JP2003292852A - Recording liquid composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a recording liquid composition containing a coloring component suitable for printing/recording such as an inkjet recording system. <P>SOLUTION: The recording liquid composition contains the coloring component, a specified water soluble organic solvent, a surfactant and a water soluble resin, wherein the coloring component has a ratio of the integrated value of the maximum diffraction ray when the Bragg angle θ is 15° (2θ±0.2°) or less to the integrated value of the diffraction ray at an area when θ is 4°-40° being 90/(n+1)<SP>1/2</SP>% or more, wherein n (n: an integer of 1 or more) represents the number of the diffraction ray with a peak value of 1/10 or more of the maximum diffraction ray in a X-ray spectrum when the Bragg angle θ is 4°-40° (2θ±0.2°) and wherein the electric potential at that time has no isoelectric point at least in neutral area. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording liquid composition containing a coloring component (colorant) suitable for printing / recording including an ink jet recording system, and a recording apparatus using the recording liquid composition. Is. The recording liquid composition of the present invention can also be used for various marking tools and instruments.

[0002]

2. Description of the Related Art An ink jet recording system is a system for recording an image by ejecting small droplets of a recording liquid composition by various mechanisms, depositing the small droplets on a medium, and forming dots. Inkjet recording system has less noise during recording because recording is performed by ejecting small droplets.
Since dots of the recording liquid composition are formed on the medium to record an image, colorization is easy, and since development and fixing are unnecessary, high-speed image recording is possible. have. In recent years, this ink jet recording method has been attracting attention as a method for printing images, various figures, originals, and the like displayed on a display or the like, and has rapidly spread.

The recording liquid composition used in the ink jet recording system has a seemingly contradictory characteristic that it quickly dries and fixes on a medium, but does not easily dry in a nozzle or an orifice, and is unlikely to cause clogging in the nozzle or the orifice. Is required. Further, as the basic performance, the recording liquid composition is required to have storage safety and safety. Further, the penetrability and absorption state of the recording liquid composition to the medium are greatly different depending on the type of the medium, so that there is a problem that the medium that can be used for recording is limited. In particular, in recent years, it has been required that good recording can be performed even on plain paper (specifically, copy paper, report paper, notebook, notepaper, etc.) which is a medium generally used in the office and personal fields. There is a demand for immediate improvement of the problem.

The recording liquid composition is a composition mainly composed of a coloring component composed of a dye or a pigment and a solvent for dissolving or dispersing the coloring component. Various additives are included accordingly.

A recording liquid composition containing a pigment is used in an office,
It is superior in water resistance and light resistance to a recording liquid composition that uses a water-soluble dye that is widely used in the personal field, has a design,
Practical application is progressing in the field of large-format printing for the display market. However, it is difficult to apply a recording liquid composition containing a pigment for offices and personal fields, which requires high-quality output to various media.

As an aqueous recording liquid composition using a pigment as a coloring component, for example, porous carbon black having a relatively high polarity disclosed in JP-A-8-3498 and JP-A-10-510862. And an aqueous recording liquid composition using a microencapsulated organic pigment disclosed in JP-A-9-151342 and JP-A-10-140065. The degree, the drying speed, the scratch resistance, etc. are not yet sufficient as a recording liquid composition.

In the pigment-based recording liquid composition, the storage stability required to stably disperse the pigment in the solvent for a long period of time,
It is particularly required that the nozzles and orifices of the recording device are not clogged with the recording liquid composition. For example, JP-A-6-212106 discloses that a pigment is dispersed in a solvent by using a dispersant such as a polymer dispersant and a surfactant to improve storage stability and to improve the nozzle stability of a recording device. A technique for preventing clogging of the orifice is disclosed. However, the addition of such a dispersant is
Generally, it causes bubbling of the recording liquid composition, which adversely affects the ejection process of small droplets of the recording liquid composition, resulting in uneven printing in recording on the medium.

Japanese Patent No. 3000672 discloses a recording liquid for ink jet recording in which the occurrence of bleeding is suppressed by controlling the particle diameter of a coloring component as a dispersoid and the surface tension characteristic of a dispersion medium within a specific range. Compositions are disclosed.

[0009]

However, when a coloring component composed of a pigment is used in the recording liquid composition, the water resistance,
Although the light resistance can be easily improved, as a recording liquid composition of an inkjet recording system, the ejection stability of the recording liquid composition is ensured, the storage stability of the recording liquid composition,
Fixability to media becomes a problem, and high color density and improvement in scratch resistance have not been achieved yet. Further, when recording is performed using a pigment as a coloring component and three primary colors of cyan, magenta, and yellow as basic colors, turbidity, blurring, and show-through are likely to occur due to a mixed color of cyan, magenta, and yellow. -Currently, it is not possible to realize high-quality recording with high coloring.

Therefore, the present invention has been made in view of the above-mentioned conventional problems, and an object thereof is to provide excellent water resistance and scratch resistance with respect to media recording, particularly plain paper recording, and a recording liquid composition. By discharging the material stably, it is possible to prevent uneven printing on the media and improve storage stability, and there is no bleeding or show-through, high color density, high definition, and high saturation. An object of the present invention is to provide a recording liquid composition and a recording apparatus using the same, which enables high quality recording.

[0011]

In order to solve the above problems, the recording liquid composition of the present invention is a recording liquid composition containing a coloring component, wherein the coloring component is CuKα as an X-ray source.
Bragg angle θ in the X-ray diffraction spectrum using
The number of diffraction lines having a peak value of 1/10 or more of the maximum diffraction line in the range of ° to 40 ° (2θ ± 0.2 °) is n (n: 1
If the above integer), the Bragg angle θ is 15 ° (2θ ±
The integrated value of the maximum diffraction line of 0.2 ° or less and the Bragg angle θ
Is 90 / (n + 1) 1/ ² % or more in the range of 4 ° to 40 ° with respect to the integrated value of the diffraction line.

As a result, it is possible to obtain a recording liquid composition containing a coloring component having high reflection density and color vividness.

In order to solve the above-mentioned problems, the recording liquid composition of the present invention has a coloring component dispersed in water, p
It is characterized by not having an isoelectric point in the neutral region of H5-7.

As a result, it is possible to obtain a recording liquid composition which is more excellent in storage stability and further has improved fixability and scratch resistance.

In the recording liquid composition of the present invention, in order to solve the above problems, the coloring component is a diffraction line having the maximum intensity in the above X-ray diffraction spectrum and its m-th order (m: an integer of 2 or more). The feature is that only diffraction lines are shown.

As a result, the storage stability is further improved, and
It is possible to obtain a recording liquid composition having improved fixability and scratch resistance.

In the recording liquid composition of the present invention, in order to solve the above problems, the coloring component is at least one selected from the group consisting of a sulfonic acid group, a carboxylic acid group, a phosphonic acid group and derivative groups thereof. It is characterized by having a functional group of.

As a result, the coloring component can obtain hydrophilicity and has a self-dispersing recording liquid composition which does not have an isoelectric point in the neutral region of pH 5 to 7 and can be easily dispersed in water. Obtainable.

In order to solve the above problems, the recording liquid composition of the present invention is characterized in that the coloring component is acid-treated.

As a result, with a simple operation, 1000 cm ^-1 ~
At least one functional group selected from the group consisting of a sulfonic acid group, a carboxylic acid group, a phosphone group and an derivative group thereof having an infrared absorption peak at 1400 cm ⁻¹ can be easily introduced into a coloring component. Thus, a recording liquid composition containing a hydrophilic coloring component can be obtained. Further, this makes it possible to obtain a recording liquid composition in which the coloring component is more uniformly dispersed in water.

In order to solve the above problems, the recording liquid composition of the present invention has a geometric mean diameter of the primary particles of the coloring component of a wavelength at which the maximum absorption peak in the ultraviolet-visible absorption spectrum of the coloring component is reached. It is characterized by being in the range of 1/24 to 1/4 and having a geometric standard deviation of 1.5 or less.

As a result, it is possible to obtain a recording liquid composition having improved transparency and dispersion stability.

In order to solve the above problems, the recording liquid composition of the present invention is characterized in that the content of the coloring component is in the range of 1% by weight to 10% by weight.

As a result, it is possible to obtain a recording liquid composition having higher printing density, higher dispersion stability, and further excellent storage stability.

In order to solve the above problems, the recording liquid composition of the present invention is characterized in that the zeta potential of the coloring component when dispersed in water has the opposite sign to the zeta potential of the recording material. I am trying.

As a result, a recording liquid composition is obtained in which a coloring component is more rapidly and firmly adhered and fixed in a dispersed state, has excellent rubbing property, and a recording screen having a brighter color can be obtained. Obtainable.

In order to solve the above problems, the recording liquid composition of the present invention further comprises a water-soluble organic solvent, a surfactant,
And at least one selected from the group consisting of water-soluble resins
It is characterized by containing a seed.

As a result, it is possible to obtain a recording liquid composition having a higher color density and capable of performing higher quality recording.

The above water-soluble organic solvent, surfactant, and water-soluble resin can achieve the above-mentioned effects even if they are combined with a coloring component alone, but a combination of a plurality of them is more effective and preferable.

In order to solve the above problems, the recording liquid composition of the present invention has at least the water-soluble organic solvent selected from the group consisting of glycol ethers, nitrogen-containing heterocyclic ketones, and propylene glycols. It is characterized by being one type of compound.

As a result, high quality recording with a higher color density is possible, and in the case of glycol ethers, the effect of accelerating the drying property of the recording liquid composition and more efficiently fixing the coloring component to the medium surface. Alternatively, it has the effect of further preventing bleeding prevention on media, especially plain paper. Further, in the case of nitrogen-containing heterocyclic ketones, clogging of nozzles and orifices due to drying of the recording liquid composition is further prevented, storage stability of the recording liquid composition is improved, and fluidity with respect to high viscosity recording liquid is improved. Is further improved. In the case of propylene glycols, the storage stability of the recording liquid composition is further improved, and it contributes to the further improvement of the recording characteristics and the fixing property to the medium. Further, the clogging of the nozzles and orifices due to the drying of the recording liquid composition is further prevented.

In order to solve the above-mentioned problems, the recording liquid composition of the present invention is characterized in that the surfactant is an acetylene diol-based surfactant.

As a result, it is possible to obtain a recording liquid composition in which the dispersion stability and printing durability of the recording liquid composition are further improved, and in particular, bleeding and show-through on plain paper are further suppressed. Further, it is possible to obtain a recording liquid composition capable of forming an image with less bleeding.

In order to solve the above problems, the recording liquid composition of the present invention is characterized in that the water-soluble resin is a terpolymer of styrene-α-methylstyrene-acrylic acid.

As a result, a recording liquid composition having improved dispersion stability, water resistance and redissolvability can be obtained.

The recording apparatus of the present invention is characterized in that recording is carried out using the above recording liquid composition.

As a result, the recording apparatus uses a recording liquid composition containing extremely high-definition recording with no color turbidity, and cyan, magenta, and yellow, respectively, so as to prevent show-through, double-sided printing. Simultaneous printing can be possible. Further, the recording liquid composition makes it possible to secure stable recording liquid ejection performance even after being left for a long period of time. Therefore, it is possible to prevent the nozzles and the orifices from being clogged when the recording apparatus is restarted.

[0038]

BEST MODE FOR CARRYING OUT THE INVENTION The recording liquid composition of the present invention is a recording liquid composition containing a coloring component, wherein the coloring component has a Bragg angle θ in an X-ray diffraction spectrum using CuKα rays as an X-ray source. If the number of diffraction lines having a peak value of 1/10 or more of the maximum diffraction line in the range of 4 ° to 40 ° (2θ ± 0.2 °) is n (n: integer of 1 or more), the Bragg angle The ratio of the integral value (a) of the maximum diffraction line of θ = 15 ° (2θ ± 0.2 °) or less and the integral value (b) of the diffraction line in the range of Bragg angle θ = 4 ° to 40 ° ( a / b) is 90 / (n +
1) The composition is 1 ^/2 % or more. The coloring component is dispersed in water and has no isoelectric point in the neutral region of pH 5 to 7. Furthermore, the coloring component,
In the X-ray diffraction spectrum, only the diffraction line having the maximum intensity and its m-th order (m: an integer of 2 or more) diffraction line are shown. Further, it is a constitution containing a specific water-soluble organic solvent, a surfactant, and a water-soluble resin, if necessary.

The geometric mean diameter of the primary particles, which is the minimum unit of the particles of the coloring component of the present invention, is the geometric mean diameter of the particles of the pigment contained in the conventional recording liquid composition (for example, 100 nm).
.About.2000 nm), and by limiting the particle size of the coloring component in this way, the recording liquid composition of the present invention has excellent effects such as bleeding characteristics, show-through characteristics, and storage stability. .

The geometric mean diameter of the primary particles of the coloring component particles is within the range of 1/24 to 1/4 of the wavelength showing the maximum absorption peak in the UV-visible absorption spectrum, and the geometric standard deviation thereof is 1.5 or less. With such a coloring component, the transparency of the recording liquid composition is further improved, and the dispersion stability of the coloring component is further improved. When the geometric average diameter of the primary particles of the coloring component is larger than 1/4 of the wavelength of the maximum absorption peak of the UV-visible absorption spectrum, the storage stability of the recording liquid composition and the recording liquid compositions are overlaid. When recording, it may be difficult to realize high-quality recording having high definition and high saturation. Further, when the geometric average diameter of the primary particles of the coloring component is smaller than 1/24 of the wavelength of the maximum absorption peak of the UV-visible absorption spectrum, the bleeding of the recording liquid composition on the surface of the medium becomes large, resulting in high definition. Recording may be difficult.

The coloring component has an infrared absorption spectrum of 10
It is desirable to have at least one functional group selected from the group consisting of a sulfonic acid group, a carboxylic acid group, a phosphone group, and a derivative group thereof having a peak at 00 cm ^{-1 to} 1400 cm ^-1 . This makes it possible to obtain a recording liquid composition which is hydrophilic and has no isoelectric point in the vicinity of pH 5 to 7 and which can be easily dispersed in water. As a method of introducing the functional group into the coloring component, for example, in the atmosphere, wet, fuming sulfuric acid,
The operation of performing an acid treatment using chlorosulfonic acid or sulfuric acid is more preferable because it is simple in operation and the coloring component is uniformly dispersed in water. Other methods for introducing the functional group into the coloring component include, for example, an ultraviolet irradiation method of irradiating a low pressure mercury lamp (wavelength λ = 185 nm) in an oxygen gas atmosphere, and, for example, a glow of low pressure oxygen gas under vacuum. A method of directly acting on the pigment surface by chemical treatment and / or a physical treatment such as a method of exposing in a discharge plasma, a method of exposing in a reactive plasma gas, and a method of introducing an acidic group, Various modification treatment techniques may be used, but the method is not limited to these.

In the above-described color component modification treatment technique, depending on the color component, decomposition or discoloration of the color component may occur during the modification process. It is preferable to select a pigment that does not cause decomposition or discoloration as the coloring component.

The coloring component used in the present invention is obtained by modifying a pigment or the like used as a coloring component such as a printing recording liquid, a toner and a paint by the modifying treatment technique described above.

Pigments used as coloring components include, for example, yellow pigments, magenta pigments, cyan and blue pigments. Specific examples of these are shown below.

Examples of the yellow pigment include monoazo yellow pigments such as CI pigment yellow 3,74,165 and benzimidazolone pigments such as CI pigment yellow 151,180,194.

As the magenta pigment, C.I. Pigment Red 122,202.209, a quinacridone pigment, C.I. Pigment Red 149,190,224
Perylene pigments such as C.I. Pigment Red 2,5,23,112,184,185,206 and other naphthol azo pigments.

Cyan and blue pigments include C.I.
I. Pigment Blue 15, C.I. Pigment Blue 15: 3 and C.I. Pigment Blue 15:
4, such as copper phthalocyanine pigment and CyanineBlue A-13R, 13Y
Pigments having a phthalocyanine structure such as aluminum phthalocyanine (such as Sanyo Dye Co., Ltd.) can be used.

In the recording liquid composition, one kind or two or more kinds of pigments of the above-mentioned coloring components can be appropriately combined and used. The content of the coloring component in the recording liquid composition is more preferably in the range of 1% by weight to 10% by weight, and even more preferably in the range of 2% by weight to 5% by weight. When the content of the coloring component is less than 1% by weight, the density of the recorded image may be low. Further, when the content of the coloring component exceeds 10% by weight,
Not only the viscosity of the recording liquid composition becomes high, but also the interaction between particles of the coloring component becomes large, so that the dispersion stability may be deteriorated and the storage stability as the recording liquid composition may be deteriorated.

The recording liquid composition preferably contains the above-mentioned coloring component and a water-soluble organic solvent. Examples of the water-soluble organic solvent include glycol ethers.

Examples of the glycol ethers include ethylene glycol-n-butyl ether, diethylene glycol-n-butyl ether, triethylene glycol-n-butyl ether, propylene glycol-n-butyl ether and dipropylene glycol-n-butyl ether. The glycol ethers not only have the effect of accelerating the drying property of the recording liquid composition,
It has an effect as a fixing agent for efficiently fixing the coloring component to the surface of the medium, or an effect as a penetrant for preventing bleeding on the medium, particularly plain paper. Further, glycol ethers remarkably reduce the viscosity of the recording liquid composition depending on the type of coloring component. The content of glycol ethers in the recording liquid composition is 1% by weight to 1
More preferably within the range of 5% by weight, 2% by weight
More preferably, it is within the range of 10% by weight. When the content of glycol ethers is less than 1% by weight,
The above-mentioned effects may not be obtained in some cases. Further, if the content of glycol ethers exceeds 15% by weight, the dispersion stability of the coloring component may decrease.

Examples of penetrants other than the above include anionic ammonium salts of perfluoroalkyl sulfonic acid, potassium salt of perfluoroalkyl sulfonic acid and potassium salt of perfluoroalkyl carboxylic acid. It is not limited to these as long as it has a function of lowering the tension. The content of the above penetrant in the recording liquid composition is from 0.1% by weight to
More preferably, it is within the range of 5% by weight. If the content is out of the above range, the effect of preventing the recording liquid composition from bleeding into the medium and the drying property of the recording liquid composition on the medium surface may decrease.

Examples of the water-soluble organic solvent include nitrogen-containing heterocyclic ketones.

The nitrogen-containing heterocyclic ketones include 2
-Pyrrolidone, N-methyl 2-pyrrolidone, 1,3-dimethylimidazolidinone and the like. The nitrogen-containing heterocyclic ketones not only have the effect of preventing clogging of the nozzles and orifices associated with the drying of the recording liquid composition, but also improve the storage stability of the recording liquid composition in combination with the coloring component. In the high viscosity region of the recording liquid composition, it has an effect of improving fluidity. The content of the nitrogen-containing heterocyclic ketone in the recording liquid composition is more preferably in the range of 1% by weight to 10% by weight, and 2% by weight to 6% by weight.
It is even more preferable that it is within the range. If the content of the nitrogen-containing heterocyclic ketone is less than 1% by weight, the above-mentioned effects may not be obtained. On the other hand, when the content of the nitrogen-containing heterocyclic ketones in the recording liquid composition exceeds 10% by weight, the viscosity of the recording liquid composition may increase and the dispersion stability may decrease. Further, in order to prevent clogging at the nozzles and orifices due to the drying of the recording liquid composition, in addition to the above nitrogen-containing heterocyclic ketones, use a nitrogen-containing organic solvent such as urea, diethanolamine or triethanolamine. You can also

Examples of the water-soluble organic solvent include propylene glycols.

Examples of the propylene glycols include propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol and the like. These are storage stability of the recording liquid composition, recording characteristics, and media. The fixability of the recording liquid composition is improved. It also has the effect of preventing clogging at the nozzles and orifices due to the drying of the recording liquid composition. The content of propylene glycols in the recording liquid composition is more preferably in the range of 1% by weight to 30% by weight, and even more preferably in the range of 2% by weight to 25% by weight. If the content of propylene glycols is less than 2% by weight, the above effect may not be obtained. Further, when the content of propylene glycols exceeds 30% by weight, the recording liquid may exhibit bleeding characteristics, and the drying property of the recording liquid composition may be deteriorated.

The recording liquid composition preferably contains the above-mentioned coloring component and a surfactant.

As the above-mentioned surfactant, 2,4,7,9-
Tetramethyl-5-decyne-4,7-diol, 3,6-
Examples thereof include acetylene diol-based surfactants such as dimethyl-4-oxine-3,6-diol and 3,5-dimethyl-1-hexyne-3-ol. A commercially available product can be used as the acetylene diol-based surfactant, and specific examples thereof include Surfynol 104, 82, 465, 48.
5,504 or TG (both Air Products and Chem
available from icals. Inc.). The content of the acetylene diol-based surfactant in the recording liquid composition of the present invention is more preferably in the range of 0.1% by weight to 2% by weight, and is 0.5% by weight or more and 1.5% by weight or less. Is more preferable. When the content of the acetylene diol-based surfactant is within the above range, an image with less bleeding can be realized. In addition, for example, the acetylene diol-based surfactants such as Surfynol 104 and TG described above have a hydrophilic-lipophilic balance value (HLB: hydroph
Due to its low ile-lypophile balance), its solubility in water is low. In this case, the solubility can be improved by further containing a component such as a glycol ether, a glycol or a surfactant in the recording liquid composition.

Nonionic surfactants are preferable as the surfactants other than the above acetylene diol surfactants, for example, alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether and polyoxyethylene cetyl ether. Type; alkylphenol type such as polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether; alkyl ester type such as polyoxyethylene monostearate; sorbitan ester type such as sorbitan monostearate and sorbitan monolaurate; polyoxyethylene Examples thereof include sorbitan ester ether types such as sorbitan monolaurate.

The content of the surfactant other than the above-mentioned acetylene diol-based surfactant in the recording liquid composition of the present invention is more preferably in the range of 0.1% by weight to 2% by weight, and is 0.5% by weight. It is more preferable that the content is not less than 1.5% by weight and not more than 1.5% by weight. When the content of the surfactant other than the acetylene diol-based surfactant is within the above range, an image with less bleeding can be realized.

Depending on the combination with the coloring component, the anionic surfactant and the cationic surfactant tend to generate bubbles, and the dispersion stability of the coloring component is inferior. This is not preferable because the image will become larger.

The recording liquid composition preferably contains the above-mentioned coloring component and a water-soluble resin. Examples of the water-soluble resin include a terpolymer of styrene-α-methylstyrene-acrylic acid.

The water-soluble resin of the terpolymer of styrene-α-methylstyrene-acrylic acid can be obtained by a known method. The above terpolymer is a total of 3 styrene and α-methylstyrene for 1 mol of acrylic acid.
It is more preferable that the copolymerization is within the range of 5 to 5 mol. Furthermore, it is more preferable to copolymerize styrene within a range of 1.5 mol to 2.5 mol and α-methylstyrene within a range of 1.5 mol to 2.5 mol with respect to 1 mol of acrylic acid. It is particularly preferable to copolymerize styrene with 1.7 mol to 2.3 mol and α-methyl styrene with 1.8 mol to 2.2 mol per 1 mol of acrylic acid. By copolymerizing at the above-mentioned ratio, the dispersion stability of the coloring component and the water resistance and redissolvability of the recording liquid composition are improved. In addition, commercially available products can also be used. As a specific example of a commercial product, John Krill 57,6
0,62,63 (manufactured by Johnson Polymer Co., Ltd.) and the like.

The weight average molecular weight of the terpolymer is 20.
More preferably in the range of 00 to 8000, 2
It is more preferably in the range of 000 to 5000 from the viewpoint of dispersibility of the coloring component and ejection stability of the recording liquid composition. The acid value of the terpolymer should be in the range of 90 to 130 so that the water resistance of the recording liquid composition on the surface of the medium, particularly the surface of plain paper, and the reproducibility of the recording liquid composition on the head part. It is preferable because the solubility is further improved.

In the recording liquid composition of the present invention, it is desirable to use a neutralizing agent in order to stably dissolve the terpolymer, specifically, sodium hydroxide, potassium hydroxide; fat. Group amines; alcohol amines such as ethanolamine, propanolamine, and methylethanolamine; morpholine, N-methylmorpholine, dimethylaminoethanol, diethylaminoethanol and the like are preferably used. When these neutralizing agents are used in an equimolar amount or a few% excess with respect to acrylic acid in the terpolymer, the solubility of the terpolymer, the resolubility of the terpolymer, This is preferable because the water resistance of the recording liquid composition is further improved. The content of the terpolymer in the recording liquid composition is more preferably in the range of 0.5% by weight to 8% by weight. If it is less than the above range, the above-mentioned effects may not be obtained, and if it is more than the above range, it may be difficult to reduce the viscosity of the recording liquid composition, and image recording may be difficult. In some cases, the formation of small droplets of the recording liquid composition may be insufficient.

The above water-soluble organic solvent, surfactant, and water-soluble resin can achieve the above-mentioned effects even if they are used alone in combination with a coloring component, but a combination of a plurality of them is more effective and preferable.

The recording liquid composition of the present invention may further contain the following various additives, if necessary, in order to improve various physical properties of the recording liquid composition.

Examples of the wetting agent include diethylene glycol, polyethylene glycol, polypropylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, ethylene glycol, butylene glycol, triethylene glycol, 1,2,6- Hexanetriol, thioglycol, hexylene glycol, trimethylolethane, trimethylolpropane and the like can be mentioned. The above wetting agent also contributes to improvement of storage stability of the recording liquid composition, recording characteristics and fixing property of the recording liquid composition to a medium. The above wetting agent has the effect of preventing clogging at the nozzles and orifices due to the drying of the recording liquid composition. The content of the wetting agent in the recording liquid composition is more preferably in the range of 0.5% by weight to 40% by weight.

Further, it is more preferable that the recording liquid composition contains a low boiling point organic solvent. As the low boiling point organic solvent, for example, methanol, ethanol, n-propanol, iso-propanol, n-butanol, se
Examples thereof include c-butanol, tert-butanol, iso-butanol, n-pentanol and the like. The low boiling point organic solvent is particularly preferably a monohydric alcohol. The content of the low boiling point organic solvent in the recording liquid composition is
More preferably in the range of 0.5 wt% to 10 wt%,
The range of 1.5 to 6% by weight is more preferable.

The recording liquid composition of the present invention further contains, if necessary, for example, a viscosity adjusting agent for adjusting the viscosity of the recording liquid composition or a recording liquid composition in order to improve various physical properties of the recording liquid composition. It may contain a preservative or the like for preventing the preservation of the product.

The recording liquid composition of the present invention can be produced by dispersing or mixing the above components in water by an appropriate method. Examples of the method for dispersing the colored component in the agglomerated state to the primary particles in the fine particle state include Dynomill dispersion method, paint shaker dispersion method, ball mill dispersion method, sand mill dispersion method, bead mill dispersion method, ultrasonic dispersion method and the like. However, the method is not limited to these methods.

Up to this point, the recording liquid composition using a hydrophilic coloring component has been described, but the present invention is not limited to this, and the technical idea of the present invention is to use a non-hydrophilic crystalline coloring component. It can also be applied to the recording liquid composition.

According to the recording liquid composition of the present invention, recording with high color density can be realized, at the same time, vivid color reproduction (high color recording) can be obtained, and bleeding and show-through on a medium, particularly plain paper, can be prevented. Extremely low. In addition, the dispersion stability and storage stability of the recording liquid composition are also improved. Furthermore, by performing recording using the recording liquid composition of the present invention, it is possible to obtain a recording apparatus that can realize extremely high quality recording. Further, the recording liquid composition enables recording with very little blurring and show-through. Therefore, a recording device capable of double-sided recording,
The recording liquid composition can be preferably used.

[0073]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Further, various characteristics of the recording liquid compositions obtained in Examples and Comparative Examples were measured and evaluated by the methods described below. (Geometric mean diameter of primary particles) The geometric mean diameter of the primary particles of the coloring component is the electrophoretic light scattering photometer E manufactured by Otsuka Electronics Co., Ltd.
It was measured using LS-8000. (Zeta potential) The zeta potential when the coloring component is dispersed in water is a laser zeta potentiometer ELS manufactured by Otsuka Electronics Co., Ltd.
It was measured using -8000. (X-ray diffraction) X-ray diffraction pattern is powder X-ray diffractometer M
XP-18 (Max Science: X-ray source CuKα =
0.15405 nm). (Reflection Density) A fixed amount (1.0 ml) of the recording liquid composition was sampled, and an applicator coated on plain paper was dried and then measured using a densitometer RD-918 (manufactured by Macbeth). (Show-through) As in the reflection density measurement sample, the reflection density of the back surface of the sample coated on plain paper was measured to evaluate the degree of show-through. Then, when the reflection density on the back surface was a value of 0.12 or less, it was determined that double-sided printing with the recording liquid composition was possible. (Color characteristics) X-Ri
te938 (manufactured by Nippon Lithographic Equipment Co., Ltd.) was used to evaluate the color characteristics (lightness, chromaticity) in the L ^* a ^* b color system. The vividness of the color was evaluated by chroma (C ^* ) = {(a ^* ) ² + (b ^* ) ² } ^1/2 . (Bleed characteristic) A certain amount of recording liquid composition (0.7 μl) was attached to a plain paper (SF-4AM3) surface with a microsyringe, and the spread (dot diameter) of the recording liquid on the plain paper surface was measured. Moreover, the standard deviation was calculated as a standard of the roundness. When the spread of the recording liquid composition was 1.5 mm or less, it was evaluated as “⊚”, when it was 2.5 mm or less, it was evaluated as “◯”, and when it was more than this, it was evaluated as “x”. (Storage stability) Epson P containing the recording liquid composition injected
After storing M760 cartridge at 60 ℃ for 1 month,
The above cartridge was mounted on a printer, the recording liquid composition was discharged, and a storage stability test was conducted. Visually
The prints with good printability with almost no clogging were evaluated as “◯”, those printable with about 50% or more were evaluated as “Δ”, and those printable with less than 50% were evaluated as “x”. (Fixing / Scratching) Spread the recording liquid composition on plain paper,
The fixing and scratching properties on plain paper were examined. A plain paper copier (plane pape) is used to check the fixing and scratching properties of the scattered plain paper.
R copy (hereinafter abbreviated as "PPC") The surface of the paper sprinkled with paper was rubbed 50 times, and the degree of color transfer to the surface of the PPC paper was visually confirmed. "O" indicates that almost no color was transferred by visual inspection, "△" indicates that about 50% of the print remained on the plain paper surface, and "X" indicates that almost no print was transferred on the plain paper surface. It was evaluated.

[Example 1] CI Pigment Yellow 180 was added to 2 parts in concentrated sulfuric acid (98%) cooled to about 10 ° C.
After stirring for an hour, the concentrated sulfuric acid was rapidly dropped into water at 0 ° C. and stirred to obtain a colored component. The X-ray diffraction spectrum of the obtained coloring component is shown in FIG. Bragg angle θ of the obtained coloring component
Is 15 ° (2θ ± 0.2 °) or less, the integrated value (n = 3) of the maximum diffraction line and the ratio of the integrated value of the diffraction line within the Bragg angle θ of 4 ° to 40 ° is about 64. %, And the Bragg angle θ
Shows the maximum diffraction peak when is 5.4 °, and the second and third diffraction peaks are Bragg angles θ = 10.8 ° and 16.0 °.
Was observed in.

The zeta potential of the obtained coloring component was measured. The result is shown in FIG. As is clear from FIG.
It was confirmed that the coloring component has no isoelectric point in the neutral region of pH 5 to 7.

The infrared absorption spectrum of the coloring component is shown in FIG. The peak that seems to be a sulfone group is 1000c
It was confirmed around m ^{-1 to} 1400 cm ^-1 .

[Example 2] CI Pigment Red 1 was prepared in the same manner as in Example 1 except that concentrated sulfuric acid was heated to 50 ° C.
A colored component consisting of 85 was obtained. The X-ray diffraction spectrum of the obtained coloring component is shown in FIG. The integrated value (n = 1) of the maximum diffraction line with the Bragg angle θ of the obtained coloring component of 15 ° (2θ ± 0.2 °) or less, and the diffraction line with the Bragg angle θ within the range of 4 ° to 40 ° Is about 88%, and shows the maximum diffraction peak when the Bragg angle θ is 5.7 °.
The next diffraction peak was observed at a Bragg angle θ of 11.8 °.

The results of measuring the zeta potential of the obtained coloring component are shown in FIG. As shown in this figure, the coloring component has a pH of 5
It was confirmed that the neutral region of ~ 7 does not have an isoelectric point.

The infrared absorption spectrum of the coloring component obtained above is shown in FIG. 100 thought to be a sulphonic group
It confirmed the peak in the vicinity of 0cm ^-1 ~1400cm ^-1.

Example 3 A coloring component consisting of CI Pigment Cyan 15: 3 was obtained in the same manner as in Example 1 except that concentrated sulfuric acid was heated to 150 ° C. The X-ray diffraction spectrum of the obtained coloring component is shown in FIG. The Bragg angle θ of the obtained coloring component is 15 ° (2θ ± 0.2 °) or less and the integrated value (n = 1) of the maximum diffraction line and the Bragg angle θ is 4 ° to 40 °.
The ratio with the integrated value of the diffraction line in the range of ° is about 95%,
The maximum diffraction peak was observed when the Bragg angle θ was 5.7 °, but the second and higher diffraction peaks were not clearly observed.

The measurement results of the zeta potential of the obtained coloring component are shown in FIG. As is clear from FIG. 8, the coloring component is p
It was confirmed that H5-7 did not have an isoelectric point in the neutral region.

The infrared absorption spectrum of the coloring component is shown in FIG. 1000 cm ^{-1 to} 14 thought to be a sulfo group
A peak near 00 cm ^-1 was confirmed.

[Comparative Example 1] CI Pigment Yellow 1
2, 13, 15, 17, 81, 83, 110, 155
Coloring components, such as C.I. Phi Pigment Red 254, 264 are less resistant to concentrated sulfuric acid, to varying / fading by modification techniques, or, the light fastness obtain a colored component that can be used in the present invention to deteriorate I couldn't.

Example 4 CI Pigment Yellow 180 of Example 1 2.5% by weight Diethylene glycol 5% by weight Tetrapropylene glycol 5% by weight Triethylene glycol n-butyl ether 8% by weight n-Propanol 3% by weight Urea 5% by weight 2-Pyrrolidone 5% by weight Surfynol 465 0.2% by weight Johncryl 60 5% by weight Ion-exchanged water Remaining amount diethylene glycol, tetrapropylene glycol,
Triethylene glycol n-butyl ether, n-propanol, urea, 2-pyrrolidone, Surfynol 46
5, the above components except John Cryl 60 were mixed and subjected to a dispersion treatment for 8 hours together with zirconia beads having a diameter of 0.8 mm by a paint conditioner device (manufactured by Red Level Co.). After removing the zirconia beads, the remaining constituents were mixed and filtered through a 0.45 μm membrane filter to obtain a recording liquid composition. The geometric average diameter of the primary particles of the obtained coloring component was 76 nm, and the geometric standard deviation thereof was 1.24.

Example 5 CI Pigment Red 185 of Example 2 2.5 wt% diethylene glycol 5 wt% tetrapropylene glycol 5 wt% triethylene glycol n-butyl ether 8 wt% n-propanol 3 wt% Urea 5% by weight 2-Pyrrolidone 5% by weight Surfynol 465 0.2% by weight Johncryl 60 5% by weight Ion-exchanged water Remaining amount diethylene glycol, tetrapropylene glycol,
Triethylene glyco-n-butyl ether, n-propanol, urea, 2-pyrrolidone, Surfynol 46
5, the above components except John Cryl 60 were mixed and subjected to a dispersion treatment for 8 hours together with zirconia beads having a diameter of 0.8 mm by a paint conditioner device (manufactured by Red Level Co.). After removing the zirconia beads, the remaining constituents were mixed and filtered through a 0.45 μm membrane filter to obtain a recording liquid composition. The geometric mean diameter of the primary particles of the obtained coloring component was 64 nm, and the geometric standard deviation thereof was 1.22.

[Example 6] CI Pigment Blue 15: 3 of Example 3 2.5% by weight Diethylene glycol 5% by weight Tetrapropylene glycol 5% by weight Triethylene glycol n-butyl ether 8% by weight n-Propanol 3 Weight% Urea 5 weight% 2-Pyrrolidone 5 weight% Surfynol 465 0.2 weight% Johncryl 60 5 weight% Ion-exchanged water Remaining amount diethylene glycol, tetrapropylene glycol,
Triethylene glyco-n-butyl ether, n-propanol, urea, 2-pyrrolidone, Surfynol 46
5, the above components except John Cryl 60 were mixed and subjected to a dispersion treatment for 8 hours together with zirconia beads having a diameter of 0.8 mm by a paint conditioner device (manufactured by Red Level Co.). After removing the zirconia beads, the remaining constituents were mixed and filtered through a 0.45 μm membrane filter to obtain a recording liquid composition. The geometric mean diameter of the primary particles of the obtained coloring component was 53 nm, and the geometric standard deviation thereof was 1.25.

Comparative Example 2 Pigment CI Pigment Yellow 180 4.5% by weight Diethylene glycol 5% by weight Tetrapropylene glycol 5% by weight Triethylene glycol n-butyl ether 8% by weight n-Propanol 3% by weight Urea 5% by weight % 2-pyrrolidone 5% by weight Surfynol 465 0.2% by weight Johncryl 60 5% by weight Ion-exchanged water Remaining amount diethylene glycol, tetrapropylene glycol,
Triethylene glyco-n-butyl ether, n-propanol, urea, 2-pyrrolidone, Surfynol 46
5, the above components except John Cryl 60 were mixed and subjected to a dispersion treatment for 8 hours together with zirconia beads having a diameter of 0.8 mm by a paint conditioner device (manufactured by Red Level Co.). After removing the glass beads, the remaining components were mixed and filtered with a 0.45 μm membrane filter to obtain a recording liquid composition. Figure 1 shows the X-ray diffraction spectrum of the colored components.
It shows in 0. The Bragg angle θ of the coloring component is 15 ° (2θ ±
The ratio between the integrated value of the maximum diffraction line of 0.2 ° or less and the integrated value of the diffraction line in the Bragg angle θ within the range of 4 ° to 40 ° is about 2.
It was 3%, and many peaks other than the m-th order were confirmed.

The measurement results of the zeta potential of the obtained coloring component are shown in FIG. As is clear from FIG. 11, it was confirmed that the coloring component has an isoelectric point near pH = 4.

The infrared absorption spectrum of the coloring component obtained above is shown in FIG. The geometric average diameter of the primary particles of the obtained coloring component was 89 nm, and the geometric standard deviation thereof was 1.36.

Comparative Example 3 Pigment CI Pigment Yellow 185 4.5% by weight Diethylene glycol 5% by weight Tetrapropylene glycol 5% by weight Triethylene glycol n-butyl ether 8% by weight n-Propanol 3% by weight Urea 5% by weight % 2-pyrrolidone 5% by weight Surfynol 465 0.2% by weight Johncryl 60 5% by weight Ion-exchanged water Remaining amount diethylene glycol, tetrapropylene glycol,
Triethylene glyco-n-butyl ether, n-propanol, urea, 2-pyrrolidone, Surfynol 46
5, the above components except John Cryl 60 were mixed and subjected to a dispersion treatment for 8 hours together with zirconia beads having a diameter of 0.8 mm by a paint conditioner device (manufactured by Red Level Co.). After removing the glass beads, the remaining components were mixed and filtered with a 0.45 μm membrane filter to obtain a recording liquid composition. Figure 1 shows the X-ray diffraction spectrum of the colored components.
2 shows. The Bragg angle θ of the coloring component is 15 ° (2θ ±
The integrated value of the maximum diffraction line of 0.2 ° or less and the Bragg angle θ
The ratio with the integrated value of the diffraction line in the range of 4 ° to 40 ° is about 2
It was 4%, and many peaks other than the m-th order were confirmed.

The measurement results of the zeta potential of the obtained coloring component are shown in FIG. As is clear from FIG. 13, it was confirmed that the coloring component has an isoelectric point near pH = 6.

The infrared absorption spectrum of the coloring component obtained above is shown in FIG. The geometric average diameter of the primary particles of the obtained coloring component was 78 nm, and the geometric standard deviation thereof was 1.40.

Comparative Example 4 Pigment CI Pigment Blue 15: 3 4.5% by weight Diethylene glycol 5% by weight Tetrapropylene glycol 5% by weight Triethylene glycol n-butyl ether 8% by weight n-Propanol 3% by weight Urea 5% by weight 2-pyrrolidone 5% by weight Surfynol 465 0.2% by weight Johncryl 60 5% by weight Ion-exchanged water Remaining amount diethylene glycol, tetrapropylene glycol,
Triethylene glyco-n-butyl ether, n-propanol, urea, 2-pyrrolidone, Surfynol 46
5. Mix the above components except John Cryl 60, and use a paint conditioner (made by Red Level Co.) to perform dispersion treatment for 8 hours with zirconia beads having a diameter of 0.8 mm, remove the glass beads, and then mix the remaining components. Then, it was filtered through a 0.45 μm membrane filter to obtain a recording liquid. The X-ray diffraction spectrum of the colored component is shown in FIG. The Bragg angle θ of the coloring component is 15 ° (2θ ± 0.2
°) and maximum Bragg angle θ is 4 °
The ratio of the integrated values of the diffraction lines in the range of -40 ° was about 28%, and many peaks other than the m-th order were confirmed.

The measurement result of the zeta potential of the obtained coloring component is shown in FIG. As is clear from FIG. 15, it was confirmed that the coloring component has an isoelectric point near pH = 5.

The infrared absorption spectrum of the coloring component obtained above is shown in FIG. The geometric mean diameter of the primary particles of the obtained coloring component was 94 nm, and the geometric standard deviation thereof was 1.37.

Table 1 shows a summary of the above results.

[0097]

[Table 1]

As is clear from this table, the recording liquid composition of the present invention provides high reflection density and vividness of color,
It was found that a recording liquid composition having less blurring and show-through on plain paper, excellent fixing and rubbing properties, and high storage stability and dischargeability can be obtained.

[Comparative Example 5] Diethylene glycol 5% by weight, tetrapropylene glycol 5% by weight, triethylene glycol n-butyl ether 8% by weight, and n-propanol 3% by weight were removed, and the amount of ion-exchanged water was increased by that amount. Others were the same as in Example 4. Glycol ethers as a water-soluble organic solvent are excluded from the recording liquid composition. Therefore, as a result of the storage stability test, not only the recording liquid was hardly ejected, but also the bleeding of the recording liquid was observed along the paper fibers on the paper surface.

Further, 5% by weight of 2-pyrrolidone was removed, and the amount of ion-exchanged water was increased by the same amount as in Examples 5 and 6.
The same test was conducted on the above, but similar results were obtained.

[Comparative Example 6] The same procedure as in Example 4 was carried out except that 5% by weight of 2-pyrrolidone was removed and the amount of ion-exchanged water was increased by that amount. The recording liquid composition does not contain nitrogen-containing heterocyclic ketones as a water-soluble organic solvent. Therefore, as a result of the storage stability test, the recording liquid was clogged and the recording liquid could not be ejected.

Further, 5% by weight of the component 2-pyrrolidone was removed, the amount of ion-exchanged water was increased by that amount, and the same test was conducted for Examples 5 and 6, but similar results were obtained.

[Comparative Example 7] Component Surfynol 465-
The same procedure as in Example 4 was performed except that 0.2% by weight was removed and the amount of ion-exchanged water was increased by that amount. The recording liquid composition does not contain an acetylene diol-based surfactant. Therefore, as a result of the printing test, bleeding of the recording liquid was observed along the paper fibers on the paper surface.

Further, when surfinol 465-0.2% by weight was removed and the amount of ion% exchanged water was increased by that amount, the examples 5 and 6 were also examined, and similar results were obtained.

[Comparative Example 8] The same procedure as in Example 4 was carried out except that 60-5% by weight of the component John Cryl was removed and the amount of ion-exchanged water was increased by that amount. Further, the same test was performed on Comparative Example 2. The recording liquid composition contains no water-soluble resin. Therefore, as a result of the fixing / rubbing test, it was confirmed that the coloring component was peeled from the paper surface by rubbing about 40 times with the PPC paper.

Further, 60% by weight of the component John Cryl was removed, and the amount of ion exchanged water was increased by that amount, and Example 5, Comparative Example 3, and Example 6, Comparative Example 4 were also examined. However, similar results were obtained.

Example 7 The recording liquid composition obtained in Example 4 was sprinkled on a recording material (hereinafter referred to as “paper A”) (SF-4AM3 manufactured by Sharp Corporation), and the surface thereof was covered. PP
The C paper was rubbed 50 times, and the degree of color transfer to the surface of the PPC paper was visually observed to evaluate the fixability / rubbing property. As a result of confirming scratchability, no color transfer was confirmed on PPC paper.

The measurement result of the zeta potential of the paper A is shown in FIG. From FIG. 16, the zeta potential of the paper A has a positive value in a wide pH range, and when compared with the measurement result of the zeta potential of the coloring component used in the recording liquid composition, the coloring component has the opposite sign to the paper A. It has a potential of This means that the coloring component and the recording material are quickly and firmly adhered / fixed in a state where the coloring component is dispersed, have excellent scratch resistance, and a recording screen with vivid colors can be obtained. To do.

[Comparative Example 9] The recording liquid composition obtained in Comparative Example 2 was sprayed on a paper A, and the surface thereof was rubbed with PPC paper 50 times, and the degree of color transfer to the surface of the PPC paper was visually observed. As a result of evaluating fixability / rubbing property, color transfer to PPC paper occurred, and 30 of the recording liquid composition sprayed on paper A was observed.
It was confirmed that about 100% remained on the surface of the paper A.

Comparative Example 10 The recording liquid obtained in Example 4 was sprayed on a recording material (hereinafter referred to as “paper B”) (MJOHPSIN manufactured by Seiko Epson Corporation). In addition, the measurement result of the zeta potential of the paper B is shown in FIG. From FIG. 17, the zeta potential of the paper B has a negative value in a wide pH range, and comparing the measurement results of the zeta potential of the coloring component used in the recording liquid composition, the coloring component is the recording agent (paper B). It can be seen that the zeta potential has the same sign as. The surface of the paper B sprayed with the recording liquid obtained in Example 4 was rubbed with PPC paper 50 times, and the degree of color transfer to the surface of PPC paper was visually observed. As a result of examining
Color transfer on C paper was confirmed.

[Comparative Example 11] The recording liquid composition obtained in Comparative Example 2 was dispersed on the above-mentioned paper B, and the surface thereof was rubbed with PPC paper 50 times, and the degree of color transfer to the surface of the PPC paper was visually observed. It was observed and the fixability and scratching property were evaluated. As a result, PP
There is a lot of color transfer on paper C, and most of the recording liquid composition is paper B.
It was confirmed that it did not remain on the surface.

[Comparative Example 12] The procedure of Example 4 was repeated except that the concentration of the coloring component obtained in Example 1 was adjusted to 12% by weight and the amount of the ion exchanged water was reduced. As a result of the storage stability test, clogging with the recording liquid composition occurred and the recording liquid composition could not be discharged.

Further, a printing test was conducted in the same manner as in Example 4 except that the concentration of the coloring component obtained in Example 1 was changed to 0.5% by weight and the amount of ion-exchanged water was increased by that amount. It was confirmed by visual observation that the print density was lowered.

[0114]

As described above, the recording liquid composition of the present invention is a recording liquid composition containing a coloring component, and the coloring component is a Bragg angle in an X-ray diffraction spectrum using CuKα as an X-ray source. θ is 4 ° to 40 ° (2θ ± 0.2
If the number of diffraction lines having a peak value of 1/10 or more of the maximum diffraction line in the range of (°) is n (n is an integer of 1 or more), the Bragg angle θ is 15 ° (2θ ± 0.2 °). ) The ratio of the integrated value of the maximum diffraction line below to the integrated value of the diffraction line in the Bragg angle θ within the range of 4 ° to 40 ° is 90 / (n + 1) 1/ ² %.
The configuration is as described above.

Therefore, it is possible to obtain a recording liquid composition containing a coloring component having high reflection density and color vividness.

The recording liquid composition of the present invention, as described above,
The coloring component is dispersed in water and does not have an isoelectric point in the neutral region of pH 5 to 7.

Therefore, there is an effect that it is possible to obtain a recording liquid composition which is more excellent in storage stability and further improved in fixing property and scratching property.

The recording liquid composition of the present invention is as described above.
The coloring component shows only the diffraction line having the maximum intensity in the X-ray diffraction spectrum and the m-th order (m: an integer of 2 or more) diffraction line.

Therefore, it is more excellent in storage stability, and
The recording liquid composition having improved fixability and scratch resistance can be obtained.

The recording liquid composition of the present invention is as described above.
The coloring component has a structure having at least one functional group selected from the group consisting of a sulfonic acid group, a carboxylic acid group, a phosphonic acid group, and a derivative group thereof.

Therefore, the coloring component can obtain hydrophilicity and has a self-dispersing recording liquid composition which does not have an isoelectric point in the neutral near pH range of 5 to 7 and can be easily dispersed in water. There is an effect that can be obtained.

The recording liquid composition of the present invention, as described above,
The coloring component is acid-treated.

Therefore, it is possible to perform a simple operation from 1000 cm ^-1 to
At least one functional group selected from the group consisting of a sulfonic acid group having an infrared absorption peak at 1400 cm ⁻¹ , a carboxylic acid group, a phosphon group, and a derivative group thereof can be easily introduced into the coloring component, This brings about an effect that a recording liquid composition containing a coloring component having hydrophilicity can be obtained. Further, this brings about an effect that it is possible to obtain a recording liquid composition in which the coloring component is more uniformly dispersed in water.

The recording liquid composition of the present invention, as described above,
The geometric mean diameter of the primary particles of the coloring component particles is within the range of 1/24 to 1/4 of the wavelength showing the maximum absorption peak in the ultraviolet-visible absorption spectrum of the coloring component, and the geometric standard deviation thereof is 1.5. The configuration is as follows.

Therefore, it is possible to obtain a recording liquid composition having improved transparency and dispersion stability.

The recording liquid composition of the present invention, as described above,
The content of the coloring component is in the range of 1% by weight to 10% by weight.

Therefore, it is possible to obtain a recording liquid composition having higher printing density, higher dispersion stability, and further excellent storage stability.

The recording liquid composition of the present invention is as described above.
The zeta potential of the coloring component when dispersed in water has the opposite sign to the zeta potential of the recording material.

Therefore, a recording liquid composition can be more rapidly and strongly adhered and fixed in a dispersed state of a coloring component, and further has excellent scratch resistance, and a recording screen having a brighter color can be obtained. There is an effect that can be obtained.

The recording liquid composition of the present invention is as described above.
Further, it is a constitution containing at least one selected from the group consisting of a water-soluble organic solvent, a surfactant, and a water-soluble resin.

Therefore, there is an effect that it is possible to obtain a recording liquid composition having higher color density and capable of recording with higher quality.

The above-mentioned effects can be obtained by combining the above water-soluble organic solvent, surfactant, and water-soluble resin alone with the coloring component, but a combination of a plurality of them is more effective and preferable.

The recording liquid composition of the present invention, as described above,
The water-soluble organic solvent is at least one compound selected from the group consisting of glycol ethers, nitrogen-containing heterocyclic ketones, and propylene glycols.

Therefore, high quality recording with higher color density is possible, and in the case of a glycol ether compound, the drying property of the recording liquid composition is further accelerated, and the coloring component is more efficiently fixed to the surface of the medium. It also has the effect of preventing bleeding on media, especially plain paper. Further, in the case of a compound of nitrogen-containing heterocyclic ketones, clogging of nozzles and orifices due to drying of the recording liquid composition is further prevented, storage stability of the recording liquid composition becomes good, and high viscosity recording liquid Liquidity is further improved.
In the case of propylene glycols, the storage stability of the recording liquid composition is further improved, and it contributes to the further improvement of the recording characteristics and the fixing property to the medium. Further, there is an effect that the clogging of the nozzle or the orifice due to the drying of the recording liquid composition is further prevented.

The recording liquid composition of the present invention is as described above.
The surfactant is an acetylene diol-based surfactant.

Therefore, it is possible to obtain a recording liquid composition in which the dispersion stability and printing durability of the recording liquid composition are further improved, and in particular, bleeding and show-through on plain paper are further suppressed. Further, there is an effect that a recording liquid composition capable of forming an image with less bleeding can be obtained.

The recording liquid composition of the present invention is as described above.
The water-soluble resin is a terpolymer of styrene-α-methylstyrene-acrylic acid.

Therefore, it is possible to obtain a recording liquid composition having improved dispersion stability, water resistance and redissolvability.

Further, the recording apparatus of the present invention is constructed so as to record by using the above recording liquid composition.

Therefore, the recording apparatus does not show show-through, double-sided recording by using a combination of recording liquid compositions containing cyan, magenta, and yellow, which are extremely high-definition recording without color turbidity. This has the effect of enabling simultaneous printing. Further, the recording liquid composition makes it possible to secure stable recording liquid ejection performance even after being left for a long period of time. Therefore, it is possible to prevent the nozzles and the orifices from being clogged when the recording apparatus is restarted.

[Brief description of drawings]

FIG. 1 shows an embodiment of a recording liquid composition according to the present invention, and is an X-ray diffraction spectrum of a coloring component of Example 1.

2 is the zeta potential of the coloring component of Example 1. FIG.

3 is an infrared absorption spectrum of the coloring components of Example 1 and Comparative Example 2. FIG.

4 is an X-ray diffraction spectrum of the coloring component of Example 2. FIG.

5 is a zeta potential of the coloring component of Example 2. FIG.

6 is an infrared absorption spectrum of the coloring components of Example 2 and Comparative Example 3. FIG.

7 is an X-ray diffraction spectrum of the coloring component of Example 3. FIG.

FIG. 8 is the zeta potential of the coloring component of Example 3.

9 is an infrared absorption spectrum of coloring components of Example 3 and Comparative Example 4. FIG.

10 is an X-ray diffraction spectrum of the colored component of Comparative Example 2. FIG.

11 is a zeta potential of a coloring component of Comparative Example 2. FIG.

12 is an X-ray diffraction spectrum of the colored component of Comparative Example 3. FIG.

13 is a zeta potential of a coloring component of Comparative Example 3. FIG.

14 is an X-ray diffraction spectrum of the colored component of Comparative Example 4. FIG.

15 is a zeta potential of a coloring component of Comparative Example 4. FIG.

16 is the zeta potential of paper A of Example 11. FIG.

FIG. 17 is the zeta potential of paper B of Example 12.

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Claims (13)

[Claims] 1. A recording liquid composition containing a coloring component, wherein the coloring component has a Bragg angle θ of 4 ° to 40 ° (2θ ± 2) in an X-ray diffraction spectrum using CuKα as an X-ray source.
If the number of diffraction lines having a peak value of 1/10 or more of the maximum diffraction line in the range of 0.2 °) is n (n: an integer of 1 or more), the Bragg angle θ is 15 ° (2θ ± 0). The ratio between the integrated value of the maximum diffraction line of 0.2 ° or less and the integrated value of the diffraction line within the Bragg angle θ within the range of 4 ° to 40 ° is 90 / (n + 1).
A recording liquid composition having a content of ^1/2 % or more. 2. A coloring component in a state of being dispersed in water,
The recording liquid composition according to claim 1, which has no isoelectric point in the neutral region of 5 to 7. 3. The colored component shows only the diffraction line having the maximum intensity in the X-ray diffraction spectrum and its m-th order (m: an integer of 2 or more) diffraction line.
Or the recording liquid composition described in 2. 4. The coloring component has at least one functional group selected from the group consisting of a sulfonic acid group, a carboxylic acid group, a phosphonic acid group and derivatives thereof. The recording liquid composition according to item 3. 5. The recording liquid composition according to any one of claims 1 to 4, wherein the coloring component is acid-treated. 6. The geometric mean diameter of the primary particles of the coloring component particles is within the range of 1/24 to 1/4 of the wavelength showing the maximum absorption peak in the ultraviolet-visible absorption spectrum of the coloring component, and its geometric standard. The recording liquid composition according to claim 1, wherein the deviation is 1.5 or less. 7. The content of the coloring component is 1% by weight to 10% by weight.
The recording liquid composition according to claim 1, wherein the recording liquid composition is in the range of. 8. The recording according to claim 1, wherein the zeta potential of the coloring component when dispersed in water has the opposite sign to the zeta potential of the recording material. Liquid composition. 9. The method according to claim 1, further comprising at least one selected from the group consisting of a water-soluble organic solvent, a surfactant, and a water-soluble resin.
The recording liquid composition according to the item. 10. The method according to claim 9, wherein the water-soluble organic solvent is at least one compound selected from the group consisting of glycol ethers, nitrogen-containing heterocyclic ketones, and propylene glycols. Recording liquid composition. 11. The recording liquid composition according to claim 9, wherein the surfactant is an acetylene diol-based surfactant. 12. The recording liquid composition according to claim 9, wherein the water-soluble resin is a terpolymer of styrene-α-methylstyrene-acrylic acid. 13. A recording apparatus, which is adapted to perform recording using the recording liquid composition according to any one of claims 1 to 12.