JP2003055585A - Ink set, method for ink jet recording, recording unit, ink cartridge and ink jet recording device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To keep the color balance after long-term preservation of formed recorded images by using an ink set having nearly equal fading properties ΔE of respective color inks when preserved for a long period. SOLUTION: The ink set comprises inks containing coloring materials and an aqueous medium. The ink set has light fading properties of a difference ΔE of colors within 10 in the CIELAB color space and >=70% light fading properties of the colors of respective inks expressed in terms of reflection density residual ratio in light resistance tests under conditions causing fading corresponding to simulated indoor light fading for >=3 years.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink set suitable for inkjet recording, an inkjet recording method using the same, a recording unit, an ink cartridge and an inkjet recording apparatus.

[0002]

2. Description of the Related Art Conventionally, for color recording using an ink jet recording method, an aqueous ink in which a dye having each color tone is dissolved in a water-soluble medium is used. Generally, as color inks, three colors of cyan, magenta, and yellow are mainly used.

In addition to the reliability of these inks when used in ink jets, they must provide sufficient image density, have good drying properties, and have no bleeding on recorded images.
It is required that the recorded image does not flow out even when it comes into contact with water, alcohol, etc. and that the recorded image has good weather resistance. In particular, in recent years, high-quality inkjet images comparable to silver halide photographs have been realized, and not only good image quality but also long-term storage stability of recorded images is required. .

[0004]

A major contributor to image storability is photobleaching due to exposure. Therefore, it is required to form an image having more excellent light resistance. When the recorded image is exposed, the dye used in the ink is photo-deteriorated and the color is faded. Therefore, the light fastness of an image has been improved by using a dye having a structure excellent in light fastness as a color ink or by using a recording medium that prevents photobleaching.

However, if there is a large difference in the photobleaching properties of the images obtained by the color inks for forming a color image, the color balance of the entire image after the photobleaching is disturbed, and the image quality is greatly deteriorated. It tends to be given. For example, in a multi-color image formed of cyan, magenta, and yellow, if the light resistance of the image obtained by the cyan ink is smaller than the images obtained by the other two colors, the fading of the portion using the cyan ink becomes large, The image after photobleaching becomes a bluish image compared to the image immediately after printing.

Japanese Unexamined Patent Publication No. 10-329403 discloses that one-year pseudo fading (ΔE) due to office light of yellow, magenta, and cyan inks on plain paper is 25, 30, respectively.
Ink sets that are less than 15 are disclosed. However, the reflection density residual ratio of each color has not been discussed, and since ΔE of each color is large, it cannot be said that the light resistance is good.
In addition, there is no description about the color balance of a full-color image using these three colors, and this does not assume long-term storage.

Therefore, in the present invention, when stored for a long time,
By using an ink set in which the color fading ΔE of the image formed by each color ink is almost equal and the reflection density residual ratio of each image is good, the color balance after long-term storage of the formed recorded image can be improved. The purpose is to maintain and maintain good image quality.

[0008]

In view of the above object, the inventors of the present invention have made various studies on various inks, and as a result, the photobleachability ΔE of an image obtained by each ink for forming a color image is almost the same. By using an ink set that is uniform and has a good reflection density residual ratio of each image, it is possible to prevent deterioration of image quality after long-term storage without impairing the color balance of the entire image,
The present invention has been completed.

The ink set according to the present invention for achieving the above object is an ink set using an ink containing a coloring material and an aqueous medium, and contains at least three kinds of color inks, and is obtained by each ink. Regarding the photobleaching property in the light fastness test under the condition of fading corresponding to the fading of sunlight over the pseudo indoor window for 3 years or more for each image, the difference of ΔE of each image in the CIELAB color space display system is 1
It is characterized in that it is within 0, and the photobleaching property of each image is 70% or more in terms of the reflection density residual rate. The difference of ΔE here includes the case where the difference is zero.

Further, another ink set according to the present invention for achieving the above object is an ink set using an ink containing a coloring material and an aqueous medium.
The CIELAB color space display system is used for the photobleaching property in the light fastness test under the condition that the color fading that corresponds to the fading of the sunlight through the pseudo indoor window for 3 years or more is generated for each image obtained by each ink, which contains more than one kind of color ink. Δ of each image in
The difference in E is 10 or less, and the photobleaching property of each image is 80% or more in terms of the reflection density residual rate. The difference of ΔE here includes the case where the difference is zero.

Further, by using the ink set having such a constitution, an ink jet recording apparatus and its related parts or the like for obtaining a recorded image capable of maintaining a color balance after long-term storage and maintaining a good image quality, an ink jet recording method, etc. Various recording methods can be provided.

An ink jet recording method according to the present invention is an ink jet recording method in which ink is ejected from an orifice according to a recording signal to record on a recording material, and the ink set is used for ink jet recording. Ink.

Further, the recording unit according to the present invention is a recording unit having an ink containing portion containing ink and a head portion for ejecting the ink, and the ink containing portion constitutes an ink set. It is characterized in that it has a portion containing each of the inks, and the ink set is the above-mentioned ink set used for inkjet recording.

Furthermore, the ink cartridge according to the present invention is an ink cartridge having an ink containing portion containing ink, and the ink cartridge has a portion containing each of the inks constituting the ink set. However, the ink set is the above-mentioned ink set.

Another aspect of the ink jet recording apparatus according to the present invention is an ink jet recording apparatus including a recording unit having an ink containing portion containing ink and a head portion for ejecting the ink. Has a portion containing each of the inks constituting the ink set, and the ink set is the ink set used for inkjet recording.

Another aspect of the ink jet recording apparatus according to the present invention is a recording head for ejecting ink, an ink cartridge having an ink accommodating portion for accommodating the ink, and the ink is supplied from the ink cartridge to the recording head. In an ink jet recording apparatus having an ink supply unit for use in the ink set, the ink containing unit has a part containing each of the inks constituting the ink set, and the ink set is used for ink jet recording. Is characterized in that.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is characterized in that the light resistance of an image obtained by each color ink forming a color image is at the same level. Here, the color of the color ink can be represented by using a color space such as CIELAB. In the CIELAB color space, colors are three terms, L *, a
Displayed using *, b *. L * defines the brightness of the color,
It is in the range of 0 (black) to 100 (white). a * and b *
Defines the hue and chromaticity characteristics of a color.

The ΔE used here indicates the color difference between the initial image and the image after photobleaching in the CIELAB color space, and the difference in ΔE is the difference in fading between the two color images. As the difference in ΔE increases, the difference in fading between the two colors increases. ΔE is expressed by the following equation.

[0019]

[Equation 1] The reflection density residual ratio is a numerical value showing the reflection density after photobleaching when the reflection density of the image immediately after printing is 100 (%), and how much the reflection density is maintained after photobleaching. Is shown.

Using this ΔE and the reflection density residual rate, the light resistance of the color ink can be known. That is, if the reflection density residual ratio is high and ΔE of the image immediately after printing and after the photobleaching is small, the photobleaching is small. When ΔE is at the same level for each color, the color balance is maintained even if some overall photobleaching of the image is recognized, so that the image quality of the entire image is slightly degraded.

Hereinafter, preferred embodiments of the present invention will be described in detail. (Lightfastness test) As a means for evaluating the photobleaching in the present invention, a lightfastness test is used. Further, as the lightfastness test, in consideration of the environment in which the image is stored, indoors, the sun through the window is used. It is preferable to carry out under the condition of assuming light. The irradiation dose in the light resistance test is more preferably 6000 klux · hr or more in consideration of long-term storage. For example, by performing a test for 100 hours with an illuminance of 63 klux, the test assumes that the amount of sunlight in the room per day is 5 klux · hr and storage for 3 years or more is assumed.

Further, more preferably, it is carried out under each condition assuming sunlight through an indoor window conforming to ISO10977.

Regarding the illuminance, the ISO standard is 6 klux, but if a test of 6000 klux · hr or more is performed, the test time becomes long. Therefore, even if the test time is shortened by increasing the illuminance, it is sufficient if the results obtained do not conflict with each other.

(Recording Medium) The recording medium used in the present invention is not particularly limited, but it is preferable to use a recording medium having a coating layer called glossy paper, coated paper, or glossy film. A recording medium having, for example, a porous particle layer, a porous polymer layer or the like on a substrate is preferable in order to improve absorption, color development and resolution.

More specifically, one example of the recording medium used in the present invention will be described. A coloring material such as a dye or a pigment is adsorbed on the fine particles forming the porous structure in the ink receiving layer, and at least the adsorbed fine particles are adsorbed. It is a recording medium on which an image is formed, and is particularly suitable when an inkjet method is used. Such a recording medium is preferably a so-called absorption type in which ink is absorbed by the voids formed in the ink receiving layer on the support. The absorption type ink receiving layer is mainly composed of fine particles and is constituted as a porous layer containing a binder and other additives as required. Examples of the fine particles include silica, clay, talc, calcium carbonate, kaolin, aluminum oxide such as alumina or alumina hydrate, diatomaceous earth, titanium oxide, hydrotalcite, zinc oxide and other inorganic pigments, urea formalin resin, ethylene resin. , An organic pigment such as a styrene resin, and one or more of these are used. Water-soluble polymers and latices can be cited as those preferably used as the binder. For example, polyvinyl alcohol or a modified product thereof, starch or a modified product thereof, gelatin or a modified product thereof, gum arabic, carboxymethyl cellulose, hydroxyethyl cellulose,
Cellulose derivatives such as hydroxypro-oil methyl cellulose, SBR latex, NBR latex, methyl methacrylate-butadiene copolymer latex, functional group-modified polymer latex, vinyl-based copolymer latex such as ethylene-vinyl acetate copolymer, polyvinylpyrrolidone, anhydrous Maleic acid or a copolymer thereof, an acrylic acid ester copolymer and the like are used, and if necessary, two or more kinds may be used in combination. In addition, it is also possible to use additives, for example, a dispersant, if necessary,
Thickeners, pH adjusters, lubricants, fluidity modifiers, surfactants, defoamers, mold release agents, fluorescent whitening agents, ultraviolet absorbers, antioxidants and the like are used.

In particular, as the above-mentioned fine particles, those having an ink receiving layer mainly composed of fine particles having an average particle diameter of 1 μm or less are preferable, and particularly preferable fine particles are, for example, silica or aluminum oxide fine particles. Can be mentioned. Preferred silica fine particles are
It is a silica fine particle represented by colloidal silica. Colloidal silica itself is also commercially available, but as particularly preferable one, for example, Japanese Patent No. 28031
Nos. 34 and 2881847 can be cited. Preferable examples of the aluminum oxide fine particles include alumina hydrate fine particles. As one of such alumina pigments, an alumina hydrate represented by the following general formula (1) can be mentioned as a preferable example.

[0027] Al₂O_3-n(OH)_2n・ MH₂O ... (1) In the above formula (1), n is an integer of 1, 2 or 3
And m represents a value of 0 to 10, preferably 0 to 5.
However, m and n do not become 0 at the same time. mH ₂O is
Often mH₂Detachable without participating in O crystal lattice formation
M is an integer or an integer because it also represents the active water phase.
It can take a non-value. Also heat this kind of material
Then m can reach a value of zero. Alumina hydration
Items are generally described in US Pat. No. 4,242,271, US patents.
Alumini as described in Xu 4202870
Hydrolysis of um alkoxide and sodium aluminate
Hydrolysis-like and Japanese Patent Publication No. 57-44605
To the aqueous solution of sodium aluminate etc.
Medium with an aqueous solution of sodium acid, aluminum chloride, etc.
Use products manufactured by known methods such as summing
Those that are suitable are preferred.

FIG. 24 schematically shows a sectional structure of an example of so-called coated paper in which an ink receiving layer is provided on a support made of paper or the like. In FIG. 24, 1000 is a support, and 1003 is a coat layer as an ink receiving layer held by the support 1000. Coat layer 1003 is fine particles 1005
, And the fine particles are fixed by a binder 1007. Then, the ink droplets applied to such a coated paper, in the process of soaking into the coat layer 1003, the coloring material 1009 contained in the ink is adsorbed on the surface of the fine particles 1005, and the coloring material adsorbed on the fine particles is the same. An image is formed by being fixed in position.

(Coloring Material) The color ink according to one embodiment of the present invention comprises, for example, two or three color inks selected from cyan, magenta and yellow.
Furthermore, the respective color inks may have the same color tone and may include two or more kinds of color inks having different concentrations of color materials. The coloring materials used in these color inks are not particularly limited, but they are water-soluble xanthene-based, triphenylmethane-based, anthraquinone-based, monoazo-based, disazo-based, and trisazo-based color indexes. Dyes of the system type, tetraazo type and copper phthalocyanine type are preferred. An ink is prepared by combining one kind or two or more kinds of these coloring materials in the same ink. Generally, the content of the coloring material in the ink is preferably in the range of 0.1 to 15.0% by weight, more preferably 0.5 to 5.0% by weight, based on the whole ink.

When the ink set according to one embodiment of the present invention contains magenta ink, it is preferable to use at least a coloring material represented by the following general formula (I).

[0031]

[Chemical 4] (In the general formula (I), R ₁ represents a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryl group, R ₂ and R ₄ are each independently a hydrogen atom or a substituted or unsubstituted aryl group. Represents an alkyl group, R ₃ is a hydrogen atom,
It represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group or a halogen atom. X ₁ represents a carboxyl group or a salt thereof, or a sulfonic acid group or a salt thereof. n represents 1 or 2. ) Regarding R _{1 to} R ₄ in the above general formula (I), more specifically, R ₁ is, for example, a linear or branched alkoxy group having 1 to 4 carbon atoms or a substituted or unsubstituted alkoxy group. Phenyl group and the like. Here, as the substituent for the phenyl group include a methyl group, a hydroxyl group, a nitro group, a sulfonic acid group or a salt thereof, a carboxyl group or a salt thereof, or a halogen atom (fluorine, chlorine, bromine and the like) and the like. Examples of R ₂ include a hydrogen atom and a linear or branched lower alkyl group having 1 to 4 carbon atoms, and examples of R ₃ include a hydrogen atom and a linear chain having 1 to 4 carbon atoms. Examples of the linear or branched alkyl group, the linear or branched alkoxy group having 1 to 4 carbon atoms, and the aryloxy group include a phenoxy group. The aryl group constituting the aryloxy group is, for example, a linear or branched alkyl group having 1 to 10 carbon atoms, a sulfonic acid group or a salt thereof,
It may be substituted with a carboxyl group or a salt thereof. Further, R ₄ is, for example, a hydrogen atom or a carbon number 1
4 straight chain or branched lower alkyl groups and the like. Further, when X ₁ is detailed, as X ₁ ,
For example, -COOM and -SO ₃ M [where, M is a hydrogen atom, an alkali metal (e.g., Li, Na, or the like), ammonium (NH _4), an organic ammonium (N (R _{8) 4)]} and the like . Here, examples of R ₈ include a methyl group and an ethyl group.

Specific examples of the coloring material represented by the general formula (I) are shown below, but the coloring materials are not limited to these. Also,
Two or more kinds of these coloring materials may be used in the same ink at the same time.

Specific examples of the coloring material contained in the compound of the general formula (I) have the following structures.

[0034]

[Chemical 5]

[0035]

[Chemical 6]

[0036]

[Chemical 7] Further, as the coloring material of the magenta ink, at least one kind of coloring material represented by the general formula (I), and the coloring material represented by the following general formula (II) and the following general formula (III) and the xanthene structure are included. It is more preferable to include at least one of the coloring materials.

[0037]

[Chemical 8] In the general formula (II), Ar ₁ represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group, Ar ₂ represents an acetyl group, a benzoyl group, 1,3,5
- triazinyl group, SO ₂ -C ₆ H ₅ group or SO ₂ -C ₆ H ₄
It represents any of -CH ₃ groups. M is a counter ion of a sulfonic acid group, a hydrogen atom, an alkali metal (for example, L
i, Na, etc.), ammonium (NH4) and organic ammonium (N (R9) 4). here,
Examples of R9 include a methyl group and an ethyl group. The phenyl group and naphthyl group of Ar ₁ are, for example,
A carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a linear or branched alkyl group having 1 to 4 carbon atoms, a halogen atom (fluorine, chlorine, bromine, etc.), an alkoxy group having 1 to 4 carbon atoms, It may be substituted with one or more groups or atoms selected from aryloxy groups such as phenoxy group. When Ar ₂ is a benzoyl group or a 1,3,5-triazinyl group, at least one hydrogen atom in the benzene ring or the 1,3,5-triazine ring is a carboxyl group, a salt thereof, a halogen atom or a halogen group. Atoms (fluorine, chlorine, bromine, etc.), 1-3
It may be substituted with a primary amino group, an alkoxy group or a hydroxyl group.

[0038]

[Chemical 9] In the general formula (III), Ar ₃ and Ar ₄ each independently represent a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group. Examples of the substituent of the phenyl group or the naphthyl group include a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxyl group having 1 to 4 carbon atoms, a hydroxyl group, Examples thereof include a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a halogen atom (fluorine, chlorine, bromine, etc.), and at least one of Ar ₃ and Ar ₄ is a carboxyl group or a salt thereof, or a sulfonic acid group or a salt thereof. It has a salt substituent. M is a counter ion of a sulfonic acid group, and is a hydrogen atom, an alkali metal (eg, Li, Na
Etc.), ammonium (NH ₄ ) and organic ammonium (N (R ₁₀ ) ₄ ). Here, examples of R ₁₀ include a methyl group and an ethyl group. R ₅ is
1,3,5-triazinediyl group is represented, 1,3,5-
At least one hydrogen atom in the triazine ring may be substituted with a carboxyl group or a salt thereof, a halogen atom (fluorine, chlorine, bromine and the like), a primary to tertiary amino group, an alkoxy group, a hydroxyl group and the like.

R ₆ and R ₇ are independently required for forming a perhydroxyazine ring with a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, or N. Represents an atomic group, and L represents a divalent organic connecting group. More specifically, R ₆ and R ₇ include, for example, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkenyl group having 1 to 4 carbon atoms, and benzyl. Groups and the like. Here, examples of the substituent of the alkyl group, alkenyl group and benzyl group include a hydroxyl group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, and the like.

Examples of the coloring material of the compound represented by the general formula (II) include CI Reactive Red 180 and those having the following structures, and further, JP-A-8-73791 and JP-A-1.
Examples thereof include compounds having the structures described in JP-A No. 1-209673.

[0041]

[Chemical 10]

[0042]

[Chemical 11]

[0043]

[Chemical 12] Examples of the coloring material of the compound of the general formula (III) include those having the following structures.

[0044]

[Chemical 13]

[0045]

[Chemical 14]

[0046]

[Chemical 15]

[0047]

[Chemical 16]

[0048]

[Chemical 17] Specific examples of the colorant having a xanthene structure include CIAc
id Red 52, 92, 94, 289 etc. are mentioned.

The coloring material represented by the general formula (I) in the magenta ink according to one embodiment of the present invention and the coloring materials other than the general formula (I) (represented by the general formula (II) and the general formula (III)). Color materials,
Includes at least one coloring material having a xanthene structure)
In consideration of the effect of obtaining a clear color tone, high image density and further excellent light resistance, the weight ratio of
The range of 20:80 is preferable.

When the ink set according to one aspect of the present invention contains a cyan ink, it is more preferable to use a copper phthalocyanine dye as a coloring material for the cyan ink. Specific examples of the coloring material having a copper phthalocyanine structure include C.I.
I. Acid Blue 249, CI Direct Blue 86, CI Direc
Examples include t Blue 199 and CI Direct Blue 307. In addition to these copper phthalocyanine dyes, other cyan coloring materials may be used together. However, when used in combination, the weight ratio of the copper phthalocyanine dye to the other dye is 95: 5 to 20: 8.
The range of 0 is more preferable.

When the yellow ink is included in the ink set according to one embodiment of the present invention, it is preferable to use Direct Yellow 132 as the coloring material of the yellow ink.

The ink set according to one embodiment of the present invention may further contain a black ink, and in that case, as with other color inks, the photobleaching property after pseudo indoor photobleaching for 3 years or more is Difference of ΔE in CIELAB color space display system is 1
0 or less, and the residual ratio of reflection density is 70% or more, preferably
The ink is preferably 80% or more. Examples of such black ink include dye-based black ink and pigment-based black ink.

When a dye-based black ink is used,
Examples of the dye that can be used in the ink include at least one selected from those represented by the following general formulas (IV) to (VI).

[0054]

[Chemical 18] (In the formula, W is a carboxyl group, X is a hydrogen atom, a carboxyl group or a sulfone group, Y is a hydrogen atom, a carboxyl group or a sulfone group, Z is a hydrogen atom, a carboxyl group or a sulfone group, and R ₁ is hydrogen. And an alkyl group substituted with at least one of an atom, a carboxyl group and an alkoxyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted alkanoyl group, respectively, wherein the phenyl group and the alkanoyl group are substituents. Examples thereof include a hydroxyl group, a carboxyl group, a sulfone group, an alkoxy group, etc.) In the general formula (IV), the carboxylalkyl group represented by R ₁ is preferably an alkyl group having C _1-6 (having 1 carbon atom).
~ 6, the same applies hereinafter), and more preferably a carboxyalkyl group whose alkyl group is C _1-4 .

[0055]

[Chemical 19] (In the formula, Q1 represents a phenyl group or naphthyl group substituted with at least one selected from a lower alkylcarbonylamino group and a lower alkoxy group; or a naphthyl group substituted with a sulfone group, and Q2 represents a sulfone group. naphthyl group; represents or a phenyl group substituted with a lower alkoxy group, Q3 represents a phenyl group or a naphthyl group substituted with unsubstituted or SO ₃ M group, R ₂ and R ₃ are each independently Represents a lower alkyl group, a lower alkoxy group or a lower alkylcarbonyl group, R4 represents a hydrogen atom or a phenyl group substituted with a sulfone group, n is 0 or 1, and M is an alkali metal (eg, Li, Na, etc.). ), Ammonium (NH ₄ ), organic ammonium (N (R ₅ ) ₄ ), etc. Here, as R ₅ Is, for example, a methyl group or an ethyl group.) As the lower alkylcarbonylamino group in the dye structure represented by the general formulas (V) and (VI), a C _1-4 alkylcarbonylamino group is preferable and a lower alkoxy group is used. The group is preferably a C _1-4 alkoxy group, and the lower alkyl group is preferably a C _1-4 alkyl group.

Specific examples of the dye represented by the general formula (V) include structural formulas 23 to 27 below.

[0057]

[Chemical 20] Examples of the dye represented by the general formula (VI) include Exemplified Compounds Nos. 28 to 32 shown below.

[0058]

[Chemical 21] Besides this, for example, CI Direct Black 17, 1
9, 32, 51, 71, 90, 108, 146, 15
4, 168, 195, CI Food Black 1, 2, etc. can also be mentioned. These black dyes may be used alone or in an appropriate combination without departing from the scope of the present invention.

Examples of the pigment-based black ink include pigment inks containing self-dispersion type carbon black as a coloring material as described in JP-A-10-195360. Further, such an ink is excellent in light resistance and also very good in terms of character quality. Therefore, by combining with the color ink set described above, it is possible to provide a printed matter with less deterioration of a multicolor image over time and excellent in character quality.

By the way, the yellow, magenta and cyan color inks containing the above-mentioned various coloring materials are particularly suitable for the recording medium described above, which contains alumina hydrate fine particles in the ink receiving layer. The compatibility is good, and the difference in ΔE is 1 with respect to the photofading property in the light resistance test according to the present invention.
It is possible to achieve the condition that the ratio is 0 or less and the reflection density residual rate is 70% or more, particularly 80% or more. The reason why the compatibility between the coloring material and the recording medium is good is not clear, but it is considered that the adsorbed state of the coloring material on the alumina hydrate contributes to the suppression of the deterioration of the coloring material.

The following are examples of combinations of the color materials of the color inks that can achieve the color tone of the color inks and good light resistance at an extremely high level. Magenta ink: the above general formula (I) and the above general formula (I)
I), a mixture with at least one colorant selected from the above general formula (III) and a colorant having a xanthene structure, and more specifically, the exemplified compound I-7 and the exemplified compound II-8.
And CIAcid Red289 mixed ・ Cyan ink: Direct Blue 199 ・ Yellow ink: Direct Yellow 132 When adding black ink to the ink set composed of the above YMC color inks,
As the coloring material, for example, C.I. I. An ink containing Food Black 2, the exemplified compound 23, and the exemplified compound 28 is preferable.

As another ink set according to the present invention,
The above-mentioned ink set includes at least two inks having different color material concentrations and the same color tone. Of the above two inks, the ink having a low coloring material concentration is preferably, for example, about 2% or less of the total weight of the ink, and the light resistance of the image obtained by the ink having a low coloring material concentration is the other. It is preferable that the light resistance of the image obtained by the above ink (ink having a high coloring material concentration) is equal to or higher than the light resistance. In the case of an ink set having two types of ink with different color material concentrations as magenta ink,
In the case of an ink set having two types of inks having different color material concentrations as cyan ink, a magenta ink having a low color material concentration containing the dye represented by the general formula (I) as the only color material is used. Direct B for low density cyan ink
It is preferable to use the one containing lue 199 as the only coloring material.

Further, a preferable ink set according to the present invention is composed of an ink in which each ΔE of the obtained image is 20 or less, more preferably 15 or less.

(Aqueous medium) In the ink constituting the ink set according to the present invention, a water-based aqueous medium is used as a liquid medium for dissolving or dispersing the coloring material used in the present invention. As this aqueous medium, water alone or a medium containing water and a water-soluble organic solvent can be used. The water-soluble organic solvent is not particularly limited as long as it shows water solubility, and examples thereof include alcohols, polyhydric alcohols, polyglycols, glycol ethers, nitrogen-containing polar solvents, sulfur-containing polar solvents and the like. These solvents are used for maintaining the moisturizing properties of ink, improving the solubility of coloring materials, and penetrating agents for ink into recording paper. Generally, the content of the water-soluble organic solvent is preferably in the range of 1 to 40% by weight, and more preferably 3 to 30% by weight based on the total weight of the ink.
Further, the content of water in the ink is preferably in the range of 30 to 95% by weight in order to maintain good dye solubility and ink ejection stability.

(Additive) Further, in order to maintain the moisturizing property of the ink, a moisturizing solid content such as urea, urea derivative, trimethylolpropane may be used as an ink component. urea,
The content of moisturizing solids such as urea derivatives and trimethylolpropane in the ink is generally 0.1 to the ink.
The range of 20.0% by weight is preferable, and more preferably 3.
It is in the range of 0 to 10.0% by weight. In addition to the above components, the ink of the present invention may further contain a surfactant, a pH
Various additives such as a regulator, an anticorrosive, an antiseptic, an antifungal agent, an antioxidant, an anti-reducing agent, an evaporation accelerator, a chelating agent and a water-soluble polymer may be contained.

(PH) In the ink used in the present invention, when a coloring material whose solubility in water is lowered in a low pH range is used, from the viewpoints of preventing clogging at the tip of the nozzle and long-term storage stability of the ink, The pH of the ink is preferably maintained in the alkaline region. Further, if the pH of the ink exceeds 11.0, the members constituting the recording means that come into contact with the ink may be easily dissolved or corroded. From these facts, the pH of the ink is preferably in the range of 7.0 to 11.0.

(Inkjet Recording Device, Inkjet Recording Method) FIGS. 1 and 2 show an example of a head structure which is a main part of a device utilizing thermal energy as an inkjet recording device to which the ink set according to the present invention can be applied.

FIG. 1 is a sectional view of the head 13 taken along the ink flow path, and FIG. 2 is a sectional view taken along the line AB of FIG.
The head 13 is obtained by bonding a glass, ceramic, silicon or plastic plate or the like having a flow path (nozzle) 14 for passing ink and a heating element substrate 15. The heating element substrate 15 includes a protective layer 16 made of silicon oxide, silicon nitride, silicon carbide, etc., electrodes 17-1, 17-2, HfB ₂ , TaN, TaAl made of aluminum, gold, aluminum-copper alloy, etc. A heat generating resistor layer 18 formed of a high melting point material such as, a heat storage layer 19 formed of thermally oxidized silicon, aluminum oxide or the like, and a substrate 20 formed of a material having good heat dissipation such as silicon, aluminum or aluminum nitride. Is made up of.

When a pulsed electric signal is applied to the electrodes 17-1 and 17-2 of the head, the area indicated by n on the heating element substrate 15 rapidly generates heat, and the ink in contact with this surface Bubbles are generated, the meniscus 23 is projected by the generated pressure, the ink is ejected through the nozzle 14 of the head, and becomes an ink droplet 24 from the ejection orifice 22 and fly toward the recording material 25.

FIG. 3 shows an external view of a multi-head in which a large number of the heads shown in FIG. 1 are arranged. This multi-head is made by bonding a glass plate 27 having a multi-nozzle 26 and a heating head 28 similar to that described in FIG.

FIG. 4 shows an example of an ink jet recording apparatus incorporating this head. In FIG. 4, 61 is a blade as a wiping member, one end of which is a blade.
It is held and fixed by a cable holding member, and cantilever
Form. The blade 61 is arranged at a position adjacent to the recording area of the recording head 65, and in the case of this example, is held in the form of protrusion in the movement path of the recording head 65.

Reference numeral 62 denotes a cap on the projecting opening surface of the recording head 65, which is arranged at a home position adjacent to the blade 61 and moves in a direction perpendicular to the moving direction of the recording head 65.
It is configured to come into contact with the ink ejection port surface and perform capping. Further, 63 is an ink absorber provided adjacent to the blade 61, and like the blade 61, is held in a protruding form in the moving path of the recording head 65. Blade 6 above
1, the cap 62 and the ink absorber 63, the discharge recovery unit 6
4, the blade 61 and the ink absorber 63 remove water, dust and the like from the ejection port surface.

Reference numeral 65 denotes a recording head having ejection energy generating means for ejecting ink to a recording material facing the ejection port surface where the ejection port is arranged for recording, and 66 is equipped with the recording head 65. A carriage for moving the recording head 65. The carriage 66 slidably engages with a guide shaft 67, and a part of the carriage 66 is connected (not shown) to a belt 69 driven by a motor 68. This makes the carriage
66 can move along the guide shaft 67, and the recording head
It becomes possible to move the recording area and the adjacent area by the 65. Reference numeral 51 is a paper feeding section for inserting a recording material, and 52 is a paper feeding roller driven by a motor (not shown).

With these constructions, the recording material is fed to a position facing the 65 ejection port surface of the recording head, and is ejected to the ejection section provided with the ejection roller 53 as the recording progresses. In the above configuration, when the recording head 65 finishes recording and returns to the home position, the cap 62 of the ejection recovery unit 64 is retracted from the moving path of the recording head 65, but the blade 61 is not moved during the moving path. It is protruding. As a result, the ejection port of the recording head 65 is wiped. The cap 62 is the recording head.
When capping is performed by contacting the ejection surface of 65, the cap 62 moves so as to project into the movement path of the recording head. When the recording head 65 moves from the home position to the recording start position, the cap 62 and the blade 61 are in the same positions as those in the above wiping. As a result,
Even in this movement, the ejection port surface of the recording head 65 is wiped.

The above-described movement of the recording head to the home position is performed not only at the end of recording or at the time of ejection recovery, but also at a predetermined interval while adjoining the recording area while the recording head moves for recording. To the home position, and the wiping is performed in association with this movement.

FIG. 5 is a diagram showing an example of an ink cartridge 45 in which the ink is supplied to the recording head via an ink supply member, for example, a tube. Here, 40 is an ink containing portion for containing the supply ink, for example, an ink bag, and a rubber stopper 42 is provided at the tip thereof. By inserting a needle (not shown) into this stopper 42, the ink in the ink bag 40 can be supplied to the head. 44 is an ink absorber that receives waste ink. As the ink container, it is preferable that the surface in contact with the ink is made of polyolefin, especially polyethylene.

The ink jet recording apparatus used in the present invention is not limited to the one in which the head and the ink cartridge are separated as described above, but may be one in which they are integrated as shown in FIG. Is also preferably used. In FIG. 6, reference numeral 70 denotes a recording unit, in which an ink containing portion that contains ink, for example, an ink absorber is contained, and the ink in the ink absorber from the head portion 71 having a plurality of orifices. It is configured to be ejected as an ink droplet. It is preferable for the present invention to use polyurethane as the material of the ink absorber. Further, the structure may be such that the ink containing portion is an ink bag having a spring or the like inside, without using the ink absorber. Reference numeral 72 is an atmosphere communication port for communicating the inside of the cartridge with the atmosphere. The recording unit 70 is used in place of the recording head 65 shown in FIG. 4, and is detachable from the carriage 66.

Next, as a form of an ink jet recording apparatus utilizing the second mechanical energy, a nozzle forming substrate having a plurality of nozzles, a pressure generating element composed of a piezoelectric material and a conductive material arranged facing the nozzles. An on-demand ink jet recording head that includes ink that fills the circumference of the pressure generating element, displaces the pressure generating element by an applied voltage, and ejects a small droplet of ink from a nozzle.

FIG. 23 shows a structural example of a recording head which is a main part of the recording apparatus. The head of this example includes an ink channel 80 communicating with an ink chamber (not shown), an orifice plate 81 for ejecting an ink droplet of a desired volume, a vibrating plate 82 for directly exerting a pressure on the ink, A substrate for bonding and fixing the pressure transmission element 83, which is joined to the vibration plate 82 and displaced by an electric signal, the orifice plate 81, the vibration plate, and the like.
It is composed of 84 and.

In FIG. 23, the ink flow path 80 is formed of a photosensitive resin or the like, and the orifice plate 81 is formed with a discharge port 85 by electroforming or punching a metal such as nickel by electroforming or press working, and vibrates. Plate 82 is stainless steel,
The piezoelectric element 83 is formed of a metal film of nickel, titanium, or the like, a highly elastic resin film, or the like.
It is formed of a dielectric material such as PZT (Pb [ZrTi] O ₂ ).

The recording head having the above-mentioned structure applies a pulsed voltage to the piezoelectric element 83 to generate strain stress,
The energy deforms the vibration plate joined to the piezoelectric element 83, vertically pressurizes the ink in the ink flow path 80, and ejects an ink droplet (not shown) from the ejection port 85 of the orifice plate to perform recording. Operate.

Such a recording head is used by incorporating it in a recording device similar to that shown in FIG. The detailed operation of the recording device is the same as that described above and may be performed.

Next, other specific examples of the recording apparatus and the recording head which can be preferably used in the present invention will be described.

FIG. 7 is a schematic diagram showing the essential parts of an example of a liquid ejection head as a liquid ejection head of an ejection system for communicating bubbles with the atmosphere at the time of ejection according to the present invention and an ink jet printer as a liquid ejection device using this head. It is a perspective view. In FIG. 7, the inkjet printer is
A conveyance device 1030 that intermittently conveys a sheet 1028 as a recording medium provided in the casing 1008 as a recording medium in a direction indicated by an arrow P in FIG. 7, and a conveyance direction P of the sheet 1028 by the conveyance device 1030 are substantially in the conveyance direction P. A recording unit 1010 that is reciprocated substantially parallel to the orthogonal direction S.
And a movement drive unit 1006 as a drive unit for reciprocating the recording unit 1010.

The transport device 1030 includes a pair of roller units 1022a and 102 which are arranged to face each other substantially in parallel.
22b and a pair of roller units 1024a and 10
24b and a drive unit 1020 for driving each of these roller units. Accordingly, the driving unit 102
When 0 is activated, the paper 1028 is moved in the direction of arrow P shown in FIG. 7 to the respective roller units 1022a and 1022b and the roller units 1024a and
It is pinched by 24b and conveyed by intermittent feeding.

The movement driving unit 1006 is arranged substantially parallel to the belt 1016 wound around the pulleys 1026a and 1026b arranged on the rotating shafts facing each other with a predetermined interval, and the roller units 1022a and 1022b, and is arranged in the recording unit 1010. The motor 1018 is configured to drive the belt 1016 connected to the carriage member 1010a in the forward and reverse directions.

When the motor 1018 is activated and the belt 1016 rotates in the direction of arrow R in FIG.
The carriage member 1010a of 010 is moved in the direction of arrow S in FIG. In addition, the motor 1018
7 is activated and the belt 1016 rotates in the direction opposite to the arrow R direction in FIG. 7, the carriage member 1010a of the recording unit 1010 moves in a direction opposite to the arrow S direction in FIG. 7 by a predetermined movement amount. Will be done. Further, the carriage member 1010 is provided at one end of the movement driving unit 1006.
A recovery unit 1026 for performing the ejection recovery process of the recording unit 1010 is provided at the home position of a, facing the ink ejection port array of the recording unit 1010.

The recording unit 1010 includes ink jet cartridges (hereinafter sometimes simply referred to as cartridges) 1012Y, 1012M, 1012C and 101.
2B is detachably attached to the carriage member 1010a for each color, for example, yellow, magenta, cyan, and black.

FIG. 8 shows an example of an ink jet cartridge which can be mounted on the above ink jet recording apparatus. The cartridge 1012 in this example is of a serial type, and its main part is composed of the inkjet recording head 100 and a liquid tank 1001 that stores a liquid such as ink. The inkjet recording head 100 is formed with a large number of ejection ports 832 for ejecting liquid, and liquid such as ink is supplied from a liquid tank 1001 through a liquid supply passage (not shown) to a common liquid chamber of the liquid ejection head 100 (see FIG. 9)). The cartridge 1012 is the ink jet recording head 10.
0 and the liquid tank 1001 are integrally formed so that the liquid can be replenished into the liquid tank 1001 as needed. The liquid tank 1001 is replaceably connected to the liquid ejection head 100. The structure may be adopted.

A specific example of the above-mentioned liquid ejection head which can be mounted on the ink jet printer having such a structure will be described in more detail below.

FIG. 9 is a schematic perspective view schematically showing a main part of a liquid ejection head showing a basic form of the present invention.
0 to 13 are front views showing the shapes of the ejection openings of the liquid ejection head shown in FIG. In addition, electrical wiring for driving the electrothermal converting element is omitted.

In the liquid discharge head of this example, a substrate 934 made of glass, ceramics, plastic, metal or the like as shown in FIG. 9 is used. The material of such a substrate is not the essence of the present invention,
It is not particularly limited as long as it functions as a part of the flow path constituent member, an ink discharge energy generating element, and a liquid flow path to be described later, a support of a material layer forming a discharge port, as long as it can function. Absent. Therefore, in this example, a case of using a Si substrate (wafer) will be described. In addition to the method of forming the discharge port by laser light, for example, an orifice plate (discharge port plate) 935 described later is used as a photosensitive resin, and
It can also be formed by an exposure device such as a PA (Mirror Projection Aliner).

In FIG. 9, reference numeral 934 denotes a substrate provided with an electrothermal conversion element (hereinafter, also referred to as a heater) 931 and an ink supply port 933 composed of a long groove-shaped through hole serving as a common liquid chamber. The heaters 931 as heat energy generating means are arranged in a zigzag pattern on each side of the mouth 933 in the longitudinal direction.
arranged by i. On the substrate 934, an ink flow path wall 936 for forming an ink flow path is provided. The ink flow path wall 936 is further provided with an ejection port plate 935 having an ejection port 832.

Here, in FIG. 9, the ink flow path wall 936.
Although the discharge port plate 935 and the discharge port plate 935 are shown as separate members, the ink flow channel wall 936 and the discharge port plate 935 are formed by forming the ink flow channel wall 936 on the substrate 934 by a method such as spin coating. It is also possible to form the same member at the same time. In this example, a water repellent treatment is further applied to the discharge port surface (upper surface) 935a side.

In this example, a serial type head for recording while scanning in the direction of arrow S in FIG.
Record at 200 dpi. The driving frequency is 10kHz,
One discharge port discharges at the shortest time interval of 100 μs.

As an example of the actual size of the head,
For example, as shown in FIG. 10, the partition 936a that fluidly isolates adjacent nozzles has a width w = 14 μm. Figure 1
As shown in FIG. 3, the foaming chamber 1337 formed by the ink flow path wall 936 has N ₁ (width dimension of the foaming chamber) = 33 μm, N
₂ (length of foaming chamber) = 35 μm. The size of the heater 931 is 30 μm × 30 μm, the heater resistance value is 53Ω, and the driving voltage is 10.3V. The height of the ink flow path wall 936 and the partition wall 936a is 12 μm, and the thickness of the ejection port plate is 11 μm.

Of the cross section of the discharge port portion 940 provided on the discharge port plate including the discharge port 832, the shape of the cross section cut along the direction intersecting the ink discharge direction (thickness direction of the orifice plate 935) is roughly It has a star shape and is roughly composed of six ridges 832a having obtuse angles and six ridges 832b alternately arranged between the ridges 832a and having acute angles. That is, the bottom part 832b as a region locally separated from the center O of the discharge port is its top part, and the raised part 832a as a region locally close to the center O of the discharge port adjacent to this region is its base part. 6 grooves 11 in the thickness direction of the orifice plate (liquid discharge direction) shown in FIG.
41 is formed.

In this example, the discharge port portion 940 has, for example, a cross section of one side 27 cut in a direction intersecting the thickness direction.
It has a shape in which two equilateral triangles of μm are rotated by 60 degrees, and T ₁ shown in FIG. 11 is 8 μm. The angles of the raised portions 832a are all 120 degrees,
The angles of 32b are all 60 degrees. Therefore, a polygon formed by connecting the center O of the discharge port and the center of the groove adjacent to each other (the center (center of gravity) of a figure formed by connecting the top of the groove and two bases adjacent to this top) The center of gravity G of is matched. The opening area of the discharge port 832 of this example is 400 μm ² , and the opening area of the groove (the area of the figure formed by connecting the top of the groove and the two bases adjacent to this top) is about 33 μm ² . Has become. FIG. 12 is a schematic diagram showing a state of the ink (C) attached to the ejection port portion shown in FIG.

Next, the liquid discharge operation of the ink jet recording head having the above-mentioned structure will be described with reference to FIGS. 14 to 21 are sectional views for explaining the liquid ejecting operation of the liquid ejecting head shown in FIGS. 9 to 13, and are XX sectional views of the bubbling chamber 1337 shown in FIG.
In this cross section, the end of the orifice 940 in the thickness direction of the orifice plate is the top 1141a of the groove 1141. Figure 1
4 shows a state in which film-like bubbles are generated on the heater.
5 is about 1 μs in FIG. 14, and FIG. 16 is about 2 μs in FIG.
14, FIG. 17 shows about 3 μs after FIG. 14, FIG. 18 shows about 4 μs after FIG. 14, FIG. 19 shows about 5 μs after FIG. 14, and FIG.
4 after about 6 μs, and FIG. 21 shows the state after about 7 μs in FIG. In the following explanation, "falling"
Alternatively, “drop” and “drop” do not mean so-called drop in the direction of gravity, but the movement in the direction of the electrothermal conversion element regardless of the mounting direction of the head.

First, as shown in FIG. 14, as the heater 931 is energized based on a recording signal or the like, the liquid flow path on the heater 931 is
When the bubble 101 is generated in the 1338, it is shown in FIG.
As shown in FIG. 5 and FIG. 16, the volume rapidly expands and grows. The height of the bubble 101 at the maximum volume is 93
Although it exceeds 5a, at this time, the pressure of the bubble is reduced from a fraction of atmospheric pressure to a fraction of ten. Next, bubble 1
At about 2 μs after the generation of 01, the bubble 101 turns from the maximum volume to the volume decrease as described above, but at the same time, the formation of the meniscus 102 also starts. This meniscus 102 also retreats toward the heater 931 side, that is, falls, as shown in FIG. Here, in this example,
By having the plurality of grooves 1141 dispersed in the discharge port portion, when the meniscus 102 retreats, a capillary force acts in the direction of the groove 1141 in the direction F _C opposite to the meniscus retreating direction F _M. As a result, the air bubbles 10
Even if some variation is recognized in the state of No. 1, the shape of the meniscus and the main liquid droplet (hereinafter, also referred to as liquid or ink) I _a when the meniscus retreats is substantially equal to the ejection port center. It is corrected to have a symmetrical shape.

In this example, the meniscus 102 is
Since the falling speed of is faster than the contraction speed of the bubble 101,
As shown in FIG. 18, the bubble 101 communicates with the atmosphere in the vicinity of the lower surface of the discharge port 832 at a time point about 4 μs after the generation of the bubble.
At this time, the liquid (ink) near the central axis of the ejection port 832 drops toward the heater 931. This is because the liquid (ink) I _a drawn back to the heater 931 side by the negative pressure of the bubble 101 before communicating with the atmosphere retains the velocity in the heater 931 surface direction due to inertia even after the bubble 101 communicates with the atmosphere. Because. The liquid (ink) falling toward the heater 931 reaches the surface of the heater 931 about 5 μs after the formation of the bubble 101 as shown in FIG. 19, and as shown in FIG. It spreads to cover the surface. The liquid thus spread so as to cover the surface of the heater 931 has a horizontal vector along the surface of the heater 931, but intersects with the surface of the heater 931, for example, the vertical vector disappears, The liquid tends to stay on the surface, and the liquid above it, that is, the liquid that maintains the velocity vector in the ejection direction, is pulled downward. After that, the liquid I _b between the liquid spread on the surface of the heater 931 and the upper liquid (main liquid droplet) becomes thin, and about 7 μs after the generation of the bubble 101, the heater is heated as shown in FIG. The liquid I _b is cut at the center of the surface of No. 1 and is separated into a main droplet I _a that maintains the velocity vector in the ejection direction and a liquid I _c that has spread on the surface of the heater 931. Thus, the separation position is preferably inside the liquid flow path 1338, more preferably on the electrothermal conversion element 931 side of the discharge port 832. The main liquid droplet I _a has no deviation in the ejection direction, is ejected from the central portion of the ejection port 832 without being deflected, and is landed at a predetermined position on the recording surface of the recording medium. Further, the liquid I _c spread on the surface of the heater 931 will fly as satellite droplets following the main droplets in the past, but stays on the surface of the heater 931 and is not discharged. Since the ejection of satellite droplets can be suppressed in this way, it is possible to prevent the splash that is likely to occur due to the ejection of satellite droplets, and it is possible to reliably prevent the recording surface of the recording medium from becoming dirty due to mist floating in a mist. Can be prevented. 18 to 21, Id is the ink attached to the groove (ink in the groove)
And Ie represents the ink remaining in the liquid flow path.

Thus, in the liquid ejection head of this example,
When the liquid is ejected in the volume reduction stage after the bubbles have grown to the maximum volume, the direction of the main liquid droplet at the time of ejection can be stabilized by the plurality of grooves dispersed with respect to the center of the ejection port. As a result, it is possible to provide a liquid ejection head with high accuracy in landing, which is free from deflection in the ejection direction. In addition, high-speed and high-definition printing can be realized because stable ejection can be performed even with foaming variations at high driving frequencies.

In particular, by ejecting the liquid by starting the bubble and communicating with the atmosphere at the stage of reducing the volume of the bubble, it is possible to prevent the mist generated when the bubble is communicated with the atmosphere and the droplet is discharged. It is also possible to suppress the so-called state in which droplets adhere to the ejection port surface, which is a cause of sudden ejection failure.

Further, as another embodiment of the recording head of the discharge system which allows the air bubbles to communicate with the atmosphere at the time of discharge that can be preferably used in the present invention, for example, as described in Japanese Patent Registration No. 2783647, a so-called edge shooter type is used. Can be mentioned.

The present invention provides excellent effects particularly in an ink jet type recording head and a recording apparatus for recording by forming flying droplets by utilizing thermal energy among the ink jet recording systems.

With regard to its typical structure and principle, see, for example, US Pat. Nos. 4,723,129 and 4740.
What is done using the basic principles disclosed in 796 is preferred. This method can be applied to both the so-called on-demand type and continuous type, but especially in the case of the on-demand type, liquid (ink)
By applying at least one drive signal to the electrothermal converter arranged corresponding to the sheet or liquid path in which is stored, a rapid temperature rise corresponding to the recorded information and exceeding nucleate boiling is applied. , It is effective because it generates heat energy in the electrothermal converter, causes film boiling on the heat-acting surface of the recording head, and as a result, can form bubbles in the liquid (ink) that correspond one-to-one to this drive signal. Is. The liquid (ink) is ejected through the ejection openings by the growth and contraction of the bubbles to form at least one droplet. It is more preferable to make the driving signal into a pulse shape because bubbles can be grown and contracted immediately and appropriately, and thus a liquid (ink) with excellent responsiveness can be ejected.

As the pulse-shaped drive signal, those described in US Pat. Nos. 4,463,359 and 4,345,262 are suitable. If the conditions described in US Pat. No. 4,313,124 of the invention relating to the rate of temperature rise of the heat acting surface are adopted, more excellent recording can be performed.

As the constitution of the recording head, in addition to the combination constitution of the ejection port, the liquid passage, and the electrothermal converter (the linear liquid passage or the right-angled liquid passage) as disclosed in the above-mentioned respective specifications. The present invention also includes configurations using US Pat. No. 4,558,333 and US Pat. No. 4,459,600, which disclose a configuration in which a heat acting portion is arranged in a bending region.

In addition, Japanese Patent Application Laid-Open No. 59-123670 discloses a structure in which a common slit is used as a discharge portion of a plurality of electrothermal converters, and a pressure wave of thermal energy is absorbed. The present invention is also effective as a configuration based on Japanese Patent Application Laid-Open No. 59-138461, which discloses a configuration in which an opening corresponds to a discharge portion.

Further, as a full line type recording head having a length corresponding to the width of the maximum recording medium which can be recorded by the recording apparatus, the length can be increased by combining a plurality of recording heads as disclosed in the above-mentioned specification. The present invention can exert the above-mentioned effects more effectively, although it may have a configuration that satisfies the above requirement or a configuration as one recording head integrally formed.

In addition, by being attached to the apparatus main body, it can be electrically connected to the apparatus main body and can be supplied with ink from the apparatus main body by a replaceable chip type recording head or the recording head itself. The present invention is also effective when a cartridge-type recording head provided with an ink tank is used.

Further, it is preferable to add recovery means for the recording head, preliminary auxiliary means, etc., which are provided as a configuration of the recording apparatus of the present invention, because the effects of the present invention can be further stabilized. If you list these specifically,
Capping means, cleaning means, pressurizing or sucking means for the recording head, preheating means using an electrothermal converter or another heating element or a combination thereof, and a preliminary ejection mode for performing ejection other than recording It is also effective to perform stable recording.

Further, the recording mode of the recording apparatus is not limited to the recording mode of only the mainstream color such as black, but the recording head may be integrally formed or a plurality of combinations may be used. The present invention is also extremely effective for a device provided with at least one of full colors by color mixing.

In the embodiment of the present invention described above,
Although the ink is described as a liquid, it is an ink that solidifies at room temperature or lower and softens at room temperature, or is a liquid, or the ink itself is 30 ° C. or higher and 70 ° C. or lower in the above-mentioned inkjet method. Since the temperature is generally adjusted within the range to control the temperature of the ink so that the viscosity of the ink is within the stable ejection range, it is sufficient that the ink is in a liquid state when the use recording signal is applied.

In addition, the temperature rise due to the thermal energy is positively prevented by using it as the energy for changing the state of the ink from the solid state to the liquid state, or the ink is solidified in a standing state for the purpose of preventing evaporation of the ink. In some cases, such as ink that is liquefied by applying heat energy according to a recording signal and ejected as a liquid ink, or one that has already started to solidify when it reaches a recording medium. The use of an ink having a property of being liquefied only by heat energy is also applicable to the present invention. In such a case, the ink is disclosed in JP-A-54-5684.
No. 7 or JP-A-60-71260, a mode in which the porous sheet is opposed to the electrothermal converter in the state of being held as a liquid or solid in the recess or through hole of the porous sheet. Also good. In the present invention, the most effective one for each of the above-mentioned inks is to execute the above-mentioned film boiling method.

In addition, as a form of the recording apparatus according to the present invention, in addition to a recording apparatus provided integrally or separately as an image output terminal of information processing equipment such as a word processor and a computer, a copying apparatus combined with a reader, It may take the form of a facsimile machine having a transmission / reception function.

Next, an outline of a liquid ejecting apparatus equipped with the above-mentioned liquid ejecting head will be described.

FIG. 22 is a schematic perspective view of an ink jet recording apparatus 600 which is an example of a liquid ejecting apparatus to which the liquid ejecting head of the present invention can be attached and applied. Figure 2
2, the inkjet head cartridge 601
Is a combination of the above-described liquid ejection head and an ink tank that holds ink to be supplied to the liquid ejection head. This inkjet head cartridge 6
Reference numeral 01 denotes a carriage 6 that engages with the spiral groove 606 of the lead screw 605 that rotates via the driving force transmission gears 603 and 604 in association with the forward / reverse rotation of the drive motor 602.
It is mounted on 07 and is reciprocally moved along with the carriage 607 along the guide 608 in the directions of arrows a and b by the power of the drive motor 602. The recording material P is conveyed on the platen roller 609 by a recording material conveying means (not shown), and is pressed against the platen roller 609 by the paper pressing plate 610 in the moving direction of the carriage 607.

In the vicinity of one end of the lead screw 605,
Photo couplers 611 and 612 are provided. These are home position detecting means for confirming the existence of the lever 607a of the carriage 607 in this area and switching the rotation direction of the drive motor 602 and the like.

The support member 613 supports the cap member 614 which covers the front surface (ejection port surface) of the ink jet head cartridge 601 having the ejection port.
The ink suction means 615 suctions the ink that has accumulated in the cap member 614 due to idle ejection from the inkjet head cartridge 601. By the ink suction means 615, the inkjet head cartridge 601 is opened through an opening (not shown) in the cap.
Suction recovery is performed. The cleaning blade 617 for wiping the ejection opening surface of the inkjet head cartridge 601 is provided so as to be movable in the front-rear direction (direction orthogonal to the moving direction of the carriage 607) by the moving member 618. These cleaning blades 61
7 and the moving member 618 are supported by the main body support 619. The cleaning blade 617 is not limited to this form and may be another known cleaning blade.

In the suction recovery operation of the liquid discharge head, the lever 620 for starting suction moves along with the movement of the cam 621 that engages with the carriage 607,
The drive force from the drive motor 602 is movement-controlled by a known transmission means such as clutch switching. An inkjet recording control unit that gives a signal to a heating element provided in the liquid ejection head of the inkjet head cartridge 601 and controls the drive of each mechanism described above is provided on the apparatus main body side. Not shown.

In the ink jet recording apparatus 600 having the above structure, the ink jet head cartridge 601 reciprocates over the entire width of the recording material P with respect to the recording material P conveyed on the platen roller 609 by the recording material conveying means (not shown). Record while moving.

[0123]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. Ink components mean “parts by weight” unless otherwise specified. (Preparation of Ink) Each component shown in the following ink composition 1 and each coloring material shown in the following Table 1 (one kind or a combination of two or more kinds) were used, and ion-exchanged water was added to these to make 100 parts in total. Were mixed and subjected to pressure filtration with a 0.20 μm filter to obtain each ink.

Ink composition 1 Glycerin 5.0 parts Urea 5.0 parts Diethylene glycol 10.0 parts Acetylenol EH (Kawaken Fine Chemicals Co., Ltd.) 0.7 parts Ethanol 5.0 parts Coloring material Ion-exchanged water balance (Total 100 copies) (Image sample preparation method) Using the above ink, printing was performed using an on-demand type ink jet printer using a heating element as an energy source for ink ejection as an ink jet recording apparatus. (1) Remaining reflection density, ΔE A printer was filled with each ink of C1 to Bk2 shown in Table 1, and a solid portion with reflection density of 1.0 of each color was printed on glossy paper (PR-101; made by Canon). After that, the printed matter was naturally dried for 24 hours, and a light resistance test was performed with a xenon fade meter Ci3000 (manufactured by Atlas Co.) on the glass cover. Illuminance 63klux, irradiation time 100
It was time. Other lamps, filters, temperature inside the soda,
Humidity was based on the conditions of sunlight through ISO10977 indoor windows (internal temperature 25 ° C, relative humidity 55%). The illuminance is 6klux according to the ISO standard, but if a test of 6000klux · hr or more is performed, the test time will be long, so
It was performed at 63 klux for 100 hours, and it was confirmed that there was no reciprocity at the same irradiation amount.

The reflection density of the solid part of the printed matter before and after the test,
X-Rite 93 reflection densitometer for color coordinates L *, a *, b *
8 (trade name: manufactured by X-Rite), and the reflection density residual rate and the photobleaching property ΔE were calculated according to the above-mentioned formula 1.
The results are shown in Table 1.

[0126]

[Table 1] Note that LC, LM, and LY in Table 1 above represent light-colored cyan, magenta, and yellow inks, respectively.

(2) A color balance printer is prepared with a predetermined combination of ink sets shown in Table 2 below, and each ink set is filled with ink and the glossy paper (PR -101; manufactured by Canon Inc.), a full-color image was printed using each filled ink. After printing, it was naturally dried for 24 hours and the above light resistance test was conducted. The color balance of the printed matter after the test was visually evaluated.

[0128]

[Table 2] Evaluation results In each of Examples 1 to 4, the color balance was not lost even after the light resistance test, and the images were clear. In Comparative Example 1, the yellow ink portion was discolored, and in Comparative Example 2, the Bk ink portion was discolored and the color balance was lost. Comparative Example 3
The area where light yellow or light cyan ink was used was greatly discolored, and the Bk ink area was discolored, resulting in a loss of color balance and a significant change in image quality. In Comparative Example 4, the residual density of reflection density in the cyan and magenta ink portions was low, and the image quality of the entire image was deteriorated.

[0129]

As described above, according to the present invention,
It is possible to provide a color image in which the color balance is not lost even when exposed for a long period of time and good image quality can be maintained.

[Brief description of drawings]

FIG. 1 is a vertical sectional view showing an embodiment of a head of an inkjet recording apparatus.

FIG. 2 is a sectional view taken along the line AB of FIG.

FIG. 3 is a schematic explanatory diagram of a multi-head.

FIG. 4 is a schematic perspective view showing an embodiment of an inkjet recording apparatus.

FIG. 5 is a vertical sectional view showing an embodiment of an ink cartridge.

FIG. 6 is a perspective view showing an example of a recording unit.

FIG. 7 is a schematic perspective view showing a main part of an example of an inkjet printer that can mount a liquid ejection head.

FIG. 8 is a schematic perspective view showing an example of an inkjet cartridge including a liquid ejection head.

FIG. 9 is a schematic perspective view schematically showing a main part of an example of a liquid ejection head.

FIG. 10 is a conceptual diagram in which a part of an example of a liquid ejection head is extracted.

11 is an enlarged view of a portion of a discharge port shown in FIG.

FIG. 12 is a schematic diagram showing an ink adhering state at a portion of the ejection port shown in FIG.

FIG. 13 is a schematic diagram of a main part in FIG.

FIG. 14 is a schematic cross-sectional view corresponding to the cross-sectional shape taken along the line XX in FIG. 13 and for explaining the liquid discharge operation of the liquid discharge head with time along with FIGS. 15 to 21.

FIG. 15 is a schematic cross-sectional view corresponding to the cross-sectional shape taken along the line XX in FIG. 13 and for explaining the liquid discharge operation of the liquid discharge head with time, together with FIGS. 14 and 16 to 21.

FIG. 16 is a schematic cross-sectional view corresponding to the cross-sectional shape taken along the line XX in FIG. 13 and for explaining the liquid discharge operation of the liquid discharge head with time along with FIGS. 14, 15 and 17 to 21. is there.

FIG. 17 is a schematic cross-sectional view corresponding to the cross-sectional shape taken along the line XX in FIG. 13 and for explaining the liquid discharge operation of the liquid discharge head with time along with FIGS. 14 to 16 and FIGS. is there.

FIG. 18 is a schematic cross-sectional view corresponding to the cross-sectional shape taken along the line XX in FIG. 13 and for explaining the liquid discharge operation of the liquid discharge head with time along with FIGS. 14 to 17 and 19 to 21. is there.

FIG. 19 is a schematic cross-sectional view corresponding to the cross-sectional shape taken along the line XX in FIG. 13 and for explaining with time the liquid discharge operation of the liquid discharge head together with FIGS. 14 to 18, 20 and 21. is there.

20 is a schematic cross-sectional view corresponding to the cross-sectional shape taken along the line XX in FIG. 13 and for explaining the liquid discharge operation of the liquid discharge head with time along with FIGS. 14 to 19 and 21.

FIG. 21 is a schematic cross-sectional view corresponding to the cross-sectional shape taken along the line XX in FIG. 13 and for explaining the liquid discharge operation of the liquid discharge head with time along with FIGS. 14 to 20.

FIG. 22 is a diagram showing a configuration of an inkjet recording apparatus to which the present invention can be applied.

FIG. 23 is a schematic diagram showing another configuration example of an inkjet recording head.

FIG. 24 is a schematic view schematically showing a cross-sectional structure of an example of a recording medium used in the present invention.

[Explanation of symbols]

13 head 14 ink groove 15 heating head 16 protective films 17-1 and 17-2 electrode 18 heating resistor layer 19 heat storage layer 20 substrate 21 ink 22 ejection orifice (fine hole) 23 meniscus 24 ink droplet 25 recording material 26 multi Groove 27 Glass plate 28 Heat-generating head 40 Ink bag 42 Plug 44 Ink absorber 45 Ink cartridge 51 Paper feed unit 52 Paper feed roller 53 Paper discharge roller 61 Blade 62 Cap 63 Ink absorber 64 Ejection recovery unit 65 Recording head 66 Carriage 67 Guide Shaft 68 Motor 69 Belt 70 Recording unit 71 Head part 72 Atmosphere communication port 832 Discharge port 832a Raising part 832b Rough part 931 Electrothermal conversion element (heater, ink discharge energy generating element) 933 Ink supply port (opening part) 934 Substrate 935 Orifice Plate (vomit Mouth plate) 935a Discharge port surface 936 Ink flow channel wall 936a Partition wall 940 Discharge port section 1337 Foaming chamber 1338 Liquid flow path 1141 Groove 1141a Top 100 Ink jet recording head 101 Air bubble 102 Meniscus 1001 Liquid tank 1006 Moving drive unit 1008 Casing 1010 Recording unit 1010a Carriage member 1012 Cartridge 1012Y, M, C, B Inkjet cartridge 1016 Belt 1018 Motor 1020 Driving unit 1022a, 1022b Roller unit 1024a, 1024b Roller unit 1026 Recovery unit 1026a, 1026b Pulley 1028 Paper 1030 Transport device C Wet ink F _M Meniscus backward direction F _C Meniscus retreat direction opposite direction G Center of gravity I Ink I _a Main droplets (liquid, ink) I _b , I _c : Liquid (ink) I _d : Ink attached to the groove (ink in the groove) I _e : Ink remaining in the liquid flow path L: Line N ₁ from the liquid chamber (ink supply port) to the ejection port: Width dimension N _{2 of} foaming chamber: Length dimension of foaming chamber O: Center of ejection port P: Paper conveying direction R Belt rotation direction S: Direction substantially orthogonal to paper conveying direction w Partition wall width dimension

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] December 6, 2001 (2001.12.
6)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Correction content]

[Claims]

[Chemical 1] (In the general formula (I), R ₁ represents a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryl group, R ₂ and R ₄ are each independently a hydrogen atom or a substituted or unsubstituted aryl group. Represents an alkyl group, R ₃ is a hydrogen atom,
It represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group or a halogen atom. X ₁ represents a carboxyl group or a salt thereof, or a sulfonic acid group or a salt thereof. n represents 1 or 2. )

[Chemical 2] (In the general formula (II), Ar ₁ represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group, and Ar ₂ represents an acetyl group, a benzoyl group, 1, 3,
5-triazinyl group, SO ₂ -C ₆ H ₅ group or SO ₂ -C ₆
H ₄ represents any of -CH ₃ groups. M is a counter ion of a sulfonic acid group and represents any one of a hydrogen atom, an alkali metal, ammonium and organic ammonium. )

[Chemical 3] (In the general formula (III), Ar ₃ and Ar ₄ each independently represent a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group, and at least one of Ar ₃ and Ar ₄ is a carboxyl group. Or a salt thereof, or a substituent of a sulfonic acid group or a salt thereof, M is a counter ion of the sulfonic acid group, and a hydrogen atom, an alkali metal,
Represents either ammonium or organic ammonium.
R ₅ represents a 1,3,5-triazinediyl group. R ₆ and R ₇ independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aralkyl group, a substituted aralkyl group or an atomic group necessary for forming a perhydroxyazine ring together with N. , L represents a divalent organic linking group. )

[Chemical formula 22] (In the general formula (I), R ₁ is a substituted or unsubstituted
An alkoxy group, or a substituted or unsubstituted aryl group
And R ₂ and R ₄ are each independently a hydrogen atom or a substituted
Or an unsubstituted alkyl group, R ₃ is a hydrogen atom,
Substituted or unsubstituted alkyl group, substituted or unsubstituted
Alkoxy group, substituted or unsubstituted aryloxy
Represents a group or a halogen atom. X ₁ is a carboxyl group
Or its salt, or sulfonic acid group or its salt.
You n represents 1 or 2. )

[Chemical formula 23] (In the above general formula (II), Ar ₁ is a substituted or unsubstituted
A phenyl group, or a substituted or unsubstituted naphthyl group
Ar ₂ is an acetyl group, a benzoyl group, 1, 3,
5-triazinyl group, SO ₂ -C ₆ H ₅ group or SO ₂ -C ₆
H ₄ represents any of -CH ₃ groups. M is a sulfonic acid group
Counterion, hydrogen atom, alkali metal, ammonium
Or organic ammonium. )

[Chemical formula 24] (In the general formula (III), Ar ₃ and Ar ₄ are each independently
A substituted or unsubstituted phenyl group, or a substituted
Represents an unsubstituted naphthyl group, and a small amount of Ar ₃ and Ar ₄
At least one is a carboxyl group or its salt, or
It has a substituent of a rufonic acid group or a salt thereof. M is a sul
It is a counter ion of a phosphonic acid group, and is a hydrogen atom, an alkali metal,
Represents either ammonium or organic ammonium.
R ₅ represents a 1,3,5-triazinediyl group. R ₆ and
And R ₇ are independently a hydrogen atom, an alkyl group or a substituted alkyl group.
Group, alkenyl group, substituted alkenyl group, aralkyl
Groups, substituted aralkyl groups or N with perhydroxyazide
Represents a group of atoms required to form a ring, and L is a divalent
Represents a machine linking group. )

[Chemical 25] (In the general formula (I), R ₁ is a substituted or unsubstituted
An alkoxy group, or a substituted or unsubstituted aryl group
And R ₂ and R ₄ are each independently a hydrogen atom or a substituted
Or an unsubstituted alkyl group, R ₃ is a hydrogen atom,
Substituted or unsubstituted alkyl group, substituted or unsubstituted
Alkoxy group, substituted or unsubstituted aryloxy
Represents a group or a halogen atom. X ₁ is a carboxyl group
Or its salt, or sulfonic acid group or its salt.
You n represents 1 or 2. )

[Chemical formula 26] (In the above general formula (II), Ar ₁ is a substituted or unsubstituted
A phenyl group, or a substituted or unsubstituted naphthyl group
Ar ₂ is an acetyl group, a benzoyl group, 1, 3,
5-triazinyl group, SO ₂ -C ₆ H ₅ group or SO ₂ -C ₆
H ₄ represents any of -CH ₃ groups. M is a sulfonic acid group
Counterion, hydrogen atom, alkali metal, ammonium
Or organic ammonium. )

[Chemical 27] (In the general formula (III), Ar ₃ and Ar ₄ are each independently
A substituted or unsubstituted phenyl group, or a substituted
Represents an unsubstituted naphthyl group, and a small amount of Ar ₃ and Ar ₄
At least one is a carboxyl group or its salt, or
It has a substituent of a rufonic acid group or a salt thereof. M is a sul
It is a counter ion of a phosphonic acid group, and is a hydrogen atom, an alkali metal,
Represents either ammonium or organic ammonium.
R ₅ represents a 1,3,5-triazinediyl group. R ₆ and
And R ₇ are independently a hydrogen atom, an alkyl group or a substituted alkyl group.
Group, alkenyl group, substituted alkenyl group, aralkyl
Groups, substituted aralkyl groups or N with perhydroxyazide
Represents a group of atoms required to form a ring, and L is a divalent
Represents a machine linking group. )

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction content]

Other ink sets according to the present invention are less
At least cyan, magenta, and yellow inks are included.
In the ink set, each of the three types of ink is dyed.
And an aqueous medium, and obtained by the three inks
Sunlight through simulated indoor windows for more than 3 years for each image captured
Light in a light resistance test under conditions that cause fading corresponding to color
Regarding the fading property of each image in the CIELAB color space display system
The difference in ΔE is within 10 and the photobleaching property of each image is
The residual density of reflection density is 70% or more.
The ink is represented by the general formula (I) described below as a coloring material.
And a dye represented by the general formula (II) described later,
A dye represented by the general formula (III) and a xanthene structure.
At least one selected from the dyes
It is characterized by. The difference between ΔE here is
Including the case of 0. Further, by using the ink set having each of the above-mentioned configurations , an inkjet recording apparatus and its related parts for obtaining a recorded image capable of maintaining a color balance after long-term storage and maintaining good image quality, or various recordings such as an inkjet recording method. A method can be provided.

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0025

[Correction method] Change

[Correction content]

More specifically, one example of the recording medium used in the present invention will be described. A coloring material such as a dye or a pigment is adsorbed on the fine particles forming the porous structure in the ink receiving layer, and at least the adsorbed fine particles are adsorbed. It is a recording medium on which an image is formed, and is particularly suitable when an inkjet method is used. It is preferable that such a recording medium is a so-called absorption type in which the ink is absorbed by the voids formed in the ink receiving layer on the support. The absorption type ink receiving layer is mainly composed of fine particles and is constituted as a porous layer containing a binder and other additives as required. Examples of the fine particles include silica, clay, talc, calcium carbonate, kaolin, aluminum oxide such as alumina or alumina hydrate, diatomaceous earth, titanium oxide, hydrotalcite, zinc oxide and other inorganic pigments, urea formalin resin, ethylene resin. , An organic pigment such as a styrene resin, and one or more of these are used. Water-soluble polymers and latices can be cited as those preferably used as the binder. For example, polyvinyl alcohol or a modified product thereof, starch or a modified product thereof, gelatin or a modified product thereof, gum arabic, carboxymethyl cellulose, hydroxyethyl cellulose,
Cellulose derivatives such as hydroxypropylmethyl cellulose, SBR latex, NBR latex, methyl methacrylate-butadiene copolymer latex, functional group-modified polymer latex, vinyl-based copolymer latex such as ethylene vinyl acetate copolymer, polyvinylpyrrolidone, maleic anhydride. An acid or its copolymer, an acrylic acid ester copolymer, etc. are used, and if necessary, two or more kinds can be used in combination. In addition, additives can be used. For example, if necessary, a dispersant, a thickener, a pH adjuster, a lubricant, a fluidity modifier, a surfactant, an antifoaming agent, a release agent, a fluorescence enhancer. Whitening agents, UV absorbers, antioxidants, etc. are used.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction content]

R ₆ and R ₇ independently form a perhydroxyazine ring together with a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group or N. It represents a necessary atomic group, and L represents a divalent organic linking group. Regarding R ₆ and R ₇ , more specifically, for example, a straight chain having 1 to 6 carbon atoms
-Like or branched alkyl groups and straight chains with 1 to 4 carbon atoms
Jo or branched alkenyl group or a benzyl group, and the like. Here, examples of the substituent of the alkyl group, alkenyl group and benzyl group include a hydroxyl group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, and the like.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kumiko Mayune             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation (72) Inventor Tsuyoshi Sugae             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation (72) Inventor Yoshihisa Takizawa             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation F-term (reference) 2C056 EA13 FA03 FC01 FC02 HA20                       JC10 JC14 KC02 KC11 KC14                       KC16 KC21                 2H086 BA04 BA53 BA55 BA56 BA60                 4J039 BA29 BC03 BC06 BC16 BC19                       BC20 BC33 BC34 BC40 BC44                       BC50 BC52 BC53 BC54 BC61                       BC65 BC66 BC68 BC69 BC72                       BC73 BC74 BC77 BC79 EA15                       EA16 EA17 EA35 EA48 GA24

Claims (24)

[Claims] 1. An ink set using an ink containing a coloring material and an aqueous medium, which contains at least three or more kinds of color inks, and sunlight for three years or more for each image obtained by each ink through a pseudo indoor window. Regarding the photobleaching property in the light fastness test under the condition of fading corresponding to fading, the difference of ΔE of each image in the CIELAB color space display system is 1
An ink set which is 0 or less, and the photobleaching property of each image is 70% or more in terms of the reflection density residual rate. 2. An ink set using an ink containing a colorant and an aqueous medium, containing at least two or more kinds of color inks, and sunlight for 3 years or more for each image obtained by each ink through a pseudo indoor window. Regarding the photobleaching property in the light fastness test under the condition of fading corresponding to fading, the difference of ΔE of each image in the CIELAB color space display system is 1
An ink set characterized in that it is within 0 and the photobleaching property of each image is 80% or more in terms of the reflection density residual rate. 3. The ink set according to claim 1, wherein the light resistance test is a test with an irradiation amount of 6000 klux · hr or more assuming sunlight through an indoor window. 4. The ink set according to claim 1, wherein the light fastness test is a condition assuming sunlight through an indoor window conforming to the ISO standard. 5. The light resistance test, as a recording medium,
The ink set according to any one of claims 1 to 4, which is tested by an image using a special medium. 6. The ink set according to claim 1, wherein at least two inks having different color material concentrations and having the same color tone are included. 7. The ink set according to claim 1, which contains at least cyan, magenta, and yellow inks. 8. At least one color ink selected from cyan, magenta and yellow inks has different color material densities,
The ink set according to claim 7, which is composed of at least two types of ink having the same color tone. 9. The ink set according to claim 7, wherein the magenta ink contains at least one dye represented by the following general formula (I) as a coloring material. [Chemical 1] (In the general formula (I), R ₁ represents a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryl group, R ₂ and R ₄ are each independently a hydrogen atom or a substituted or unsubstituted aryl group. Represents an alkyl group, R ₃ is a hydrogen atom,
It represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group or a halogen atom. X ₁ represents a carboxyl group or a salt thereof, or a sulfonic acid group or a salt thereof. n represents 1 or 2. ) 10. A coloring material for magenta ink, further comprising:
10. At least one of the following general formula (II), the following general formula (III) and a dye having a xanthene structure is included.
Ink set described in. [Chemical 2] (In the general formula (II), Ar ₁ represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group, and Ar ₂ represents an acetyl group, a benzoyl group, 1, 3,
5-triazinyl group, SO ₂ -C ₆ H ₅ group or SO ₂ -C ₆
H ₄ represents any of -CH ₃ groups. M is a counter ion of a sulfonic acid group and represents any one of a hydrogen atom, an alkali metal, ammonium and organic ammonium. ) [Chemical 3] (In the general formula (III), Ar ₃ and Ar ₄ each independently represent a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group, and at least one of Ar ₃ and Ar ₄ is a carboxyl group. Or a salt thereof, or a substituent of a sulfonic acid group or a salt thereof, M is a counter ion of the sulfonic acid group, and a hydrogen atom, an alkali metal,
Represents either ammonium or organic ammonium.
R ₅ represents a 1,3,5-triazinediyl group. R ₆ and R ₇ independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aralkyl group, a substituted aralkyl group or an atomic group necessary for forming a perhydroxyazine ring together with N. , L represents a divalent organic linking group. ) 11. The ink set according to claim 7, wherein the cyan ink contains at least one dye having a copper phthalocyanine structure as a coloring material. 12. Cyan ink is used as a coloring material in Direct B
The ink set according to claim 11, which includes lue 199. 13. A yellow ink is used as a color material for Direct ink.
The ink set according to claim 7, which contains Yellow 132. 14. A magenta ink comprising a dye represented by the general formula (I) as a coloring material and at least one selected from the general formula (II), the general formula (III) and a dye having a xanthene structure. The ink set according to claim 7, wherein the cyan ink includes Direct Blue 199 as a coloring material, and the yellow ink includes Direct Yellow 132 as a coloring material. 15. The ink set according to claim 1, wherein the ink is used for ink jet recording. 16. In an ink jet recording method for recording on a recording material by ejecting ink from an orifice according to a recording signal, the ink is an ink constituting the ink set according to claim 15. Characteristic inkjet recording method. 17. The ink jet recording method according to claim 16, wherein thermal energy is applied to the ink to eject the ink. 18. A recording unit comprising an ink containing section containing ink and a head section for ejecting the ink, wherein the ink containing section contains a part containing each of the inks constituting the ink set. A recording unit, comprising: the ink set according to claim 15. 19. The head unit includes a head for ejecting the ink by applying thermal energy to the ink.
The recording unit according to 8. 20. An ink cartridge having an ink containing portion containing ink, wherein the ink cartridge has a portion containing each of the inks constituting the ink set, the ink set comprising: 1-1
An ink cartridge according to item 5. 21. An ink jet recording apparatus comprising a recording unit having an ink containing section containing ink and a head section for ejecting the ink, wherein each ink containing section constitutes an ink set. 16. The ink set according to claim 15, wherein the ink set has a portion containing
An ink jet recording apparatus comprising the ink set according to item 1. 22. The head portion is a head for ejecting ink by applying thermal energy to the ink.
1. The inkjet recording device according to 1. 23. A recording head for ejecting ink,
In an ink jet recording apparatus having an ink cartridge having an ink containing portion containing ink and an ink supply portion for supplying ink from the ink cartridge to a recording head, the ink containing portion constitutes an ink set. Has a part accommodating each of the
An ink jet recording apparatus, wherein the ink set is the ink set according to claim 15. 24. The ink jet recording apparatus according to claim 23, wherein the recording head is a head which applies thermal energy to ink to eject the ink.