered to be relatively difficult to occur.
- the water resistance is extremely inferior to that of a pigment ink, and an improvement to the problem is strongly desired.
- dye ink tends to cause a problem that a dye attached to the surface of plain paper by ink jet recording penetrates more quickly toward the back side of the paper, resulting in a decrease in color density.
- the ink receiving layer As one method for obtaining a photographic image-recorded inkjet image, there is a method of providing an ink receiving layer on the surface of a recording material.
- the ink receiving layer provided for such a purpose often contains a porous white inorganic substance in order to speed up drying of the ink and to reduce bleeding of the pigment with high image quality.
- the discoloration due to the ozone gas is noticeable.
- the above-mentioned color change of recorded images due to oxidizing gas is regarded as a problem. .
- yellow dyes Compared to the other three primary colors, magenta and cyan, yellow dyes have been proposed that have good resistance to oxidizing gas as well as light resistance. However, yellow dyes and yellow inks for inkjet recording that sufficiently satisfy the high sharpness and various fastnesses required by the market have not been obtained yet.
- Patent Document 1 discloses a yellow water-soluble azo compound having high solubility in water and having moisture resistance and light resistance.
- Patent Document 2 discloses a yellow water-soluble azo compound that is highly soluble in water and has moisture resistance, ozone gas resistance, and light resistance.
- Patent Document 3 discloses a yellow water-soluble azo compound that has high solubility in water and has moisture resistance, water resistance, ozone gas resistance, and light resistance.
- Patent Document 4 discloses a yellow water-soluble azo compound that is highly soluble in water and has moisture resistance, water resistance, ozone gas resistance, and light resistance.
- the present invention provides a water-soluble yellow coloring matter (compound) having high solubility in water and excellent balance between chroma and ozone gas resistance, and various yellow ink compositions containing the same, particularly for inkjet recording. Objective.
- the present invention 1) A water-soluble azo compound represented by the following formula (1) or a salt thereof, (In the formula, Q represents a halogen atom, x represents an integer of 2 to 4, and the group A represents an amino group represented by any one of the following formulas (2) to (7).) (In the formula (2), m represents an integer of 1 to 5.) (In formula (4), n represents an integer of 2 to 5) (In formula (6), Z represents a hydrogen atom, a carboxy group, or a sulfo group, and k represents an integer of 0 to 2.) (In formula (7), w represents an integer of 0 to 3.)
- a colored product colored by any of the ink composition containing a water-soluble azo compound or a salt thereof and a water-soluble organic solvent 13) A colored body colored by the inkjet recording method according to 9), 14) An ink jet printer loaded with a container containing the ink composition according to 6), About.
- the water-soluble azo compound of the present invention represented by the above formula (1) or a salt thereof has a high solubility in water, and for example, in the process of producing the ink composition of the present invention containing the compound or a salt thereof, It has the characteristic that the filterability with respect to a membrane filter is favorable.
- an image recorded by the ink composition of the present invention containing the compound of the present invention is excellent in the balance of chroma and ozone gas resistance as compared with the image using the conventional compound.
- the water-soluble azo compound of the present invention represented by the formula (1) or a salt thereof, and the ink composition containing the same are extremely useful for various recording ink applications, particularly ink jet recording ink applications. It is.
- the water-soluble azo compound of the present invention represented by the above formula (1) or a salt thereof is a water-soluble yellow dye.
- acidic functional groups such as sulfo groups and carboxy groups are represented in the form of free acids.
- the present invention includes both the water-soluble azo compound represented by the formula (1) or a salt of the compound, but it is complicated to always describe both of them as “compound or salt thereof”. It is. Therefore, unless otherwise specified, for convenience, the “water-soluble azo compound of the present invention or a salt thereof” including both the “water-soluble azo compound of the present invention” will be simply described as “the (water-soluble azo) compound of the present invention”.
- the compound of the present invention is represented by the above formula (1).
- Q represents a halogen atom.
- the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- a fluorine atom or a chlorine atom is preferable, and a chlorine atom is particularly preferable.
- x represents an integer of 2 to 4, preferably 3.
- the group A represents an amino group represented by any one of the above formulas (2) to (7).
- m in the formula (2) represents an integer of 1 to 5, preferably 1 or 2, and more preferably 1.
- N in Formula (4) represents an integer of 2 to 5, preferably 2.
- Z in Formula (6) represents a hydrogen atom, a carboxy group, or a sulfo group, and preferably represents a sulfo group.
- K represents an integer of 0 to 2, preferably 0 or 1, more preferably 1.
- W in Formula (7) represents an integer of 0 to 3, preferably 0. That is, the amino group represented by the formula (7) is preferably a monomethylamino group.
- an amino group represented by the formula (2), the formula (6), or the formula (7) is more preferable.
- the compound of the present invention represented by the above formula (1) can be produced, for example, as follows.
- Q, x, m, n, Z, k, and w used appropriately in the following formulas (AA) to (K) represent the same meanings as described above.
- a compound represented by the following formula (AA) obtained using a commercially available 2-amino-4-halogenophenol as a raw material is obtained using sodium bisulfite and formalin.
- Specific examples of the amine represented by the formula (F) include glycine, ⁇ -alanine, 4-aminobutyric acid, 5-aminovaleric acid, and 6-aminohexanoic acid.
- the amine of the said formula (G) can obtain a commercial item easily as iminodiacetic acid.
- Specific examples of the amine of the above formula (H) include 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, and 5-aminopentanol.
- the amine of the said formula (I) can obtain a commercial item easily as diethanolamine.
- Examples of the amine represented by the above formula (J) include 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, and 4-aminobenzoic acid.
- Specific examples include acid, aniline, benzylamine, phenethylamine, 4-aminomethylbenzenesulfonic acid, 4-aminoethylbenzenesulfonic acid, and 4-aminomethylbenzoic acid.
- Specific examples of the amine represented by the formula (K) include methylamine, ethylamine, n-propylamine, and n-butylamine, and methylamine is preferable.
- the compound represented by the above formula (1) exists also as a free acid or a salt thereof.
- the salt of the compound represented by the formula (1) include salts with inorganic or organic cations.
- Specific examples of the inorganic cation salt include alkali metal salts such as lithium salts, sodium salts, potassium salts and the like; and ammonium salts (NH 4 + ).
- Examples of organic cation salts include, but are not limited to, quaternary ammonium salts represented by the following formula (11).
- Z 1 to Z 4 each independently represent a hydrogen atom, a C1-C4 alkyl group, a hydroxy C1-C4 alkyl group, a hydroxy C1-C4 alkoxy C1-C4 alkyl group, and Z 1 -Z 4 At least one of is a group other than a hydrogen atom.
- examples of the C1-C4 alkyl group in Z 1 to Z 4 include methyl, ethyl and the like.
- examples of the hydroxy C1-C4 alkyl group include hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl and the like.
- examples of the hydroxy C1-C4 alkoxy C1-C4 alkyl group include hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3- (hydroxyethoxy) propyl, 3- (hydroxyethoxy) butyl, 2- (hydroxyethoxy ) Butyl and the like.
- alkali metal salts such as sodium, potassium and lithium
- organic quaternary ammonium salts such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine and triisopropanolamine salts
- Ammonium salt and the like.
- lithium salts, sodium salts, and ammonium salts are more preferable.
- the salt or free acid of the compound represented by the above formula (1) can be easily obtained by the following method or the like.
- the reaction solution after completion of the final step or the aqueous solution containing the salt of the compound represented by the formula (1) for example, acetone or C1-C4 alcohol
- a method of adding a water-soluble organic solvent, a method of salting out by adding sodium chloride, and the like for example, acetone or C1-C4 alcohol
- a mineral acid for example, hydrochloric acid, sulfuric acid, etc.
- the wet cake of the free acid of the compound represented by the formula (1) is added to water and stirred, for example, potassium hydroxide; lithium hydroxide; aqueous ammonia; or represented by the formula (11)
- An organic quaternary ammonium hydroxide; etc. can be added to form a salt to obtain a potassium salt, a lithium salt, an ammonium salt, a quaternary ammonium salt, etc. according to each added compound.
- a mixed salt of lithium salt and sodium salt, etc . for example, a mixed salt of lithium salt and sodium salt, etc .; and a mixture of lithium salt, sodium salt, and ammonium salt Salts and the like can also be prepared.
- the salt of the compound represented by the above formula (1) may change the physical properties such as solubility or the ink performance when used as an ink depending on the type of the salt. For this reason, it is also preferable to select the type of salt according to the intended ink performance.
- the compound of the present invention represented by the above formula (1) can be isolated as a solid free acid by adding a mineral acid such as hydrochloric acid after completion of the final step in the synthesis reaction, and the obtained free acid By washing the solid with water or acidic water such as hydrochloric acid, inorganic salts (inorganic impurities) contained as impurities, such as sodium chloride and sodium sulfate, can be removed.
- a mineral acid such as hydrochloric acid
- inorganic salts contained as impurities, such as sodium chloride and sodium sulfate
- Examples of the inorganic base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate; ammonium hydroxide (ammonia water); Etc.
- Examples of the organic base include, for example, organic amines corresponding to the quaternary ammonium represented by the above formula (11), for example, alkanolamines such as diethanolamine and triethanolamine, but are not limited thereto. .
- the compound of the present invention is suitable for dyeing natural and synthetic fiber materials or blended products, and also for producing inks for writing and ink jet recording.
- the reaction solution after completion of the final step in the synthesis reaction of the compound of the present invention represented by the above formula (1) can be directly used for the production of the ink composition of the present invention.
- the reaction solution or the like is dried by the above-described method or a spray drying method to isolate the compound, the obtained compound can be processed into an ink composition.
- the compound represented by the above formula (1) is mixed with water or a mixed solution (also referred to as an aqueous medium) of water and a water-soluble organic solvent (an organic solvent that can be mixed with water). It is dissolved and an ink preparation agent is added if necessary.
- a metal cation chloride contained as an impurity such as sodium chloride
- sulfate such as sodium sulfate
- Is preferred when this ink composition is used as an ink for an ink jet printer, a metal cation chloride contained as an impurity, such as sodium chloride; sulfate, such as sodium sulfate; Is preferred.
- the total content of sodium chloride and sodium sulfate is about 1% by mass or less with respect to the total mass of the compound represented by the formula (1), and the lower limit is 0% by mass, that is, the detection instrument. It may be below the detection limit.
- Examples of a method for producing a compound having a small amount of inorganic impurities include a method using a known reverse osmosis membrane; a dry product or a wet cake of the compound of the present invention, for example, acetone or C1-C4 alcohol (for example, methanol, ethanol, isopropanol, etc.)
- a water-soluble organic solvent such as
- a water-containing water-soluble organic solvent a suspension purification or crystallization method; and the like, and desalting treatment may be performed by these methods.
- the compound represented by the formula (1) is usually 0.1 to 20% by mass, preferably 1 to 10% by mass, more preferably 2 to 2% by mass in the total mass of the ink composition. 8% by mass is contained.
- the ink composition of the present invention is prepared using water as a medium, and may optionally contain a water-soluble organic solvent and an ink preparation agent as long as the effects of the present invention are not impaired.
- the water-soluble organic solvent dissolves the dye; prevents the composition from drying (maintains a wet state); adjusts the viscosity of the composition; promotes penetration of the dye into the recording material; adjusts the surface tension of the composition; It is preferably used in the ink composition of the present invention in view of the effect of defoaming the product.
- ink preparation agent examples include antiseptic / antifungal agents, pH adjusting agents, chelating reagents, rust preventive agents, ultraviolet absorbers, viscosity adjusting agents, dye dissolving agents, antifading agents, surface tension adjusting agents, antifoaming agents, etc.
- Known additives may be mentioned.
- the content of the water-soluble organic solvent is 0 to 60% by mass, preferably 10 to 50% by mass, and the ink preparation agent is 0 to 20% by mass, preferably 0%, based on the total mass of the ink composition of the present invention. It is good to use up to 15 mass%.
- the balance other than the compound represented by the above formula (1), the water-soluble organic solvent, and the ink preparation agent is water.
- water-soluble organic solvent examples include C1-C4 alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol and tert-butanol; N, N-dimethylformamide, N Amides such as N-dimethylacetamide; 2-pyrrolidone, N-methyl-2-pyrrolidone, hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidin-2-one, 1,3-dimethylhexahydropyrimido Heterocyclic ketones such as -2-one; ketones or ketoalcohols such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one; cyclic ethers such as tetrahydrofuran, dioxane; ethylene glycol, 1,2- or 1,3-propylene glycol, 1,2 Or mono having a
- the water-soluble organic solvent includes substances that are solid at room temperature, such as trimethylolpropane.
- the substance or the like shows water solubility, and an aqueous solution containing the substance or the like shows the same properties as the water-soluble organic solvent and can be used with the expectation of the same effect. Therefore, in this specification, for the sake of convenience, such a solid substance is included in the category of a water-soluble organic solvent as long as it can be used in expectation of the same effect as described above.
- water-soluble organic solvent examples include isopropanol, glycerin, mono-, di- or triethylene glycol, dipropylene glycol, 2-pyrrolidone, hydroxyethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, trimethylolpropane, And butyl carbitol, more preferably isopropanol, glycerin, diethylene glycol, 2-pyrrolidone, N-methyl-2-pyrrolidone, and butyl carbitol. These water-soluble organic solvents are used alone or in combination.
- antiseptic / antifungal agent examples include organic sulfur, organic nitrogen sulfur, organic halogen, haloallylsulfone, iodopropargyl, N-haloalkylthio, benzothiazole, nitrile, pyridine, 8-oxyquinoline, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiadiazine, anilide, adamantane, dithiocarbamate, bromo Indanone compound, benzyl bromacetate compound, inorganic salt compound and the like can be mentioned.
- An example of the organic halogen compound is sodium pentachlorophenol.
- Examples of pyridine oxide compounds include sodium 2-pyridinethiol-1-oxide.
- Examples of the isothiazoline compounds include 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazoline-3-one, 5 -Chloro-2-methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4-isothiazolin-3-one calcium chloride, etc.
- Other antiseptic and fungicide include sodium acetate, sodium sorbate, sodium benzoate and; more Arch Chemicals, Inc. under the trade name Proxel RTM GXL (S) and Proxel RTM XL-2 (S); and the like, Each is listed. In the present specification, the superscript “RTM” means a registered trademark.
- any substance can be used as long as it can control the pH of the ink in the range of 6.0 to 11.0 for the purpose of improving the storage stability of the ink.
- alkanolamines such as diethanolamine and triethanolamine
- hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide
- ammonium hydroxides or alkali metals such as lithium carbonate, sodium carbonate and potassium carbonate And carbonates
- aminosulfonic acids such as taurine; and the like.
- chelating reagent examples include disodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uracil diacetate, and the like.
- rust preventive examples include acid sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and the like.
- the ultraviolet absorber examples include benzophenone compounds, benzotriazole compounds, cinnamic acid compounds, triazine compounds, and stilbene compounds.
- a compound that absorbs ultraviolet rays such as a benzoxazole-based compound and emits fluorescence, a so-called fluorescent whitening agent, and the like can also be used.
- examples of the viscosity modifier include water-soluble polymer compounds in addition to water-soluble organic solvents, and examples thereof include polyvinyl alcohol, cellulose derivatives, polyamines, and polyimines.
- dye solubilizer examples include urea, ⁇ -caprolactam, ethylene carbonate, and the like. Of these, urea is preferably used.
- the anti-fading agent is used for the purpose of improving image storage stability.
- various organic and metal complex antifading agents can be used.
- organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc. Includes nickel complexes and zinc complexes.
- Examples of the surface tension adjusting agent include surfactants, and examples include anionic surfactants, amphoteric surfactants, cationic surfactants, and nonionic surfactants.
- anionic surfactants include alkyl sulfocarboxylates, ⁇ -olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and salts thereof, N-acyl methyl taurate, alkyl sulfate polyoxyalkyl ethers Sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate ester, lauryl alcohol sulfate ester, alkylphenol type phosphate ester, alkyl type phosphate ester, alkylaryl sulfonate, diethylsulfosuccinate Salts, diethylhexylsulfosuccinate, dioctylsulfosuccinate and the like.
- Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives.
- Amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, and other imidazoline derivatives. Etc.
- Nonionic surfactants include ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether; Ester systems such as polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl -1-hexyne-3-acetylene glycol (alcohol) -based ol; Nissin Chemical Industry Co., Ltd. trade name Surfynol
- antifoaming agents include highly oxidized oils, glycerin fatty acid esters, fluorines, and silicone compounds.
- the surface tension of the ink composition of the present invention is usually 25 to 70 mN / m, more preferably 25 to 60 mN / m, and the viscosity is preferably 30 mPa ⁇ s or less, more preferably 20 mPa ⁇ s or less. .
- the ink composition of the present invention there is no particular limitation on the order of dissolving each agent such as an additive.
- the water used for preparing the ink composition is preferably water with few impurities such as ion exchange water and distilled water. Further, if necessary, after the ink composition is prepared, fine filtration may be performed using a membrane filter or the like to remove impurities in the ink composition.
- fine filtration may be performed using a membrane filter or the like to remove impurities in the ink composition.
- the pore size of the filter used for microfiltration is usually 1 to 0.1 ⁇ m, preferably 0.8 to 0.1 ⁇ m.
- the ink composition containing the compound of the present invention is suitable for use in printing, copying, marking, writing, drafting, stamping, or recording (printing), particularly inkjet recording.
- the ink composition of the present invention is less likely to precipitate solids even when dried in the vicinity of the nozzles of the recording head of an ink jet printer, and for this reason, the recording head is also less likely to block.
- the ink jet recording method of the present invention As a method for recording on a recording material by the ink jet recording method of the present invention, the following method may be mentioned. That is, a container filled with the ink composition of the present invention is loaded into a predetermined position of an ink jet printer, the ink composition of the present invention is used as ink, and ink droplets of the ink are ejected according to a recording signal to be recorded. This is a method for recording on a material.
- Some inkjet printers use, for example, a piezo method using mechanical vibration; a bubble jet (registered trademark) method using bubbles generated by heating; and the like.
- the ink jet recording method of the present invention can be used by any method.
- ink composition of the present invention can also be used as such an ink set. Further, the ink composition of the present invention may be used for one of the ink sets, and a known ink (composition) may be used for the other.
- the ink composition of the present invention may be a yellow ink composition containing the compound of the present invention and a known yellow dye for the purpose of fine-tuning the hue within a range that does not impair the effects obtained by the present invention.
- the compound of the present invention can be used in combination with a magenta dye or a cyan dye for the purpose of toning inks of other colors, such as black ink, or for preparing red ink or green ink.
- the ink composition of the present invention can be used in combination with inks of various colors such as magenta, cyan, and, if necessary, green, blue (or violet), red, and black. .
- each color ink may be filled in each container, and these containers may be loaded into a predetermined position of the ink jet printer and used for ink jet recording.
- Examples of the recording material used in the inkjet recording method of the present invention include information transmission sheets such as paper and film, fibers and fabrics (cellulose, nylon, wool, etc.), leather, base materials for color filters, and the like.
- a transmission sheet is preferred.
- the information transmission sheet is not particularly limited, and a plain paper as well as a surface-treated sheet, specifically, a paper, synthetic paper, a substrate such as a film provided with an ink receiving layer, or the like is used.
- the ink receiving layer is a layer having an action such as absorbing ink and accelerating its drying.
- the ink receiving layer is formed by, for example, a method of impregnating or coating the base material with a cationic polymer; inorganic fine particles capable of absorbing the pigment in the ink, together with a hydrophilic polymer such as polyvinyl alcohol or polyvinylpyrrolidone, on the surface of the base material. It is provided by the method of coating; Examples of the material of the inorganic fine particles that can absorb the pigment in the ink include porous silica, alumina sol, special ceramics, and the like.
- the information transmission sheet having such an ink receiving layer is usually called an inkjet exclusive paper, an inkjet exclusive film, a glossy paper, a glossy film or the like.
- Examples of representative commercial products of information transmission sheets having an ink receiving layer include products manufactured by Canon Inc., trade name Professional Photo Paper, Canon Photo Paper / Glossy Pro [Platinum Grade], and Glossy Gold; Seiko Epson ( Co., Ltd., trade name photo paper Crispia (high gloss), photo paper (gloss); Nihon Hewlett-Packard Co., Ltd., trade name Advanced Photo Paper (gloss); Fuji Film Co., Ltd. Pro; manufactured by Brother Industries, Ltd., trade name: photographic glossy paper BP71G; Also, plain paper means paper that is not particularly provided with an ink receiving layer, and many different types are commercially available depending on the application.
- plain paper Of the commercially available plain papers, double-sided plain plain paper (manufactured by Seiko Epson Corporation); PB PAPER GF-500 (manufactured by Canon Inc.); Multipurpose Paper, All-in-one Printing Paper ( Hewlett Packard).
- plain paper copy (PPC) paper or the like whose use is not limited to ink jet recording is also plain paper.
- the colored product of the present invention comprises: (a) the water-soluble azo compound of the present invention; (b) the ink composition of the present invention containing the compound; (c) the ink of the present invention containing the compound and a water-soluble organic solvent.
- a composition means a colored material.
- the substance to be colored is not particularly limited, and examples thereof include, but are not limited to, the recording material described above.
- the above-mentioned recording material is colored.
- a coloring method for the substance is not particularly limited, and examples thereof include a printing method such as a dip dyeing method, a textile printing method, and screen printing, an ink jet recording method of the present invention, and the ink jet recording method of the present invention is preferable.
- a colored body colored by the ink jet recording method of the present invention is preferable.
- the water-soluble azo compound of the present invention represented by the above formula (1) is excellent in solubility in water or a water-soluble organic solvent. Moreover, it has the characteristic that the filterability with respect to a membrane filter, for example in the process of manufacturing the ink composition of this invention is favorable.
- the ink composition of the present invention is very clear on a recording material such as plain paper and an information transmission sheet having an ink receiving layer, has a high saturation and printing density, and is capable of producing a yellow recorded image of an ideal hue. give. Therefore, it is also possible to faithfully reproduce a photographic color image on paper.
- the ink composition of the present invention has very good storage stability without solid deposition, physical property change, hue change, etc. after long-term storage.
- the ink composition of the present invention uses a continuous ink jet printer, and is used physically even when the ink is recirculated at a relatively long time interval or intermittently used by an on-demand ink jet printer. No change in properties. Furthermore, with the ink composition of the present invention, the image recorded on the information transmission sheet having the ink receiving layer has high saturation, and the water resistance, moisture resistance, ozone gas resistance, abrasion resistance, light resistance, etc.
- the water-soluble azo compound of the present invention represented by the formula (1) and the ink composition of the present invention containing the compound are extremely useful for various recording ink applications, particularly for ink jet recording ink applications. is there.
- Example 1 (Process 1) 20.8 parts of 5-amino-2-chlorobenzenesulfonic acid was dissolved in 200 parts of water while adjusting the pH to 6 with sodium hydroxide, and then 7.2 parts of sodium nitrite was added. This solution was added dropwise to 200 parts of 5% hydrochloric acid at 0 to 10 ° C. over 30 minutes, followed by stirring at 10 ° C. or lower for 1 hour to carry out diazotization reaction to prepare a diazo reaction liquid.
- the obtained reaction solution was cooled to 20 to 25 ° C., 800 parts of acetone was added to the reaction solution, and the mixture was stirred at 20 to 25 ° C. for 1 hour.
- the precipitated solid was separated by filtration to obtain 50.0 parts of a wet cake.
- the wet cake was dried with a hot air dryer at 80 ° C. to obtain 13.5 parts of a sodium salt ( ⁇ max: 411.0 nm) of the water-soluble azo compound of the present invention represented by the following formula (13).
- Example 2 The water-solubility of the present invention represented by the following formula (14) is obtained in the same manner as in Example 1 except that 40.0 parts of iminodiacetic acid is used instead of 22.5 parts of glycine in Example 1 (Step 2). 14.0 parts ( ⁇ max: 418.5 nm) of the sodium salt of the azo compound was obtained.
- Example 3 In the same manner as in Example 1 except that 18.3 parts of 2-aminoethanol was used instead of 22.5 parts of glycine in Example 1 (Step 2), the present invention represented by the following formula (15) was used. 14.5 parts ( ⁇ max: 416.5 nm) of a sodium salt of a water-soluble azo compound was obtained.
- Example 4 The water-soluble azo compound of the present invention represented by the following formula (16) was obtained in the same manner as in Example 1 except that 31.5 parts of diethanolamine was used instead of 22.5 parts of glycine in Example 1 (Step 2). 14.5 parts ( ⁇ max: 420.5 nm) of a sodium salt of the compound was obtained.
- Example 5 It is represented by the following formula (17) in the same manner as in Example 1 except that 56.2 parts of 4-aminomethylbenzenesulfonic acid is used instead of 22.5 parts of glycine in Example 1 (Step 2). 15.0 parts ( ⁇ max: 413.0 nm) of the sodium salt of the water-soluble azo compound of the present invention were obtained.
- Example 6 This is represented by the following formula (18) in the same manner as in Example 1 except that 52.0 parts of 3-aminobenzenesulfonic acid is used instead of 22.5 parts of glycine in Example 1 (Step 2). 12.0 parts ( ⁇ max: 413.0 nm) of the sodium salt of the water-soluble azo compound of the invention was obtained.
- Example 7 The present invention represented by the following formula (19) in the same manner as in Example 1 except that 41.1 parts of 3-aminobenzoic acid was used instead of 22.5 parts of glycine in Example 1 (Step 2). 11.0 parts of a sodium salt of a water-soluble azo compound ( ⁇ max: 417.0 nm) was obtained.
- Example 8 The present invention represented by the following formula (20) in the same manner as in Example 1 except that 30.0 parts of 40% methylamine aqueous solution was used instead of 22.5 parts of glycine in Example 1 (Step 2). 13.5 parts of a sodium salt of a water-soluble azo compound ( ⁇ max: 412.0 nm) was obtained.
- Example 9 to 16 [(A) Preparation of ink]
- Each of the azo compounds of the present invention obtained in Examples 1 to 8 above [sodium salt of formula (13) to formula (20)] is used as a dye, and the compositions shown in Table 2 below are mixed to form a solution.
- an ink composition of the present invention was obtained.
- the obtained ink composition was filtered through a 0.45 ⁇ m membrane filter to remove impurities, and a test ink was prepared.
- the pH of the test ink was in the range of 8.0 to 9.5.
- surfactant trade name Surfinol RTM 104PG50 manufactured by Nissin Chemical Co., Ltd. was used.
- Preparation of each ink using the compounds obtained in Examples 1 to 8 is referred to as Examples 9 to 16, respectively.
- Comparative inks were prepared in the same manner as in Examples 9 to 16 except that a compound represented by the following formula (21) was used instead of the compound of the present invention obtained in each Example. This ink preparation is referred to as Comparative Example 1.
- the compound used in Comparative Example 1 is disclosed in Japanese Patent Publication No. 55-011708, and Japanese Patent Application Laid-Open No. 2002-285022 describes that it can be used in an inkjet ink.
- Comparative Example 2 Comparative inks were prepared in the same manner as in Examples 9 to 16, except that the dye described in Example 1 of Patent Document 1 was used instead of the compound of the present invention obtained in each Example. This ink preparation is referred to as Comparative Example 2.
- the structural formula of the compound used in Comparative Example 2 is shown in the following formula (22).
- Comparative Example 3 Comparative inks were prepared in the same manner as in Examples 9 to 16 except that the coloring matter described in Example 1 of Patent Document 2 was used instead of the compound of the present invention obtained in each Example. This ink preparation is referred to as Comparative Example 3.
- the structural formula of the compound used in Comparative Example 3 is shown in the following formula (23).
- Comparative Example 4 Comparative inks were prepared in the same manner as in Examples 9 to 16, except that the coloring matter described in Example 1 of Patent Document 3 was used instead of the compound of the present invention obtained in each Example. This ink preparation is referred to as Comparative Example 4.
- the structural formula of the compound used in Comparative Example 4 is shown in the following formula (24).
- Comparative Example 5 Comparative inks were prepared in the same manner as in Examples 9 to 16, except that the coloring matter described in Example 1 of Patent Document 4 was used instead of the compound of the present invention obtained in each Example. This ink preparation is referred to as Comparative Example 5.
- the structural formula of the compound used in Comparative Example 5 is shown in the following formula (25).
- Comparative inks were prepared in the same manner as in Examples 9 to 16, except that the coloring matter described in Example 6 of Patent Document 4 was used instead of the compound of the present invention obtained in each Example. This ink preparation is referred to as Comparative Example 6.
- the structural formula of the compound used in Comparative Example 6 is shown in the following formula (26).
- Comparative Example 7 Comparative inks were prepared in the same manner as in Examples 9 to 16 except that the coloring matter described in Example 4 of Patent Document 4 was used instead of the compound of the present invention obtained in each Example. This ink preparation is referred to as Comparative Example 7.
- the structural formula of the compound used in Comparative Example 7 is shown in the following formula (27).
- Comparative Example 8 Comparative inks were prepared in the same manner as in Examples 9 to 16 except that the coloring matter described in Example 2 of Patent Document 4 was used instead of the compound of the present invention obtained in each Example. This ink preparation is referred to as Comparative Example 8.
- the structural formula of the compound used in Comparative Example 8 is shown in the following formula (28).
- Comparative Example 9 Comparative inks were prepared in the same manner as in Examples 9 to 16, except that the coloring matter described in Example 3 of Patent Document 4 was used instead of the compound of the present invention obtained in each Example. This ink preparation is referred to as Comparative Example 9.
- the structural formula of the compound used in Comparative Example 9 is shown in the following formula (29).
- the reflection density was measured for the portion where the reflection density D value of the recorded matter before the test was closest to 1.0.
- a colorimetric system (trade name: SpectroEye RTM , manufactured by X-right) was used. Colorimetry was performed under the conditions of DIN, a viewing angle of 2 degrees, and a light source D65 as a density standard.
- Various test methods for recorded images and evaluation methods for test results are described below.
- each example of the present invention has a saturation that is equal to or higher than that of each comparative example and is excellent in sharpness. Further, as is apparent from the results in Table 4, it can be seen that each example of the present invention is superior in ozone gas resistance to each comparative example.
- the water-soluble azo compound of the present invention and the ink composition of the present invention containing the compound have a clear hue and excellent ozone gas resistance, saturation and ozone gas resistance It can be seen that the balance of sex is excellent.
- the water-soluble azo compound of the present invention which is a yellow pigment and the yellow ink composition of the present invention containing the same give a recorded image with high saturation. In addition to this, it is excellent in various fastness properties such as ozone gas resistance. Therefore, the compound and the ink composition containing the compound are very useful for various recording applications, particularly for inkjet recording applications.
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Abstract
Disclosed is a yellow pigment having a hue with high clarity suitable for inkjet recording, and having high levels and different types of fastness of recorded material, and excellent storage stability of an ink composition when said ink composition is produced; also disclosed is the ink composition containing said yellow pigment. By means of using the water-soluble azo compound represented by formula (1) or a salt thereof, and the ink composition containing the same, an ink composition is obtained having saturation and hue suitable for inject recording, having high levels and different types of fastness of recorded material, in particular high resistance to ozone gas, and having excellent storage stability of recorded images. In formula (1), Q represents a halogen atom, x represents an integer between 2 and 4, and base A represents an amino base represented by formulas (2), (6), or (7). In formula (2), m represents an integer from 1 to 5. In formula (6), Z represents a hydrogen atom, a caboxy group, or a sulfo group, and k represents an integer from 0 to 2. In formula (7), w represents an integer from 0 to 3.
Description
本発明は、水溶性のジスアゾ化合物又はその塩、これを含有するインク組成物、及びこれらにより着色された着色体に関する。
The present invention relates to a water-soluble disazo compound or a salt thereof, an ink composition containing the same, and a colored body colored with these.
各種カラー記録方法の中で、その代表的方法の1つであるインクジェットプリンタによる記録方法は、インクの吐出方式が各種開発されている。これらは、いずれもインクの小滴を発生させ、これを種々の被記録材(紙、フィルム、布帛等)に付着させ記録を行うものである。この方法は、記録ヘッドと被記録材とが直接接触しないため、音の発生がなく静かである。また、小型化、高速化、カラー化が容易であるという特長を有するため、近年急速に普及しつつあり、今後とも大きな伸長が期待されている。
従来、万年筆やフェルトペン等のインク、及びインクジェット記録用のインクとしては、水溶性の色素(染料)を水性媒体に溶解したインクが使用されている。これらの水性インクには、ペン先やインク吐出ノズルでのインクの目詰まりを防止すべく、一般に水溶性の有機溶剤が添加されている。これらのインクには、十分な濃度の記録画像を与えること、ペン先やノズルの目詰まりを生じないこと、被記録材上での乾燥性が良いこと、滲みが少ないこと、保存安定性に優れること等の性能が要求される。 Among various color recording methods, various ink ejection methods have been developed as recording methods using an ink jet printer, which is one of the representative methods. These all generate ink droplets and attach them to various recording materials (paper, film, fabric, etc.) for recording. In this method, since the recording head and the recording material are not in direct contact with each other, no noise is generated and the method is quiet. In addition, since it has the features that it is easy to downsize, speed up, and colorize, it has been spreading rapidly in recent years and is expected to grow greatly in the future.
Conventionally, inks such as fountain pens and felt pens, and inks for ink-jet recording have been used in which water-soluble pigments (dyes) are dissolved in an aqueous medium. In general, a water-soluble organic solvent is added to these water-based inks in order to prevent clogging of ink at a pen tip or an ink discharge nozzle. These inks give a recorded image of sufficient density, do not cause clogging of the pen tip and nozzles, have good drying properties on the recording material, have little bleeding, and have excellent storage stability. Such performance is required.
従来、万年筆やフェルトペン等のインク、及びインクジェット記録用のインクとしては、水溶性の色素(染料)を水性媒体に溶解したインクが使用されている。これらの水性インクには、ペン先やインク吐出ノズルでのインクの目詰まりを防止すべく、一般に水溶性の有機溶剤が添加されている。これらのインクには、十分な濃度の記録画像を与えること、ペン先やノズルの目詰まりを生じないこと、被記録材上での乾燥性が良いこと、滲みが少ないこと、保存安定性に優れること等の性能が要求される。 Among various color recording methods, various ink ejection methods have been developed as recording methods using an ink jet printer, which is one of the representative methods. These all generate ink droplets and attach them to various recording materials (paper, film, fabric, etc.) for recording. In this method, since the recording head and the recording material are not in direct contact with each other, no noise is generated and the method is quiet. In addition, since it has the features that it is easy to downsize, speed up, and colorize, it has been spreading rapidly in recent years and is expected to grow greatly in the future.
Conventionally, inks such as fountain pens and felt pens, and inks for ink-jet recording have been used in which water-soluble pigments (dyes) are dissolved in an aqueous medium. In general, a water-soluble organic solvent is added to these water-based inks in order to prevent clogging of ink at a pen tip or an ink discharge nozzle. These inks give a recorded image of sufficient density, do not cause clogging of the pen tip and nozzles, have good drying properties on the recording material, have little bleeding, and have excellent storage stability. Such performance is required.
インクジェットのノズル詰まりは、ノズル付近でインク中の水分が他の溶剤や添加剤よりも先に蒸発し、水分が少なく溶剤や添加剤が多いという組成状態になったときに、色素が固化し析出することに由来するものが多い。よって、インク中の水分が少ない状態になった場合においても固体が析出しにくいということが非常に重要な要求性能の1つである。この理由から、溶剤や添加剤に対する高い溶解性も色素に求められる性質の1つである。また、ノズル詰まりを解消する方法として、印字濃度の高い色素を用いる手法が知られている。印字濃度が高い色素を用いることで、従来の印字濃度を保ちつつ、インク中の色素含有量を減らすことができる。これは色素を析出しにくくするだけでなく、コスト面でも有利であり、高い印字濃度を持つ色素の開発が望まれている。
Ink jet nozzle clogging occurs when the water in the ink evaporates in the vicinity of the nozzle before other solvents and additives, and the pigment solidifies and precipitates when the composition state is low in water and high in solvents and additives. There are many things that come from doing. Accordingly, one of the very important required performances is that solids are not easily deposited even when the moisture content in the ink is low. For this reason, high solubility in solvents and additives is one of the properties required for pigments. As a method for eliminating nozzle clogging, a method using a dye having a high printing density is known. By using a pigment having a high printing density, the pigment content in the ink can be reduced while maintaining the conventional printing density. This not only makes it difficult to precipitate the dye, but is also advantageous in terms of cost, and development of a dye having a high printing density is desired.
ところで、コンピューターのカラーディスプレイ上の画像又は文字情報をインクジェットプリンタによりカラーで記録するには、一般にイエロー(Y)、マゼンタ(M)、シアン(C)、ブラック(K)の4色のインクによる減法混色が用いられ、これにより記録画像がカラーで表現される。CRT(ブラウン管)ディスプレイ等におけるレッド(R)、グリーン(G)、ブルー(B)による加法混色画像を、減法混色画像でできるだけ忠実に再現するために、インクに使用される各色素、中でもY、M、Cのそれぞれが、標準色に近い色相を有し、且つ鮮明であることが望まれる。ここで言う鮮明さとは、一般的に高い彩度を持つことを意味する。彩度が低いY、M、Cの3原色を用いた場合、単色又は混色で表現できる色領域が狭くなり、表現したい色領域の範囲としては不十分となる場合がある。このため、高彩度な色素と、それを含有するインクの開発が望まれている。
また、インクの性能としては、長期の保存に対して安定であり、記録画像の濃度が高く、しかもその画像が耐水性、耐湿性、耐光性、耐ガス性等の堅牢性に優れることが求められる。ここで耐ガス性とは、空気中に存在する酸化作用を持つガス(酸化性ガスとも呼ばれる)が、被記録材上又は被記録材中で、記録画像の色素(染料)と反応し、記録画像を変退色させるという現象に対する耐性のことである。酸化性ガスの中でも特にオゾンガスは、インクジェット記録画像の変退色現象を促進させる主要な原因物質とされている。この変退色現象はインクジェット記録画像に特徴的なものであるため、耐オゾンガス性の向上はこの分野における重要な技術的課題である。 By the way, in order to record image or character information on a color display of a computer in color by an ink jet printer, generally a subtraction method using four colors of ink of yellow (Y), magenta (M), cyan (C), and black (K). Mixed colors are used, whereby the recorded image is expressed in color. In order to reproduce an additive color mixture image of red (R), green (G), and blue (B) on a CRT (CRT) display etc. as faithfully as possible with a subtractive color mixture image, each dye used in the ink, particularly Y, Each of M and C is desired to have a hue close to a standard color and to be clear. The clearness mentioned here generally means having a high saturation. When the three primary colors Y, M, and C with low saturation are used, the color area that can be expressed in a single color or mixed color becomes narrow, and the range of the color area that is desired to be expressed may be insufficient. For this reason, development of highly saturated pigments and inks containing them is desired.
In addition, the ink performance is required to be stable for long-term storage, high in recorded image density, and excellent in fastness such as water resistance, moisture resistance, light resistance and gas resistance. It is done. Here, the gas resistance means that a gas having an oxidizing action (also referred to as an oxidizing gas) existing in the air reacts with a dye (dye) of a recorded image on the recording material or in the recording material to record. This is the resistance to the phenomenon of discoloration of images. Among oxidizing gases, ozone gas is considered to be a main causative substance that promotes the discoloration and fading phenomenon of ink jet recorded images. Since this discoloration phenomenon is characteristic of ink jet recorded images, improvement of ozone gas resistance is an important technical problem in this field.
また、インクの性能としては、長期の保存に対して安定であり、記録画像の濃度が高く、しかもその画像が耐水性、耐湿性、耐光性、耐ガス性等の堅牢性に優れることが求められる。ここで耐ガス性とは、空気中に存在する酸化作用を持つガス(酸化性ガスとも呼ばれる)が、被記録材上又は被記録材中で、記録画像の色素(染料)と反応し、記録画像を変退色させるという現象に対する耐性のことである。酸化性ガスの中でも特にオゾンガスは、インクジェット記録画像の変退色現象を促進させる主要な原因物質とされている。この変退色現象はインクジェット記録画像に特徴的なものであるため、耐オゾンガス性の向上はこの分野における重要な技術的課題である。 By the way, in order to record image or character information on a color display of a computer in color by an ink jet printer, generally a subtraction method using four colors of ink of yellow (Y), magenta (M), cyan (C), and black (K). Mixed colors are used, whereby the recorded image is expressed in color. In order to reproduce an additive color mixture image of red (R), green (G), and blue (B) on a CRT (CRT) display etc. as faithfully as possible with a subtractive color mixture image, each dye used in the ink, particularly Y, Each of M and C is desired to have a hue close to a standard color and to be clear. The clearness mentioned here generally means having a high saturation. When the three primary colors Y, M, and C with low saturation are used, the color area that can be expressed in a single color or mixed color becomes narrow, and the range of the color area that is desired to be expressed may be insufficient. For this reason, development of highly saturated pigments and inks containing them is desired.
In addition, the ink performance is required to be stable for long-term storage, high in recorded image density, and excellent in fastness such as water resistance, moisture resistance, light resistance and gas resistance. It is done. Here, the gas resistance means that a gas having an oxidizing action (also referred to as an oxidizing gas) existing in the air reacts with a dye (dye) of a recorded image on the recording material or in the recording material to record. This is the resistance to the phenomenon of discoloration of images. Among oxidizing gases, ozone gas is considered to be a main causative substance that promotes the discoloration and fading phenomenon of ink jet recorded images. Since this discoloration phenomenon is characteristic of ink jet recorded images, improvement of ozone gas resistance is an important technical problem in this field.
近年のインクジェット技術の発達により、インクジェット記録(印刷)のスピードの向上がめざましい。このため、電子トナーを用いたレーザープリンタと同様に、オフィス環境での主用途である普通紙へのドキュメントの印刷に、インクジェットプリンタを用いる市場の動きがある。インクジェットプリンタは記録紙の種類を選ばず、またプリンタ自体の価格が安いという利点があり、特にスモールオフィス・ホームオフィス(SOHO)等の小~中規模オフィス環境で普及が進んでいる。このように普通紙への印刷用途でインクジェットプリンタを使用する場合、印刷物に求められる品質の中では、色相、発色(印字)濃度、及び耐水性がより重視される傾向がある。
これらの性能を満たす目的で、顔料インクを用いる方法が提案されている。しかし、顔料インクは色素が水性インク中には溶解しないため溶液状態とはならず、分散状態のインクであるため、これをインクジェット記録に用いると、インク自体の安定性の問題や記録ヘッドのノズル詰まりの問題等が生じる。また、顔料インクを使用した場合、耐擦性にも問題を生じることが多い。染料インクの場合、このような問題は比較的起こりにくいとされるが、特に耐水性において顔料インクと比較して著しく劣り、それに対する改良が強く望まれている。また、染料インクは顔料インクと異なり、インクジェット記録により普通紙の表面に付着させた色素が、より速く紙の裏面方向へ浸透し、その結果、発色濃度が低下するという問題が起こりやすい。 With the recent development of inkjet technology, the speed of inkjet recording (printing) has been remarkably improved. For this reason, similar to laser printers using electronic toner, there is a market trend to use inkjet printers for printing documents on plain paper, which is the main application in office environments. Inkjet printers have the advantage that the type of recording paper is not limited, and the price of the printer itself is low, and the spread is particularly widespread in small to medium-sized office environments such as small offices and home offices (SOHO). As described above, when an inkjet printer is used for printing on plain paper, hue, color (printing) density, and water resistance tend to be more important among the qualities required for printed matter.
In order to satisfy these performances, a method using a pigment ink has been proposed. However, since pigment ink does not dissolve in water-based ink, it does not enter a solution state, but is a dispersed ink. Therefore, when this is used for ink jet recording, there are problems with the stability of the ink itself and the nozzles of the recording head. Problems such as clogging occur. In addition, when pigment ink is used, there is often a problem in abrasion resistance. In the case of a dye ink, such a problem is considered to be relatively difficult to occur. However, in particular, the water resistance is extremely inferior to that of a pigment ink, and an improvement to the problem is strongly desired. In addition, unlike pigment ink, dye ink tends to cause a problem that a dye attached to the surface of plain paper by ink jet recording penetrates more quickly toward the back side of the paper, resulting in a decrease in color density.
これらの性能を満たす目的で、顔料インクを用いる方法が提案されている。しかし、顔料インクは色素が水性インク中には溶解しないため溶液状態とはならず、分散状態のインクであるため、これをインクジェット記録に用いると、インク自体の安定性の問題や記録ヘッドのノズル詰まりの問題等が生じる。また、顔料インクを使用した場合、耐擦性にも問題を生じることが多い。染料インクの場合、このような問題は比較的起こりにくいとされるが、特に耐水性において顔料インクと比較して著しく劣り、それに対する改良が強く望まれている。また、染料インクは顔料インクと異なり、インクジェット記録により普通紙の表面に付着させた色素が、より速く紙の裏面方向へ浸透し、その結果、発色濃度が低下するという問題が起こりやすい。 With the recent development of inkjet technology, the speed of inkjet recording (printing) has been remarkably improved. For this reason, similar to laser printers using electronic toner, there is a market trend to use inkjet printers for printing documents on plain paper, which is the main application in office environments. Inkjet printers have the advantage that the type of recording paper is not limited, and the price of the printer itself is low, and the spread is particularly widespread in small to medium-sized office environments such as small offices and home offices (SOHO). As described above, when an inkjet printer is used for printing on plain paper, hue, color (printing) density, and water resistance tend to be more important among the qualities required for printed matter.
In order to satisfy these performances, a method using a pigment ink has been proposed. However, since pigment ink does not dissolve in water-based ink, it does not enter a solution state, but is a dispersed ink. Therefore, when this is used for ink jet recording, there are problems with the stability of the ink itself and the nozzles of the recording head. Problems such as clogging occur. In addition, when pigment ink is used, there is often a problem in abrasion resistance. In the case of a dye ink, such a problem is considered to be relatively difficult to occur. However, in particular, the water resistance is extremely inferior to that of a pigment ink, and an improvement to the problem is strongly desired. In addition, unlike pigment ink, dye ink tends to cause a problem that a dye attached to the surface of plain paper by ink jet recording penetrates more quickly toward the back side of the paper, resulting in a decrease in color density.
写真画質のインクジェット記録画像を得る方法の1つとして、被記録材の表面にインク受容層を設ける方法がある。このような目的で設けられるインク受容層は、インクの乾燥を早め、また高画質での色素の滲みを少なくするために、多孔性白色無機物を含むことが多い。しかし、特にこのような被記録材において、前記オゾンガスによる変退色が顕著に見られる。最近のデジタルカメラ及びカラープリンタの普及と共に、家庭でもデジタルカメラ等で得られた画像を写真画質として印刷する機会が増しているため、上記の酸化性ガスによる記録画像の変退色が問題視される。他の3原色であるマゼンタやシアンと比較すると、イエロー色素については耐光性と共に、良好な酸化性ガスへの耐性を有する色素が提案されてきている。しかし、市場が要求するような高い鮮明性と各種堅牢性とを十分に満足するインクジェット記録用の黄色色素やイエローインクは、未だ得られていない。
As one method for obtaining a photographic image-recorded inkjet image, there is a method of providing an ink receiving layer on the surface of a recording material. The ink receiving layer provided for such a purpose often contains a porous white inorganic substance in order to speed up drying of the ink and to reduce bleeding of the pigment with high image quality. However, particularly in such a recording material, the discoloration due to the ozone gas is noticeable. With the recent spread of digital cameras and color printers, there are increasing opportunities to print images obtained with digital cameras and the like as photographic image quality at home, so the above-mentioned color change of recorded images due to oxidizing gas is regarded as a problem. . Compared to the other three primary colors, magenta and cyan, yellow dyes have been proposed that have good resistance to oxidizing gas as well as light resistance. However, yellow dyes and yellow inks for inkjet recording that sufficiently satisfy the high sharpness and various fastnesses required by the market have not been obtained yet.
水溶性及び鮮明性に優れる公知のインクジェット用の黄色色素としては、C.I.(カラーインデックス)ダイレクト・イエロー132やダイレクト・イエロー142が挙げられる。また、近年のインクジェット記録用の黄色色素の開発により高堅牢性のアゾ系色素が複数提案されている。
特許文献1には、水に対する溶解性が高く、耐湿性及び耐光性を有する黄色の水溶性アゾ化合物が開示されている。
特許文献2には、水に対する溶解性が高く、耐湿性、耐オゾンガス性、及び耐光性を有する黄色の水溶性アゾ化合物が開示されている。
特許文献3には、水に対する溶解性が高く、耐湿性、耐水性、耐オゾンガス性、及び耐光性を有する黄色の水溶性アゾ化合物が開示されている。
特許文献4には、水に対する溶解性が高く、耐湿性、耐水性、耐オゾンガス性、及び耐光性を有する黄色の水溶性アゾ化合物が開示されている。 Examples of known yellow pigments for inkjet which are excellent in water solubility and sharpness include C.I. I. (Color index) Direct yellow 132 and direct yellow 142 are listed. In addition, a plurality of highly fast azo dyes have been proposed due to the recent development of yellow dyes for inkjet recording.
Patent Document 1 discloses a yellow water-soluble azo compound having high solubility in water and having moisture resistance and light resistance.
Patent Document 2 discloses a yellow water-soluble azo compound that is highly soluble in water and has moisture resistance, ozone gas resistance, and light resistance.
Patent Document 3 discloses a yellow water-soluble azo compound that has high solubility in water and has moisture resistance, water resistance, ozone gas resistance, and light resistance.
Patent Document 4 discloses a yellow water-soluble azo compound that is highly soluble in water and has moisture resistance, water resistance, ozone gas resistance, and light resistance.
特許文献1には、水に対する溶解性が高く、耐湿性及び耐光性を有する黄色の水溶性アゾ化合物が開示されている。
特許文献2には、水に対する溶解性が高く、耐湿性、耐オゾンガス性、及び耐光性を有する黄色の水溶性アゾ化合物が開示されている。
特許文献3には、水に対する溶解性が高く、耐湿性、耐水性、耐オゾンガス性、及び耐光性を有する黄色の水溶性アゾ化合物が開示されている。
特許文献4には、水に対する溶解性が高く、耐湿性、耐水性、耐オゾンガス性、及び耐光性を有する黄色の水溶性アゾ化合物が開示されている。 Examples of known yellow pigments for inkjet which are excellent in water solubility and sharpness include C.I. I. (Color index) Direct yellow 132 and direct yellow 142 are listed. In addition, a plurality of highly fast azo dyes have been proposed due to the recent development of yellow dyes for inkjet recording.
Patent Document 1 discloses a yellow water-soluble azo compound having high solubility in water and having moisture resistance and light resistance.
Patent Document 2 discloses a yellow water-soluble azo compound that is highly soluble in water and has moisture resistance, ozone gas resistance, and light resistance.
Patent Document 3 discloses a yellow water-soluble azo compound that has high solubility in water and has moisture resistance, water resistance, ozone gas resistance, and light resistance.
Patent Document 4 discloses a yellow water-soluble azo compound that is highly soluble in water and has moisture resistance, water resistance, ozone gas resistance, and light resistance.
本発明は、水に対する溶解性が高く、彩度及び耐オゾンガス性のバランスに優れる水溶性の黄色色素(化合物)及びそれを含有する各種記録用、特にインクジェット記録用のイエローインク組成物の提供を目的とする。
The present invention provides a water-soluble yellow coloring matter (compound) having high solubility in water and excellent balance between chroma and ozone gas resistance, and various yellow ink compositions containing the same, particularly for inkjet recording. Objective.
本発明者等は上記課題を解決すべく、鋭意検討の結果、特定の式で表される水溶性アゾ化合物及びそれを含有するインク組成物が上記課題を解決するものであることを見出し、本発明を完成させた。
As a result of intensive studies, the present inventors have found that a water-soluble azo compound represented by a specific formula and an ink composition containing the same solve the above-described problems. Completed the invention.
すなわち、本発明は、
1)
下記式(1)で表される水溶性アゾ化合物又はその塩、
(式中、Qはハロゲン原子を表し、xは2から4の整数を表し、基Aは下記式(2)~(7)のいずれか1つで表されるアミノ基を表す。)
(式(2)中、mは1から5の整数を表す。)
(式(4)中、nは2から5の整数を表す。)
(式(6)中、Zは水素原子、カルボキシ基、又はスルホ基を表し、kは0から2の整数を表す。)
(式(7)中、wは0から3の整数を表す。)
That is, the present invention
1)
A water-soluble azo compound represented by the following formula (1) or a salt thereof,
(In the formula, Q represents a halogen atom, x represents an integer of 2 to 4, and the group A represents an amino group represented by any one of the following formulas (2) to (7).)
(In the formula (2), m represents an integer of 1 to 5.)
(In formula (4), n represents an integer of 2 to 5)
(In formula (6), Z represents a hydrogen atom, a carboxy group, or a sulfo group, and k represents an integer of 0 to 2.)
(In formula (7), w represents an integer of 0 to 3.)
1)
下記式(1)で表される水溶性アゾ化合物又はその塩、
1)
A water-soluble azo compound represented by the following formula (1) or a salt thereof,
2)
上記式(1)において、Qが塩素原子であり、xが3である上記1)に記載の水溶性アゾ化合物又はその塩、 2)
In the above formula (1), Q is a chlorine atom, and x is 3, the water-soluble azo compound or salt thereof according to 1) above,
上記式(1)において、Qが塩素原子であり、xが3である上記1)に記載の水溶性アゾ化合物又はその塩、 2)
In the above formula (1), Q is a chlorine atom, and x is 3, the water-soluble azo compound or salt thereof according to 1) above,
3)
上記式(1)で表される水溶性アゾ化合物が下記式(8)で表される上記1)に記載の水溶性アゾ化合物又はその塩、
3)
The water-soluble azo compound represented by the above formula (1) or a salt thereof according to the above 1) represented by the following formula (8):
上記式(1)で表される水溶性アゾ化合物が下記式(8)で表される上記1)に記載の水溶性アゾ化合物又はその塩、
The water-soluble azo compound represented by the above formula (1) or a salt thereof according to the above 1) represented by the following formula (8):
4)
上記式(1)で表される水溶性アゾ化合物が下記式(9)で表される上記1)に記載の水溶性アゾ化合物又はその塩、
4)
The water-soluble azo compound represented by the above formula (1) or a salt thereof according to the above 1) represented by the following formula (9):
上記式(1)で表される水溶性アゾ化合物が下記式(9)で表される上記1)に記載の水溶性アゾ化合物又はその塩、
The water-soluble azo compound represented by the above formula (1) or a salt thereof according to the above 1) represented by the following formula (9):
5)
上記式(1)で表される水溶性アゾ化合物が下記式(10)で表される上記1)に記載の水溶性アゾ化合物又はその塩、
5)
The water-soluble azo compound represented by the above formula (1) or a salt thereof according to the above 1) represented by the following formula (10):
上記式(1)で表される水溶性アゾ化合物が下記式(10)で表される上記1)に記載の水溶性アゾ化合物又はその塩、
The water-soluble azo compound represented by the above formula (1) or a salt thereof according to the above 1) represented by the following formula (10):
6)
上記1)乃至5)のいずれか一項に記載の水溶性アゾ化合物又はその塩を含有するインク組成物、
7)
水溶性有機溶剤をさらに含有する上記6)に記載のインク組成物、
8)
インクジェット記録用である上記6)又は7)に記載のインク組成物、
9)
上記6)乃至8)のいずれか一項に記載のインク組成物をインクとして用い、該インクのインク滴を記録信号に応じて吐出させて被記録材に付着させ、記録を行うインクジェット記録方法、
10)
上記被記録材が情報伝達用シートである上記9)に記載のインクジェット記録方法、
11)
上記情報伝達用シートが普通紙又は多孔性白色無機物を含むインク受容層を有するシートである上記10)に記載のインクジェット記録方法、
12)
(a)上記1)乃至5)のいずれか一項に記載の水溶性アゾ化合物又はその塩、
(b)上記1)乃至5)のいずれか一項に記載の水溶性アゾ化合物又はその塩を含有するインク組成物、及び
(c)上記1)乃至5)のいずれか一項に記載の水溶性アゾ化合物又はその塩及び水溶性有機溶剤を含有するインク組成物、のいずれかにより着色された着色体、
13)
上記9)に記載のインクジェット記録方法により着色された着色体、
14)
上記6)に記載のインク組成物を含む容器が装填されたインクジェットプリンタ、
に関する。 6)
An ink composition containing the water-soluble azo compound or a salt thereof according to any one of 1) to 5) above;
7)
The ink composition as described in 6) above, further comprising a water-soluble organic solvent,
8)
The ink composition according to 6) or 7), which is for inkjet recording;
9)
An ink jet recording method in which the ink composition according to any one of 6) to 8) above is used as an ink, and ink droplets of the ink are ejected in accordance with a recording signal to adhere to a recording material, and recording is performed;
10)
The inkjet recording method according to 9), wherein the recording material is an information transmission sheet;
11)
The inkjet recording method according to 10), wherein the information transmission sheet is a sheet having an ink receiving layer containing plain paper or a porous white inorganic substance,
12)
(A) The water-soluble azo compound or a salt thereof according to any one of 1) to 5) above,
(B) An ink composition containing the water-soluble azo compound or salt thereof according to any one of 1) to 5) above, and (c) the water-soluble solution according to any one of 1) to 5) above. A colored product colored by any of the ink composition containing a water-soluble azo compound or a salt thereof and a water-soluble organic solvent,
13)
A colored body colored by the inkjet recording method according to 9),
14)
An ink jet printer loaded with a container containing the ink composition according to 6),
About.
上記1)乃至5)のいずれか一項に記載の水溶性アゾ化合物又はその塩を含有するインク組成物、
7)
水溶性有機溶剤をさらに含有する上記6)に記載のインク組成物、
8)
インクジェット記録用である上記6)又は7)に記載のインク組成物、
9)
上記6)乃至8)のいずれか一項に記載のインク組成物をインクとして用い、該インクのインク滴を記録信号に応じて吐出させて被記録材に付着させ、記録を行うインクジェット記録方法、
10)
上記被記録材が情報伝達用シートである上記9)に記載のインクジェット記録方法、
11)
上記情報伝達用シートが普通紙又は多孔性白色無機物を含むインク受容層を有するシートである上記10)に記載のインクジェット記録方法、
12)
(a)上記1)乃至5)のいずれか一項に記載の水溶性アゾ化合物又はその塩、
(b)上記1)乃至5)のいずれか一項に記載の水溶性アゾ化合物又はその塩を含有するインク組成物、及び
(c)上記1)乃至5)のいずれか一項に記載の水溶性アゾ化合物又はその塩及び水溶性有機溶剤を含有するインク組成物、のいずれかにより着色された着色体、
13)
上記9)に記載のインクジェット記録方法により着色された着色体、
14)
上記6)に記載のインク組成物を含む容器が装填されたインクジェットプリンタ、
に関する。 6)
An ink composition containing the water-soluble azo compound or a salt thereof according to any one of 1) to 5) above;
7)
The ink composition as described in 6) above, further comprising a water-soluble organic solvent,
8)
The ink composition according to 6) or 7), which is for inkjet recording;
9)
An ink jet recording method in which the ink composition according to any one of 6) to 8) above is used as an ink, and ink droplets of the ink are ejected in accordance with a recording signal to adhere to a recording material, and recording is performed;
10)
The inkjet recording method according to 9), wherein the recording material is an information transmission sheet;
11)
The inkjet recording method according to 10), wherein the information transmission sheet is a sheet having an ink receiving layer containing plain paper or a porous white inorganic substance,
12)
(A) The water-soluble azo compound or a salt thereof according to any one of 1) to 5) above,
(B) An ink composition containing the water-soluble azo compound or salt thereof according to any one of 1) to 5) above, and (c) the water-soluble solution according to any one of 1) to 5) above. A colored product colored by any of the ink composition containing a water-soluble azo compound or a salt thereof and a water-soluble organic solvent,
13)
A colored body colored by the inkjet recording method according to 9),
14)
An ink jet printer loaded with a container containing the ink composition according to 6),
About.
上記式(1)で表される本発明の水溶性アゾ化合物又はその塩は、水に対する溶解性が高く、該化合物又はその塩を含有する本発明のインク組成物を製造する過程での、例えばメンブランフィルタに対する濾過性が良好であるという特徴を有する。また、本発明の化合物を含有する本発明のインク組成物により記録された画像は、従来の化合物を用いたものと比較して彩度及び耐オゾンガス性のバランスに優れる。このように、式(1)で表される本発明の水溶性アゾ化合物又はその塩、及びこれを含有するインク組成物は、各種記録用のインク用途、特にインクジェット記録用のインク用途に極めて有用である。
The water-soluble azo compound of the present invention represented by the above formula (1) or a salt thereof has a high solubility in water, and for example, in the process of producing the ink composition of the present invention containing the compound or a salt thereof, It has the characteristic that the filterability with respect to a membrane filter is favorable. In addition, an image recorded by the ink composition of the present invention containing the compound of the present invention is excellent in the balance of chroma and ozone gas resistance as compared with the image using the conventional compound. As described above, the water-soluble azo compound of the present invention represented by the formula (1) or a salt thereof, and the ink composition containing the same are extremely useful for various recording ink applications, particularly ink jet recording ink applications. It is.
本発明を詳細に説明する。
上記式(1)で表される本発明の水溶性アゾ化合物又はその塩は、水溶性の黄色色素である。本明細書においては特に断りがない限り、スルホ基、カルボキシ基等の酸性官能基は遊離酸の形で表す。また、本発明は、上記の通り、式(1)で表される水溶性アゾ化合物又は該化合物の塩の両者を含むものであるが、両者を常に「化合物又はその塩」等と併記するのは煩雑である。このため特に断りがない限り、便宜上、「本発明の(水溶性アゾ)化合物又はその塩」の両者を含めて単に「本発明の(水溶性アゾ)化合物」と簡略して、以下記載する。 The present invention will be described in detail.
The water-soluble azo compound of the present invention represented by the above formula (1) or a salt thereof is a water-soluble yellow dye. In the present specification, unless otherwise specified, acidic functional groups such as sulfo groups and carboxy groups are represented in the form of free acids. Further, as described above, the present invention includes both the water-soluble azo compound represented by the formula (1) or a salt of the compound, but it is complicated to always describe both of them as “compound or salt thereof”. It is. Therefore, unless otherwise specified, for convenience, the “water-soluble azo compound of the present invention or a salt thereof” including both the “water-soluble azo compound of the present invention” will be simply described as “the (water-soluble azo) compound of the present invention”.
上記式(1)で表される本発明の水溶性アゾ化合物又はその塩は、水溶性の黄色色素である。本明細書においては特に断りがない限り、スルホ基、カルボキシ基等の酸性官能基は遊離酸の形で表す。また、本発明は、上記の通り、式(1)で表される水溶性アゾ化合物又は該化合物の塩の両者を含むものであるが、両者を常に「化合物又はその塩」等と併記するのは煩雑である。このため特に断りがない限り、便宜上、「本発明の(水溶性アゾ)化合物又はその塩」の両者を含めて単に「本発明の(水溶性アゾ)化合物」と簡略して、以下記載する。 The present invention will be described in detail.
The water-soluble azo compound of the present invention represented by the above formula (1) or a salt thereof is a water-soluble yellow dye. In the present specification, unless otherwise specified, acidic functional groups such as sulfo groups and carboxy groups are represented in the form of free acids. Further, as described above, the present invention includes both the water-soluble azo compound represented by the formula (1) or a salt of the compound, but it is complicated to always describe both of them as “compound or salt thereof”. It is. Therefore, unless otherwise specified, for convenience, the “water-soluble azo compound of the present invention or a salt thereof” including both the “water-soluble azo compound of the present invention” will be simply described as “the (water-soluble azo) compound of the present invention”.
本発明の化合物は上記式(1)で表される。
式(1)中、Qはハロゲン原子を表す。ハロゲン原子の具体例としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられ、フッ素原子又は塩素原子が好ましく、塩素原子が特に好ましい。 The compound of the present invention is represented by the above formula (1).
In formula (1), Q represents a halogen atom. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. A fluorine atom or a chlorine atom is preferable, and a chlorine atom is particularly preferable.
式(1)中、Qはハロゲン原子を表す。ハロゲン原子の具体例としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられ、フッ素原子又は塩素原子が好ましく、塩素原子が特に好ましい。 The compound of the present invention is represented by the above formula (1).
In formula (1), Q represents a halogen atom. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. A fluorine atom or a chlorine atom is preferable, and a chlorine atom is particularly preferable.
式(1)中、xは2から4の整数、好ましくは3を表す。
In the formula (1), x represents an integer of 2 to 4, preferably 3.
式(1)中、基Aは、上記式(2)~(7)のいずれか1つで表されるアミノ基を表す。
ここで、式(2)におけるmは1から5の整数、好ましくは1又は2、より好ましくは1を表す。
式(4)におけるnは2から5の整数、好ましくは2を表す。
式(6)におけるZは水素原子、カルボキシ基、又はスルホ基を表し、好ましくはスルホ基を表す。また、kは0から2の整数、好ましくは0又は1、より好ましくは1を表す。
式(7)におけるwは0から3の整数、好ましくは0を表す。すなわち、式(7)で表されるアミノ基としては、モノメチルアミノ基であるものが好ましい。
上記のうち、基Aとしては、式(2)、式(6)、又は式(7)で表されるアミノ基がより好ましい。 In the formula (1), the group A represents an amino group represented by any one of the above formulas (2) to (7).
Here, m in the formula (2) represents an integer of 1 to 5, preferably 1 or 2, and more preferably 1.
N in Formula (4) represents an integer of 2 to 5, preferably 2.
Z in Formula (6) represents a hydrogen atom, a carboxy group, or a sulfo group, and preferably represents a sulfo group. K represents an integer of 0 to 2, preferably 0 or 1, more preferably 1.
W in Formula (7) represents an integer of 0 to 3, preferably 0. That is, the amino group represented by the formula (7) is preferably a monomethylamino group.
Among the above, as the group A, an amino group represented by the formula (2), the formula (6), or the formula (7) is more preferable.
ここで、式(2)におけるmは1から5の整数、好ましくは1又は2、より好ましくは1を表す。
式(4)におけるnは2から5の整数、好ましくは2を表す。
式(6)におけるZは水素原子、カルボキシ基、又はスルホ基を表し、好ましくはスルホ基を表す。また、kは0から2の整数、好ましくは0又は1、より好ましくは1を表す。
式(7)におけるwは0から3の整数、好ましくは0を表す。すなわち、式(7)で表されるアミノ基としては、モノメチルアミノ基であるものが好ましい。
上記のうち、基Aとしては、式(2)、式(6)、又は式(7)で表されるアミノ基がより好ましい。 In the formula (1), the group A represents an amino group represented by any one of the above formulas (2) to (7).
Here, m in the formula (2) represents an integer of 1 to 5, preferably 1 or 2, and more preferably 1.
N in Formula (4) represents an integer of 2 to 5, preferably 2.
Z in Formula (6) represents a hydrogen atom, a carboxy group, or a sulfo group, and preferably represents a sulfo group. K represents an integer of 0 to 2, preferably 0 or 1, more preferably 1.
W in Formula (7) represents an integer of 0 to 3, preferably 0. That is, the amino group represented by the formula (7) is preferably a monomethylamino group.
Among the above, as the group A, an amino group represented by the formula (2), the formula (6), or the formula (7) is more preferable.
上記のQ、基A、x、m、n、Z、k、及びwのうち、好ましいものを組み合わせた化合物はより好ましく、より好ましいものを組み合わせた化合物はさらに好ましい。好ましいものと、より好ましいものとの組み合わせ等についても同様である。
Among the above Q, groups A, x, m, n, Z, k, and w, a compound in which preferable ones are combined is more preferable, and a compound in which more preferable ones are combined is more preferable. The same applies to combinations of preferable and more preferable ones.
上記式(1)で表される化合物のうち、特に好ましい化合物が上記式(8)、式(9)、又は式(10)で表される化合物である。
Among the compounds represented by the above formula (1), particularly preferred compounds are the compounds represented by the above formula (8), formula (9), or formula (10).
上記式(1)で表される本発明の化合物は、例えば次のようにして製造することができる。なお、下記式(AA)から(K)において適宜使用されるQ、x、m、n、Z、k、及びwは、それぞれ上記と同じ意味を表す。
特開2004-75719号公報に記載の方法に準じて、市販品の2-アミノ-4-ハロゲノフェノールを原料として得られる下記式(AA)で表される化合物を、重亜硫酸ナトリウム及びホルマリンを用いて下記式(B)で表されるメチル-ω-スルホン酸誘導体に変換する。次いで、常法により、下記式(C)で表される5-アミノ-2-クロロ安息香酸をジアゾ化し、先に得られた下記式(B)で表されるメチル-ω-スルホン酸誘導体と、反応温度0~15℃、pH2~4でカップリング反応を行い、引き続き、反応温度80~95℃、pH10.5~11.5で加水分解反応を行うことにより、下記式(D)で表される化合物が得られる。 The compound of the present invention represented by the above formula (1) can be produced, for example, as follows. In addition, Q, x, m, n, Z, k, and w used appropriately in the following formulas (AA) to (K) represent the same meanings as described above.
In accordance with the method described in JP-A-2004-75719, a compound represented by the following formula (AA) obtained using a commercially available 2-amino-4-halogenophenol as a raw material is obtained using sodium bisulfite and formalin. To a methyl-ω-sulfonic acid derivative represented by the following formula (B). Then, by a conventional method, 5-amino-2-chlorobenzoic acid represented by the following formula (C) is diazotized, and the methyl-ω-sulfonic acid derivative represented by the following formula (B) obtained above is A coupling reaction is carried out at a reaction temperature of 0 to 15 ° C. and a pH of 2 to 4, followed by a hydrolysis reaction at a reaction temperature of 80 to 95 ° C. and a pH of 10.5 to 11.5. Is obtained.
特開2004-75719号公報に記載の方法に準じて、市販品の2-アミノ-4-ハロゲノフェノールを原料として得られる下記式(AA)で表される化合物を、重亜硫酸ナトリウム及びホルマリンを用いて下記式(B)で表されるメチル-ω-スルホン酸誘導体に変換する。次いで、常法により、下記式(C)で表される5-アミノ-2-クロロ安息香酸をジアゾ化し、先に得られた下記式(B)で表されるメチル-ω-スルホン酸誘導体と、反応温度0~15℃、pH2~4でカップリング反応を行い、引き続き、反応温度80~95℃、pH10.5~11.5で加水分解反応を行うことにより、下記式(D)で表される化合物が得られる。 The compound of the present invention represented by the above formula (1) can be produced, for example, as follows. In addition, Q, x, m, n, Z, k, and w used appropriately in the following formulas (AA) to (K) represent the same meanings as described above.
In accordance with the method described in JP-A-2004-75719, a compound represented by the following formula (AA) obtained using a commercially available 2-amino-4-halogenophenol as a raw material is obtained using sodium bisulfite and formalin. To a methyl-ω-sulfonic acid derivative represented by the following formula (B). Then, by a conventional method, 5-amino-2-chlorobenzoic acid represented by the following formula (C) is diazotized, and the methyl-ω-sulfonic acid derivative represented by the following formula (B) obtained above is A coupling reaction is carried out at a reaction temperature of 0 to 15 ° C. and a pH of 2 to 4, followed by a hydrolysis reaction at a reaction temperature of 80 to 95 ° C. and a pH of 10.5 to 11.5. Is obtained.
次いで、上記式(D)で表される化合物(2当量)とハロゲン化シアヌル(1当量)、例えば塩化シアヌル(1当量)とを、反応温度15~45℃、pH5~8で縮合することにより、下記式(E)で表される化合物が得られる。
Subsequently, the compound represented by the above formula (D) (2 equivalents) and cyanuric halide (1 equivalent), for example, cyanuric chloride (1 equivalent) are condensed at a reaction temperature of 15 to 45 ° C. and a pH of 5 to 8. A compound represented by the following formula (E) is obtained.
さらに、得られた上記式(E)で表される化合物におけるトリアジン環上の塩素原子を、反応温度75~90℃、pH7~9の条件下、基Aに対応する下記式(F)~(K)で表されるアミンで置換することにより、上記式(1)で表される本発明の化合物を得ることができる。
Further, the chlorine atom on the triazine ring in the obtained compound represented by the formula (E) is converted into the following formulas (F) to (C) corresponding to the group A under the conditions of reaction temperature 75 to 90 ° C. By substituting with the amine represented by K), the compound of the present invention represented by the above formula (1) can be obtained.
上記式(F)で表されるアミンとしては、グリシン、β-アラニン、4-アミノ酪酸、5-アミノ吉草酸、6-アミノヘキサン酸が具体例として挙げられる。
上記式(G)のアミンは、イミノジ酢酸として、容易に市販品を入手できる。
上記式(H)のアミンとしては、2-アミノエタノール、3-アミノプロパノール、4-アミノブタノール、5-アミノペンタノールが具体例として挙げられる。
上記式(I)のアミンは、ジエタノールアミンとして、容易に市販品を入手できる。
上記式(J)で表されるアミンとしては、2-アミノベンゼンスルホン酸、3-アミノベンゼンスルホン酸、4-アミノベンゼンスルホン酸、2-アミノ安息香酸、3-アミノ安息香酸、4-アミノ安息香酸、アニリン、ベンジルアミン、フェネチルアミン、4-アミノメチルベンゼンスルホン酸、4-アミノエチルベンゼンスルホン酸、4-アミノメチル安息香酸が具体例として挙げられる。
上記式(K)で表されるアミンとしては、メチルアミン、エチルアミン、n-プロピルアミン、n-ブチルアミンが具体例として挙げられ、メチルアミンが好ましい。 Specific examples of the amine represented by the formula (F) include glycine, β-alanine, 4-aminobutyric acid, 5-aminovaleric acid, and 6-aminohexanoic acid.
The amine of the said formula (G) can obtain a commercial item easily as iminodiacetic acid.
Specific examples of the amine of the above formula (H) include 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, and 5-aminopentanol.
The amine of the said formula (I) can obtain a commercial item easily as diethanolamine.
Examples of the amine represented by the above formula (J) include 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, and 4-aminobenzoic acid. Specific examples include acid, aniline, benzylamine, phenethylamine, 4-aminomethylbenzenesulfonic acid, 4-aminoethylbenzenesulfonic acid, and 4-aminomethylbenzoic acid.
Specific examples of the amine represented by the formula (K) include methylamine, ethylamine, n-propylamine, and n-butylamine, and methylamine is preferable.
上記式(G)のアミンは、イミノジ酢酸として、容易に市販品を入手できる。
上記式(H)のアミンとしては、2-アミノエタノール、3-アミノプロパノール、4-アミノブタノール、5-アミノペンタノールが具体例として挙げられる。
上記式(I)のアミンは、ジエタノールアミンとして、容易に市販品を入手できる。
上記式(J)で表されるアミンとしては、2-アミノベンゼンスルホン酸、3-アミノベンゼンスルホン酸、4-アミノベンゼンスルホン酸、2-アミノ安息香酸、3-アミノ安息香酸、4-アミノ安息香酸、アニリン、ベンジルアミン、フェネチルアミン、4-アミノメチルベンゼンスルホン酸、4-アミノエチルベンゼンスルホン酸、4-アミノメチル安息香酸が具体例として挙げられる。
上記式(K)で表されるアミンとしては、メチルアミン、エチルアミン、n-プロピルアミン、n-ブチルアミンが具体例として挙げられ、メチルアミンが好ましい。 Specific examples of the amine represented by the formula (F) include glycine, β-alanine, 4-aminobutyric acid, 5-aminovaleric acid, and 6-aminohexanoic acid.
The amine of the said formula (G) can obtain a commercial item easily as iminodiacetic acid.
Specific examples of the amine of the above formula (H) include 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, and 5-aminopentanol.
The amine of the said formula (I) can obtain a commercial item easily as diethanolamine.
Examples of the amine represented by the above formula (J) include 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, and 4-aminobenzoic acid. Specific examples include acid, aniline, benzylamine, phenethylamine, 4-aminomethylbenzenesulfonic acid, 4-aminoethylbenzenesulfonic acid, and 4-aminomethylbenzoic acid.
Specific examples of the amine represented by the formula (K) include methylamine, ethylamine, n-propylamine, and n-butylamine, and methylamine is preferable.
上記式(1)で表される本発明の化合物の具体例を下記表1に示すが、本発明はこれらの具体例に限定されるものではない。下記表1中、Q、x、m、n、Z、k、及びwは、上記式(1)又は式(2)~(7)におけるQ、x、m、n、Z、k、及びwに対応する。化合物番号1乃至10は基Aが上記式(2)で表されるアミノ基であるものの具体例であり、化合物番号11は基Aが上記式(3)で表されるアミノ基であるものの具体例であり、化合物番号12乃至15は基Aが上記式(4)で表されるアミノ基であるものの具体例であり、化合物番号16は基Aが上記式(5)で表されるアミノ基であるものの具体例である。また、化合物番号17乃至33は基Aが上記式(6)で表されるアミノ基であるものの具体例であり、化合物番号34乃至42は基Aが上記式(7)で表されるアミノ基であるものの具体例である。なお、表中「-」で示される記号は、相当するものを有しないことを意味する。
Specific examples of the compound of the present invention represented by the above formula (1) are shown in Table 1 below, but the present invention is not limited to these specific examples. In the following Table 1, Q, x, m, n, Z, k, and w are Q, x, m, n, Z, k, and w in the above formula (1) or formulas (2) to (7). Corresponding to Compound Nos. 1 to 10 are specific examples in which the group A is an amino group represented by the above formula (2), and the compound number 11 is a specific example in which the group A is an amino group represented by the above formula (3). Compound Nos. 12 to 15 are specific examples in which the group A is an amino group represented by the above formula (4), and the compound number 16 is an amino group in which the group A is represented by the above formula (5). It is a specific example of what is. Further, compound numbers 17 to 33 are specific examples of the group A being an amino group represented by the above formula (6), and compound numbers 34 to 42 are amino groups having the group A represented by the above formula (7). It is a specific example of what is. In the table, the symbol “−” means that there is no equivalent.
上記式(1)で表される化合物は、遊離酸、あるいはその塩としても存在する。上記式(1)で表される化合物の塩としては、無機又は有機陽イオンとの塩が挙げられる。無機陽イオンの塩の具体例としては、アルカリ金属塩、例えばリチウム塩、ナトリウム塩、カリウム塩等の塩;及びアンモニウム塩(NH4
+)が挙げられる。また、有機陽イオンの塩としては、例えば下記式(11)で表される4級アンモニウムの塩が挙げられるが、これらに限定されるものではない。
The compound represented by the above formula (1) exists also as a free acid or a salt thereof. Examples of the salt of the compound represented by the formula (1) include salts with inorganic or organic cations. Specific examples of the inorganic cation salt include alkali metal salts such as lithium salts, sodium salts, potassium salts and the like; and ammonium salts (NH 4 + ). Examples of organic cation salts include, but are not limited to, quaternary ammonium salts represented by the following formula (11).
上記式(11)中、Z1~Z4はそれぞれ独立に水素原子、C1-C4アルキル基、ヒドロキシC1-C4アルキル基、ヒドロキシC1-C4アルコキシC1-C4アルキル基を表し、Z1~Z4の少なくとも1つは水素原子以外の基である。
In the above formula (11), Z 1 to Z 4 each independently represent a hydrogen atom, a C1-C4 alkyl group, a hydroxy C1-C4 alkyl group, a hydroxy C1-C4 alkoxy C1-C4 alkyl group, and Z 1 -Z 4 At least one of is a group other than a hydrogen atom.
ここで、Z1~Z4における上記C1-C4アルキル基の例としては、メチル、エチル等が挙げられる。同様に、上記ヒドロキシC1-C4アルキル基の例としては、ヒドロキシメチル、ヒドロキシエチル、3-ヒドロキシプロピル、2-ヒドロキシプロピル、4-ヒドロキシブチル、3-ヒドロキシブチル、2-ヒドロキシブチル等が挙げられる。同様に、上記ヒドロキシC1-C4アルコキシC1-C4アルキル基の例としては、ヒドロキシエトキシメチル、2-ヒドロキシエトキシエチル、3-(ヒドロキシエトキシ)プロピル、3-(ヒドロキシエトキシ)ブチル、2-(ヒドロキシエトキシ)ブチル等が挙げられる。
Here, examples of the C1-C4 alkyl group in Z 1 to Z 4 include methyl, ethyl and the like. Similarly, examples of the hydroxy C1-C4 alkyl group include hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl and the like. Similarly, examples of the hydroxy C1-C4 alkoxy C1-C4 alkyl group include hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3- (hydroxyethoxy) propyl, 3- (hydroxyethoxy) butyl, 2- (hydroxyethoxy ) Butyl and the like.
上記塩のうち好ましいものは、ナトリウム、カリウム、リチウム等のアルカリ金属塩;モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノイソプロパノールアミン、ジイソプロパノールアミン、トリイソプロパノールアミンの塩等の有機4級アンモニウム塩;アンモニウム塩;等が挙げられる。これらのうち、より好ましくは、リチウム塩、ナトリウム塩、及びアンモニウム塩である。
Among the above salts, preferred are alkali metal salts such as sodium, potassium and lithium; organic quaternary ammonium salts such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine and triisopropanolamine salts; Ammonium salt; and the like. Of these, lithium salts, sodium salts, and ammonium salts are more preferable.
当業者においては明らかなように、上記式(1)で表される化合物の塩又は遊離酸は、以下の方法等により容易に得ることができる。
例えば、式(1)で表される化合物の合成反応における、最終工程終了後の反応液、あるいは式(1)で表される化合物の塩を含む水溶液等に、例えばアセトンやC1-C4アルコール等の水溶性有機溶剤を加える方法;塩化ナトリウムを加えて塩析する方法;等の方法によって析出した固体を濾過分離することにより、上記式(1)で表される化合物のナトリウム塩等をウェットケーキとして得ることができる。
また、得られたナトリウム塩のウェットケーキを水に溶解後、塩酸等の酸を加えてそのpHを適宜調整し、析出した固体を濾過分離することにより、上記式(1)で表される化合物の遊離酸を、あるいは式(1)で表される化合物の一部がナトリウム塩である遊離酸とナトリウム塩の混合物を得ることもできる。
また、得られたナトリウム塩のウェットケーキ又はその乾燥固体を水に溶解後、塩化アンモニウム等のアンモニウム塩を添加し、塩酸等の酸を加えてそのpHを適宜、例えばpH1~3に調整し、析出した固体を濾過分離することにより、上記式(1)で表される化合物のアンモニウム塩を得ることができる。添加する塩化アンモニウムの量又は/及びpHを適宜調整することにより、式(1)で表される化合物のアンモニウム塩と式(1)で表される化合物のナトリウム塩との混合物;又は式(1)で表される化合物の遊離酸とアンモニウム塩との混合物;等を得ることもできる。
また、後記するように上記反応終了後の反応液に、鉱酸(例えば塩酸、硫酸等)を加えて直接遊離酸の固体を得ることもできる。この場合には、式(1)で表される化合物の遊離酸のウェットケーキを水に加えて撹拌し、例えば、水酸化カリウム;水酸化リチウム;アンモニア水;又は式(11)で表される有機4級アンモニウムの水酸化物;等を添加して造塩することにより、各々添加した化合物に応じたカリウム塩;リチウム塩;アンモニウム塩;4級アンモニウム塩;等を得ることもできる。遊離酸のモル数に対して、加える上記の水酸化物等のモル数を制限することにより、例えばリチウム塩とナトリウム塩との混塩等;さらにはリチウム塩、ナトリウム塩、及びアンモニウム塩の混塩等;も調製することが可能である。上記式(1)で表される化合物の塩は、その塩の種類により溶解性等の物理的な性質、あるいはインクとして用いた場合のインクの性能が変化する場合もある。このため目的とするインク性能等に応じて塩の種類を選択することも好ましく行われる。 As will be apparent to those skilled in the art, the salt or free acid of the compound represented by the above formula (1) can be easily obtained by the following method or the like.
For example, in the synthesis reaction of the compound represented by the formula (1), the reaction solution after completion of the final step or the aqueous solution containing the salt of the compound represented by the formula (1), for example, acetone or C1-C4 alcohol A method of adding a water-soluble organic solvent, a method of salting out by adding sodium chloride, and the like. Can be obtained as
Moreover, after dissolving the obtained sodium salt wet cake in water, an acid such as hydrochloric acid is added to adjust the pH appropriately, and the precipitated solid is separated by filtration, whereby the compound represented by the above formula (1) Or a mixture of a free acid and a sodium salt, in which a part of the compound represented by the formula (1) is a sodium salt.
Further, after dissolving the obtained sodium salt wet cake or the dried solid thereof in water, an ammonium salt such as ammonium chloride is added, and an acid such as hydrochloric acid is added to adjust the pH appropriately to, for example, pH 1 to 3, An ammonium salt of the compound represented by the above formula (1) can be obtained by separating the precipitated solid by filtration. A mixture of an ammonium salt of the compound represented by formula (1) and a sodium salt of the compound represented by formula (1) by appropriately adjusting the amount or / and pH of ammonium chloride to be added; or formula (1) It is also possible to obtain a mixture of a free acid and an ammonium salt of a compound represented by
Further, as described later, a free acid solid can be directly obtained by adding a mineral acid (for example, hydrochloric acid, sulfuric acid, etc.) to the reaction solution after completion of the above reaction. In this case, the wet cake of the free acid of the compound represented by the formula (1) is added to water and stirred, for example, potassium hydroxide; lithium hydroxide; aqueous ammonia; or represented by the formula (11) An organic quaternary ammonium hydroxide; etc. can be added to form a salt to obtain a potassium salt, a lithium salt, an ammonium salt, a quaternary ammonium salt, etc. according to each added compound. By limiting the number of moles of the above-mentioned hydroxide to be added with respect to the number of moles of free acid, for example, a mixed salt of lithium salt and sodium salt, etc .; and a mixture of lithium salt, sodium salt, and ammonium salt Salts and the like can also be prepared. The salt of the compound represented by the above formula (1) may change the physical properties such as solubility or the ink performance when used as an ink depending on the type of the salt. For this reason, it is also preferable to select the type of salt according to the intended ink performance.
例えば、式(1)で表される化合物の合成反応における、最終工程終了後の反応液、あるいは式(1)で表される化合物の塩を含む水溶液等に、例えばアセトンやC1-C4アルコール等の水溶性有機溶剤を加える方法;塩化ナトリウムを加えて塩析する方法;等の方法によって析出した固体を濾過分離することにより、上記式(1)で表される化合物のナトリウム塩等をウェットケーキとして得ることができる。
また、得られたナトリウム塩のウェットケーキを水に溶解後、塩酸等の酸を加えてそのpHを適宜調整し、析出した固体を濾過分離することにより、上記式(1)で表される化合物の遊離酸を、あるいは式(1)で表される化合物の一部がナトリウム塩である遊離酸とナトリウム塩の混合物を得ることもできる。
また、得られたナトリウム塩のウェットケーキ又はその乾燥固体を水に溶解後、塩化アンモニウム等のアンモニウム塩を添加し、塩酸等の酸を加えてそのpHを適宜、例えばpH1~3に調整し、析出した固体を濾過分離することにより、上記式(1)で表される化合物のアンモニウム塩を得ることができる。添加する塩化アンモニウムの量又は/及びpHを適宜調整することにより、式(1)で表される化合物のアンモニウム塩と式(1)で表される化合物のナトリウム塩との混合物;又は式(1)で表される化合物の遊離酸とアンモニウム塩との混合物;等を得ることもできる。
また、後記するように上記反応終了後の反応液に、鉱酸(例えば塩酸、硫酸等)を加えて直接遊離酸の固体を得ることもできる。この場合には、式(1)で表される化合物の遊離酸のウェットケーキを水に加えて撹拌し、例えば、水酸化カリウム;水酸化リチウム;アンモニア水;又は式(11)で表される有機4級アンモニウムの水酸化物;等を添加して造塩することにより、各々添加した化合物に応じたカリウム塩;リチウム塩;アンモニウム塩;4級アンモニウム塩;等を得ることもできる。遊離酸のモル数に対して、加える上記の水酸化物等のモル数を制限することにより、例えばリチウム塩とナトリウム塩との混塩等;さらにはリチウム塩、ナトリウム塩、及びアンモニウム塩の混塩等;も調製することが可能である。上記式(1)で表される化合物の塩は、その塩の種類により溶解性等の物理的な性質、あるいはインクとして用いた場合のインクの性能が変化する場合もある。このため目的とするインク性能等に応じて塩の種類を選択することも好ましく行われる。 As will be apparent to those skilled in the art, the salt or free acid of the compound represented by the above formula (1) can be easily obtained by the following method or the like.
For example, in the synthesis reaction of the compound represented by the formula (1), the reaction solution after completion of the final step or the aqueous solution containing the salt of the compound represented by the formula (1), for example, acetone or C1-C4 alcohol A method of adding a water-soluble organic solvent, a method of salting out by adding sodium chloride, and the like. Can be obtained as
Moreover, after dissolving the obtained sodium salt wet cake in water, an acid such as hydrochloric acid is added to adjust the pH appropriately, and the precipitated solid is separated by filtration, whereby the compound represented by the above formula (1) Or a mixture of a free acid and a sodium salt, in which a part of the compound represented by the formula (1) is a sodium salt.
Further, after dissolving the obtained sodium salt wet cake or the dried solid thereof in water, an ammonium salt such as ammonium chloride is added, and an acid such as hydrochloric acid is added to adjust the pH appropriately to, for example, pH 1 to 3, An ammonium salt of the compound represented by the above formula (1) can be obtained by separating the precipitated solid by filtration. A mixture of an ammonium salt of the compound represented by formula (1) and a sodium salt of the compound represented by formula (1) by appropriately adjusting the amount or / and pH of ammonium chloride to be added; or formula (1) It is also possible to obtain a mixture of a free acid and an ammonium salt of a compound represented by
Further, as described later, a free acid solid can be directly obtained by adding a mineral acid (for example, hydrochloric acid, sulfuric acid, etc.) to the reaction solution after completion of the above reaction. In this case, the wet cake of the free acid of the compound represented by the formula (1) is added to water and stirred, for example, potassium hydroxide; lithium hydroxide; aqueous ammonia; or represented by the formula (11) An organic quaternary ammonium hydroxide; etc. can be added to form a salt to obtain a potassium salt, a lithium salt, an ammonium salt, a quaternary ammonium salt, etc. according to each added compound. By limiting the number of moles of the above-mentioned hydroxide to be added with respect to the number of moles of free acid, for example, a mixed salt of lithium salt and sodium salt, etc .; and a mixture of lithium salt, sodium salt, and ammonium salt Salts and the like can also be prepared. The salt of the compound represented by the above formula (1) may change the physical properties such as solubility or the ink performance when used as an ink depending on the type of the salt. For this reason, it is also preferable to select the type of salt according to the intended ink performance.
上記式(1)で表される本発明の化合物は、その合成反応における最終工程の終了後、塩酸等の鉱酸の添加により固体の遊離酸として単離することができ、得られた遊離酸の固体を水又は例えば塩酸水等の酸性水で洗浄すること等により、不純物として含有する無機塩(無機不純物)、例えば塩化ナトリウムや硫酸ナトリウム等を除去することができる。上記のようにして得られる本発明の化合物の遊離酸は、上記の通り、得られたウェットケーキやその乾燥固体を、水中で所望の無機又は有機塩基と処理することにより、対応する化合物の塩の溶液を得ることができる。無機塩基としては、例えば水酸化リチウム、水酸化ナトリウム、水酸化カリウム等のアルカリ金属の水酸化物;炭酸リチウム、炭酸ナトリウム、炭酸カリウム等のアルカリ金属の炭酸塩;水酸化アンモニウム(アンモニア水);等が挙げられる。有機塩基の例としては、例えば上記式(11)で表される4級アンモニウムに対応する有機アミン、例えばジエタノールアミン、トリエタノールアミン等のアルカノールアミン等が挙げられるが、これらに限定されるものではない。
The compound of the present invention represented by the above formula (1) can be isolated as a solid free acid by adding a mineral acid such as hydrochloric acid after completion of the final step in the synthesis reaction, and the obtained free acid By washing the solid with water or acidic water such as hydrochloric acid, inorganic salts (inorganic impurities) contained as impurities, such as sodium chloride and sodium sulfate, can be removed. As described above, the free acid of the compound of the present invention obtained as described above is obtained by treating the obtained wet cake or its dried solid with a desired inorganic or organic base in water to give a salt of the corresponding compound. Solution. Examples of the inorganic base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate; ammonium hydroxide (ammonia water); Etc. Examples of the organic base include, for example, organic amines corresponding to the quaternary ammonium represented by the above formula (11), for example, alkanolamines such as diethanolamine and triethanolamine, but are not limited thereto. .
本発明の化合物は、天然及び合成繊維材料又は混紡品の染色、さらには、筆記用インク及びインクジェット記録用インク組成物の製造に適している。例えば、上記式(1)で表される本発明の化合物の合成反応における、最終工程終了後の反応液は、本発明のインク組成物の製造に直接使用することもできる。しかし、例えば上記の方法や、スプレー乾燥等の方法により反応液等を乾燥して該化合物を単離した後、得られた化合物をインク組成物に加工することもできる。
The compound of the present invention is suitable for dyeing natural and synthetic fiber materials or blended products, and also for producing inks for writing and ink jet recording. For example, the reaction solution after completion of the final step in the synthesis reaction of the compound of the present invention represented by the above formula (1) can be directly used for the production of the ink composition of the present invention. However, for example, after the reaction solution or the like is dried by the above-described method or a spray drying method to isolate the compound, the obtained compound can be processed into an ink composition.
本発明のインク組成物は、上記式(1)で表される化合物を水又は、水と水溶性有機溶剤(水との混和が可能な有機溶剤)との混合溶液(水性媒体ともいう)に溶解し、必要に応じインク調製剤を添加したものである。このインク組成物をインクジェットプリンタ用のインクとして使用する場合、不純物として含有する金属陽イオンの塩化物、例えば塩化ナトリウム;硫酸塩、例えば硫酸ナトリウム;等の無機不純物の含有量が少ないものを用いるのが好ましい。この場合、例えば塩化ナトリウムと硫酸ナトリウムとの総含有量は、式(1)で表される化合物の総質量に対して1質量%以下程度であり、下限値は0質量%、すなわち検出機器の検出限界以下でよい。無機不純物の少ない化合物を製造する方法としては、例えばそれ自体公知の逆浸透膜による方法;本発明の化合物の乾燥品あるいはウェットケーキを、例えばアセトンやC1-C4アルコール(例えばメタノール、エタノール、イソプロパノール等)等の水溶性有機溶剤、又は含水水溶性有機溶剤中に加え、懸濁精製又は晶析する方法;等の方法が挙げられ、これらの方法により脱塩処理等をすればよい。
In the ink composition of the present invention, the compound represented by the above formula (1) is mixed with water or a mixed solution (also referred to as an aqueous medium) of water and a water-soluble organic solvent (an organic solvent that can be mixed with water). It is dissolved and an ink preparation agent is added if necessary. When this ink composition is used as an ink for an ink jet printer, a metal cation chloride contained as an impurity, such as sodium chloride; sulfate, such as sodium sulfate; Is preferred. In this case, for example, the total content of sodium chloride and sodium sulfate is about 1% by mass or less with respect to the total mass of the compound represented by the formula (1), and the lower limit is 0% by mass, that is, the detection instrument. It may be below the detection limit. Examples of a method for producing a compound having a small amount of inorganic impurities include a method using a known reverse osmosis membrane; a dry product or a wet cake of the compound of the present invention, for example, acetone or C1-C4 alcohol (for example, methanol, ethanol, isopropanol, etc.) In addition to a water-soluble organic solvent such as), or a water-containing water-soluble organic solvent, a suspension purification or crystallization method; and the like, and desalting treatment may be performed by these methods.
本発明のインク組成物は、インク組成物の総質量中に、上記式(1)で表される化合物を通常0.1~20質量%、好ましくは1~10質量%、より好ましくは2~8質量%含有する。
In the ink composition of the present invention, the compound represented by the formula (1) is usually 0.1 to 20% by mass, preferably 1 to 10% by mass, more preferably 2 to 2% by mass in the total mass of the ink composition. 8% by mass is contained.
本発明のインク組成物は水を媒体として調製され、本発明の効果を害しない範囲内において必要に応じ、水溶性有機溶剤やインク調製剤を適宜含有してもよい。
The ink composition of the present invention is prepared using water as a medium, and may optionally contain a water-soluble organic solvent and an ink preparation agent as long as the effects of the present invention are not impaired.
水溶性有機溶剤は、染料の溶解;組成物の乾燥の防止(湿潤状態の保持);組成物の粘度の調整;色素の被記録材への浸透の促進;組成物の表面張力の調整;組成物の消泡;等の効果を期待して使用され、本発明のインク組成物には含有する方が好ましい。
The water-soluble organic solvent dissolves the dye; prevents the composition from drying (maintains a wet state); adjusts the viscosity of the composition; promotes penetration of the dye into the recording material; adjusts the surface tension of the composition; It is preferably used in the ink composition of the present invention in view of the effect of defoaming the product.
インク調製剤としては、例えば、防腐防黴剤、pH調整剤、キレート試薬、防錆剤、紫外線吸収剤、粘度調整剤、染料溶解剤、褪色防止剤、表面張力調整剤、消泡剤等の公知の添加剤が挙げられる。
Examples of the ink preparation agent include antiseptic / antifungal agents, pH adjusting agents, chelating reagents, rust preventive agents, ultraviolet absorbers, viscosity adjusting agents, dye dissolving agents, antifading agents, surface tension adjusting agents, antifoaming agents, etc. Known additives may be mentioned.
本発明のインク組成物の総質量に対して、水溶性有機溶剤の含有量は0~60質量%、好ましくは10~50質量%であり、インク調製剤は0~20質量%、好ましくは0~15質量%用いるのが良い。本発明のインク組成物において、上記式(1)で表される化合物、水溶性有機溶剤、及びインク調製剤以外の残部は水である。
The content of the water-soluble organic solvent is 0 to 60% by mass, preferably 10 to 50% by mass, and the ink preparation agent is 0 to 20% by mass, preferably 0%, based on the total mass of the ink composition of the present invention. It is good to use up to 15 mass%. In the ink composition of the present invention, the balance other than the compound represented by the above formula (1), the water-soluble organic solvent, and the ink preparation agent is water.
上記の水溶性有機溶剤としては、例えば、メタノール、エタノール、n-プロパノール、イソプロパノール、n-ブタノール、イソブタノール、第二ブタノール、第三ブタノール等のC1-C4アルコール;N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド等のアミド類;2-ピロリドン、N-メチル-2-ピロリドン、ヒドロキシエチル-2-ピロリドン、1,3-ジメチルイミダゾリジン-2-オン、1,3-ジメチルヘキサヒドロピリミド-2-オン等の複素環式ケトン;アセトン、メチルエチルケトン、2-メチル-2-ヒドロキシペンタン-4-オン等のケトン又はケトアルコール;テトラヒドロフラン、ジオキサン等の環状エーテル;エチレングリコール、1,2-又は1,3-プロピレングリコール、1,2-又は1,4-ブチレングリコール、1,6-ヘキシレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ジプロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール、チオジグリコール等のC2-C6アルキレン単位を有するモノ、オリゴ、若しくはポリアルキレングリコール又はチオグリコール;トリメチロールプロパン、グリセリン、ヘキサン-1,2,6-トリオール等のポリオール(好ましくはトリオール);エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル(ブチルカルビトール)、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル等の多価アルコールのC1-C4モノアルキルエーテル;γ-ブチロラクトン;ジメチルスルホキシド;等が挙げられる。
Examples of the water-soluble organic solvent include C1-C4 alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol and tert-butanol; N, N-dimethylformamide, N Amides such as N-dimethylacetamide; 2-pyrrolidone, N-methyl-2-pyrrolidone, hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidin-2-one, 1,3-dimethylhexahydropyrimido Heterocyclic ketones such as -2-one; ketones or ketoalcohols such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one; cyclic ethers such as tetrahydrofuran, dioxane; ethylene glycol, 1,2- or 1,3-propylene glycol, 1,2 Or mono having a C2-C6 alkylene unit such as 1,4-butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, thiodiglycol, Oligo, or polyalkylene glycol or thioglycol; polyol (preferably triol) such as trimethylolpropane, glycerin, hexane-1,2,6-triol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol), triethylene Recall monomethyl ether, C1-C4 monoalkyl ether of polyhydric alcohol such as triethylene glycol monoethyl ether; .gamma.-butyrolactone; dimethyl sulfoxide; and the like.
なお、上記の水溶性有機溶剤には、例えばトリメチロールプロパン等のように、常温で固体の物質も含まれている。しかし、該物質等は固体であっても水溶性を示し、さらに該物質等を含有する水溶液は水溶性有機溶剤と同様の性質を示し、同じ効果を期待して使用することができる。このため本明細書においては、便宜上、このような固体の物質であっても上記と同じ効果を期待して使用できる限り、水溶性有機溶剤の範疇に含むこととする。
Note that the water-soluble organic solvent includes substances that are solid at room temperature, such as trimethylolpropane. However, even if the substance or the like is solid, it shows water solubility, and an aqueous solution containing the substance or the like shows the same properties as the water-soluble organic solvent and can be used with the expectation of the same effect. Therefore, in this specification, for the sake of convenience, such a solid substance is included in the category of a water-soluble organic solvent as long as it can be used in expectation of the same effect as described above.
上記の水溶性有機溶剤として好ましいものは、イソプロパノール、グリセリン、モノ、ジ又はトリエチレングリコール、ジプロピレングリコール、2-ピロリドン、ヒドロキシエチル-2-ピロリドン、N-メチル-2-ピロリドン、トリメチロールプロパン、及びブチルカルビトールであり、より好ましくはイソプロパノール、グリセリン、ジエチレングリコール、2-ピロリドン、N-メチル-2-ピロリドン、及びブチルカルビトールである。これらの水溶性有機溶剤は、単独又は混合して用いられる。
Preferred examples of the water-soluble organic solvent include isopropanol, glycerin, mono-, di- or triethylene glycol, dipropylene glycol, 2-pyrrolidone, hydroxyethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, trimethylolpropane, And butyl carbitol, more preferably isopropanol, glycerin, diethylene glycol, 2-pyrrolidone, N-methyl-2-pyrrolidone, and butyl carbitol. These water-soluble organic solvents are used alone or in combination.
上記の防腐防黴剤としては、例えば、有機硫黄系、有機窒素硫黄系、有機ハロゲン系、ハロアリルスルホン系、ヨードプロパギル系、N-ハロアルキルチオ系、ベンゾチアゾール系、ニトリル系、ピリジン系、8-オキシキノリン系、イソチアゾリン系、ジチオール系、ピリジンオキシド系、ニトロプロパン系、有機スズ系、フェノール系、第4アンモニウム塩系、トリアジン系、チアジアジン系、アニリド系、アダマンタン系、ジチオカーバメイト系、ブロム化インダノン系、ベンジルブロムアセテート系、無機塩系等の化合物が挙げられる。
有機ハロゲン系化合物としては、例えばペンタクロロフェノールナトリウムが挙げられる。ピリジンオキシド系化合物としては、例えば2-ピリジンチオール-1-オキサイドナトリウムが挙げられる。イソチアゾリン系化合物としては、例えば、1,2-ベンズイソチアゾリン-3-オン、2-n-オクチル-4-イソチアゾリン-3-オン、5-クロロ-2-メチル-4-イソチアゾリン-3-オン、5-クロロ-2-メチル-4-イソチアゾリン-3-オンマグネシウムクロライド、5-クロロ-2-メチル-4-イソチアゾリン-3-オンカルシウムクロライド、2-メチル-4-イソチアゾリン-3-オンカルシウムクロライド等が挙げられる。その他の防腐防黴剤としては、酢酸ナトリウム、ソルビン酸ナトリウム、安息香酸ナトリウム等が;さらにはアーチケミカル社製の商品名プロクセルRTMGXL(S)及びプロクセルRTMXL-2(S);等が、それぞれ挙げられる。なお、本明細書中において、上付きの「RTM」は登録商標を意味する。 Examples of the antiseptic / antifungal agent include organic sulfur, organic nitrogen sulfur, organic halogen, haloallylsulfone, iodopropargyl, N-haloalkylthio, benzothiazole, nitrile, pyridine, 8-oxyquinoline, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiadiazine, anilide, adamantane, dithiocarbamate, bromo Indanone compound, benzyl bromacetate compound, inorganic salt compound and the like can be mentioned.
An example of the organic halogen compound is sodium pentachlorophenol. Examples of pyridine oxide compounds include sodium 2-pyridinethiol-1-oxide. Examples of the isothiazoline compounds include 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazoline-3-one, 5 -Chloro-2-methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4-isothiazolin-3-one calcium chloride, etc. Can be mentioned. Other antiseptic and fungicide include sodium acetate, sodium sorbate, sodium benzoate and; more Arch Chemicals, Inc. under the trade name Proxel RTM GXL (S) and Proxel RTM XL-2 (S); and the like, Each is listed. In the present specification, the superscript “RTM” means a registered trademark.
有機ハロゲン系化合物としては、例えばペンタクロロフェノールナトリウムが挙げられる。ピリジンオキシド系化合物としては、例えば2-ピリジンチオール-1-オキサイドナトリウムが挙げられる。イソチアゾリン系化合物としては、例えば、1,2-ベンズイソチアゾリン-3-オン、2-n-オクチル-4-イソチアゾリン-3-オン、5-クロロ-2-メチル-4-イソチアゾリン-3-オン、5-クロロ-2-メチル-4-イソチアゾリン-3-オンマグネシウムクロライド、5-クロロ-2-メチル-4-イソチアゾリン-3-オンカルシウムクロライド、2-メチル-4-イソチアゾリン-3-オンカルシウムクロライド等が挙げられる。その他の防腐防黴剤としては、酢酸ナトリウム、ソルビン酸ナトリウム、安息香酸ナトリウム等が;さらにはアーチケミカル社製の商品名プロクセルRTMGXL(S)及びプロクセルRTMXL-2(S);等が、それぞれ挙げられる。なお、本明細書中において、上付きの「RTM」は登録商標を意味する。 Examples of the antiseptic / antifungal agent include organic sulfur, organic nitrogen sulfur, organic halogen, haloallylsulfone, iodopropargyl, N-haloalkylthio, benzothiazole, nitrile, pyridine, 8-oxyquinoline, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiadiazine, anilide, adamantane, dithiocarbamate, bromo Indanone compound, benzyl bromacetate compound, inorganic salt compound and the like can be mentioned.
An example of the organic halogen compound is sodium pentachlorophenol. Examples of pyridine oxide compounds include sodium 2-pyridinethiol-1-oxide. Examples of the isothiazoline compounds include 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazoline-3-one, 5 -Chloro-2-methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4-isothiazolin-3-one calcium chloride, etc. Can be mentioned. Other antiseptic and fungicide include sodium acetate, sodium sorbate, sodium benzoate and; more Arch Chemicals, Inc. under the trade name Proxel RTM GXL (S) and Proxel RTM XL-2 (S); and the like, Each is listed. In the present specification, the superscript “RTM” means a registered trademark.
pH調整剤は、インクの保存安定性を向上させる目的で、インクのpHを6.0~11.0の範囲に制御できるものであれば任意の物質を使用することができる。例えば、ジエタノールアミン、トリエタノールアミン等のアルカノールアミン;水酸化リチウム、水酸化ナトリウム、水酸化カリウム等のアルカリ金属の水酸化物;水酸化アンモニウム;あるいは炭酸リチウム、炭酸ナトリウム、炭酸カリウム等のアルカリ金属の炭酸塩;タウリン等のアミノスルホン酸;等が挙げられる。
As the pH adjuster, any substance can be used as long as it can control the pH of the ink in the range of 6.0 to 11.0 for the purpose of improving the storage stability of the ink. For example, alkanolamines such as diethanolamine and triethanolamine; hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide; ammonium hydroxides; or alkali metals such as lithium carbonate, sodium carbonate and potassium carbonate And carbonates; aminosulfonic acids such as taurine; and the like.
キレート試薬としては、例えば、エチレンジアミン四酢酸二ナトリウム、ニトリロ三酢酸ナトリウム、ヒドロキシエチルエチレンジアミン三酢酸ナトリウム、ジエチレントリアミン五酢酸ナトリウム、ウラシル二酢酸ナトリウム等が挙げられる。
Examples of the chelating reagent include disodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uracil diacetate, and the like.
防錆剤としては、例えば、酸性亜硫酸塩、チオ硫酸ナトリウム、チオグリコール酸アンモニウム、ジイソプロピルアンモニウムナイトライト、四硝酸ペンタエリスリトール、ジシクロヘキシルアンモニウムナイトライト等が挙げられる。
Examples of the rust preventive include acid sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and the like.
紫外線吸収剤としては、例えば、ベンゾフェノン系化合物、ベンゾトリアゾール系化合物、桂皮酸系化合物、トリアジン系化合物、スチルベン系化合物が挙げられる。また、ベンズオキサゾール系化合物に代表される紫外線を吸収して蛍光を発する化合物、いわゆる蛍光増白剤等も使用できる。
Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, cinnamic acid compounds, triazine compounds, and stilbene compounds. In addition, a compound that absorbs ultraviolet rays such as a benzoxazole-based compound and emits fluorescence, a so-called fluorescent whitening agent, and the like can also be used.
粘度調整剤としては、水溶性有機溶剤の他に、水溶性高分子化合物が挙げられ、例えば、ポリビニルアルコール、セルロース誘導体、ポリアミン、ポリイミン等が挙げられる。
Examples of the viscosity modifier include water-soluble polymer compounds in addition to water-soluble organic solvents, and examples thereof include polyvinyl alcohol, cellulose derivatives, polyamines, and polyimines.
染料溶解剤としては、例えば、尿素、ε-カプロラクタム、エチレンカーボネート等が挙げられる。その中でも尿素を使用するのが好ましい。
Examples of the dye solubilizer include urea, ε-caprolactam, ethylene carbonate, and the like. Of these, urea is preferably used.
褪色防止剤は、画像の保存性を向上させる目的で使用される。褪色防止剤としては、各種の有機系及び金属錯体系の褪色防止剤を使用することができる。有機の褪色防止剤としては、ハイドロキノン類、アルコキシフェノール類、ジアルコキシフェノール類、フェノール類、アニリン類、アミン類、インダン類、クロマン類、アルコキシアニリン類、ヘテロ環類等が挙げられ、金属錯体としては、ニッケル錯体、亜鉛錯体等が挙げられる。
The anti-fading agent is used for the purpose of improving image storage stability. As the antifading agent, various organic and metal complex antifading agents can be used. Examples of organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc. Includes nickel complexes and zinc complexes.
表面張力調整剤としては、界面活性剤が挙げられ、例えば、アニオン界面活性剤、両性界面活性剤、カチオン界面活性剤、ノニオン界面活性剤等が挙げられる。
Examples of the surface tension adjusting agent include surfactants, and examples include anionic surfactants, amphoteric surfactants, cationic surfactants, and nonionic surfactants.
アニオン界面活性剤としては、アルキルスルホカルボン酸塩、α-オレフィンスルホン酸塩、ポリオキシエチレンアルキルエーテル酢酸塩、N-アシルアミノ酸及びその塩、N-アシルメチルタウリン塩、アルキル硫酸塩ポリオキシアルキルエーテル硫酸塩、アルキル硫酸塩ポリオキシエチレンアルキルエーテル燐酸塩、ロジン酸石鹸、ヒマシ油硫酸エステル塩、ラウリルアルコール硫酸エステル塩、アルキルフェノール型燐酸エステル、アルキル型燐酸エステル、アルキルアリールスルホン酸塩、ジエチルスルホ琥珀酸塩、ジエチルヘキシルスルホ琥珀酸塩、ジオクチルスルホ琥珀酸塩等が挙げられる。
Examples of anionic surfactants include alkyl sulfocarboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and salts thereof, N-acyl methyl taurate, alkyl sulfate polyoxyalkyl ethers Sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate ester, lauryl alcohol sulfate ester, alkylphenol type phosphate ester, alkyl type phosphate ester, alkylaryl sulfonate, diethylsulfosuccinate Salts, diethylhexylsulfosuccinate, dioctylsulfosuccinate and the like.
カチオン界面活性剤としては、2-ビニルピリジン誘導体、ポリ4-ビニルピリジン誘導体等が挙げられる。
Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives.
両性界面活性剤としては、ラウリルジメチルアミノ酢酸ベタイン、2-アルキル-N-カルボキシメチル-N-ヒドロキシエチルイミダゾリニウムベタイン、ヤシ油脂肪酸アミドプロピルジメチルアミノ酢酸ベタイン、ポリオクチルポリアミノエチルグリシン、その他イミダゾリン誘導体等が挙げられる。
Amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, and other imidazoline derivatives. Etc.
ノニオン界面活性剤としては、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンドデシルフェニルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンアルキルエーテル等のエーテル系;ポリオキシエチレンオレイン酸エステル、ポリオキシエチレンジステアリン酸エステル、ソルビタンラウレート、ソルビタンモノステアレート、ソルビタンモノオレエート、ソルビタンセスキオレエート、ポリオキシエチレンモノオレエート、ポリオキシエチレンステアレート等のエステル系;2,4,7,9-テトラメチル-5-デシン-4,7-ジオール、3,6-ジメチル-4-オクチン-3,6-ジオール、3,5-ジメチル-1-ヘキシン-3-オール等のアセチレングリコール(アルコール)系;日信化学工業株式会社製の商品名サーフィノールRTM104、同82、同465、オルフィンRTMSTG;SIGMA-ALDRICH社製の商品名TergitolRTM15-S-7;等が挙げられる。
Nonionic surfactants include ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether; Ester systems such as polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl -1-hexyne-3-acetylene glycol (alcohol) -based ol; Nissin Chemical Industry Co., Ltd. trade name Surfynol RTM 104, 82, 465, Olfine RTM STG; SIGMA-ALDRICH Corp. Product Name Tergitol RTM 15-S-7;
消泡剤としては、高酸化油系、グリセリン脂肪酸エステル系、フッ素系、シリコーン系化合物等が挙げられる。
Examples of antifoaming agents include highly oxidized oils, glycerin fatty acid esters, fluorines, and silicone compounds.
これらのインク調製剤は、単独又は混合して用いられる。なお、本発明のインク組成物の表面張力は通常25~70mN/m、より好ましくは25~60mN/mであり、粘度は30mPa・s以下が好ましく、20mPa・s以下に調整することがより好ましい。
These ink preparation agents are used alone or in combination. The surface tension of the ink composition of the present invention is usually 25 to 70 mN / m, more preferably 25 to 60 mN / m, and the viscosity is preferably 30 mPa · s or less, more preferably 20 mPa · s or less. .
本発明のインク組成物の製造において、添加剤等の各薬剤を溶解させる順序には特に制限はない。インク組成物の調製に用いる水は、イオン交換水、蒸留水等の不純物が少ないものが好ましい。また、必要に応じインク組成物の調製後に、メンブランフィルタ等を用いて精密濾過を行って、インク組成物中の夾雑物を除いても良い。特に、本発明のインク組成物をインクジェット記録用のインクとして使用する場合には、精密濾過を行うことが好ましい。精密濾過に使用するフィルタの孔径は通常1~0.1μm、好ましくは0.8~0.1μmである。
In the production of the ink composition of the present invention, there is no particular limitation on the order of dissolving each agent such as an additive. The water used for preparing the ink composition is preferably water with few impurities such as ion exchange water and distilled water. Further, if necessary, after the ink composition is prepared, fine filtration may be performed using a membrane filter or the like to remove impurities in the ink composition. In particular, when the ink composition of the present invention is used as an ink for ink jet recording, it is preferable to perform microfiltration. The pore size of the filter used for microfiltration is usually 1 to 0.1 μm, preferably 0.8 to 0.1 μm.
本発明の化合物を含有するインク組成物は、印捺、複写、マーキング、筆記、製図、スタンピング、又は記録(印刷)、特にインクジェット記録における使用に適する。また、本発明のインク組成物は、インクジェットプリンタの記録ヘッドのノズル付近における乾燥に対しても固体の析出は起こりにくく、この理由により該記録ヘッドの閉塞もまた起こしにくい。
The ink composition containing the compound of the present invention is suitable for use in printing, copying, marking, writing, drafting, stamping, or recording (printing), particularly inkjet recording. In addition, the ink composition of the present invention is less likely to precipitate solids even when dried in the vicinity of the nozzles of the recording head of an ink jet printer, and for this reason, the recording head is also less likely to block.
本発明のインクジェット記録方法で被記録材に記録を行う方法として、次の方法が挙げられる。すなわち、本発明のインク組成物が充填された容器をインクジェットプリンタの所定位置に装填し、本発明のインク組成物をインクとして用い、該インクのインク滴を記録信号に応じて吐出させて被記録材に付着させ、記録を行う方法である。インクジェットプリンタには、例えば機械的振動を利用したピエゾ方式;加熱により生ずる泡を利用したバブルジェット(登録商標)方式;等を利用したものがある。本発明のインクジェット記録方法は、いかなる方式であっても使用が可能である。
As a method for recording on a recording material by the ink jet recording method of the present invention, the following method may be mentioned. That is, a container filled with the ink composition of the present invention is loaded into a predetermined position of an ink jet printer, the ink composition of the present invention is used as ink, and ink droplets of the ink are ejected according to a recording signal to be recorded. This is a method for recording on a material. Some inkjet printers use, for example, a piezo method using mechanical vibration; a bubble jet (registered trademark) method using bubbles generated by heating; and the like. The ink jet recording method of the present invention can be used by any method.
より高精細な記録画像を得ることを目的とし、同じ色素を含有する2種類のインクを1台のインクジェットプリンタに装填する場合もある。この2種類のインクの違いは色素の含有量であり、一方は含有量の高いもの、他方は低いものとし、インクセットとして使用する。本発明のインク組成物は、このようなインクセットとして使用することもできる。また、インクセットの一方に本発明のインク組成物を使用し、他方に公知のインク(組成物)を使用してもよい。
In order to obtain a higher-definition recorded image, there are cases where two types of ink containing the same pigment are loaded into one inkjet printer. The difference between the two types of inks is the pigment content, one of which has a high content and the other of which has a low content, and is used as an ink set. The ink composition of the present invention can also be used as such an ink set. Further, the ink composition of the present invention may be used for one of the ink sets, and a known ink (composition) may be used for the other.
本発明のインク組成物は、本発明により得られる効果を阻害しない範囲で、その色相を微調整する目的等から本発明の化合物と公知のイエロー色素とを含有するイエローインク組成物としてもよい。また、他の色のインク、例えばブラックインクの調色用途、あるいはレッドインクやグリーンインクを調製する目的で、本発明の化合物をマゼンタ色素やシアン色素と併用して用いることもできる。さらに、フルカラーの記録画像を得る目的で、本発明のインク組成物と共に、マゼンタ、シアン、必要に応じて、グリーン、ブルー(又はバイオレット)、レッド、ブラック等の各色のインクを併用することもできる。この場合、各色のインクをそれぞれの容器に充填し、それらの容器をインクジェットプリンタの所定位置に装填してインクジェット記録に使用すればよい。
The ink composition of the present invention may be a yellow ink composition containing the compound of the present invention and a known yellow dye for the purpose of fine-tuning the hue within a range that does not impair the effects obtained by the present invention. In addition, the compound of the present invention can be used in combination with a magenta dye or a cyan dye for the purpose of toning inks of other colors, such as black ink, or for preparing red ink or green ink. Furthermore, for the purpose of obtaining a full-color recorded image, the ink composition of the present invention can be used in combination with inks of various colors such as magenta, cyan, and, if necessary, green, blue (or violet), red, and black. . In this case, each color ink may be filled in each container, and these containers may be loaded into a predetermined position of the ink jet printer and used for ink jet recording.
本発明のインクジェット記録方法に用いる被記録材としては、例えば紙、フィルム等の情報伝達用シート、繊維や布(セルロース、ナイロン、羊毛等)、皮革、カラーフィルター用基材等が挙げられ、情報伝達用シートが好ましい。情報伝達用シートとしては、特に制限はなく、普通紙はもちろん、表面処理されたもの、具体的には紙、合成紙、フィルム等の基材にインク受容層を設けたもの等が用いられる。インク受容層とは、インクを吸収してその乾燥を早める等の作用を有する層である。インク受容層は、例えば上記基材にカチオン系ポリマーを含浸又は塗工する方法;インク中の色素を吸収し得る無機微粒子をポリビニルアルコールやポリビニルピロリドン等の親水性ポリマーと共に、上記基材の表面に塗工する方法;等により設けられる。上記のインク中の色素を吸収し得る無機微粒子の材質としては、多孔質シリカ、アルミナゾルや特殊セラミックス等が挙げられる。このようなインク受容層を有する情報伝達用シートは、通常インクジェット専用紙、インクジェット専用フィルム、光沢紙、光沢フィルム等と呼ばれる。インク受容層を有する情報伝達用シートの代表的な市販品の例としては、キヤノン(株)製、商品名プロフェッショナルフォトペーパー、キヤノン写真用紙・光沢プロ[プラチナグレード]、及び光沢ゴールド;セイコーエプソン(株)製、商品名写真用紙クリスピア(高光沢)、写真用紙(光沢);日本ヒューレット・パッカード(株)製、商品名アドバンスフォト用紙(光沢);富士フィルム(株)製、商品名画彩 写真仕上げPro;ブラザー工業株式会社製、商品名:写真光沢紙BP71G;等が挙げられる。
また、普通紙とは、特にインク受容層を設けていない紙のことを意味し、用途によってさまざまなものが数多く市販されている。市販されている普通紙のうち、インクジェット記録用としては、両面上質普通紙(セイコーエプソン株式会社製);PB PAPER GF-500(キヤノン株式会社製);Multipurpose Paper、All-in-one Printing Paper(Hewlett Packard社製);等が挙げられる。また、特に用途をインクジェット記録に限定しないプレーンペーパーコピー(PPC)用紙等も普通紙である。 Examples of the recording material used in the inkjet recording method of the present invention include information transmission sheets such as paper and film, fibers and fabrics (cellulose, nylon, wool, etc.), leather, base materials for color filters, and the like. A transmission sheet is preferred. The information transmission sheet is not particularly limited, and a plain paper as well as a surface-treated sheet, specifically, a paper, synthetic paper, a substrate such as a film provided with an ink receiving layer, or the like is used. The ink receiving layer is a layer having an action such as absorbing ink and accelerating its drying. The ink receiving layer is formed by, for example, a method of impregnating or coating the base material with a cationic polymer; inorganic fine particles capable of absorbing the pigment in the ink, together with a hydrophilic polymer such as polyvinyl alcohol or polyvinylpyrrolidone, on the surface of the base material. It is provided by the method of coating; Examples of the material of the inorganic fine particles that can absorb the pigment in the ink include porous silica, alumina sol, special ceramics, and the like. The information transmission sheet having such an ink receiving layer is usually called an inkjet exclusive paper, an inkjet exclusive film, a glossy paper, a glossy film or the like. Examples of representative commercial products of information transmission sheets having an ink receiving layer include products manufactured by Canon Inc., trade name Professional Photo Paper, Canon Photo Paper / Glossy Pro [Platinum Grade], and Glossy Gold; Seiko Epson ( Co., Ltd., trade name photo paper Crispia (high gloss), photo paper (gloss); Nihon Hewlett-Packard Co., Ltd., trade name Advanced Photo Paper (gloss); Fuji Film Co., Ltd. Pro; manufactured by Brother Industries, Ltd., trade name: photographic glossy paper BP71G;
Also, plain paper means paper that is not particularly provided with an ink receiving layer, and many different types are commercially available depending on the application. Of the commercially available plain papers, double-sided plain plain paper (manufactured by Seiko Epson Corporation); PB PAPER GF-500 (manufactured by Canon Inc.); Multipurpose Paper, All-in-one Printing Paper ( Hewlett Packard). In addition, plain paper copy (PPC) paper or the like whose use is not limited to ink jet recording is also plain paper.
また、普通紙とは、特にインク受容層を設けていない紙のことを意味し、用途によってさまざまなものが数多く市販されている。市販されている普通紙のうち、インクジェット記録用としては、両面上質普通紙(セイコーエプソン株式会社製);PB PAPER GF-500(キヤノン株式会社製);Multipurpose Paper、All-in-one Printing Paper(Hewlett Packard社製);等が挙げられる。また、特に用途をインクジェット記録に限定しないプレーンペーパーコピー(PPC)用紙等も普通紙である。 Examples of the recording material used in the inkjet recording method of the present invention include information transmission sheets such as paper and film, fibers and fabrics (cellulose, nylon, wool, etc.), leather, base materials for color filters, and the like. A transmission sheet is preferred. The information transmission sheet is not particularly limited, and a plain paper as well as a surface-treated sheet, specifically, a paper, synthetic paper, a substrate such as a film provided with an ink receiving layer, or the like is used. The ink receiving layer is a layer having an action such as absorbing ink and accelerating its drying. The ink receiving layer is formed by, for example, a method of impregnating or coating the base material with a cationic polymer; inorganic fine particles capable of absorbing the pigment in the ink, together with a hydrophilic polymer such as polyvinyl alcohol or polyvinylpyrrolidone, on the surface of the base material. It is provided by the method of coating; Examples of the material of the inorganic fine particles that can absorb the pigment in the ink include porous silica, alumina sol, special ceramics, and the like. The information transmission sheet having such an ink receiving layer is usually called an inkjet exclusive paper, an inkjet exclusive film, a glossy paper, a glossy film or the like. Examples of representative commercial products of information transmission sheets having an ink receiving layer include products manufactured by Canon Inc., trade name Professional Photo Paper, Canon Photo Paper / Glossy Pro [Platinum Grade], and Glossy Gold; Seiko Epson ( Co., Ltd., trade name photo paper Crispia (high gloss), photo paper (gloss); Nihon Hewlett-Packard Co., Ltd., trade name Advanced Photo Paper (gloss); Fuji Film Co., Ltd. Pro; manufactured by Brother Industries, Ltd., trade name: photographic glossy paper BP71G;
Also, plain paper means paper that is not particularly provided with an ink receiving layer, and many different types are commercially available depending on the application. Of the commercially available plain papers, double-sided plain plain paper (manufactured by Seiko Epson Corporation); PB PAPER GF-500 (manufactured by Canon Inc.); Multipurpose Paper, All-in-one Printing Paper ( Hewlett Packard). In addition, plain paper copy (PPC) paper or the like whose use is not limited to ink jet recording is also plain paper.
本発明の着色体は、(a)本発明の水溶性アゾ化合物;(b)該化合物を含有する本発明のインク組成物;(c)該化合物及び水溶性有機溶剤を含有する本発明のインク組成物;の3者のいずれかにより、着色された物質を意味する。着色される物質には特に制限はなく、例えば上記の被記録材等が挙げられるが、これらに限定されない。好ましくは上記の被記録材が着色されたものが挙げられる。物質への着色方法は特に制限されないが、例えば浸染法、捺染法、スクリーン印刷等の印刷方法、本発明のインクジェット記録方法等が挙げられ、本発明のインクジェット記録方法が好ましい。上記着色体の中でも、本発明のインクジェット記録方法により着色された着色体が好ましい。
The colored product of the present invention comprises: (a) the water-soluble azo compound of the present invention; (b) the ink composition of the present invention containing the compound; (c) the ink of the present invention containing the compound and a water-soluble organic solvent. By a composition; means a colored material. The substance to be colored is not particularly limited, and examples thereof include, but are not limited to, the recording material described above. Preferably, the above-mentioned recording material is colored. A coloring method for the substance is not particularly limited, and examples thereof include a printing method such as a dip dyeing method, a textile printing method, and screen printing, an ink jet recording method of the present invention, and the ink jet recording method of the present invention is preferable. Among the colored bodies, a colored body colored by the ink jet recording method of the present invention is preferable.
上記式(1)で表される本発明の水溶性アゾ化合物は、水や水溶性有機溶剤に対する溶解性に優れる。また、本発明のインク組成物を製造する過程での、例えばメンブランフィルタに対する濾過性が良好であるという特徴を有する。本発明のインク組成物は、普通紙及びインク受容層を有する情報伝達用シートといった被記録材上で非常に鮮明で、彩度及び印字濃度が高く、理想的な色相のイエロー色の記録画像を与える。このため、写真調のカラー画像を紙の上に忠実に再現させることも可能である。また、本発明のインク組成物は長期間保存後の固体析出、物性変化、色相変化等もなく、貯蔵安定性が極めて良好である。
本発明のインク組成物をインクジェットインクとして使用しても、ノズル付近におけるインク組成物の乾燥による固体析出は非常に起こりにくく、噴射器(記録ヘッド)を閉塞することもない。また、本発明のインク組成物は連続式インクジェットプリンタを用い、比較的長い時間間隔においてインクを再循環させて使用する場合においても、又はオンデマンド式インクジェットプリンタによる断続的な使用においても、物理的性質の変化を起こさない。
さらに、本発明のインク組成物により、インク受容層を有する情報伝達用シートに記録された画像は彩度が高く、また、耐水性、耐湿性、耐オゾンガス性、耐擦性、耐光性等の各種堅牢性、特に耐オゾンガス性が良好であり、彩度及び耐オゾンガス性のバランスに優れる。この理由から、写真調の画像の長期保存安定性にも優れている。また、従来のインクと比較して、普通紙上での彩度、明度、印字濃度等の発色性にも優れている。
このように、式(1)で表される本発明の水溶性アゾ化合物、及びこれを含有する本発明のインク組成物は、各種の記録インク用途、特にインクジェット記録用のインク用途に極めて有用である。 The water-soluble azo compound of the present invention represented by the above formula (1) is excellent in solubility in water or a water-soluble organic solvent. Moreover, it has the characteristic that the filterability with respect to a membrane filter, for example in the process of manufacturing the ink composition of this invention is favorable. The ink composition of the present invention is very clear on a recording material such as plain paper and an information transmission sheet having an ink receiving layer, has a high saturation and printing density, and is capable of producing a yellow recorded image of an ideal hue. give. Therefore, it is also possible to faithfully reproduce a photographic color image on paper. In addition, the ink composition of the present invention has very good storage stability without solid deposition, physical property change, hue change, etc. after long-term storage.
Even when the ink composition of the present invention is used as an inkjet ink, solid precipitation due to drying of the ink composition in the vicinity of the nozzles is very unlikely to occur, and the ejector (recording head) is not blocked. Further, the ink composition of the present invention uses a continuous ink jet printer, and is used physically even when the ink is recirculated at a relatively long time interval or intermittently used by an on-demand ink jet printer. No change in properties.
Furthermore, with the ink composition of the present invention, the image recorded on the information transmission sheet having the ink receiving layer has high saturation, and the water resistance, moisture resistance, ozone gas resistance, abrasion resistance, light resistance, etc. Various fastness properties, particularly ozone gas resistance, and excellent balance between saturation and ozone gas resistance. For this reason, the long-term storage stability of photographic images is also excellent. Further, compared with conventional inks, it is excellent in color development such as saturation, lightness, and print density on plain paper.
As described above, the water-soluble azo compound of the present invention represented by the formula (1) and the ink composition of the present invention containing the compound are extremely useful for various recording ink applications, particularly for ink jet recording ink applications. is there.
本発明のインク組成物をインクジェットインクとして使用しても、ノズル付近におけるインク組成物の乾燥による固体析出は非常に起こりにくく、噴射器(記録ヘッド)を閉塞することもない。また、本発明のインク組成物は連続式インクジェットプリンタを用い、比較的長い時間間隔においてインクを再循環させて使用する場合においても、又はオンデマンド式インクジェットプリンタによる断続的な使用においても、物理的性質の変化を起こさない。
さらに、本発明のインク組成物により、インク受容層を有する情報伝達用シートに記録された画像は彩度が高く、また、耐水性、耐湿性、耐オゾンガス性、耐擦性、耐光性等の各種堅牢性、特に耐オゾンガス性が良好であり、彩度及び耐オゾンガス性のバランスに優れる。この理由から、写真調の画像の長期保存安定性にも優れている。また、従来のインクと比較して、普通紙上での彩度、明度、印字濃度等の発色性にも優れている。
このように、式(1)で表される本発明の水溶性アゾ化合物、及びこれを含有する本発明のインク組成物は、各種の記録インク用途、特にインクジェット記録用のインク用途に極めて有用である。 The water-soluble azo compound of the present invention represented by the above formula (1) is excellent in solubility in water or a water-soluble organic solvent. Moreover, it has the characteristic that the filterability with respect to a membrane filter, for example in the process of manufacturing the ink composition of this invention is favorable. The ink composition of the present invention is very clear on a recording material such as plain paper and an information transmission sheet having an ink receiving layer, has a high saturation and printing density, and is capable of producing a yellow recorded image of an ideal hue. give. Therefore, it is also possible to faithfully reproduce a photographic color image on paper. In addition, the ink composition of the present invention has very good storage stability without solid deposition, physical property change, hue change, etc. after long-term storage.
Even when the ink composition of the present invention is used as an inkjet ink, solid precipitation due to drying of the ink composition in the vicinity of the nozzles is very unlikely to occur, and the ejector (recording head) is not blocked. Further, the ink composition of the present invention uses a continuous ink jet printer, and is used physically even when the ink is recirculated at a relatively long time interval or intermittently used by an on-demand ink jet printer. No change in properties.
Furthermore, with the ink composition of the present invention, the image recorded on the information transmission sheet having the ink receiving layer has high saturation, and the water resistance, moisture resistance, ozone gas resistance, abrasion resistance, light resistance, etc. Various fastness properties, particularly ozone gas resistance, and excellent balance between saturation and ozone gas resistance. For this reason, the long-term storage stability of photographic images is also excellent. Further, compared with conventional inks, it is excellent in color development such as saturation, lightness, and print density on plain paper.
As described above, the water-soluble azo compound of the present invention represented by the formula (1) and the ink composition of the present invention containing the compound are extremely useful for various recording ink applications, particularly for ink jet recording ink applications. is there.
以下に本発明を実施例により、さらに具体的に説明するが、本発明は実施例に限定されるものではない。なお、特別の記載のない限り、本文中「部」及び「%」とあるのは質量基準であり、また反応温度は内温である。合成した化合物のうち、λmax(最大吸収波長)を測定したものについては、pH7~8の水溶液中での測定値を示した。また、実施例中で得た化合物の各構造式において、カルボキシ基、スルホ基等の酸性官能基は、遊離酸の形で記載した。なお、実施例で得られた本発明の化合物の室温における水に対する溶解度は、いずれも100g/リットル以上であった。
Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the examples. Unless otherwise specified, “part” and “%” in the text are based on mass, and the reaction temperature is the internal temperature. Among the synthesized compounds, those measured for λmax (maximum absorption wavelength) showed measured values in an aqueous solution having a pH of 7-8. Moreover, in each structural formula of the compound obtained in the Example, acidic functional groups, such as a carboxy group and a sulfo group, were described in the form of a free acid. The solubility of the compounds of the present invention obtained in the examples in water at room temperature was 100 g / liter or more.
[実施例1]
(工程1)
5-アミノ-2-クロロベンゼンスルホン酸20.8部を水酸化ナトリウムでpH6に調整しながら水200部に溶解し、次いで亜硝酸ナトリウム7.2部を加えた。この溶液を0~10℃で、5%塩酸200部中に30分間かけて滴下した後、10℃以下で1時間撹拌してジアゾ化反応を行い、ジアゾ反応液を調製した。
一方、2-(スルホプロポキシ)-5-クロロアニリン26.6部を、水酸化ナトリウムでpH7に調整しながら水130部に溶解し、10.4部の重亜硫酸ナトリウム及び8.6部の35%ホルマリンを用いて、常法によりメチル-ω-スルホン酸誘導体とした。得られたメチル-ω-スルホン酸誘導体を、先に調製したジアゾ反応液中に加え、0~15℃、pH2~4で24時間撹拌した。反応液を水酸化ナトリウムでpH11とした後、同pHを維持しながら80~95℃で5時間撹拌し、さらに100部の塩化ナトリウムを加えて塩析し、析出固体を濾過分離することにより、下記式(12)で表されるアゾ化合物100部をウェットケーキとして得た。 [Example 1]
(Process 1)
20.8 parts of 5-amino-2-chlorobenzenesulfonic acid was dissolved in 200 parts of water while adjusting the pH to 6 with sodium hydroxide, and then 7.2 parts of sodium nitrite was added. This solution was added dropwise to 200 parts of 5% hydrochloric acid at 0 to 10 ° C. over 30 minutes, followed by stirring at 10 ° C. or lower for 1 hour to carry out diazotization reaction to prepare a diazo reaction liquid.
On the other hand, 26.6 parts of 2- (sulfopropoxy) -5-chloroaniline were dissolved in 130 parts of water while adjusting the pH to 7 with sodium hydroxide, and 10.4 parts of sodium bisulfite and 8.6 parts of 35 Using methyl formalin, a methyl-ω-sulfonic acid derivative was obtained by a conventional method. The obtained methyl-ω-sulfonic acid derivative was added to the previously prepared diazo reaction liquid and stirred at 0 to 15 ° C. and pH 2 to 4 for 24 hours. The reaction solution was adjusted to pH 11 with sodium hydroxide, stirred at 80 to 95 ° C. for 5 hours while maintaining the same pH, further salted out by adding 100 parts of sodium chloride, and the precipitated solid was separated by filtration. 100 parts of an azo compound represented by the following formula (12) was obtained as a wet cake.
(工程1)
5-アミノ-2-クロロベンゼンスルホン酸20.8部を水酸化ナトリウムでpH6に調整しながら水200部に溶解し、次いで亜硝酸ナトリウム7.2部を加えた。この溶液を0~10℃で、5%塩酸200部中に30分間かけて滴下した後、10℃以下で1時間撹拌してジアゾ化反応を行い、ジアゾ反応液を調製した。
一方、2-(スルホプロポキシ)-5-クロロアニリン26.6部を、水酸化ナトリウムでpH7に調整しながら水130部に溶解し、10.4部の重亜硫酸ナトリウム及び8.6部の35%ホルマリンを用いて、常法によりメチル-ω-スルホン酸誘導体とした。得られたメチル-ω-スルホン酸誘導体を、先に調製したジアゾ反応液中に加え、0~15℃、pH2~4で24時間撹拌した。反応液を水酸化ナトリウムでpH11とした後、同pHを維持しながら80~95℃で5時間撹拌し、さらに100部の塩化ナトリウムを加えて塩析し、析出固体を濾過分離することにより、下記式(12)で表されるアゾ化合物100部をウェットケーキとして得た。 [Example 1]
(Process 1)
20.8 parts of 5-amino-2-chlorobenzenesulfonic acid was dissolved in 200 parts of water while adjusting the pH to 6 with sodium hydroxide, and then 7.2 parts of sodium nitrite was added. This solution was added dropwise to 200 parts of 5% hydrochloric acid at 0 to 10 ° C. over 30 minutes, followed by stirring at 10 ° C. or lower for 1 hour to carry out diazotization reaction to prepare a diazo reaction liquid.
On the other hand, 26.6 parts of 2- (sulfopropoxy) -5-chloroaniline were dissolved in 130 parts of water while adjusting the pH to 7 with sodium hydroxide, and 10.4 parts of sodium bisulfite and 8.6 parts of 35 Using methyl formalin, a methyl-ω-sulfonic acid derivative was obtained by a conventional method. The obtained methyl-ω-sulfonic acid derivative was added to the previously prepared diazo reaction liquid and stirred at 0 to 15 ° C. and pH 2 to 4 for 24 hours. The reaction solution was adjusted to pH 11 with sodium hydroxide, stirred at 80 to 95 ° C. for 5 hours while maintaining the same pH, further salted out by adding 100 parts of sodium chloride, and the precipitated solid was separated by filtration. 100 parts of an azo compound represented by the following formula (12) was obtained as a wet cake.
(工程2)
250部の氷水中にライオン社製、商品名:レオコールRTMTD90(界面活性剤)0.10部を加えて激しく撹拌し、その中に塩化シアヌル3.6部を添加し0~5℃で30分間撹拌し、懸濁液を得た。続いて、上記式(12)で表される化合物のウェットケーキ100部を水200部に溶解し、この溶液に前記の懸濁液を30分間かけて滴下した。滴下終了後pH6~8、25~45℃で6時間撹拌した。得られた液に、グリシン22.5部を加え、pH7~9、75~90℃で4時間撹拌した。得られた反応液を20~25℃まで冷却後、この反応液にアセトン800部を加え、20~25℃で1時間撹拌した。析出固体を濾過分離することによりウェットケーキ50.0部を得た。このウェットケーキを80℃の熱風乾燥機で乾燥することにより、下記式(13)で表される本発明の水溶性アゾ化合物のナトリウム塩(λmax:411.0nm)13.5部を得た。 (Process 2)
Add 0.10 parts of LIONOL RTM TD90 (surfactant) to 250 parts of ice water and stir vigorously. Add 3.6 parts of cyanuric chloride and add 30 parts at 0-5 ° C. Stir for minutes to obtain a suspension. Subsequently, 100 parts of a wet cake of the compound represented by the above formula (12) was dissolved in 200 parts of water, and the suspension was added dropwise to this solution over 30 minutes. After completion of the dropwise addition, the mixture was stirred at pH 6-8 and 25-45 ° C. for 6 hours. To the obtained liquid, 22.5 parts of glycine was added and stirred at pH 7-9, 75-90 ° C. for 4 hours. The obtained reaction solution was cooled to 20 to 25 ° C., 800 parts of acetone was added to the reaction solution, and the mixture was stirred at 20 to 25 ° C. for 1 hour. The precipitated solid was separated by filtration to obtain 50.0 parts of a wet cake. The wet cake was dried with a hot air dryer at 80 ° C. to obtain 13.5 parts of a sodium salt (λmax: 411.0 nm) of the water-soluble azo compound of the present invention represented by the following formula (13).
250部の氷水中にライオン社製、商品名:レオコールRTMTD90(界面活性剤)0.10部を加えて激しく撹拌し、その中に塩化シアヌル3.6部を添加し0~5℃で30分間撹拌し、懸濁液を得た。続いて、上記式(12)で表される化合物のウェットケーキ100部を水200部に溶解し、この溶液に前記の懸濁液を30分間かけて滴下した。滴下終了後pH6~8、25~45℃で6時間撹拌した。得られた液に、グリシン22.5部を加え、pH7~9、75~90℃で4時間撹拌した。得られた反応液を20~25℃まで冷却後、この反応液にアセトン800部を加え、20~25℃で1時間撹拌した。析出固体を濾過分離することによりウェットケーキ50.0部を得た。このウェットケーキを80℃の熱風乾燥機で乾燥することにより、下記式(13)で表される本発明の水溶性アゾ化合物のナトリウム塩(λmax:411.0nm)13.5部を得た。 (Process 2)
Add 0.10 parts of LIONOL RTM TD90 (surfactant) to 250 parts of ice water and stir vigorously. Add 3.6 parts of cyanuric chloride and add 30 parts at 0-5 ° C. Stir for minutes to obtain a suspension. Subsequently, 100 parts of a wet cake of the compound represented by the above formula (12) was dissolved in 200 parts of water, and the suspension was added dropwise to this solution over 30 minutes. After completion of the dropwise addition, the mixture was stirred at pH 6-8 and 25-45 ° C. for 6 hours. To the obtained liquid, 22.5 parts of glycine was added and stirred at pH 7-9, 75-90 ° C. for 4 hours. The obtained reaction solution was cooled to 20 to 25 ° C., 800 parts of acetone was added to the reaction solution, and the mixture was stirred at 20 to 25 ° C. for 1 hour. The precipitated solid was separated by filtration to obtain 50.0 parts of a wet cake. The wet cake was dried with a hot air dryer at 80 ° C. to obtain 13.5 parts of a sodium salt (λmax: 411.0 nm) of the water-soluble azo compound of the present invention represented by the following formula (13).
[実施例2]
実施例1(工程2)におけるグリシン22.5部の代わりに、イミノジ酢酸40.0部を使用する以外は実施例1と同様にして、下記式(14)で表される本発明の水溶性アゾ化合物のナトリウム塩14.0部(λmax:418.5nm)を得た。 [Example 2]
The water-solubility of the present invention represented by the following formula (14) is obtained in the same manner as in Example 1 except that 40.0 parts of iminodiacetic acid is used instead of 22.5 parts of glycine in Example 1 (Step 2). 14.0 parts (λmax: 418.5 nm) of the sodium salt of the azo compound was obtained.
実施例1(工程2)におけるグリシン22.5部の代わりに、イミノジ酢酸40.0部を使用する以外は実施例1と同様にして、下記式(14)で表される本発明の水溶性アゾ化合物のナトリウム塩14.0部(λmax:418.5nm)を得た。 [Example 2]
The water-solubility of the present invention represented by the following formula (14) is obtained in the same manner as in Example 1 except that 40.0 parts of iminodiacetic acid is used instead of 22.5 parts of glycine in Example 1 (Step 2). 14.0 parts (λmax: 418.5 nm) of the sodium salt of the azo compound was obtained.
[実施例3]
実施例1(工程2)におけるグリシン22.5部の代わりに、2-アミノエタノール18.3部を使用する以外は実施例1と同様にして、下記式(15)で表される本発明の水溶性アゾ化合物のナトリウム塩14.5部(λmax:416.5nm)を得た。 [Example 3]
In the same manner as in Example 1 except that 18.3 parts of 2-aminoethanol was used instead of 22.5 parts of glycine in Example 1 (Step 2), the present invention represented by the following formula (15) was used. 14.5 parts (λmax: 416.5 nm) of a sodium salt of a water-soluble azo compound was obtained.
実施例1(工程2)におけるグリシン22.5部の代わりに、2-アミノエタノール18.3部を使用する以外は実施例1と同様にして、下記式(15)で表される本発明の水溶性アゾ化合物のナトリウム塩14.5部(λmax:416.5nm)を得た。 [Example 3]
In the same manner as in Example 1 except that 18.3 parts of 2-aminoethanol was used instead of 22.5 parts of glycine in Example 1 (Step 2), the present invention represented by the following formula (15) was used. 14.5 parts (λmax: 416.5 nm) of a sodium salt of a water-soluble azo compound was obtained.
[実施例4]
実施例1(工程2)におけるグリシン22.5部の代わりに、ジエタノールアミン31.5部を使用する以外は実施例1と同様にして、下記式(16)で表される本発明の水溶性アゾ化合物のナトリウム塩14.5部(λmax:420.5nm)を得た。 [Example 4]
The water-soluble azo compound of the present invention represented by the following formula (16) was obtained in the same manner as in Example 1 except that 31.5 parts of diethanolamine was used instead of 22.5 parts of glycine in Example 1 (Step 2). 14.5 parts (λmax: 420.5 nm) of a sodium salt of the compound was obtained.
実施例1(工程2)におけるグリシン22.5部の代わりに、ジエタノールアミン31.5部を使用する以外は実施例1と同様にして、下記式(16)で表される本発明の水溶性アゾ化合物のナトリウム塩14.5部(λmax:420.5nm)を得た。 [Example 4]
The water-soluble azo compound of the present invention represented by the following formula (16) was obtained in the same manner as in Example 1 except that 31.5 parts of diethanolamine was used instead of 22.5 parts of glycine in Example 1 (Step 2). 14.5 parts (λmax: 420.5 nm) of a sodium salt of the compound was obtained.
[実施例5]
実施例1(工程2)におけるグリシン22.5部の代わりに、4-アミノメチルベンゼンスルホン酸56.2部を使用する以外は実施例1と同様にして、下記式(17)で表される本発明の水溶性アゾ化合物のナトリウム塩15.0部(λmax:413.0nm)を得た。 [Example 5]
It is represented by the following formula (17) in the same manner as in Example 1 except that 56.2 parts of 4-aminomethylbenzenesulfonic acid is used instead of 22.5 parts of glycine in Example 1 (Step 2). 15.0 parts (λmax: 413.0 nm) of the sodium salt of the water-soluble azo compound of the present invention were obtained.
実施例1(工程2)におけるグリシン22.5部の代わりに、4-アミノメチルベンゼンスルホン酸56.2部を使用する以外は実施例1と同様にして、下記式(17)で表される本発明の水溶性アゾ化合物のナトリウム塩15.0部(λmax:413.0nm)を得た。 [Example 5]
It is represented by the following formula (17) in the same manner as in Example 1 except that 56.2 parts of 4-aminomethylbenzenesulfonic acid is used instead of 22.5 parts of glycine in Example 1 (Step 2). 15.0 parts (λmax: 413.0 nm) of the sodium salt of the water-soluble azo compound of the present invention were obtained.
[実施例6]
実施例1(工程2)におけるグリシン22.5部の代わりに、3-アミノベンゼンスルホン酸52.0部を使用する以外は実施例1と同様にして、下記式(18)で表される本発明の水溶性アゾ化合物のナトリウム塩12.0部(λmax:413.0nm)を得た。 [Example 6]
This is represented by the following formula (18) in the same manner as in Example 1 except that 52.0 parts of 3-aminobenzenesulfonic acid is used instead of 22.5 parts of glycine in Example 1 (Step 2). 12.0 parts (λmax: 413.0 nm) of the sodium salt of the water-soluble azo compound of the invention was obtained.
実施例1(工程2)におけるグリシン22.5部の代わりに、3-アミノベンゼンスルホン酸52.0部を使用する以外は実施例1と同様にして、下記式(18)で表される本発明の水溶性アゾ化合物のナトリウム塩12.0部(λmax:413.0nm)を得た。 [Example 6]
This is represented by the following formula (18) in the same manner as in Example 1 except that 52.0 parts of 3-aminobenzenesulfonic acid is used instead of 22.5 parts of glycine in Example 1 (Step 2). 12.0 parts (λmax: 413.0 nm) of the sodium salt of the water-soluble azo compound of the invention was obtained.
[実施例7]
実施例1(工程2)におけるグリシン22.5部の代わりに、3-アミノ安息香酸41.1部を使用する以外は実施例1と同様にして、下記式(19)で表される本発明の水溶性アゾ化合物のナトリウム塩11.0部(λmax:417.0nm)を得た。 [Example 7]
The present invention represented by the following formula (19) in the same manner as in Example 1 except that 41.1 parts of 3-aminobenzoic acid was used instead of 22.5 parts of glycine in Example 1 (Step 2). 11.0 parts of a sodium salt of a water-soluble azo compound (λmax: 417.0 nm) was obtained.
実施例1(工程2)におけるグリシン22.5部の代わりに、3-アミノ安息香酸41.1部を使用する以外は実施例1と同様にして、下記式(19)で表される本発明の水溶性アゾ化合物のナトリウム塩11.0部(λmax:417.0nm)を得た。 [Example 7]
The present invention represented by the following formula (19) in the same manner as in Example 1 except that 41.1 parts of 3-aminobenzoic acid was used instead of 22.5 parts of glycine in Example 1 (Step 2). 11.0 parts of a sodium salt of a water-soluble azo compound (λmax: 417.0 nm) was obtained.
[実施例8]
実施例1(工程2)におけるグリシン22.5部の代わりに、40%メチルアミン水溶液30.0部を使用する以外は実施例1と同様にして、下記式(20)で表される本発明の水溶性アゾ化合物のナトリウム塩13.5部(λmax:412.0nm)を得た。 [Example 8]
The present invention represented by the following formula (20) in the same manner as in Example 1 except that 30.0 parts of 40% methylamine aqueous solution was used instead of 22.5 parts of glycine in Example 1 (Step 2). 13.5 parts of a sodium salt of a water-soluble azo compound (λmax: 412.0 nm) was obtained.
実施例1(工程2)におけるグリシン22.5部の代わりに、40%メチルアミン水溶液30.0部を使用する以外は実施例1と同様にして、下記式(20)で表される本発明の水溶性アゾ化合物のナトリウム塩13.5部(λmax:412.0nm)を得た。 [Example 8]
The present invention represented by the following formula (20) in the same manner as in Example 1 except that 30.0 parts of 40% methylamine aqueous solution was used instead of 22.5 parts of glycine in Example 1 (Step 2). 13.5 parts of a sodium salt of a water-soluble azo compound (λmax: 412.0 nm) was obtained.
[実施例9~16]
[(A)インクの調製]
上記実施例1乃至8で得られた本発明のアゾ化合物[式(13)~式(20)のナトリウム塩]のそれぞれを色素として用い、下記表2に示した組成を混合して溶液とすることにより、本発明のインク組成物を得た。得られたインク組成物を、それぞれ0.45μmのメンブランフィルタで濾過して夾雑物を除き、試験用のインクを調製した。なお、この試験用インクのpHは8.0~9.5の範囲であった。また、下記表2中、「界面活性剤」としては、日信化学株式会社製の商品名サーフィノールRTM104PG50を使用した。実施例1~8で得た化合物を使用した各インクの調製を、それぞれ実施例9~16とする。 [Examples 9 to 16]
[(A) Preparation of ink]
Each of the azo compounds of the present invention obtained in Examples 1 to 8 above [sodium salt of formula (13) to formula (20)] is used as a dye, and the compositions shown in Table 2 below are mixed to form a solution. As a result, an ink composition of the present invention was obtained. The obtained ink composition was filtered through a 0.45 μm membrane filter to remove impurities, and a test ink was prepared. The pH of the test ink was in the range of 8.0 to 9.5. In Table 2 below, as the “surfactant”, trade name Surfinol RTM 104PG50 manufactured by Nissin Chemical Co., Ltd. was used. Preparation of each ink using the compounds obtained in Examples 1 to 8 is referred to as Examples 9 to 16, respectively.
[(A)インクの調製]
上記実施例1乃至8で得られた本発明のアゾ化合物[式(13)~式(20)のナトリウム塩]のそれぞれを色素として用い、下記表2に示した組成を混合して溶液とすることにより、本発明のインク組成物を得た。得られたインク組成物を、それぞれ0.45μmのメンブランフィルタで濾過して夾雑物を除き、試験用のインクを調製した。なお、この試験用インクのpHは8.0~9.5の範囲であった。また、下記表2中、「界面活性剤」としては、日信化学株式会社製の商品名サーフィノールRTM104PG50を使用した。実施例1~8で得た化合物を使用した各インクの調製を、それぞれ実施例9~16とする。 [Examples 9 to 16]
[(A) Preparation of ink]
Each of the azo compounds of the present invention obtained in Examples 1 to 8 above [sodium salt of formula (13) to formula (20)] is used as a dye, and the compositions shown in Table 2 below are mixed to form a solution. As a result, an ink composition of the present invention was obtained. The obtained ink composition was filtered through a 0.45 μm membrane filter to remove impurities, and a test ink was prepared. The pH of the test ink was in the range of 8.0 to 9.5. In Table 2 below, as the “surfactant”, trade name Surfinol RTM 104PG50 manufactured by Nissin Chemical Co., Ltd. was used. Preparation of each ink using the compounds obtained in Examples 1 to 8 is referred to as Examples 9 to 16, respectively.
[比較例1]
各実施例で得た本発明の化合物の代わりに、下記式(21)で表される化合物を用いる以外は、実施例9~16と同様にして比較用のインクを調製した。このインクの調製を比較例1とする。比較例1に用いた化合物は特公昭55-011708号公報に開示され、特開2002-285022号公報にはインクジェットインクに使用できることが記載されている。 [Comparative Example 1]
Comparative inks were prepared in the same manner as in Examples 9 to 16 except that a compound represented by the following formula (21) was used instead of the compound of the present invention obtained in each Example. This ink preparation is referred to as Comparative Example 1. The compound used in Comparative Example 1 is disclosed in Japanese Patent Publication No. 55-011708, and Japanese Patent Application Laid-Open No. 2002-285022 describes that it can be used in an inkjet ink.
各実施例で得た本発明の化合物の代わりに、下記式(21)で表される化合物を用いる以外は、実施例9~16と同様にして比較用のインクを調製した。このインクの調製を比較例1とする。比較例1に用いた化合物は特公昭55-011708号公報に開示され、特開2002-285022号公報にはインクジェットインクに使用できることが記載されている。 [Comparative Example 1]
Comparative inks were prepared in the same manner as in Examples 9 to 16 except that a compound represented by the following formula (21) was used instead of the compound of the present invention obtained in each Example. This ink preparation is referred to as Comparative Example 1. The compound used in Comparative Example 1 is disclosed in Japanese Patent Publication No. 55-011708, and Japanese Patent Application Laid-Open No. 2002-285022 describes that it can be used in an inkjet ink.
[比較例2]
各実施例で得た本発明の化合物の代わりに、特許文献1の実施例1に記載の色素を用いる以外は、実施例9~16と同様にして比較用のインクを調製した。このインクの調製を比較例2とする。比較例2に用いた化合物の構造式を下記式(22)に示す。 [Comparative Example 2]
Comparative inks were prepared in the same manner as in Examples 9 to 16, except that the dye described in Example 1 of Patent Document 1 was used instead of the compound of the present invention obtained in each Example. This ink preparation is referred to as Comparative Example 2. The structural formula of the compound used in Comparative Example 2 is shown in the following formula (22).
各実施例で得た本発明の化合物の代わりに、特許文献1の実施例1に記載の色素を用いる以外は、実施例9~16と同様にして比較用のインクを調製した。このインクの調製を比較例2とする。比較例2に用いた化合物の構造式を下記式(22)に示す。 [Comparative Example 2]
Comparative inks were prepared in the same manner as in Examples 9 to 16, except that the dye described in Example 1 of Patent Document 1 was used instead of the compound of the present invention obtained in each Example. This ink preparation is referred to as Comparative Example 2. The structural formula of the compound used in Comparative Example 2 is shown in the following formula (22).
[比較例3]
各実施例で得た本発明の化合物のかわりに、特許文献2の実施例1に記載の色素を用いる以外は、実施例9~16と同様にして比較用のインクを調製した。このインクの調製を比較例3とする。比較例3に用いた化合物の構造式を下記式(23)に示す。 [Comparative Example 3]
Comparative inks were prepared in the same manner as in Examples 9 to 16 except that the coloring matter described in Example 1 of Patent Document 2 was used instead of the compound of the present invention obtained in each Example. This ink preparation is referred to as Comparative Example 3. The structural formula of the compound used in Comparative Example 3 is shown in the following formula (23).
各実施例で得た本発明の化合物のかわりに、特許文献2の実施例1に記載の色素を用いる以外は、実施例9~16と同様にして比較用のインクを調製した。このインクの調製を比較例3とする。比較例3に用いた化合物の構造式を下記式(23)に示す。 [Comparative Example 3]
Comparative inks were prepared in the same manner as in Examples 9 to 16 except that the coloring matter described in Example 1 of Patent Document 2 was used instead of the compound of the present invention obtained in each Example. This ink preparation is referred to as Comparative Example 3. The structural formula of the compound used in Comparative Example 3 is shown in the following formula (23).
[比較例4]
各実施例で得た本発明の化合物のかわりに、特許文献3の実施例1に記載の色素を用いる以外は、実施例9~16と同様にして比較用のインクを調製した。このインクの調製を比較例4とする。比較例4に用いた化合物の構造式を下記式(24)に示す。 [Comparative Example 4]
Comparative inks were prepared in the same manner as in Examples 9 to 16, except that the coloring matter described in Example 1 of Patent Document 3 was used instead of the compound of the present invention obtained in each Example. This ink preparation is referred to as Comparative Example 4. The structural formula of the compound used in Comparative Example 4 is shown in the following formula (24).
各実施例で得た本発明の化合物のかわりに、特許文献3の実施例1に記載の色素を用いる以外は、実施例9~16と同様にして比較用のインクを調製した。このインクの調製を比較例4とする。比較例4に用いた化合物の構造式を下記式(24)に示す。 [Comparative Example 4]
Comparative inks were prepared in the same manner as in Examples 9 to 16, except that the coloring matter described in Example 1 of Patent Document 3 was used instead of the compound of the present invention obtained in each Example. This ink preparation is referred to as Comparative Example 4. The structural formula of the compound used in Comparative Example 4 is shown in the following formula (24).
[比較例5]
各実施例で得た本発明の化合物のかわりに、特許文献4の実施例1に記載の色素を用いる以外は、実施例9~16と同様にして比較用のインクを調製した。このインクの調製を比較例5とする。比較例5に用いた化合物の構造式を下記式(25)に示す。 [Comparative Example 5]
Comparative inks were prepared in the same manner as in Examples 9 to 16, except that the coloring matter described in Example 1 of Patent Document 4 was used instead of the compound of the present invention obtained in each Example. This ink preparation is referred to as Comparative Example 5. The structural formula of the compound used in Comparative Example 5 is shown in the following formula (25).
各実施例で得た本発明の化合物のかわりに、特許文献4の実施例1に記載の色素を用いる以外は、実施例9~16と同様にして比較用のインクを調製した。このインクの調製を比較例5とする。比較例5に用いた化合物の構造式を下記式(25)に示す。 [Comparative Example 5]
Comparative inks were prepared in the same manner as in Examples 9 to 16, except that the coloring matter described in Example 1 of Patent Document 4 was used instead of the compound of the present invention obtained in each Example. This ink preparation is referred to as Comparative Example 5. The structural formula of the compound used in Comparative Example 5 is shown in the following formula (25).
[比較例6]
各実施例で得た本発明の化合物のかわりに、特許文献4の実施例6に記載の色素を用いる以外は、実施例9~16と同様にして比較用のインクを調製した。このインクの調製を比較例6とする。比較例6に用いた化合物の構造式を下記式(26)に示す。 [Comparative Example 6]
Comparative inks were prepared in the same manner as in Examples 9 to 16, except that the coloring matter described in Example 6 of Patent Document 4 was used instead of the compound of the present invention obtained in each Example. This ink preparation is referred to as Comparative Example 6. The structural formula of the compound used in Comparative Example 6 is shown in the following formula (26).
各実施例で得た本発明の化合物のかわりに、特許文献4の実施例6に記載の色素を用いる以外は、実施例9~16と同様にして比較用のインクを調製した。このインクの調製を比較例6とする。比較例6に用いた化合物の構造式を下記式(26)に示す。 [Comparative Example 6]
Comparative inks were prepared in the same manner as in Examples 9 to 16, except that the coloring matter described in Example 6 of Patent Document 4 was used instead of the compound of the present invention obtained in each Example. This ink preparation is referred to as Comparative Example 6. The structural formula of the compound used in Comparative Example 6 is shown in the following formula (26).
[比較例7]
各実施例で得た本発明の化合物のかわりに、特許文献4の実施例4に記載の色素を用いる以外は、実施例9~16と同様にして比較用のインクを調製した。このインクの調製を比較例7とする。比較例7に用いた化合物の構造式を下記式(27)に示す。 [Comparative Example 7]
Comparative inks were prepared in the same manner as in Examples 9 to 16 except that the coloring matter described in Example 4 of Patent Document 4 was used instead of the compound of the present invention obtained in each Example. This ink preparation is referred to as Comparative Example 7. The structural formula of the compound used in Comparative Example 7 is shown in the following formula (27).
各実施例で得た本発明の化合物のかわりに、特許文献4の実施例4に記載の色素を用いる以外は、実施例9~16と同様にして比較用のインクを調製した。このインクの調製を比較例7とする。比較例7に用いた化合物の構造式を下記式(27)に示す。 [Comparative Example 7]
Comparative inks were prepared in the same manner as in Examples 9 to 16 except that the coloring matter described in Example 4 of Patent Document 4 was used instead of the compound of the present invention obtained in each Example. This ink preparation is referred to as Comparative Example 7. The structural formula of the compound used in Comparative Example 7 is shown in the following formula (27).
[比較例8]
各実施例で得た本発明の化合物のかわりに、特許文献4の実施例2に記載の色素を用いる以外は、実施例9~16と同様にして比較用のインクを調製した。このインクの調製を比較例8とする。比較例8に用いた化合物の構造式を下記式(28)に示す。 [Comparative Example 8]
Comparative inks were prepared in the same manner as in Examples 9 to 16 except that the coloring matter described in Example 2 of Patent Document 4 was used instead of the compound of the present invention obtained in each Example. This ink preparation is referred to as Comparative Example 8. The structural formula of the compound used in Comparative Example 8 is shown in the following formula (28).
各実施例で得た本発明の化合物のかわりに、特許文献4の実施例2に記載の色素を用いる以外は、実施例9~16と同様にして比較用のインクを調製した。このインクの調製を比較例8とする。比較例8に用いた化合物の構造式を下記式(28)に示す。 [Comparative Example 8]
Comparative inks were prepared in the same manner as in Examples 9 to 16 except that the coloring matter described in Example 2 of Patent Document 4 was used instead of the compound of the present invention obtained in each Example. This ink preparation is referred to as Comparative Example 8. The structural formula of the compound used in Comparative Example 8 is shown in the following formula (28).
[比較例9]
各実施例で得た本発明の化合物のかわりに、特許文献4の実施例3に記載の色素を用いる以外は、実施例9~16と同様にして比較用のインクを調製した。このインクの調製を比較例9とする。比較例9に用いた化合物の構造式を下記式(29)に示す。 [Comparative Example 9]
Comparative inks were prepared in the same manner as in Examples 9 to 16, except that the coloring matter described in Example 3 of Patent Document 4 was used instead of the compound of the present invention obtained in each Example. This ink preparation is referred to as Comparative Example 9. The structural formula of the compound used in Comparative Example 9 is shown in the following formula (29).
各実施例で得た本発明の化合物のかわりに、特許文献4の実施例3に記載の色素を用いる以外は、実施例9~16と同様にして比較用のインクを調製した。このインクの調製を比較例9とする。比較例9に用いた化合物の構造式を下記式(29)に示す。 [Comparative Example 9]
Comparative inks were prepared in the same manner as in Examples 9 to 16, except that the coloring matter described in Example 3 of Patent Document 4 was used instead of the compound of the present invention obtained in each Example. This ink preparation is referred to as Comparative Example 9. The structural formula of the compound used in Comparative Example 9 is shown in the following formula (29).
[(B)インクジェット記録]
上記実施例9~16、及び各比較例で調製した各インクを、インクジェットプリンタ(キヤノン株式会社製、商品名:PIXUSRTM ip4500)を用いて、下記3種類の光沢紙にインクジェット記録を行った。インクジェット記録の際、反射濃度が数段階の階調で得られるように画像パターンを作り、黄色のグラデーションを有する記録物を得た。得られた記録物を試験片とし、各種の試験を行った。
光沢紙1:
キヤノン株式会社製、商品名:キヤノン写真用紙・光沢プロ[プラチナグレード]。
光沢紙2:
キヤノン株式会社製、商品名:キヤノン写真用紙・光沢ゴールド。
光沢紙3:
セイコーエプソン社製、商品名:写真用紙クリスピア(高光沢紙)。 [(B) Inkjet recording]
Each ink prepared in Examples 9 to 16 and Comparative Examples was subjected to inkjet recording on the following three types of glossy paper using an inkjet printer (trade name: PIXUS RTM ip4500, manufactured by Canon Inc.). During ink jet recording, an image pattern was prepared so that the reflection density was obtained in several gradations, and a recorded matter having a yellow gradation was obtained. Various tests were performed using the obtained recorded matter as a test piece.
Glossy paper 1:
Product name: Canon Photo Paper / Glossy Professional [Platinum Grade], manufactured by Canon Inc.
Glossy paper 2:
Product name: Canon Photographic Paper / Glossy Gold, manufactured by Canon Inc.
Glossy paper 3:
Product name: Photographic paper Krispia (high gloss paper), manufactured by Seiko Epson Corporation.
上記実施例9~16、及び各比較例で調製した各インクを、インクジェットプリンタ(キヤノン株式会社製、商品名:PIXUSRTM ip4500)を用いて、下記3種類の光沢紙にインクジェット記録を行った。インクジェット記録の際、反射濃度が数段階の階調で得られるように画像パターンを作り、黄色のグラデーションを有する記録物を得た。得られた記録物を試験片とし、各種の試験を行った。
光沢紙1:
キヤノン株式会社製、商品名:キヤノン写真用紙・光沢プロ[プラチナグレード]。
光沢紙2:
キヤノン株式会社製、商品名:キヤノン写真用紙・光沢ゴールド。
光沢紙3:
セイコーエプソン社製、商品名:写真用紙クリスピア(高光沢紙)。 [(B) Inkjet recording]
Each ink prepared in Examples 9 to 16 and Comparative Examples was subjected to inkjet recording on the following three types of glossy paper using an inkjet printer (trade name: PIXUS RTM ip4500, manufactured by Canon Inc.). During ink jet recording, an image pattern was prepared so that the reflection density was obtained in several gradations, and a recorded matter having a yellow gradation was obtained. Various tests were performed using the obtained recorded matter as a test piece.
Glossy paper 1:
Product name: Canon Photo Paper / Glossy Professional [Platinum Grade], manufactured by Canon Inc.
Glossy paper 2:
Product name: Canon Photographic Paper / Glossy Gold, manufactured by Canon Inc.
Glossy paper 3:
Product name: Photographic paper Krispia (high gloss paper), manufactured by Seiko Epson Corporation.
耐オゾンガス性試験は、試験前の記録物の反射濃度D値が1.0に最も近い部分について反射濃度の測定を行った。反射濃度の測定には、測色システム(商品名SpectroEyeRTM、X-right社製)を使用した。測色は、濃度基準にDIN、視野角2度、光源D65の条件で行った。
記録画像の各種試験方法及び試験結果の評価方法を以下に記載する。 In the ozone gas resistance test, the reflection density was measured for the portion where the reflection density D value of the recorded matter before the test was closest to 1.0. For the measurement of the reflection density, a colorimetric system (trade name: SpectroEye RTM , manufactured by X-right) was used. Colorimetry was performed under the conditions of DIN, a viewing angle of 2 degrees, and a light source D65 as a density standard.
Various test methods for recorded images and evaluation methods for test results are described below.
記録画像の各種試験方法及び試験結果の評価方法を以下に記載する。 In the ozone gas resistance test, the reflection density was measured for the portion where the reflection density D value of the recorded matter before the test was closest to 1.0. For the measurement of the reflection density, a colorimetric system (trade name: SpectroEye RTM , manufactured by X-right) was used. Colorimetry was performed under the conditions of DIN, a viewing angle of 2 degrees, and a light source D65 as a density standard.
Various test methods for recorded images and evaluation methods for test results are described below.
[(C)彩度試験]
各試験片のうち、反射濃度が最も高い階調部分について、前記測色システムによりイエロー彩度C*値を測定した。評価基準は以下の通りである。
C*値が110以上・・・・・・・・・・A
C*値が110未満・・・・・・・・・・B
結果を下記表3に示す。 [(C) Saturation test]
Among each test piece, the yellow saturation C * value was measured by the colorimetry system for the gradation portion having the highest reflection density. The evaluation criteria are as follows.
C * Value is 110 or more A
C * Value is less than 110 ... B
The results are shown in Table 3 below.
各試験片のうち、反射濃度が最も高い階調部分について、前記測色システムによりイエロー彩度C*値を測定した。評価基準は以下の通りである。
C*値が110以上・・・・・・・・・・A
C*値が110未満・・・・・・・・・・B
結果を下記表3に示す。 [(C) Saturation test]
Among each test piece, the yellow saturation C * value was measured by the colorimetry system for the gradation portion having the highest reflection density. The evaluation criteria are as follows.
C * Value is 110 or more A
C * Value is less than 110 ... B
The results are shown in Table 3 below.
[(D)耐オゾンガス性試験]
オゾンウェザーメーター OMS-H〔スガ試験機社製〕を用いてオゾン濃度10ppm、湿度50%RH、温度30℃の環境下に16時間放置した。試験後の各試験片の反射濃度を前記測色システムにより測色し、色素残存率を(試験後の反射濃度/試験前の反射濃度)×100(%)で計算して求め、以下の3段階で評価した。
色素残存率が90%以上・・・・・・・・・A
色素残存率が90%未満80%以上・・・・B
色素残存率が80%未満・・・・・・・・・C
結果を下記表4に示す。 [(D) Ozone gas resistance test]
Using an ozone weather meter OMS-H (manufactured by Suga Test Instruments Co., Ltd.), it was left for 16 hours in an environment of ozone concentration 10 ppm, humidity 50% RH, and temperature 30 ° C. The reflection density of each test piece after the test is measured by the above colorimetry system, and the residual ratio of the dye is calculated by (reflection density after test / reflection density before test) × 100 (%). Rated by stage.
Dye remaining rate is 90% or more ... A
Dye remaining ratio is less than 90% and 80% or more ... B
Dye remaining rate is less than 80% ... C
The results are shown in Table 4 below.
オゾンウェザーメーター OMS-H〔スガ試験機社製〕を用いてオゾン濃度10ppm、湿度50%RH、温度30℃の環境下に16時間放置した。試験後の各試験片の反射濃度を前記測色システムにより測色し、色素残存率を(試験後の反射濃度/試験前の反射濃度)×100(%)で計算して求め、以下の3段階で評価した。
色素残存率が90%以上・・・・・・・・・A
色素残存率が90%未満80%以上・・・・B
色素残存率が80%未満・・・・・・・・・C
結果を下記表4に示す。 [(D) Ozone gas resistance test]
Using an ozone weather meter OMS-H (manufactured by Suga Test Instruments Co., Ltd.), it was left for 16 hours in an environment of ozone concentration 10 ppm, humidity 50% RH, and temperature 30 ° C. The reflection density of each test piece after the test is measured by the above colorimetry system, and the residual ratio of the dye is calculated by (reflection density after test / reflection density before test) × 100 (%). Rated by stage.
Dye remaining rate is 90% or more ... A
Dye remaining ratio is less than 90% and 80% or more ... B
Dye remaining rate is less than 80% ... C
The results are shown in Table 4 below.
表3の結果より明らかなように、本発明の各実施例は、各比較例と同等以上に彩度が高く、鮮明性に優れることが分かる。
また、表4の結果より明らかなように、本発明の各実施例は、各比較例に対して耐オゾンガス性が優れていることが分かる。 As is clear from the results in Table 3, it can be seen that each example of the present invention has a saturation that is equal to or higher than that of each comparative example and is excellent in sharpness.
Further, as is apparent from the results in Table 4, it can be seen that each example of the present invention is superior in ozone gas resistance to each comparative example.
また、表4の結果より明らかなように、本発明の各実施例は、各比較例に対して耐オゾンガス性が優れていることが分かる。 As is clear from the results in Table 3, it can be seen that each example of the present invention has a saturation that is equal to or higher than that of each comparative example and is excellent in sharpness.
Further, as is apparent from the results in Table 4, it can be seen that each example of the present invention is superior in ozone gas resistance to each comparative example.
したがって、本発明の水溶性アゾ化合物、及び該化合物を含有する本発明のインク組成物は、鮮明性の高い色相を有しており、耐オゾンガス性にも優れているため、彩度及び耐オゾンガス性のバランスに優れることが分かる。
Therefore, since the water-soluble azo compound of the present invention and the ink composition of the present invention containing the compound have a clear hue and excellent ozone gas resistance, saturation and ozone gas resistance It can be seen that the balance of sex is excellent.
黄色色素である本発明の水溶性アゾ化合物、及びこれを含有する本発明のイエローインク組成物は、高彩度の記録画像を与える。これに加えて耐オゾンガス性等の各種の堅牢性にも優れている。したがって、該化合物、及びこれを含有するインク組成物は、各種の記録用途、特にインクジェット記録用途に非常に有用である。
The water-soluble azo compound of the present invention which is a yellow pigment and the yellow ink composition of the present invention containing the same give a recorded image with high saturation. In addition to this, it is excellent in various fastness properties such as ozone gas resistance. Therefore, the compound and the ink composition containing the compound are very useful for various recording applications, particularly for inkjet recording applications.
Claims (14)
- 下記式(1)で表される水溶性アゾ化合物又はその塩。
- 前記式(1)において、Qが塩素原子であり、xが3である請求項1に記載の水溶性アゾ化合物又はその塩。 The water-soluble azo compound or a salt thereof according to claim 1, wherein, in the formula (1), Q is a chlorine atom and x is 3.
- 請求項1乃至5のいずれか一項に記載の水溶性アゾ化合物又はその塩を含有するインク組成物。 An ink composition comprising the water-soluble azo compound or a salt thereof according to any one of claims 1 to 5.
- 水溶性有機溶剤をさらに含有する請求項6に記載のインク組成物。 The ink composition according to claim 6, further comprising a water-soluble organic solvent.
- インクジェット記録用である請求項6又は7に記載のインク組成物。 The ink composition according to claim 6 or 7, which is for inkjet recording.
- 請求項6乃至8のいずれか一項に記載のインク組成物をインクとして用い、該インクのインク滴を記録信号に応じて吐出させて被記録材に付着させ、記録を行うインクジェット記録方法。 An ink jet recording method in which the ink composition according to any one of claims 6 to 8 is used as an ink, and ink droplets of the ink are ejected according to a recording signal to adhere to a recording material to perform recording.
- 前記被記録材が情報伝達用シートである請求項9に記載のインクジェット記録方法。 10. The ink jet recording method according to claim 9, wherein the recording material is an information transmission sheet.
- 前記情報伝達用シートが普通紙又は多孔性白色無機物を含むインク受容層を有するシ-トである請求項10に記載のインクジェット記録方法。 11. The ink jet recording method according to claim 10, wherein the information transmission sheet is a sheet having an ink receiving layer containing plain paper or a porous white inorganic substance.
- (a)請求項1乃至5のいずれか一項に記載の水溶性アゾ化合物又はその塩、
(b)請求項1乃至5のいずれか一項に記載の水溶性アゾ化合物又はその塩を含有するインク組成物、及び
(c)請求項1乃至5のいずれか一項に記載の水溶性アゾ化合物又はその塩及び水溶性有機溶剤を含有するインク組成物、のいずれかにより着色された着色体。 (A) The water-soluble azo compound or a salt thereof according to any one of claims 1 to 5,
(B) an ink composition containing the water-soluble azo compound or salt thereof according to any one of claims 1 to 5, and (c) the water-soluble azo according to any one of claims 1 to 5. A colored product colored with any of an ink composition containing a compound or a salt thereof and a water-soluble organic solvent. - 請求項9に記載のインクジェット記録方法により着色された着色体。 A colored product colored by the ink jet recording method according to claim 9.
- 請求項6に記載のインク組成物を含む容器が装填されたインクジェットプリンタ。 An inkjet printer loaded with a container containing the ink composition according to claim 6.
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