JPH0872393A - Liquid composition, ink set, and method and device using the composition and set - Google Patents

Abstract

PURPOSE: To provide sufficient image density of good fixing properties and also good printing quality level and perform the ink jet recording of high uniformity of solid image by containing fine crushed cellulose in a liquid composition containing at least cationic substances. CONSTITUTION: When ink containing a dye is used for a liquid composition and the composition is mixed with ink on a position of permeating into a recording medium, in the first stage of reaction of cationic substances contained in the liquid composition, association is generated by the ionic mutual action of a low-molecular-weight substance, out of the cationic substances contained in the liquid composition and an anionic compound in ink, and a dye in ions is agglomerated instantaneously and separated from solution. In the second stage, an associated body of the anionic compound and the low-molecular-weight cationic substance is adsorbed by very fine crushed cellulose contained in the liquid composition, and the size of an agglomerate of dye formed by the association gets larger further to make it harder to permeate into spaces among fibers of recording paper. As a result, solid-liquid separation is performed, and the liquid section only is permeated into the recording paper.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a technique for reducing the so-called color bleeding (phenomenon) that occurs when a color image is formed on plain paper and obtaining an image having water resistance, and more particularly to ink jet recording. TECHNICAL FIELD The present invention relates to a liquid composition optimally used for image formation using a system, an ink set in which the liquid composition is combined, an image forming method using the same, and an image forming apparatus.

[0002]

2. Description of the Related Art An ink jet recording method is one in which a droplet of ink is ejected and the ink is adhered to a recording medium such as paper for recording. In particular, Japanese Patent Publication No. 61-59911, Japanese Patent Publication No. 61-59912, and Japanese Patent Publication No. 61-5.
According to the ink jet recording method of the type disclosed in Japanese Patent No. 9914, in which an electrothermal converter is used as the ejection energy supply means and thermal energy is applied to ink to generate bubbles, the droplets are ejected. High-density multi-orifice can be easily realized, and high-resolution and high-quality images can be recorded at high speed.

However, the ink used in the conventional ink jet recording method contains water as a main component and contains a water-soluble high-boiling point solvent such as glycol for the purpose of preventing drying and preventing nozzle clogging. Therefore, it is estimated that when recording on plain paper using such ink, sufficient fixability may not be obtained, or due to uneven distribution of fillers and sizing agents on the recording paper surface. This causes a problem such as the occurrence of a non-uniform image. or,
In particular, when trying to obtain a color image, the inks of a certain color are successively superposed before the ink of a certain color is fixed on the recording paper. There is a problem that they are not uniformly mixed (hereinafter, this phenomenon is called bleeding) and a satisfactory image cannot be obtained.

On the other hand, as a means for improving the fixing property, Japanese Patent Application Laid-Open No. 55-65269 discloses a method of adding a compound such as a surfactant which enhances the permeability to ink. Further, JP-A-55-66976 discloses the use of an ink mainly composed of a volatile solvent. However, although the former method of adding a surfactant or the like to the ink increases the permeability of the ink into the recording paper and improves the fixability and bleeding of the ink to some extent, the coloring material in the ink is Since it penetrates deeply, inconveniences such as a decrease in image density and saturation occur. In addition, the ink spreads in the horizontal direction, resulting in problems such as a decrease in edge sharpness and a decrease in resolution. On the other hand, in the case of the latter method using an ink mainly composed of a volatile solvent, in addition to the same inconvenience as in the former case, clogging occurs due to evaporation of the solvent in the nozzle portion of the recording head. It was easy to do and was not preferable.

Further, in order to improve the above-mentioned problems, there has been proposed a method of depositing a liquid for improving an image in advance on a recording medium before ejecting ink. For example, JP-A-63-299971 discloses an ink containing an anionic dye after a liquid containing an organic compound having two or more cationic groups per molecule is attached to a recording medium. The method of recording is disclosed in.
Further, JP-A-64-9279 discloses a method in which an acidic liquid containing succinic acid or the like is deposited on a recording medium and then recording is performed with an ink containing an anionic dye. Further, Japanese Patent Application Laid-Open No. 64-63185 discloses a method of applying a liquid insolubilizing a dye prior to ink recording.

However, in any of the above-mentioned methods, since the bleeding and the water resistance of the image are improved by precipitating the dye itself, the effect of suppressing the bleeding between the color inks described above is insufficient, and the precipitation Since the dyes are likely to be unevenly distributed on the recording paper, the coverage of the recording paper on the pulp fibers is poor and the uniformity of the image is deteriorated.

[0007]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to solve the following five problems in view of the above circumstances. That is, there are the following two points as problems in performing inkjet recording on plain paper. Print quality should be good while having good fixability. Sufficient image density is obtained and the solid image uniformity is high. In addition to the above-mentioned points, the following three points can be raised especially when forming a color image on plain paper. Prevent bleeding. Good color reproducibility and high-definition images can be obtained. Make the recorded image completely waterproof.

[0008]

The above object can be achieved by the present invention described below. That is, the present invention is a liquid composition containing at least a cationic substance, further containing finely pulverized cellulose, a liquid composition, an ink set combining the liquid composition, and these. The image forming method and the image forming apparatus are used.

[0009]

The function of the liquid composition containing the cationic substance of the present invention during image formation will be described with reference to FIG. For the sake of simplification of the description, the case of recording using a dye ink containing a water-soluble dye containing an anionic group will be described, but a pigment ink containing an anionic compound and a pigment is used. The same applies to the case of recording.

When the liquid composition according to the present invention is used together with an ink containing an anionic compound, for example, a dye as a coloring material, when mixed with the ink on the recording paper or at the position where it penetrates into the recording paper, As shown in FIG. 9C,
As the first step of the reaction, the low molecular weight component of the cationic substance contained in the liquid composition and the anionic compound in the ink associate with each other by an ionic interaction, so that the dye in the ink is It momentarily aggregates and separates from the solution phase.

Next, in the second step of the reaction, an association product of an anionic compound and a low molecular weight cationic substance is contained in the liquid composition (preferably having an average particle diameter of 5.0 μm).
Since it is adsorbed by finely pulverized cellulose (less than m), the size of the aggregate of dyes generated by the above-mentioned association is further increased (Fig. 9 (d)), and it is difficult to enter the gap between the fibers of the recording paper. . As a result, solid-liquid separation occurs, and only the liquid portion permeates into the recording paper (shown in FIG. 9 (e)), so that it is possible to improve print quality and fixability at the same time.

At the same time, the viscosity of the aggregate formed by the low molecular weight component of the cationic substance, the anionic dye and the finely ground cellulose, which is generated by the mechanism as described above, becomes large and moves with the movement of the liquid medium. Therefore, even when adjacent dots are formed of different color inks as in the conventional full-color image formation described above, they do not mix with each other and bleeding does not occur. Further, since the above-mentioned aggregate is essentially insoluble in water, the water resistance of the formed image is perfect. or,
It also has the effect of improving the light fastness of the image formed by the shielding effect of the finely pulverized cellulose.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Next, preferred embodiments of the present invention will be described to explain the present invention in more detail. First, a liquid composition containing a cationic substance will be described. The liquid composition of the present invention is a liquid composition containing at least a cationic substance, which is a cationic substance (preferably having a molecular weight of 1,000 or less) and (preferably an average particle size of 5.
(0 μm or less) finely pulverized cellulose is contained, and preferably, a cationic polymer having a molecular weight of 2,000 or more is further contained.

The ink set of the present invention is characterized by using the liquid composition of the present invention as described above, and it is preferable that at least an anionic property is used as a colored ink for recording used together with the liquid composition. An ink containing a dye containing a group or an ink containing at least an anionic compound and a pigment is used.

The action and effect of the liquid composition of the present invention are as described above, and together with the cationic substance contained in the liquid composition and the water-soluble dye or pigment having an anionic group contained in the ink. The anionic compound used first forms an aggregate by ionic interaction.
In addition, the formation reaction rate of this aggregate needs to be extremely high.

The constituent components of the liquid composition of the present invention will be described below. The cationic substance which is an essential component of the liquid composition of the present invention preferably has a molecular weight of 1,000.
Any of the following cationic substances can be preferably used, but in the present invention, a molecular weight of 1 is more preferable.
A low molecular weight cationic material of 00-700 is used. When the molecular weight is less than 100, the water resistance improving effect is small, and 1
If it is more than 000, and more preferably more than 700, the color developability tends to decrease depending on the type of dye, which is not so preferable.

Specific examples of such a cationic substance include primary, secondary and tertiary amine salt type compounds,
Specifically, lauryl amine, coconut amine, stearyl amine, rosin amine and the like hydrochlorides, acetates and the like; quaternary ammonium salt type compounds, specifically lauryl trimethyl ammonium chloride, lauryl benzyl trimethyl chloride, lauryl dimethyl benzyl ammonium chloride , Benzyltributylammonium chloride, benzalkonium chloride, etc .; Pyridinium salt-type compounds, specifically cetylpyridinium chloride, cetylpyridinium bromide, etc .; Imidazoline-type cationic compounds, specifically 2-heptadecenyl-hydroxyethylimidazoline, etc .; Examples thereof include ethylene oxide adducts of alkyl amines, specifically dihydroxyethyl stearyl amine.

Further, in the present invention, in this case, an amphoteric surfactant exhibiting a cationic property in a certain pH range can also be used. More specifically, an amino acid type amphoteric surfactant; an R—NH—CH ₂ —CH ₂ —COOH type compound;
Betaine type compounds, specifically, stearyl dimethyl betaine, carboxylic acid salt type amphoteric surfactants such as lauryl dihydroxyethyl betaine, as well as sulfate ester type, sulfonic acid type, phosphate ester type amphoteric surfactants, etc. Can be mentioned. Of course, when these amphoteric surfactants are used, the liquid composition is adjusted so as to have a pH below their isoelectric point, or below the isoelectric point when mixed with ink on the recording medium. It is necessary to take any method of adjusting the pH so that Although examples of the low molecular weight cationic compound have been described above, it goes without saying that the compounds that can be used in the present invention are not necessarily limited to these.

Next, finely pulverized cellulose which is another essential component of the liquid composition of the present invention (preferably having an average particle size of 5.0 μm or less) will be described. The action and effect of the finely pulverized cellulose in the present invention are as described above, the second reaction of the liquid composition and the ink.
As a step, an aggregate consisting of the dye having an anionic group obtained in the first step and a low molecular weight cationic substance was adsorbed in the molecule, and the size of the aggregate of the dye formed by the association was further increased and recorded. By making it difficult for the colorant in the ink to remain on the recording paper by making it difficult for it to enter the gaps between the fibers of the paper, and allowing only the liquid portion that has been solid-liquid separated to soak into the recording paper, both print quality and fixability are achieved. To achieve.

The finely pulverized cellulose having the above-mentioned effects is obtained by further pulverizing crystalline cellulose obtained by drying plant fibers and processing it into fine particles or fine crystals. The preferable particle size of the finely pulverized cellulose used is preferably 5.0 μm or less in average particle size measured by a laser scattering method.
When it is larger than 5.0 μm, sticking easily occurs in the vicinity of the nozzle of the inkjet recording head, which is not preferable.

In order to further improve the effect of the present invention,
In addition to the finely pulverized cellulose described above in the present invention, a cationic polymer having a molecular weight of 2,000 or more may be used together. Examples of the cationic polymer used in this case include, but are not limited to, polyallylamine hydrochloride, polyaminesulfone hydrochloride, polyvinylamine hydrochloride and chitosan acetate. Further, it is not limited to the above-mentioned hydrochloride type and acetate type.

In the present invention, a compound obtained by cationizing a part of a nonionic polymer may be used as the above cationic polymer. Specific examples thereof include a copolymer of vinylpyrrolidone and a quaternary salt of aminoalkyl alkylate, and a copolymer of a quaternary salt of acrylamide and aminomethylacrylic amide. Of course, it goes without saying that it is not limited to these compounds. The molecular weight described in the present invention refers to the weight average molecular weight in terms of polyethylene oxide determined by GPC unless otherwise specified.

As the amount of these components contained in the liquid composition of the present invention, the total content of the cationic substance and the finely ground cellulose is preferably 0.05 to 20% by weight. The range is more preferably 0.5 to 5% by weight, but it is necessary to determine the optimum range depending on the combination of substances used. The mixing ratio of the cationic substance and the finely pulverized cellulose in the liquid composition is 10: 1 to 1:10 by weight, preferably 5: 1.
Is in the range of to 1: 5. If this ratio exceeds 10: 1, the water resistance of the printed matter tends to decrease, and conversely, if it is 1:10 or less, the suppression of bleeding is insufficient and the edge sharpness of the image tends to decrease, such being undesirable.

Next, other components constituting the liquid composition will be specifically described. The liquid composition according to the present invention usually comprises water, a water-soluble organic solvent and other additives in addition to the above-mentioned cationic substance and finely ground cellulose. Examples of the water-soluble organic solvent used in the present invention include amides such as dimethylformamide and dimethylacetamide, ketones such as acetone, ethers such as tetrahydrofuran and dioxane, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, and ethylene. Glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2,6
Alkylene glycols such as hexanetriol, thiodiglycol, hexylene glycol and diethylene glycol, lower alkyl ethers of polyhydric alcohols such as ethylene glycol methyl ether, diethylene glycol monomethyl ether and triethylene glycol monomethyl ether, ethanol, isopropyl alcohol, n -Monohydric alcohols such as butyl alcohol and isobutyl alcohol, glycerin and N-methyl-2-
Pyrrolidone, 1,3-dimethyl-imidazolidinone, triethanolamine, sulfolane, dimethylsulfoxide and the like are used. The content of the water-soluble organic solvent is not particularly limited, but 5 to 60% by weight of the total weight of the liquid,
More preferably, 5 to 40% by weight is a suitable range.

Further, the liquid composition of the present invention further comprises:
If necessary, additives such as a viscosity adjusting agent, a pH adjusting agent, a preservative, various surfactants, an antioxidant and an evaporation accelerator may be appropriately mixed. The selection of the surfactant is particularly important in adjusting the permeability of the liquid into the recording medium.

The liquid composition of the present invention is more preferably colorless, but may be a light color composition within a range that does not change the color tone of each color ink when mixed with ink on a recording medium. Further, as a suitable range of various physical properties of the liquid composition as described above, the pH is about 3 to 12, preferably 3 to 8, more preferably 3 to 5 and the surface tension is about 1 at about 25 ° C.
0 to 60 dyn / cm, more preferably 10 to 40 dy
n / cm, and the viscosity is 1 to 30 cps. It is what As will be described later, the surface tension of the liquid composition of the present invention is preferably lower than the surface tension of the ink used with the liquid composition.

Next, the ink constituting the ink set of the present invention will be described. The ink used in the present invention is
When a water-soluble dye containing an anionic group is used as the coloring material, or when a pigment is used as the coloring material, it is preferable to use a material in which an anionic compound is used in combination. The above-mentioned ink used in the present invention further includes water,
A water-soluble organic solvent and other components, for example, a viscosity adjusting agent, a pH adjusting agent, a preservative, a surfactant, an antioxidant and the like are contained as necessary.

The water-soluble dye containing an anionic group used in the present invention includes a color index (COLO).
There is no particular limitation as long as it is a water-soluble acid dye, direct dye or reactive dye described in UR INDEX).
Further, even those not described in the color index are not particularly limited as long as they have an anionic group such as a sulfone group and a carboxyl group. Of course, the water-soluble dyes referred to herein include those whose solubility is pH-dependent.

As the water-soluble organic solvent contained in the ink containing the water-soluble dye as the coloring material as described above,
The water-soluble organic solvent used in the liquid composition described above can be similarly used. The same applies to the preferable range of the content of these water-soluble organic solvents in the ink.
Further, the preferable physical property range of the ink is exactly the same as that of the liquid composition. However, regarding the surface tension of the ink, it is preferable that the surface tension of the ink is higher than the surface tension of the liquid composition of the present invention, because it may be effective in carrying out the image forming method of the present invention. this is,
By adjusting the surface tensions of the both in this manner, for example, in the printing process, the liquid composition ejected first exerts an effect that the wettability of the ink ejected later can be made uniform on the recording medium. However, the details are not clear.

When a pigment is used as the coloring material of the ink used in the present invention, the amount of the pigment is 1 to 20% by weight, preferably 2 to 12% by weight based on the total weight of the ink. Used in the range. Specific examples of the pigment used in the present invention include carbon black used as a black ink. For example, carbon black produced by a furnace method or a channel method may be used. Diameter is 15 to 40 mμ, specific surface area by BET method is 50 to 300 m ² / g, DBP oil absorption is 40 to 1
Those having characteristics such as 50 ml / 100 g, volatile content of 0.5 to 10%, and pH value of 2 to 9 are preferably used.
Examples of commercially available products having such characteristics include No.
2300, No. 900, MCF88, No. 33, N
o. 40, No. 45, No. 52, MA7, MA8,
No. 2200B (above, Mitsubishi Kasei), RAVEN1
255 (above, made in Colombia), REGAL400R,
REGAL330R, REGAL660R, MOGUL
L (made by Cabot), ColorBlack F
WI, COLOR Black FW18, Color
Black S170, Color Black S
150, Printex 35, Printex U
(Above, manufactured by Degussa) and the like, and any of them can be preferably used.

As the pigment used for the yellow ink, for example, C.I. I. Pigment Yellow
w 1, C.I. I. Pigment Yellow 2,
C. I. Pigment Yellow 3, C.I. I.
Pigment Yellow 13, C.I. I. Pig
ment Yellow 16, C.I. I. Pigmen
Examples of pigments used in magenta ink include C.I. I. Pig
ment Red 5, C.I. I. Pigment Re
d 7, C.I. I. Pigment Red 12, C.I.
I. Pigment Red 48 (Ca), C.I. I.
Pigment Red 48 (Mn), C.I. I. Pi
gment Red 57 (Ca), C.I. I. Pigm
entRed 112, C.I. I. Pigment Re
d122 and the like. Examples of the pigment used for the cyan ink include C.I. I. Pigment Bl
ue 1, C.I. I. Pigment Blue 2,
C. I. Pigment Blue 3, C.I. I. Pig
ment Blue 15: 3, C.I. I. Pigmen
t Blue 16, C.I. I. Pigment Blu
e 22, C.I. I. Vat Blue 4, C.I. I. V
Examples thereof include at Blue 6 and the like, but the present invention is not limited thereto. In addition to the above, it is of course possible to use pigments newly produced for the present invention.

As the dispersant to be contained in the ink when a pigment is used, any water-soluble resin can be used, but the weight average molecular weight thereof is 1,00.
The range of 0 to 30,000 is preferable, and the range of 3,000 to 15,000 is more preferably used. Specific examples of such a dispersant include styrene, styrene derivatives, vinylnaphthalene, vinylnaphthalene derivatives, α, β-ethylenically unsaturated carboxylic acid aliphatic alcohol esters, acrylic acid, acrylic acid derivatives, and maleic acid. , Maleic acid derivative, itaconic acid, itaconic acid derivative, fumaric acid, fumaric acid derivative, vinyl acetate, vinylpyrrolidone, acrylamide,
And a block copolymer composed of at least two or more monomers (at least one of which is a hydrophilic monomer) selected from derivatives thereof, a random copolymer, a graft copolymer, or a copolymer thereof. Salt etc. are mentioned. Alternatively,
Natural resins such as rosin, shellac and starch can also be preferably used. These resins are alkali-soluble resins that are soluble in an aqueous solution in which a base is dissolved.
The water-soluble resin used as the pigment dispersant is preferably contained in the range of 0.1 to 5% by weight based on the total weight of the ink.

Particularly in the case of an ink containing the above-mentioned pigment, it is preferable that the entire ink is adjusted to be neutral or alkaline. This is preferable because the solubility of the water-soluble resin used as the pigment dispersant can be improved and the ink can be further excellent in long-term storage stability. However, in this case, it may cause corrosion of various members used in the inkjet recording apparatus. Therefore, it is preferable that the pH range is 7 to 10. Examples of the pH adjusting agent used in this case include various organic amines such as diethanolamine and triethanolamine, inorganic alkali agents such as sodium hydroxide, lithium hydroxide, alkali metal hydroxides such as potassium hydroxide, and the like. Examples include organic acids and mineral acids. The water-soluble resin, which is a pigment and a dispersant as described above, is dispersed or dissolved in an aqueous liquid medium.

A suitable aqueous liquid medium in the ink containing the pigment used in the present invention is a mixed solvent of water and a water-soluble organic solvent, and the water is not ordinary water containing various ions, It is preferable to use ion-exchanged water (deionized water).

The water-soluble organic solvent used by mixing with water includes, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol and the like. Alkyl alcohols having 1 to 4 carbon atoms; amides such as dimethylformamide and dimethylacetamide; ketones or keto alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; polyalkylenes such as polyethylene glycol and polypropylene glycol Glycols; ethylene glycol, propylene glycol, butylene glycol, triethylene glycol,
1,2,6-hexanetriol, thiodiglycol,
Alkylene glycols in which the alkylene group such as hexylene glycol and diethylene glycol contains 2 to 6 carbon atoms; glycerin; ethylene glycol monomethyl (or ethyl) ether, diethylene glycol methyl (or ethyl) ether, triethylene glycol monomethyl (or ethyl) Lower alkyl ethers of polyhydric alcohols such as ethers; N-methyl-2-pyrrolidone,
2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like can be mentioned. Among these many water-soluble organic solvents, polyhydric alcohols such as diethylene glycol and lower alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl (or ethyl) ether are preferable.

The content of the water-soluble organic solvent as described above in the ink is generally in the range of 3 to 50% by weight, preferably 3 to 40% by weight based on the total weight of the ink.
Also, the content of water used is 1 of the total weight of the ink.
The range is 0 to 90% by weight, preferably 30 to 80% by weight.

Further, the ink containing the pigment used in the present invention contains, in addition to the above-mentioned components, a surfactant, a defoaming agent, and a defoaming agent in order to obtain an ink having desired physical properties, if necessary. Preservatives and the like can be added as appropriate. In addition to the above pigments, water-soluble dyes such as those described above can be added as appropriate as a coloring material. Similarly to the above, when an ink containing a pigment is used, it is preferable that the surface tension of the ink is larger than the surface tension of the liquid composition of the present invention. It is preferable to adjust the surface tension of the ink in such a manner.

As a method for producing an ink containing a pigment as described above, first, the pigment is added to an aqueous medium containing at least a water-soluble resin as a dispersant and water,
After stirring, dispersion is carried out using a dispersion means described later, and if necessary, centrifugal separation is carried out to obtain a desired dispersion liquid. Next, a sizing agent and appropriately selected additive components such as those mentioned above are added to this dispersion, and the mixture is stirred to obtain the ink used in the present invention.

When the above-mentioned alkali-soluble resin is used as the dispersant, it is necessary to add a base in order to dissolve the resin. Organic amines such as ethanolamine, diethanolamine, triethanolamine, amine methyl propanol and ammonia, or inorganic bases such as potassium hydroxide and sodium hydroxide are preferably used.

Further, in the method for producing an ink containing a pigment, it is effective to carry out premixing for 30 minutes or more before stirring and dispersing the aqueous medium containing the pigment. That is, such premixing operation is preferable because it improves wettability of the pigment surface and promotes adsorption of the dispersant on the pigment surface.

The disperser used in the dispersion treatment of the above-mentioned pigment may be any disperser generally used, and examples thereof include a ball mill, a roll mill and a sand mill. Among them, a high speed type sand mill is preferably used, and as such a thing, for example, a super mill, a sand grinder, a bead mill,
Examples thereof include agitator mill, grain mill, dyno mill, pearl mill, and cobol mill (all are trade names).

When an ink containing a pigment is used in an ink jet recording method, a pigment having an optimum particle size distribution is used due to the requirement of anti-clogging property, but it has a desired particle size distribution. As a method of obtaining a pigment,
Decrease the size of the crushing media of the disperser, increase the filling rate of the crushing media, lengthen the processing time, slow the discharge speed, classify with a filter or centrifuge after crushing, and these Methods such as a combination of the above methods can be mentioned.

In the present invention, when an ink containing a pigment is used, in addition to the various components described above in the ink, an anionic compound such as an anionic surfactant or an anionic polymer substance is used. Is preferably added. Especially when an anionic compound is not used as a dispersant, it is essential to add such an anionic substance. The addition amount at this time is from 0.05 to
It is 10% by weight, preferably 0.2 to 5% by weight. or,
It is also a preferred embodiment that the amphoteric surfactant is adjusted to a pH below its isoelectric point and contained. As an example of the anionic surfactant used at this time, generally used ones such as carboxylate type, sulfate type, sulfonate type and phosphate type can be preferably used. . Examples of the anionic polymer include alkali-soluble resins, specifically polysodium acrylate,
Alternatively, a polymer obtained by copolymerizing a part of a polymer with acrylic acid can be used, but the polymer is not limited thereto.

Next, the image forming method of the present invention will be described. In the image forming method of the present invention, the liquid composition as described above is adhered to the image forming area on the recording medium, or to the image forming area and its vicinity. And the step of ejecting ink containing a dye containing at least an anionic group, or ink containing at least an anionic compound and a pigment as droplets from an ejection orifice onto a recording medium according to a recording signal. (B) is included.
The image forming area in the present invention is an area to which ink dots are attached, and the vicinity of the image forming area is
It refers to an area outside the area where the ink dots are attached and separated by about 1 to 5 dots.

The image forming method of the present invention may be any method as long as the above-mentioned liquid composition of the present invention and the ink are in a state of coexisting on a recording medium or the like. Therefore, either the liquid composition or the ink is used. It does not matter whether is applied to the recording medium first. Further, when the liquid composition is first adhered to the recording medium, the time from adhering the liquid composition to the recording medium to adhering the ink onto the recording medium is not particularly limited. It is preferable to deposit the ink on the recording medium at substantially the same time or within a few seconds.

The recording medium used in the above-mentioned image forming method is not particularly limited, and conventionally used so-called plain paper such as copy paper and bond paper is preferably used. Of course, a coated paper specially prepared for ink jet recording and a transparent film for OHP are also suitably used. Further, it can be suitably used for general high-quality paper and glossy paper.

As a method of applying the liquid composition onto the recording medium, for example, a method of applying the liquid composition to the entire surface of the recording medium by a spray, a roller or the like can be considered, but more preferably, an image forming area to which the ink is attached, or It is preferable to carry out by an ink jet method capable of selectively and uniformly adhering the liquid composition only to the image forming area and the vicinity of the image forming area. At this time, various ink jet recording methods can be used, but a particularly preferable method is a method of ejecting droplets by using bubbles generated by thermal energy.

Next, the recording apparatus used in the present invention will be described. In the present invention, it is preferable to apply a recording signal to the recording ink of the recording head and eject the droplets by the generated thermal energy. The structure of the recording head, which is the main part of the apparatus, is shown in FIGS.

The head 13 is a heating head 15 having a glass, ceramic, or plastic plate having a groove 14 through which ink passes and a heating resistor used for heat-sensitive recording (thin film head is shown in the figure, but it is not limited to this. It is obtained by adhering and. The heating head 15 includes a protective film 16 formed of silicon oxide or the like, aluminum electrodes 17-1 and 17-2, a heating resistor layer 18 formed of nichrome or the like, a heat storage layer 19, and a substrate 20 having good heat dissipation such as alumina. Has become

The recording ink 21 reaches the ejection orifice 22 and forms a meniscus 23 by the pressure P. Here, when an electric signal is applied to the aluminum electrodes 17-1 and 17-2, the area indicated by n of the heating head 15 rapidly generates heat, and bubbles are generated in the ink 21 in contact therewith, and the pressure causes The meniscus 23 projects and becomes a small ink droplet 24 from the ejection orifice 22.
Fly towards. FIG. 3 shows a schematic view of a recording head in which a large number of nozzles shown in FIG. 1 are arranged. The recording head is made by closely adhering a glass plate or the like 27 having a large number of flow paths to a heating head 28 similar to that described in FIG.
1 is a sectional view of the head 13 along the ink flow path, and FIG. 2 is a sectional view taken along the line AB of FIG.

FIG. 4 shows an example of an ink jet recording apparatus incorporating the head. In FIG. 4, reference numeral 61 denotes a blade as a wiping member, one end of which is held by a blade holding member to be a fixed end, which is in the form of a wrench lever. The blade 61 is arranged at a position adjacent to the recording area by the recording head 65, and in the case of this example,
The recording head 65 is held in a protruding form in the moving path. Reference numeral 62 denotes a cap of the ejection port surface of the recording head 65, which is arranged at a home position adjacent to the blade 61, moves in a direction perpendicular to the moving direction of the recording head 65, and contacts the ink ejection port surface. It has a configuration for capping. Further, 63 is an ink absorber provided adjacent to the blade 61, and like the blade 61, is held in a form protruding in the movement path of the recording head 65. The blade 61, the cap 62 and the ink absorber 63 constitute an ejection recovery unit 64, and the blade 61 and the ink absorber 63 remove water, dust and the like from the ink 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 ejection ports are arranged, for recording, and 66 a recording head 65 mounted on the recording head for movement. It is a carriage for performing. The carriage 66 is slidably engaged with the guide shaft 67, and a part of the carriage 66 is connected (not shown) to a belt 69 driven by a motor-68. As a result, the carriage 66 can move along the guide shaft 67, and the recording head 65 can move the recording area and its adjacent area.

Reference numeral 51 denotes a feeding section for inserting a recording material,
52 is a feed roller driven by a motor (not shown). With these configurations, the recording material is fed to a position facing the ejection port surface of the recording head 65, and is discharged to a discharge portion provided with a discharge roller 53 as the recording progresses.

In the above structure, when the recording head 65 returns to the home position after recording is completed, 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 projected into the moving path. There is. As a result, the ejection port surface of the recording head 65 is wiped.
When the cap 62 comes into contact with the ejection port surface of the recording head 65 to perform capping, 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 the above wiping positions. As a result, the ejection opening surface of the recording head 65 is wiped even during this movement. The movement of the recording head 65 to the home position is performed not only at the end of recording or at the time of ejection recovery but also at the home position adjacent to the recording area at a predetermined interval while the recording head 65 moves in the recording area for recording. And the wiping is performed in accordance with this movement.

FIG. 5 is a diagram showing an example of an ink cartridge 45 in which ink is supplied to the head via an ink supply member, for example, a tube. Here, 40 is an ink containing portion 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.
An ink absorber 44 receives the waste ink. As the ink containing portion, the liquid contact surface with the ink is polyolefin,
Particularly, those formed of polyethylene are preferable.

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, and the one in which they are integrated as shown in FIG. 6 is also preferably used. .

In FIG. 6, reference numeral 70 denotes a recording unit in which an ink containing portion for containing ink, for example, an ink absorber is contained, and the ink in the ink absorber has a plurality of orifices. It is configured to be ejected as an ink droplet from the portion 71. As a material for the ink absorber, for example, polyurethane can be used. Reference numeral 72 is an atmosphere communication port for communicating the inside of the recording unit with the atmosphere. This recording unit 70 is shown in FIG.
The recording head is used instead of the recording head shown in FIG. Incidentally, in the recording apparatus used in the present invention, the ink jet recording apparatus in which thermal energy is applied to the ink to eject the ink droplets has been taken as an example above, but in addition to this, a piezo type ink jet recording apparatus using a piezoelectric element may also be used. Available as well.

When carrying out the recording method of the present invention, for example, a recording apparatus in which five recording heads shown in FIG. 3 are arranged on a carriage is used. FIG. 7 shows an example thereof. Recording heads 81, 82, 83, and 84 respectively eject yellow, magenta, cyan, and black recording inks. Reference numeral 85 is a head for ejecting a colorless liquid composition. The head is arranged in the above-described recording device and ejects recording ink of each color according to a recording signal. Further, the colorless liquid composition is, for example, previously attached to at least a portion where the recording inks of the respective colors are attached to the recording paper prior to that. FIG. 7 shows an example in which five recording heads are used, but the present invention is not limited to this,
As shown in FIG. 8, it is also preferable to perform the yellow, magenta, cyan, black, and colorless liquid compositions by one recording head in separate liquid flow paths. Of course, the heads may be arranged so that the recording order of the liquid composition and the ink is the reverse of the above order.

[0060]

EXAMPLES The present invention will be described more specifically by showing Examples and Comparative Examples below. In the text, "part" and "%" are based on weight unless otherwise specified. The particle size of the finely pulverized cellulose was measured by a laser scattering method.
Further, the molecular weight of the cationic substance is a polyethylene oxide-equivalent weight average molecular weight measured by GPC, and the weight average molecular weight of the dispersant of the pigment ink was measured by the GCP method using a styrene polymer as a standard.

Example 1 First, the following components were mixed and dissolved, and then pressure-filtered with a membrane filter (trade name: Fluoropore filter, manufactured by Sumitomo Electric Industries) having a pore size of 0.22 μm to obtain a pH of 4.8. The liquid composition A adjusted to the above was obtained. Components of liquid composition A -Benzyltri-n-butylammonium chloride (molecular weight: 311) 5.0 parts-Ceorus cream (average particle size 3.5 µm) [Asahi Kasei, microcrystalline cellulose, 10% slurry] 10. 0 parts-Diethylene glycol 10.0 parts-Ion-exchanged water 75.0 parts

(Preparation of Ink I) Next, the following components are mixed, and a membrane filter having a pore size of 0.22 μm (trade name: Fluoropore filter, manufactured by Sumitomo Electric Industries)
Under pressure, and the dyes containing the anionic group, the pH of which is adjusted to 4.8, are contained in the yellow, magenta, cyan, and black color inks Y1, M1, C1,
B1 was obtained. This Y1, M1, C1 and B1 is the ink I
And

Yellow ink Y1 · C. I. Direct Yellow 86 2 parts-Thiodiglycol 10 parts-Acetylenol EH 0.05 parts-Ion-exchanged water 87.95 parts

Magenta ink M1 · C. I. Acid Red 289 2.5 parts-Thiodiglycol 10 parts-Acetylenol EH 0.05 parts-Ion-exchanged water 87.45 parts

Cyan ink C1.C. I. Acid Blue 9 2.5 parts-Thiodiglycol 10 parts-Acetylenol EH 0.05 parts-Ion-exchanged water 87.45 parts

Black ink B1.C. I. Food Black 2 4.0 parts-Thiodiglycol 10 parts-Acetylenol EH 0.05 parts-Ion-exchanged water 85.95 parts

An ink set according to the present invention was constructed using the liquid composition A of this example and the ink I obtained as described above, and recording was carried out on PPC paper (manufactured by Canon Inc.).
As the inkjet recording apparatus used, a recording apparatus similar to that shown in FIG. 4 was used, and a color image was formed using the five recording heads shown in FIG. 7. At this time, the liquid composition A was first ejected and deposited on the recording paper, and then the ink I was deposited. The recording head used here is 3
The recording density was 60 dpi, and the driving condition was a driving frequency of 5 kHz. The ejection volume per dot uses heads of yellow, magenta, and cyan inks, and 40 pl for colorless liquid compositions,
For black ink, a head of 80 pl per dot was used. The recording conditions are the same throughout the examples and comparative examples when the ink containing the dye described below is used. Also, the environmental conditions during the print test are
Standardized to 25 ° C / 55% RH.

Example 2 An ink set of this example was prepared by using the combination of the liquid composition A used in Example 1 and the ink I containing a dye as a coloring material. First, the ink I was attached to a recording paper. Print recording was performed in the same manner as in Example 1 except that the liquid composition A was post-printed.

Example 3 In the same manner as the liquid composition A of Example 1, a liquid composition B of the present example comprising the following components was prepared. Ingredients of liquid composition B -Polyallylamine hydrochloride (PAA-HCI-3L, Nitto Boseki, molecular weight distribution peak = 10,000) 0.5 part-Theolas cream (average particle size 3.5 μm) [Asahi Kasei , Microcrystalline cellulose, 10% slurry] 10.0 parts-Laurylbenzyl trimethyl chloride (molecular weight: 353) 1.0 part-Diethylene glycol 10.0 parts-Ion-exchanged water 78.5 parts

An ink set according to the present invention was constructed using the liquid composition B of this example obtained as described above and the ink I containing the dye, and the same conditions as in Example 1 were used. Recording was performed on PPC paper (manufactured by Canon). At this time, the liquid composition B is first ejected and first adhered to the recording paper,
After that, the ink I was attached.

Example 4 An ink set of this example was prepared by using the combination of the liquid composition B used in Example 3 and the ink I containing a dye as a coloring material. First, the ink I was attached to a recording paper. Print recording was performed in the same manner as in Example 3 except that the liquid composition A was post-printed.

Example 5 As described below, yellow, magenta, cyan and black color inks Y2, M2, C2 and B2 respectively containing a pigment and an anionic compound were obtained. This Y2, M
Ink II was used as Nos. 2, C2 and B2, and the ink set of this example was configured with the liquid composition A used in Example 1. Using this ink set, recording was performed on PPC paper (manufactured by Canon). In this embodiment, the liquid composition A is first ejected and first applied on the recording paper, and then the ink II is used.
Was attached to print and record. The recording head used here had a recording density of 360 dpi, and the driving condition was a driving frequency of 5 kHz. The ejection volume per dot is 40 pl for the yellow, magenta and cyan inks, the liquid composition A, and 60 pl for the black ink.
I used the head. The recording conditions are the same throughout the examples when the ink containing the pigment described below is used. Also, the environmental condition during the print test is 25 ° C.
/ 55% RH is standardized.

(Preparation of Ink II) Black Ink B2 (Preparation of Pigment Dispersion) -Styrene-acrylic acid-ethyl acrylate copolymer (acid value 140, weight average molecular weight 5,000) 1.5 parts-Mono Ethanolamine 1.0 part ・ Diethylene glycol 5.0 parts ・ Ion-exchanged water 81.5 parts

The above ingredients are mixed and mixed in a water bath to 70
Warm to 0 ° C to completely dissolve the resin component. To this solution, 10 parts of a newly produced carbon black (MCF88, manufactured by Mitsubishi Kasei) and 1 part of isopropyl alcohol were added, and 3
After premixing for 0 minutes, dispersion treatment was performed under the following conditions. -Disperser: Sand grinder (Igarashi Machinery) -Grinding media: Zirconium beads, 1 mm diameter-Grinding media filling rate: 50% (volume ratio) -Grinding time: 3 hours Further, centrifugal separation treatment (12,000 rpm., 20 minutes) to remove coarse particles to obtain a dispersion liquid.

(Preparation of Ink) Using the above dispersion liquid,
Components having the following composition ratios were mixed to prepare an ink containing a pigment, which was designated as Black Ink B2. -Pigment dispersion 30.0 parts-Glycerin 10.0 parts-Ethylene glycol 5.0 parts-N-methylpyrrolidone 5.0 parts-Ethyl alcohol 2.0 parts-Ion-exchanged water 48.0 parts

Yellow Ink Y2 Pigment was contained in the same manner as in Black Ink B2 except that 10 parts of carbon black (MCF88, manufactured by Mitsubishi Kasei) used in the preparation of Black Ink B2 were replaced with Pigment Yellow 74. Yellow ink Y2 was prepared.

Magenta Ink M2 Pigment was contained in the same manner as in Black Ink B2 except that 10 parts of carbon black (MCF88, manufactured by Mitsubishi Kasei) used in the preparation of Black Ink B2 was replaced with Pigment Red 7. Magenta ink M2 was prepared.

Cyan Ink C2 Pigment was contained in the same manner as in Black Ink B2 except that 10 parts of carbon black (MCF88, manufactured by Mitsubishi Kasei) used in the preparation of Black Ink B2 was replaced with Pigment Blue 15. Cyan ink C2 was prepared.

Example 6 An ink set of this example was prepared by using the combination of the liquid composition A used in Example 1 and the ink II using a pigment as a coloring material. First, the ink II was attached to a recording paper. Print recording was performed in the same manner as in Example 1 except that the liquid composition A was post-printed.

Example 7 An ink set according to the present invention was constructed using the liquid composition B used in Example 3 and the ink II containing the pigment used in Example 5, and the ink set according to the present invention was used. Recording was performed on PPC paper (made by Canon) under the same conditions as in No. 3. In this example, the liquid composition B was first ejected and first applied on the recording paper, and then the ink II was applied to perform printing and recording.

Example 8 Using the liquid composition B used in Example 3 and the ink II containing the pigment used in Example 1, an ink set according to the present invention was constructed, and the ink set was used in Examples. Recording was performed on PPC paper (made by Canon Inc.) under the same conditions as in 1. In this example, the ink II was first applied onto the recording paper, and then the liquid composition B was post-printed to perform print recording.

Comparative Example 1 The same printing and evaluation as in Example 1 were carried out except that the liquid composition A used in Example 1 was not used.

[Evaluation] Examples 1 to 1 whose contents are summarized in Table 1
The recorded images obtained in Example 8 and Comparative Example 1 were evaluated by the following evaluation methods and evaluation criteria.

Table 1 Contents of Examples 1 to 8 and Comparative Example 1

1. Image density A solid image is formed using a liquid composition and black ink, and the reflection density after standing for 12 hours is measured by a reflection densitometer Macbeth R.
It was measured with D915 (manufactured by Macbeth). The evaluation criteria are as follows. ⊚: Reflection density is 1.30 or more O: Reflection density is 1.25 or more and less than 1.30 Δ: Reflection density is 1.15 or more and less than 1.25 ×; Reflection density is less than 1.15

2. Fixability After forming a red solid image using the liquid composition and the yellow ink and magenta ink, another white paper is superposed on the recorded image by its own weight, and the transfer of the image recorded on the back side of the paper disappears. The time until the occurrence of scumming was measured with the time at the end of recording as zero as a reference, and was used as a measure of fixing property. The evaluation criteria are as follows. ⊚: Fixability is less than 20 seconds ◯: Fixability is 20 seconds or more and less than 30 seconds Δ: Fixability is 30 seconds or more and less than 40 seconds ×; Fixability is 40 seconds or more

3. Character Quality Black alphanumeric characters were printed using the liquid composition and black ink and evaluated visually. When the feathering was hardly noticeable, it was marked with ⊚, when the feathering was slightly conspicuous but there was no practical problem, it was marked with ◯, and when it was lower than that, it was marked with x.

4. Bleeding Canon Color Bubble Jet Printer BJC-8
In the same printing mode as the 20J printing mode E (1 Pass, one-way printing), the liquid composition and the solid portions of the yellow, magenta, cyan, and black inks are printed adjacent to each other, and the bleeding at the boundary of each color is performed. The degree was visually observed. The case where bleeding hardly occurred was marked with ⊚, the case where bleeding occurred slightly but it was at a level where there was practically no problem was marked with ◯, and the other levels were marked with x.

5. Water resistance After printing solid images and alphanumeric characters of yellow, magenta, cyan and black inks and leaving them for 1 hour,
It was immersed in tap water having a water temperature of 20 ° C. for 10 seconds. Then, it was taken out from the water, a filter paper was lightly pressed to remove the water content on the surface of the recorded image, air-dried as it was, and the water resistance was visually evaluated. Of yellow, magenta, cyan and black,
The ink with the lowest water resistance was used as the water resistance evaluation result. The water resistance evaluation criteria are as follows. ⊚: The recording agent did not flow out into the blank area, and scumming was hardly seen. In addition, there is almost no blurring of alphanumeric characters. ◯: Although the recording material flowed out to the margin part slightly and the alphanumeric characters were slightly blurred, it was at a level where there was no practical problem. X: The recording agent flows out to the margin portion, and the background stain is remarkable. Also, the blurring of alphanumeric characters is terrible. The area where the liquid composition adheres to the recording medium in the above evaluation is the same area as the ink image forming area, and the printing duty is 10 for both the liquid composition and the ink.
It is 0%. Further, the printing direction is unidirectional.

Table 2 shows the evaluation results of the images obtained in Examples 1 to 8 and Comparative Example 1 with respect to the above evaluation items. As is clear from Table 2, in the examples,
While an image having good fixing property, character quality, image density, bleeding and water resistance was obtained, in Comparative Example 1,
Only low-density images with poor character quality were obtained, and the water resistance of the images was also poor.

Table 2 Evaluation results

Example 9 Using the liquid composition A used in Example 1 and the three colors of yellow, magenta and cyan in the ink I used in Example 1, a solid image was recorded at 100% duty. And a so-called process black was formed. All printed conditions were the same as in Example 1. At this time, the evaluation results of the image density, the fixability, the character quality, the water resistance and the bleeding at the boundary between the process black and other colors were all good, and the effect of the present invention was confirmed.

[0093]

As described above, according to the present invention, particularly in the case of performing color ink jet recording on plain paper, it is possible to obtain a high print quality and a sufficient image density while having a high-speed fixing property. Moreover, the uniformity of the solid image is also high, and a high-definition image with good color reproducibility can be obtained with bridging.
Moreover, an excellent ink jet recorded image can be provided in which the excellent image as described above completely satisfies the water resistance.

[Brief description of drawings]

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

FIG. 2 is a cross-sectional view of a head portion of an inkjet recording device.

FIG. 3 is an external perspective view of a head portion of the inkjet recording apparatus.

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

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

FIG. 6 is a perspective view of a recording unit.

FIG. 7 is a perspective view showing a recording unit in which a plurality of recording heads used in an embodiment of the present invention are arranged.

FIG. 8 is a perspective view of another recording head used in the present invention.

FIG. 9 is a conceptual diagram illustrating an image forming method according to the present invention.

[Explanation of Codes] 13: Head 14: Ink Grooves 15, 28: Heating Head 16: Protective Film 17: Aluminum Electrode 18: Heating Resistor Layer 19: Heat Storage Layer 20: Substrate 21: Ink 22: Discharge Orifice (Fine Hole) 23: Meniscus 24: Ink droplets 25: Recording material 26: Multi-groove 27: Glass plate 40: Ink bag 42: Rubber stopper 44: Ink absorber 45: Ink cartridge 51: Feed unit 52: Feed roller 52 : Ejection roller 61: Blade 62: Cap 63: Ink absorber 64: Ejection recovery section 65: Recording head 66: Carriage 67: Guide shaft 68: Motor 69: Belt 70: Recording unit 71: Head section 72: Atmosphere communication port

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location // C09D 11/00 PSZ

Claims (25)

[Claims] 1. A liquid composition containing at least a cationic substance, which further contains finely pulverized cellulose. 2. The liquid composition according to claim 1, which contains a cationic substance having a molecular weight of 1,000 or less. 3. The average particle size of finely pulverized cellulose is 5.0.
The liquid composition according to claim 1 or 2, which has a thickness of not more than μm. 4. The liquid composition according to claim 1, wherein the cationic substance and the finely ground cellulose are contained in a total amount of 0.05 to 20% by weight. 5. The liquid composition according to any one of claims 1 to 4, wherein the cationic substance and the finely ground cellulose are mixed together in a weight ratio of 10: 1 to 1:10. 6. The liquid composition according to claim 1, which further contains a cationic polymer. 7. The cationic polymer has a molecular weight of 2,000.
The liquid composition according to claim 6, which is 0 or more. 8. The liquid composition according to claim 1, further comprising water and a water-soluble organic solvent. 9. The liquid composition according to claim 1, wherein the cationic substance is a surfactant. 10. A liquid composition according to claim 1, and at least one ink selected from each color ink group consisting of yellow, magenta, cyan, black, red, blue and green. An ink set characterized by being combined. 11. An ink set comprising the liquid composition according to any one of claims 1 to 9 and three color inks of yellow, magenta and cyan in combination. 12. An ink set comprising the liquid composition according to claim 1 and four color inks of yellow, magenta, cyan and black in combination. 13. The ink set according to claim 10, wherein the ink contains an anionic compound. 14. The ink set according to claim 10, wherein the ink contains a water-soluble dye having an anionic group. 15. The ink set according to claim 10, wherein the ink contains a pigment and an anionic compound. 16. An ink jet recording system comprising a step (A) of adhering the liquid composition according to claim 1 to at least an image forming area of a recording medium, and an ink containing at least an anionic compound. An image forming method comprising: a step (B) of applying the recording medium to the recording medium. 17. The image forming method according to claim 16, wherein the inkjet recording method is an on-demand type inkjet recording method. 18. The image forming method according to claim 16, wherein the liquid composition is attached to a recording medium by an inkjet recording method. 19. The image forming method according to claim 16, wherein the inkjet recording method is an inkjet recording method in which thermal energy is applied to ink. 20. The image forming method according to claim 16, wherein step (A) is performed prior to step (B). 21. The image forming method according to claim 16, wherein the step (A) is performed after the step (B). 22. An image forming apparatus, comprising: the ink set storage section according to claim 10; and an inkjet recording unit. 23. A first recording unit having an accommodating portion of the liquid composition according to any one of claims 1 to 9 and an ejecting means thereof, an accommodating portion of an ink containing at least an anionic compound and the same. An image forming apparatus comprising: a second recording unit having an ejection unit. 24. The image forming apparatus according to claim 23, wherein the ejection unit is an inkjet recording unit. 25. The image forming apparatus according to claim 22, wherein the ink jet recording means is means for applying thermal energy to the ink to form ink droplets.