JP2003246135A - Treating liquid for forming image and method for forming image using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a treating liquid for forming an image in which the image having a high image density, a high quality can be obtained at a high speed on plain paper without feathering, without bleeding in a color boundary and without disorder in the image due to a drying fault of an ink and without bringing about a skin contamination or the like in an image recording system for forming the image on the paper or the like via an image formation and an intermediate transfer by an ink jet method and to provide a method for forming the image by using the same. <P>SOLUTION: The treating liquid for forming the image comprises a cationic high-molecular weight compound. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel image forming method, which comprises a first liquid capable of containing a colorant and a component which reacts with a component in the first liquid on an intermediate transfer member. An image forming method for improving image quality by transferring the mixture to a recording material after contact-mixing with a second liquid containing the same, and a treatment liquid used in the image forming method, and particularly, the image forming method. The present invention relates to an inkjet recording method in which the first liquid is discharged as droplets from a nozzle according to an image.

[0002]

2. Description of the Related Art In recent years, ink jet printers have become popular due to their advantages of low noise and low running cost, and color printers capable of printing on plain paper have been put on the market. Conventionally, dyes with high solubility have been mainly used as colorants in inks for office inkjet printers due to problems such as ink clogging, but posters that require water resistance and light resistance are created. Therefore, the use of inks containing a pigment as a colorant is also increasing.

Further, when a color image is printed on plain paper by an ink jet printer, in order to suppress bleeding at the color boundary such as a two-color overlapping portion, the ink penetrates by adding a surfactant or the like. The properties are being improved (see JP-A-55-65269). By increasing the penetrability of the ink, bleeding at the color boundary can be prevented, but on the other hand, by using an ink having a high penetrability, feathering is likely to occur in characters and fine lines.

Further, in order to prevent color boundary bleeding and feathering in black characters, it has been attempted to use ink having low penetrability only when printing black characters. Has a problem that the black ink has poor drying property and high-speed printing is difficult. That is, with the current technology, it is difficult to achieve both suppression of bleeding at color boundaries and prevention of feathering in characters and thin lines.

Therefore, in order to solve such a problem, a recording material on which a material for fixing a dye in an ink is coated in advance or an ink jet recording in which a surface is coated with a white pigment or a water-soluble polymer The recording material of JP-A-56-867
89, JP-A-55-144172, JP-A-55-81992, JP-A-52-53012, JP-A-56-89594, and the like. The image quality is remarkably improved by using a special paper suitable for these inkjet recordings.

However, even the special paper is compatible with the printer system, and it has not been possible to obtain a good image by any printer with a certain special paper, and it is costly to obtain the special paper. There is a problem including it. In addition, the special paper has a problem in that it has a thick coat layer, which makes it far from the feel of paper that is generally preferred.

In order to deal with a general recording material such as plain paper, JP-A-56-89595 discloses that a polymer solution of carboxymethyl cellulose, polyvinyl alcohol, polyvinyl acetate or the like is sprayed on the recording material in advance. Then, an ink jet recording method has been proposed in which ink is jetted onto the portion where the polymer solution is attached to print. However, with these polymer solutions, feathering could not be suppressed and the water resistance was not improved at all.

Further, Japanese Patent Laid-Open No. 5-96720 discloses that
An apparatus for forming an image using an inkjet recording head, for applying a water-absorbing resin particle that absorbs ink to a recording material and performing a recording method for forming an image with the ink on the water-absorbing resin particle. Means for applying the water-absorbent resin particles to the recording material, means for ejecting ink onto the water-absorbent resin particles applied to the recording material, and means for fixing the water-absorbent resin particles to the recording material. An image forming apparatus having the above has been proposed. However,
In this method, it takes time to absorb the ink, and border bleeding is likely to occur in high-speed printing. The water-absorbent resin particles tend to absorb moisture, and when they are stored in the apparatus or during storage, they become agglomerate, which makes it difficult to uniformly apply the water-absorbent resin powder to the recording material.

Further, after a pretreatment liquid for a recording material containing a compound insolubilizing a dye in the ink is adhered onto the recording material by an ink jet method, the ink is jetted to a portion of the recording material to which the pretreatment liquid is adhered. Inkjet recording methods for printing by printing are disclosed in JP-A-64-63185 and JP-A-8-
It is disclosed in Japanese Patent Publication No. 20159 or Japanese Patent Laid-Open Publication No. 8-20161. Both of these methods improve both color boundary bleeding and feathering to some extent.

However, in these methods, in order to stably discharge the pretreatment liquid, it is necessary to reduce the viscosity of the pretreatment liquid, so that the concentration of the compound that insolubilizes the dye must be reduced. In order to obtain a sufficient image quality improving effect with such a pretreatment liquid, it is necessary to apply a relatively large amount of the pretreatment liquid, and since a large amount of liquid containing water is applied to the recording material, Curling and cockling of the material were easy to occur. In particular, for green, blue, and red images, the amount of adhesion of the pretreatment liquid and ink at the two-color overlapping portion is large, not only cockling occurs, but also ink strike-through occurs, making double-sided printing difficult. There was also the problem of becoming.

Further, in JP-A-8-142500, a colorless liquid composition containing at least a silicone compound such as silicone oil and a cationic compound is applied to a recording medium, and then a recording containing an anionic component is carried out. An image forming method is disclosed in which ink is applied by an inkjet recording method.

However, the area where the silicone compound adheres has a very low ink permeability, so that the image area dries slowly, and when high-speed printing is performed by this image forming method,
In addition to low penetration, poor wettability to the recording medium causes coalescence of adjacent dots, causing white stripes in the solid image portion or the like along the main scanning direction of the head. Further, this colorless liquid composition has a problem that stable recording characteristics cannot be obtained because the silicone oil causes phase separation when stored for a long period of time.

Further, in JP-A-10-250216, in order to improve the permeability and wettability of the recording liquid, an image recording promoting liquid containing a compound insolubilizing a colorant and a predetermined surfactant is used as a recording material. There has been proposed a method of forming an image by applying a recording liquid as droplets to the recording material and then applying the recording liquid to the recording material. According to this method, the surfactant in the image recording promoting liquid improves the penetrability and wettability of the recording liquid with respect to the recording material, so that the drying property of the image is improved and high-speed recording is possible. However, since the amount of the component that insolubilizes the color material in the ink in the pretreatment liquid is small, the effect of preventing color boundary bleeding and feathering is insufficient, and further improvement has been demanded.

Further, JP-A-11-10856, JP-A-2000-44855, and JP-A-2000-637.
No. 19, etc. also discloses a pretreatment liquid formulation containing a water-soluble polyvalent metal salt up to a concentration of 35% by weight. However, all of the pretreatment liquids disclosed in these publications have the viscosity of 20 mPas because the pretreatment liquid is applied to the recording material by the on-demand ink jet method, as in the above publications. -It is presumed that those of less than sec are used. When a low-viscosity pretreatment liquid is used as described above, the effect of enhancing the image quality is weak, and a recording liquid containing polymer particles is used.
It was necessary to use a special recording liquid.

Further, in US Pat. Nos. 4,538,156 and 5,099,256, an ink image is formed on an intermediate transfer member by an ink jet recording method, and then the ink image is transferred from the intermediate transfer medium to the recording medium. A method called an intermediate transfer method has been proposed. In the intermediate transfer method described in these, the recording head can be arranged away from the recording paper, and the purpose can be achieved by preventing clogging of the nozzles of the recording head due to adhesion of paper dust, When ink droplets are applied onto the intermediate transfer body, they spread or flow unevenly on the intermediate transfer body, and in the case of color recording, uneven color mixing (color bleed) occurs, resulting in image distortion. It is difficult to prevent this, and the problem of improving the image quality has not been solved.

Further, Japanese Patent Laid-Open No. 62-92849 and the like disclose US Pat. Nos. 4,538,156 and 5099.
As a modification of the method described in the specification of No. 256, the ink droplets are once ejected onto a transfer medium to form an ink image, and then most of the water in the ink is evaporated on the intermediate transfer medium to concentrate the ink. There is disclosed a method of transferring the formed ink onto a recording medium such as paper. In this method, once a good image is formed on the intermediate transfer medium, an improvement effect for obtaining a good image quality on commonly used paper, so-called plain paper, is recognized. However, in these methods, since it takes time to concentrate the ink at room temperature, it is necessary to heat the intermediate transfer medium to accelerate the evaporation of the solvent in the ink, or the intermediate transfer medium having a non-absorptive surface cannot be used. Then, uneven mixing of different color ink (color bleed)
There is a problem that is likely to occur. Furthermore, if the wettability of the surface of the intermediate transfer member changes due to repeated use, the spread of ink droplets changes, which makes it difficult to keep the image quality constant.

Further, in Japanese Patent Laid-Open No. 5-200999, a layer of a polymeric water-absorbing agent such as an alkali metal salt of polyacrylic acid or a mesh layer having a small diameter is provided on the surface of an intermediate transfer member and applied to the intermediate transfer member. A device for absorbing the water component in the water-soluble ink and transferring the remaining component to a recording medium is disclosed. Such an apparatus is disclosed in Japanese Patent Laid-Open No. 62-62.
Although the occurrence of the color bleeding described in Japanese Patent No. 92849 can be reduced, ink components such as pigments and dyes are easily fixed to the holes of the small-diameter mesh and the polymeric water-absorbing agent, and repeated use causes intermediate transfer. It has been difficult to solve the problem that the water absorption of the body is lowered and the image is stained because the coloring material remains. Furthermore, a means for evaporating the liquid medium in the ink absorbed by the intermediate transfer member or for removing it by suction is necessary, and it has not been possible to sufficiently meet the demands for high-speed printing and energy saving.

Further, in the republished patent WO98 / 05504, the first liquid containing a material that reacts with the components in the ink is deposited on the intermediate transfer medium, and the first liquid deposited on the intermediate transfer medium. An inkjet recording method is disclosed in which after the recording medium is transferred to a recording material, a recording liquid that reacts with the first liquid is discharged onto the recording material to form an image. In this method, it is possible to reduce the amount of the first liquid adhering to the recording material and reduce curling and cockling of the paper used as the recording material. However, in order to achieve this method, the means for applying the recording liquid to the recording material according to the image is
A means for applying the first liquid to the intermediate transfer member of another system is required, and it is unavoidable that the image forming apparatus for carrying out this method becomes complicated and high in cost. When the liquid droplets of the recording liquid are discharged onto the recording material to form an image and then the first liquid deposited on the intermediate transfer medium is transferred to the recording material, the ink penetrates into the recording medium. Therefore, there is a drawback that it is difficult to obtain a sufficient effect for improving the image quality.
Further, even when an image is formed by using the recording liquid on the recording material after transferring the first liquid deposited on the intermediate transfer medium to the recording medium, the first liquid penetrates into the recording material. For,
Since the effect of improving the image quality is insufficient and the treatment liquid is essentially applied to the recording paper, it is necessary to add the amount of the treatment liquid that penetrates into the paper to apply it. Although the coating amount was smaller than that of No. 1, the problem that the coating amount was still large was not completely solved.

Further, in Japanese Patent Laid-Open No. 6-40025,
An inkjet recording method of ejecting an ink onto a surface of a transfer medium, and then obtaining an ink image on the recording medium. As an inkjet ink, a solvent, a pigment dispersed in a solvent, and / or a dissolved dye and / or a dispersion and / or The solvent is composed of a coloring material solid component composed of a dissolved resin, and the solvent is (a) an ink solvent penetrating component having a permeability to the transfer medium, and (b) an ink solvent non-penetrating component having no permeability to the transfer medium. Consists of ingredients, and
(1) a step of forming an ink image on a transfer medium, and (2)
A step of permeating an ink solvent permeation component from the ink image on the transfer medium into the transfer medium, and (3) an ink image comprising the solvent non-permeation component after permeation of the ink solvent permeation component, a pigment and / or a dye, and a resin. An inkjet recording method has been proposed, which comprises a step of transferring from the recording medium to a recording medium and (4) a step of removing the ink solvent permeating component from the transfer medium. In this publication, the permeation component contained in the ink permeates the transfer medium, whereby the solvent composition of the coloring material changes, and it becomes possible to control the physical properties (viscosity) suitable for transfer, and thus a good transfer image is obtained. Is going to be able to get.

However, this method utilizing the selective permeation phenomenon by the solvent species into the transfer medium has a large limitation in terms of material, and when the constitution illustrated, that is, when silicone rubber is used as the transfer medium, the ink is There is a drawback in that a liquid medium, such as a petroleum solvent, which has a problem in safety such as occurrence of fire and harmfulness to the human body must be used. Further, for repeated use, a means for removing the liquid medium that has penetrated into the intermediate transfer medium by drying, suction, etc. is required, which increases the cost of the device and the ink medium described above due to drying. Has a problem in that it evaporates into the air and pollutes the air in the environment where the image forming apparatus is used.

Further, in Japanese Patent Application Laid-Open No. 11-188858, droplets are jetted onto an intermediate transfer member in accordance with an image signal to form a visible image on the intermediate transfer member, and then the visible image is recorded. In a recording method of transferring onto a paper, a powder which can be dissolved or swelled by the droplets in advance on the entire surface of the intermediate transfer body, can increase the viscosity of the droplets, and can be peeled from the intermediate transfer body. A recording method has been proposed in which a layer is formed and then the droplets are jetted onto the powder to transfer the visible image formed on the intermediate transfer member to a recording paper.

However, as in Japanese Patent Laid-Open No. 5-96720, it takes a long time to absorb the ink by this method, and boundary bleeding is likely to occur in high-speed printing. The water-absorbent resin particles tend to absorb moisture, and when they are stored in the apparatus or during storage, they become agglomerate, which makes it difficult to uniformly apply the water-absorbent resin powder to the recording material. There was such a problem.

Further, in Japanese Patent Laid-Open No. 7-89067,
Disclosed is a method and apparatus for applying a surfactant to an intermediate transfer member, forming an image on the intermediate transfer member to which the surfactant has been applied by an inkjet recording method, and transferring the formed image to a recording material. ing. In this method, although the transfer efficiency of the ink to the recording material is improved, since the surfactant has no reactivity with the ink, the quality of the image formed on the intermediate transfer member is as described above. It was essentially the same as the conventional example, and color bleeding was likely to occur.

Further, in Japanese Patent Application Laid-Open No. 11-28862, a method of applying an ink thin film to an intermediate transfer member, printing a liquid for solidifying the ink thereon by ink jet recording, and transferring the unsolidified ink portion onto a recording paper is disclosed. Has been proposed.
This method applies ink to the entire surface of the intermediate transfer member,
There is a problem that the amount of unused ink increases and wasteful consumption of ink occurs.

Further, in Japanese Patent Application Laid-Open No. 10-58664, ink droplets are ejected by an ink ejecting means to form an image on an intermediate transfer body, and after the image is formed, the ink is conveyed by the intermediate transfer body. In an ink jet recording apparatus that is transferred to a recording material such as paper after being denatured by an action accompanied by a chemical reaction in a route, the intermediate transfer body is not affected by the ink without receiving external energy. An ink jet recording apparatus has been proposed which is characterized in that an ink is changed by a reaction to form an ink reactant that reduces the hydrophilicity of the ink and increases the transferability to a recording medium. An anion type ion exchange resin layer having cation exchangeability is provided on the intermediate transfer member, and an anionic dye having ammonium as a counter ion is used in the ink, and when the ink is applied to the intermediate transfer member, the ions in the dye are There is disclosed a device in which the hydrophilic property is changed to improve the transfer characteristics by exchanging.

Also in this apparatus, the ion exchange layer is fixed on the intermediate transfer member, and therefore, it is disclosed in JP-A-5-200999.
As in the case of the publication, it is necessary to regenerate the intermediate transfer member that has deteriorated due to repeated use. In addition, JP-A-5-20
A device according to Japanese Patent Publication No. 0999, JP-A-10-58664
In any of the devices according to the publication, the intermediate transfer member is heated in order to evaporate the water absorbed in the polymer water absorbent or the ion exchange resin and to maintain the ion exchange ability of the ion exchange resin. However, it was not suitable for high-speed printing because it required high power consumption.

As described above, various proposals have been made in order to perform high-quality recording on plain paper at high speed, but in reality, no sufficient solution has been proposed.

[0028]

SUMMARY OF THE INVENTION The present invention aims to solve the above-mentioned problems of the prior art. That is, an object of the present invention is an image forming treatment liquid capable of obtaining a high quality image at high speed on plain paper generally used as a recording material, with a high image density, and without feathering or color boundary blurring, And an image recording method using the same.

Another object of the present invention is to provide an image forming treatment liquid which does not cause image disturbance due to poor drying of ink even when printed on plain paper, and stain on the background due to offset, and the use thereof. An image recording method is provided.

Another object of the present invention is that it is suitable for double-sided printing because the ink does not penetrate deep into the paper even when printed on plain paper and the image density when viewed from the side opposite to the image printed surface is small. An image forming treatment liquid and an image recording method using the same.

Another object of the present invention is to prevent the deformation of the paper such as cockling and curling, which is caused by the absorption of the ink into the paper even when the printing is performed on the plain paper, and to record in the print recording apparatus. An object of the present invention is to provide an image forming treatment liquid capable of enhancing the reliability of conveyance of a medium and facilitating the handling of the obtained print recording material, and an image recording method using the same. Another object of the present invention is to provide an image recording method with a simple structure and low power consumption.

Another object of the present invention is to provide an image forming treatment liquid capable of high speed recording and an image recording method using the same. Another object of the present invention is to improve the water resistance of the image obtained on the final recording medium.

Further, another object of the present invention is to provide a highly reliable image forming treatment liquid in which the image quality does not deteriorate even after repeated recording, and an image recording method and apparatus using the same. That is.

[0034]

The present invention has been made to solve the above-mentioned problems of the present invention. That is, according to the present invention, firstly, an image forming treatment liquid containing a cationic polymer compound is provided.

Secondly, according to the present invention, there is provided the above-mentioned first image forming treatment liquid, wherein the cationic polymer compound is a dicyandiamide resin.

According to the present invention, thirdly, the cationic polymer compound is contained in an amount of 10 to 80% by weight, and the viscosity is 20 to.
There is provided the above-mentioned first or second image forming treatment liquid, which is characterized in that it is 10,000 mPas · sec.

According to the present invention, fourthly, there is provided the image forming treatment liquid according to any one of the above first to third, which contains 20 to 80% by weight of water and a water-soluble liquid compound. To be done.

Fifth, according to the present invention, the content of water is 0 to 40% by weight, and the content of the water-soluble liquid compound is 20 to 80% by weight. An image forming treatment liquid according to any one of the fourth to fourth aspects is provided.

Further, according to the present invention, sixthly, a surface tension of 40 m is contained, containing a surfactant and / or a wetting promoter.
There is provided the image forming treatment liquid according to any one of the first to fifth aspects, which is N / m or less.

Further, according to the present invention, seventhly, a step (A) of forming an image by applying a recording liquid containing at least a colorant to the intermediate transfer member as a droplet according to an image signal.
A step (B) of applying to the intermediate transfer member the image forming treatment liquid according to any one of the first to sixth aspects, which contains a component capable of reacting with at least one component in the recording liquid; Step (C) of contact-mixing the treatment liquid on the intermediate transfer member
And a step (D) of transferring the mixture onto a recording material.

[0041]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. As a result of earnest research, the present inventors have found that the above problems can be solved by transferring an image formed on an intermediate transfer member by an inkjet method onto a recording material.

That is, according to the present invention, a recording liquid containing a colorant is used to form an image on an intermediate transfer member by an ink jet method.
A treatment liquid containing a component that reacts with a component in the recording liquid is applied to an intermediate transfer member on which an image is formed, and the recording liquid and the treatment liquid are contact-mixed on the intermediate transfer member, and the mixture is recorded. The final image is formed by transferring to the material. When a cationic polymer compound is added to the treatment liquid and transferred to form an image, uniform image quality can be obtained regardless of the type and quality of the recording material.

Here, the reaction occurring between the components in the recording liquid and the components in the treatment liquid means all chemical reactions. Among them, the ionic reaction is preferable because the recording liquid and the treatment liquid are both liquid and the reaction proceeds rapidly.

Further, the step (B) is the step (A).
Prior to the step (C), the step (C) is included in the step (A), that is, the treatment liquid is previously applied onto the intermediate transfer member, and the recording liquid is applied thereto as droplets according to the image signal. By doing so, if the processing liquid and the recording liquid are both mixed and reacted, the overall process becomes simple. Further, when the recording liquid is applied as droplets, the recording liquid and the treatment liquid are mixed only on the intermediate transfer member, and the applying means and the like are not contaminated with the reaction product.

In the image forming method of the present invention, the reason why it is possible to obtain a high-quality image on plain paper, which is generally used as a recording material, at a high speed, with a high image density, and without feathering or color boundary bleeding It can be thought of as follows.

In the image forming method of the present invention, since the processing liquid contains a cationic polymer compound as a component capable of reacting with the material contained in the recording liquid, the recording liquid and the processing liquid are separated on the intermediate transfer member. When mixed, the compatibility with the recording liquid is high and the reaction occurs efficiently, and the viscosity of the mixed liquid becomes higher than the viscosity of the recording liquid (hereinafter referred to as thickening). For this reason, uneven spreading wetting (feathering) that reflects uneven unevenness resulting from the uneven mesh structure of plain paper after the mixed solution is transferred to plain paper is It is suppressed much more than in the case of.

Further, since the transfer method is used, no ridge of the recording liquid is formed when the recording liquid is directly jetted onto the recording material. This is also considered to be one of the reasons why feathering is suppressed. In addition, since the viscosity of the mixed solution increases,
Bleeding and color boundary bleeding are also suppressed.

In the present invention, by making the concentration of the cationic polymer compound contained in the treatment liquid as high as 10 to 80% by weight, the dispersibility or solubility of the coloring material in the recording liquid is lowered, and further, The viscosity of the treatment liquid is 20 to 10,000
By setting mPas · sec, a good image free from color boundary bleeding, feathering, and strike-through can be obtained even when the amount of the processing liquid applied to the recording material is extremely small.

The treatment liquid of the present invention has an applied amount of 0.5 g / m 2.
Good images can be obtained even with a small applied amount of ^{2 to} 10 g / m ² . In the conventional processing liquid, the content of the compound that reduces the dispersibility or solubility of the recording liquid in the processing liquid is
If it is less than 10% by weight, it is insufficient to improve the image, and in order to improve the image, it is about 10 g / m ² -3.
Since the application amount of 0 g / m ² is required and the water content in the conventional liquid is high, there is a problem that cockling occurs in the applied recording material. Further, even if a large amount of treatment liquid is applied in this way, the effect of improving color boundary bleeding and feathering is not sufficient.

When the content of the compound which deteriorates the dispersibility or solubility of the recording liquid exceeds 80% by weight, the liquid component in the liquid evaporates, and the thermal history such as cooling of the liquid causes an influence on the liquid. Precipitation easily occurs inside, and it becomes difficult to maintain the reliability of application of the liquid. Further, when the content exceeds 80% by weight, it becomes difficult to uniformly apply the liquid to the recording material.

The optimum content of the compound in the processing liquid which reduces the dispersibility or solubility of the recording liquid is
Although it varies depending on factors such as the prescription of the recording liquid and the amount of the recording liquid printed per unit area, 20 to 60% by weight is a particularly preferable range.

The viscosity of the treatment liquid can be measured by a rotational viscometer, a vibration type viscometer, a flow type viscometer and the like. In the present invention, a treatment liquid having a viscosity of 20 to 10,000 mPas · sec is preferably used. The reason why the image improving effect is great by using a high-viscosity processing liquid which has never been obtained is explained as follows. That is, in the case of the conventional low-viscosity processing liquid, if the processing liquid is made permeable, it will penetrate deep into the recording material, especially plain paper, and no reaction with the recording liquid will occur on the surface of the recording material. In addition, the effect of preventing strike-through, preventing feathering, and preventing color boundary bleeding becomes small.

Further, when the treatment liquid having a low viscosity is used as a formulation having a reduced permeability to the recording material, the reaction with the recording liquid is
It occurs on the surface of the recording material, but since the recording liquid remains on the surface of the recording material for a long time, the effect of preventing color boundary bleeding is weakened, and in the case of high-speed printing, poor penetrability, that is, image However, there is a problem that the drying property becomes poor.

The viscosity of the treatment liquid is 10,000 mPas.s.
If it exceeds ec, not only it becomes difficult to apply the liquid uniformly to the recording material, but since the treatment liquid does not penetrate into the recording material at all, a sticky feeling remains on the recording material after printing, Not preferable. A particularly preferable range of the viscosity of the processing liquid is 100 to 3000 mPas · sec, and particularly preferably 300 to 2000 mPas · sec because the effect of improving the image quality and the drying property of the processing liquid are well balanced.

In the present invention, after the treatment liquid is applied to the recording material and before the treatment liquid is dried, an image is formed by the recording liquid. If the treatment liquid is dried by heating the recording material or leaving it at room temperature for a long time, undesired results such as bleeding at color boundaries and feathering may occur. In order to print an image and improve the image quality after the dried state, a coating amount of more than 30 g / m ² is required, which is economically unfavorable.

Examples of means for contacting and applying the treatment liquid of the present invention to the intermediate transfer member include a roller applicator, a wire bar, a coating blade, and a means for contacting a foam impregnated with the treatment liquid. Further, the treatment liquid having a relatively low viscosity can be applied to the intermediate transfer member by a non-contact means such as an inkjet method. Among the non-contact imparting means, by using the inkjet method,
It is possible to uniformly apply a high-viscosity processing liquid with a simple device configuration so that the application amount is a sufficient improvement effect of image quality, and to make it compact by a low-cost application means. It will be possible.

As described above, the high-viscosity processing liquid containing the high-concentration fixing agent is applied to the intermediate transfer member by the non-contact applying means.
By applying a much smaller amount than the conventional processing liquid, it is possible to prevent cockling of the recording material, which has occurred in the conventional method, and obtain the effect of improving the image quality over the conventional method. .

Further, when an image is recorded without applying the treatment liquid on general plain paper having pulp fibers as a main component and having a size degree of 10 S or more and an air permeability of 5 to 50 S, feathering and color boundaries are recorded. Bleeding, strike-through, and reduction in image density are likely to occur. Therefore, the present invention is most effective when applied to general plain paper having pulp fibers as a main component and having a size degree of 10 S or more and an air permeability of 5 to 50 S.

Next, the recording liquid will be described in detail. As the recording liquid used in the image recording method of the present invention, it is possible to use a recording liquid conventionally used in a usual ink jet recording method, and particularly when used in the above-mentioned image recording method or image recording apparatus. A recording liquid containing a material capable of promptly reacting with the components in the processing liquid is preferred.

That is, when the component in the recording liquid that reacts with the processing liquid is a colorant, the colorant is dispersed with a dye having an ionic group, a pigment having an ionic group, and an ionic dispersant. It is preferable that the pigment is a colored emulsion that is emulsified with an ionic surfactant, and in particular, that the ionic group is an anion because the safety of the material is high and the cost is low. preferable. Furthermore, it is preferable to use an anionic material containing a carboxylic acid that has high reactivity with the treatment liquid and in which a small amount or a dilute treatment liquid reacts.

For example, a colorant containing an anionic group and a treatment liquid containing a cationic material cause aggregation of the colorant and thickening of the recording liquid due to an ionic reaction, but the ionic reaction occurs extremely quickly. In addition, when recording at high speed, it is possible to prevent image blurring and color bleeding.

In the present invention, it is preferable from the viewpoint of safety to use an aqueous recording liquid as the recording liquid. Specific examples of the anionic dye contained in the ink used in the present invention include dyes classified into acid dyes, direct dyes and food dyes in the color index.

More specifically, as acid dyes and food dyes, C.I. I. Acid Yellow 17, 23, 42, 44,
79, 142 C.I. I. Acid Red 1, 8, 13, 14, 18,
26, 27, 35, 37, 42, 52, 82, 87, 8
9, 92, 97, 106, 111, 114, 115, 1
34, 186, 249, 254, 289 C.I. I. Acid Blue 9, 29, 45, 92, 24
9 C. I. Acid Black 1, 2, 7, 24, 26,
94 C.I. I. Food Yellow 3, 4 C.I. I. Hood Red 7, 9, 14 C.I. I. There are food black 1, 2, etc.

As the direct dye, C.I. I. Direct Yellow 1, 12, 24, 26,
33, 44, 50, 86, 120, 132, 142, 1
44 C.I. I. Direct Red 1, 4, 9, 13, 17,
20, 28, 31, 39, 80, 81, 83, 89, 2
25, 227 C.I. I. Direct Orange 26, 29, 62, 10
2 C. I. Direct Blue 1, 2, 6, 15, 22,
25, 71, 76, 79, 86, 87, 90, 98, 1
63, 165, 199, 202 C.I. I. Direct Black 19, 22, 32, 3
8, 51, 56, 71, 74, 75, 77, 154, 1
68, 171, etc.

As a reactive dye, C.I. I. Reactive.
Black 3, 4, 7, 11, 12, 17, C.I. I. Reactive. Yellow 1, 5, 11, 13, 14, 20,
21, 22, 25, 40, 47, 51, 55, 65, 6
7, C.I. I. Reactive. Red 1, 14, 17, 2
5, 26, 32, 37, 44, 46, 55, 60, 6
6, 74, 79, 96, 97, C.I. I. Reactive.
Blue 1, 2, 7, 14, 15, 23, 32, 35, 3
8, 41, 63, 80, 95, etc. have high solubility,
It can be preferably used because of good color tone and water resistance when recorded by the method of the present invention.

In the present invention, since the recording liquid is transferred to the recording material after being mixed with the treatment liquid, it is not necessary to use a dye showing good water resistance when used without the reaction liquid. . As the dyes, those containing 3 or more carboxyl groups and sulfonic acid groups in the molecule have high reactivity with the cationic material in the processing liquid, and the storage stability of the recording liquid and the anti-clogging property. It is preferable because the characteristics can be secured.

As the pigment that can be used in the recording liquid of the present invention, an inorganic pigment or an organic pigment can be used. As the inorganic pigment, white pigments such as titanium oxide, zinc oxide and barium sulfate, and black pigments such as iron oxide can be used.

The organic pigments include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments, etc.), polycyclic pigments (eg, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone). Pigments, dioxazine pigments, thioindigo pigments, isoindolinone pigments, quinofuraron pigments, etc., dye chelates (for example, basic dye type chelates,
Acid dye type chelates), nitro pigments, nitroso pigments, aniline black, etc. can be used. Further, carbon black manufactured by a known method such as a contact method, a furnace method, or a thermal method can be used.

More specifically, for color, C.I.
I. Pigment Yellow 1 (Fast Yellow G),
3, 12 (Disazo Yellow AAA), 13, 14, 1
7, 24, 34, 35, 37, 42 (yellow iron oxide), 5
3, 55, 81, 83 (Disazo Yellow HR), 9
5, 97, 98, 100, 101, 104, 408, 1
09, 110, 117, 120, 138, 153, C.I.
I. Pigment Orange 5, 13, 16, 17, 36,
43, 51, C.I. I. Pigment Red 1, 2, 3,
5, 17, 22 (Brilliant First Scallet), 23, 31, 38, 48: 2 (Permanent Red 2B (Ba)), 48: 2 (Permanent Red 2B)
(Ca)), 48: 3 (Permanent Red 2B (S
r)), 48: 4 (Permanent Red 2B (M
n)), 49: 1, 52: 2, 53: 1, 57: 1 (Brilliant Carmine 6B), 60: 1, 63: 1, 6
3: 2, 64: 1, 81 (Rhodamine 6G rake), 8
3, 88, 101 (Bengala), 104, 105, 10
6, 108 (Cadmium red), 112, 114, 1
22 (quinacridone magenta), 123, 146, 14
9, 166, 168, 170, 172, 177, 17
8, 179, 185, 190, 193, 209, 21
9, C.I. I. Pigment Violet 1 (Rhodamine Lake), 3, 5: 1, 16, 19, 23, 38, C.I.
I. Pigment Blue 1, 2, 15 (phthalocyanine blue R), 15: 1, 15: 2, 15: 3 (phthalocyanine blue E), 16, 17: 1, 56, 60, 63,
C. I. Pigment Green 1, 4, 7, 8, 10, 1
There are 7, 18, 36 and so on.

When a recording liquid containing a pigment as a colorant is used in the present invention, for example, a radical formed from carbon black having a carboxyl group introduced by an oxidation reaction or a diazonium salt having a carboxyl group or a sulfonic acid group is used. Self-dispersing pigments made by reacting pigments such as carbon black, phthalocyanine, quinacridone,
Self-dispersing pigments made by reacting radical initiators containing carboxyl or sulfonic acid groups with pigments such as carbon black, phthalocyanine, quinacridone, self-dispersing properties by reacting pigment functional groups with carboxylic acid anhydrides. A pigment having an ionic group, particularly a carboxyl group, bonded by a covalent bond, such as a pigment, can be preferably used. These pigments can maintain an extremely stable dispersion state in a liquid medium mainly composed of water, and are excellent in the storage stability of the recording liquid and the anti-clogging property. Further, it has a high reactivity with the cationic material in the treatment liquid, and thus the effect of preventing image bleeding and color bleeding is extremely large.

The recording liquid using a pigment as a colorant preferably usable in the present invention is a case where the recording liquid contains a pigment dispersed by an anionic polymer dispersant.

Examples of the polymer dispersant having an anionic group include polyacrylic acid and its salts, polymethacrylic acid and its salts, acrylic acid-acrylonitrile copolymer and its salts, and acrylic acid-acrylic acid alkyl ester copolymers. Polymers and salts thereof, styrene-acrylic acid copolymers and salts thereof, styrene-methacrylic acid copolymers and salts thereof, styrene-acrylic acid-alkyl acrylate copolymers and salts thereof, styrene-methacrylic acid-acrylic acid Alkyl ester copolymer and its salt, styrene-α-methylstyrene-acrylic acid copolymer and its salt, styrene-α-methylstyrene-acrylic acid copolymer-acrylic acid alkyl ester copolymer and its salt, styrene -Maleic acid copolymer and its salt, vinyl naphthalate -Maleic acid copolymer and salts thereof, vinyl acetate-ethylene copolymer and salts thereof, vinyl acetate-crotonic acid copolymer and salts thereof, vinyl acetate-acrylic acid copolymer and salts thereof, β-naphthalene sulfonic acid Formalin condensate, etc. can be mentioned.
The polymer compound having these anionic groups can be used in the acid form, but an alkali metal salt such as sodium, potassium or lithium can also be used.

Among these dispersants, preferred dispersants for use in the recording liquid of the present invention are polyacrylic acid and its salts, polymethacrylic acid and its salts, acrylic acid-acrylonitrile copolymer and its salts, Acrylic acid-alkyl acrylate copolymer and salts thereof, styrene-acrylic acid copolymer and salts thereof, styrene-methacrylic acid copolymer and salts thereof, styrene-
Acrylic acid-acrylic acid alkyl ester copolymer and salts thereof, styrene-methacrylic acid-acrylic acid alkyl ester copolymer and salts thereof, styrene-α-methylstyrene-acrylic acid copolymer and salts thereof, styrene-α- Methylstyrene-acrylic acid-acrylic acid alkyl ester copolymer and salts thereof, styrene-maleic acid copolymer and salts thereof, vinylnaphthalene-maleic acid copolymer and salts thereof, vinyl acetate-crotonic acid copolymer and salts thereof The use of a polymeric dispersant containing a carboxyl group such as a vinyl acetate-acrylic acid copolymer and a salt thereof has high reactivity with a cationic material in the processing liquid and causes image bleeding and color bleeding. It is particularly preferable in that the prevention effect is extremely large.

Anionic surfactants can also be preferably used as the pigment dispersant. Specifically, oleic acid and its salts, lauric acid and its salts, behenic acid and its salts, stearic acid and its salts such as fatty acids and its salts, dodecyl sulfonic acid and its salts, decyl sulfonic acid and its salts, Alkylsulphonic acid and its salts, laurylsulfates, oleylsulfates and other alkylsulfates, dodecylbenzenesulphonic acid and its salts, laurylbenzenesulphonic acid and its salts, such as alkylbenzenesulphonic acid and its salts, dioctylsulfoamber Acids and salts thereof, dihexylsulfosuccinic acids and salts thereof such as dialkylsulfosuccinic acids and salts thereof,
Aromatic anionic surfactants such as naphthyl sulfonic acid and its salt, naphthyl carboxylic acid and its salt, polyoxyethylene alkyl ether acetate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl ether sulfonate, fluorine The pigment can be dispersed and used by using a fluorinated anionic surfactant such as a fluorinated alkyl carboxylic acid and its salt and a fluorinated alkyl sulfonic acid and its salt. When using these surfactants as a dispersant for the pigment, in the present invention, it is preferable to use a surfactant containing a carboxyl group such as an alkylcarboxylate, an alkylbenzenecarboxylate, and a polyoxyethylene alkyl ether acetate. It is particularly preferable in that it has a high reactivity with the cationic material in the treatment liquid and has an extremely large effect of preventing image bleeding and color bleeding.

When a recording liquid in which a pigment is dispersed is used,
The particle size of the pigment is not particularly limited, but it is preferable in the present invention to use a pigment ink having a particle size with a maximum frequency of 20 to 150 nm in terms of maximum number conversion. If the particle size exceeds 150 nm,
Not only is the pigment dispersion stability of the recording liquid deteriorated, but also the ejection stability of the recording liquid is deteriorated, and the image quality such as image density is deteriorated, which is not preferable. When the particle size is less than 20 nm, the storage stability of the recording liquid and the jetting property in the printer are stable, and when the processing liquid is used, high image quality can be obtained, but such a fine particle size can be dispersed. However, the dispersion operation and the classification operation are complicated, and it is difficult to economically produce the recording liquid.

Another preferred example of the coloring agent used in the recording liquid of the present invention is a recording liquid using a so-called colored emulsion in which colored resin fine particles are suspended. The colored resin fine particles are obtained by coloring a styrene-acrylic resin, a polyester resin, a polyurethane resin or the like with an oil dye, a disperse dye or a pigment. For example, anionic coloring can be obtained by forming the shell portion of the fine particles with a hydrophilic resin such as polyacrylic acid or polymethacrylic acid, or by suspending it with an ionic surfactant such as a reactive surfactant. It is possible to obtain a recording liquid in which fine particles are suspended in a liquid medium containing water as a main component.

Also when a recording liquid using a colored emulsion is used, it is formed by emulsifying and polymerizing with the above-mentioned anionic surfactant, and the outer shell is made of a hydrophilic resin such as polyacrylic acid or polymethacrylic acid. In the present invention, the use of an emulsion is particularly preferable because it has a high reactivity with the cationic material in the treatment liquid and has an extremely large effect of preventing image bleeding and color bleeding.

When the recording liquid is water-soluble, a hydrophilic polymer compound is added to the recording liquid of the present invention to enhance the thickening action and aggregation action of the recording liquid due to the reaction with the treatment liquid. The image quality can be improved. Particularly, by adding an anionic water-soluble polymer compound, a highly safe recording liquid can be obtained.

As the hydrophilic polymer compound which can be added to the recording liquid, in the natural system, gum arabic, traggan gum, guar gum, karaya gum, locust bean gum, arabinogalactone, pectin, quince seed starch, and other plant polymers, alginic acid, Carrageenan, seaweed macromolecules such as agar, animal macromolecules such as gelatin, casein, albumin, collagen, microbial macromolecules such as xanthene gum and dextran or shellac, and methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxy in semi-synthetic systems. Fibrin-based polymers such as propyl cellulose and ruboxymethyl cellulose, starch-based polymers such as sodium starch glycolate and sodium starch phosphate, sodium alginate, propylene glycol alginate Seaweed-based polymers such as call ester,
In pure synthetic systems, vinyl-based polymers such as polyvinyl alcohol, polyvinylpyrrolidone, and polyvinyl methyl ether,
Non-crosslinked polyacrylamide, polyacrylic acid and its alkali metal salts, acrylic resins such as water-soluble styrene-acrylic resin, water-soluble styrene-maleic acid resin, water-soluble vinylnaphthalene-acrylic resin, water-soluble vinylnaphthalene-maleic acid resin , Polyvinylpyrrolidone, polyvinyl alcohol, alkali metal salts of β-naphthalenesulfonic acid formalin condensate, and the like.

Even when the water-soluble polymer compound is used in the recording liquid, it is preferable to use a compound containing a carboxylic acid as an anion group because the reactivity with the cationic material in the processing liquid is high and image bleeding and color It is particularly preferable in that the effect of preventing bleeding is extremely large.

It is also preferable that the recording liquid of the present invention contains a saccharide, particularly a polysaccharide, as a component that reacts with the treatment liquid. Examples of sugar compounds include alginic acid and its salts, uronic acid and its salts, aldonic acid and its salts, and the like.

It is also preferable to add a colorant-free resin emulsion to the recording liquid of the present invention as a component that reacts with the treatment liquid. The resin emulsion strengthens the thickening action and the aggregating action of the recording liquid by the reaction with the processing liquid, and can improve the image quality. In particular, by including a negatively charged resin emulsion in the recording liquid, a highly safe recording liquid can be obtained. By using a resin emulsion that reacts with the processing liquid and causes a thickening / aggregating action as the recording liquid, the quality of the image on the transfer body can be improved, and at the same time, depending on the type of resin emulsion, the resin emulsion Forming a film on the recording material has the effect of improving the abrasion resistance, light resistance and water resistance of the printed matter.

In particular, like the colored emulsion, it is preferable to use a resin emulsified and dispersed with an anionic surfactant, and a capsule-type resin emulsion having an outer shell made of acrylic acid, methacrylic acid or the like is used. It is also preferable to use.

As the resin component of the suspension phase, acrylic resin, vinyl acetate resin, styrene-butadiene resin,
Examples thereof include vinyl chloride resin, acrylic-styrene resin, butadiene resin, and styrene resin. These resins are preferably polymers having both a hydrophilic portion and a hydrophobic portion. The particle size of these resin components is not particularly limited as long as it forms an emulsion.
It is preferably about 0 nm or less, more preferably 5 to 100.
is about nm

Examples of commercially available resin emulsions include Microgel E-1002 and E-5002 (styrene-
Acrylic resin emulsion, made by Nippon Paint Co., Ltd., Boncoat 4001 (acrylic resin emulsion, made by Dainippon Ink and Chemicals Co., Ltd.), Boncoat 5
454 (styrene-acrylic resin emulsion, manufactured by Dainippon Ink and Chemicals, Inc.), SAE-1014 (styrene-acrylic resin emulsion, manufactured by Nippon Zeon Co., Ltd.), Cybinol SK-200 (acrylic resin emulsion, Saiden Chemical Co., Ltd.) Company made), and so on.

In the recording liquid, the resin emulsion is preferably added so that the resin component accounts for 0.1 to 40% by weight of the recording liquid, more preferably 1 to 25% by weight.

It is preferable for safety and hygiene to use a recording liquid that uses water as a main liquid medium, but to prevent the recording liquid from having a desired physical property or to prevent clogging of nozzles of the recording head due to drying of the recording liquid. Therefore, it is preferable to use the aforementioned water-soluble organic solvent.

Specific examples of the water-soluble organic solvent include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,
4-butanediol, 1,5-pentanediol, 1,
6-hexanediol, glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, 1,2,4-butanetriol, 1,2,3-butanetriol, petriol, etc. Polyhydric alcohols, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether Alcohol ethers such as polyhydric alcohol alkyl ethers, polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether S; N- methyl-2-pyrrolidone,
N-containing heterocyclic compounds such as N-hydroxyethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethylimidazolidinone and ε-caprolactam; amides such as formamide, N-methylformamide and N, N-dimethylformamide Amines such as monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine and triethylamine, sulfur-containing compounds such as dimethyl sulfoxide, sulfolane and thiodiethanol, propylene carbonate, ethylene carbonate, γ
-Butyrolactone and the like. These solvents may be used alone or in combination with water.

As the pH adjusting agent, hydroxides of alkali metal elements such as lithium hydroxide, sodium hydroxide and potassium hydroxide, ammonium hydroxide, quaternary ammonium hydroxide, quaternary phosphonium hydroxide, Alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate, amines such as diethanolamine and triethanolamine, boric acid, hydrochloric acid, nitric acid, sulfuric acid and acetic acid can be used.

Next, the composition of the treatment liquid of the present invention will be described. Currently used aqueous recording liquids are:
The majority of cases include anionic compounds or negatively charged particles. Therefore, it reacts with an anionic dye, an anionic pigment, an anionic polymer compound, an anionic compound such as an anionic emulsion, or negatively charged particles contained in the recording liquid to reduce dispersibility and solubility. As the compound, the treatment liquid preferably contains a cationic compound. Among the cationic compounds, a cationic polymer compound is preferable because it has a high ability to react with an anionic compound and negatively charged particles in the recording liquid.

As the cationic polymer compound contained in the treatment liquid in the present invention, for example, when an anionic colorant is used as a colorant, polyallylamine,
Examples thereof include organic polymer compounds having at least one cationic group such as polyethyleneimine. By containing these compounds in the treatment liquid, a recording liquid containing a colorant such as an anionic dye can be made to be viscous,
As a result, it is possible to obtain a high-quality image having a high image density and free from feathering and color boundary blurring, and it is possible to obtain a recorded image having a high image density and excellent water resistance. The content of the cationic polymer compound in the treatment liquid is preferably 10 to 80% by weight.

Specific examples of the cationic polymer compound include dicyandiamide resin such as dicyandiamide / diethylenetriamine polycondensate, dicyandiamide / formalin polycondensate, epichlorohydrin / dimethylamine addition polymer, dimethyldiallylammonium chloride / SO ₂ copolymer. Polymer, diallylamine salt / SO ₂ copolymer, dimethyldiallylammonium chloride polymer,
Polymer of allylamine salt, quaternary salt of dialkylaminoethyl (meth) acrylate, cationic epoxy, polyethyleneimine, polyacrylamide, poly (meth)
Examples thereof include acrylic acid ester, vinylformamide, cationic silica, cationic emulsion and the like.

When a dye is used as the coloring agent of the recording liquid, the processing liquid containing the dicyandiamide resin is particularly excellent in the effect of suppressing bleeding and the image density.

Commercially available products may be used as the cationic resin used in the present invention, and for example, Cellopol YM-500 manufactured by Sanyo Chemical Co., Ltd. may be mentioned. Furthermore, as other commercially available cationic resins, Sanstat E-818, Sunfix 70, Sunfix 555C, Sunfix LC-55, Sunhooks PAC-700 Conc, Sanyo Elion A-3,
Sunfix 414, Sunfix 555, Sunfix PRO-100, Sunfix 555US
(Made by SANYO Kasei Kogyo Co., Ltd.), # 675, # FR-
2P, # 1001 (all manufactured by Sumitomo Chemical Co., Ltd.), L
UPASOL SC61B (manufactured by BASF) and the like can be mentioned. In addition, ZP-700 (vinyl formamide type),
MP-184 (polyacrylic ester type), MP-1
73H (Polymethacrylate ester), MP-180
(Polymethacrylic acid ester type), MX-0210 (Polymethacrylic acid ester type), MX-8130 (Polyacrylic acid ester type), E-395 (Polyacrylic acid ester type), E-305 (Polyacrylic acid ester type) ), Q-101 (polyamine type), Q-311 (polyamine type), Q-501 (polyamine type), Q-105.
H (dicyandiamide type), Neo-600 (polyacrylamide type), (these are manufactured by Hymo Co., Ltd.) and the like. Super Flock 2490 (polyacrylate type), 3180, 3380, 3580, 3880, 33
90, 3590, 3500, SD2081 (polyacrylamide), 1500, 1600 (polymethacrylic acid ester) (above manufactured by Mitsui Cytec Co., Ltd.) and the like.

As the cationic quaternary ammonium salt,
Ionette D46, Ionette LEC, Secryl VN,
Sunstat 1200, Sunstat KT-305C,
Cation G-50, Ionette RK-15 (above Sanyo Chemical Industry Co., Ltd.), etc. are mentioned.

As the cationic emulsion, ACRYT UW319-SX, ACRYT RKW-460, ACRYT RKW-400SX, ACRYT RKW-450.
Examples include SX and ACRIT RKW-450 (all manufactured by Taisei Kako Co., Ltd.).

As a result of diligent research conducted by the present inventor, it was confirmed that the following cationic polymers are preferably used in the treatment liquid of the present invention. That is, the examples of the cationic polymer compounds preferably used in the present invention will be given below.

Cationic polymer compound example 1 used in the present invention:

[Chemical 1] (X ⁻ is halogen ion, nitrate ion, nitrite ion,
Anion such as acetate ion, R is an alkylene group having 1 to 3 carbon atoms, and n is an integer indicating the degree of polymerization)

Cationic Polymer Compound Example 2 Used in the Present Invention: Dicyandiamide resin in which the cationic polymer compound is represented by the formula (2)

[Chemical 2] (N is an integer indicating the degree of polymerization)

Cationic Polymer Compound Example 3 Used in the Present Invention: The cationic polymer compound is a tertiary or quaternary salt of a di- or trialkylaminoethyl (meth) acrylate polymer represented by the formula (3).

[Chemical 3] (X ⁻ is halogen ion, nitrate ion, nitrite ion,
Anion such as acetate ion, R ₁ is H or a methyl group, R ₂ ,
R ₃ and R ₄ are H or an alkyl group, n is an integer indicating the degree of polymerization)

Example 4 of cationic polymer compound used in the present invention:

[Chemical 4] (X ⁻ is halogen ion, nitrate ion, nitrite ion,
Anion such as acetate ion, n is an integer indicating the degree of polymerization)

Cationic polymer compound preferably used in the present invention Example 5: Dicyandiamide resin represented by the following formula

[Chemical 5] (N is an integer of 5 to 30 indicating the degree of polymerization)

Example 6 of cationic polymer compound used in the present invention:

[Chemical 6] (N is an integer indicating the degree of polymerization)

Example 7 of cationic polymer compound used in the present invention:

[Chemical 7] (X ⁻ is halogen ion, nitrate ion, nitrite ion,
Anion such as acetate ion, n is an integer indicating the degree of polymerization)

Cationic Polymer Compound Example 8 Used in the Present Invention: Polyvinylformamide represented by the following formula.

[Chemical 8] (N is an integer indicating the degree of polymerization)

Cationic polymer compound example 9 used in the present invention:

[Chemical 9] (X, Y is independently -OCOCH _3, -OH, etc., n, l,
m is an independent integer indicating the degree of polymerization)

Cationic polymer compound example 10 used in the present invention: polyvinyl pyridine represented by the following formula.

[Chemical 10] (R is a lower alkyl group, X ⁻ is an anion such as halogen ion, nitrate ion, nitrite ion, and acetate ion, and n is an integer indicating the degree of polymerization)

Cationic Polymer Compound Example 11 Used in the Present Invention: Polyvinylbenzylphosphonium represented by the following formula.

[Chemical 11] (R ₁ and R ₂ are hydrogen or a lower alkyl group, X ⁻ is an anion such as a halogen ion, a nitrate ion, a nitrite ion and an acetate ion, and n is an integer indicating the degree of polymerization)

Cationic Polymer Compound Example 12 Used in the Present Invention: Polymer of dimethyldiallylammonium salt represented by the following formula.

[Chemical 12] (X ⁻ is halogen ion, nitrate ion, nitrite ion,
Anion such as acetate ion, n is an integer indicating the degree of polymerization)

Cationic polymer compound example 13 used in the present invention: chitosan salt represented by the following formula

[Chemical 13] (X ⁻ is halogen ion, nitrate ion, nitrite ion,
Anion such as acetate ion, n is an integer indicating the degree of polymerization)

Cationic polymer compound used in the present invention Example 14: polyalkylene polyamine represented by the following formula

[Chemical 14] (J and k are each independently an integer of 2 to 6, and n is an integer indicating the degree of polymerization)

Cationic polymer compound used in the present invention Example 15: polyamine represented by the following formula

[Chemical 15] (X ⁻ is halogen ion, nitrate ion, nitrite ion,
Anion such as acetate ion, n is an integer indicating the degree of polymerization)

Example 16 of cationic polymer compound used in the present invention:

[Chemical 16] (X ⁻ is halogen ion, nitrate ion, nitrite ion,
Anion such as acetate ion, Q is any copolymerizable monomer component, and n and m are independent integers indicating the degree of polymerization)

Cationic polymer compound used in the present invention Example 17: Polymer represented by the following formula

[Chemical 17] (X ⁻ is halogen ion, nitrate ion, nitrite ion,
Anion such as acetate ion, n is an integer indicating the degree of polymerization)

Cationic polymer compound preferably used in the present invention Example 18: Polymer represented by the following formula

[Chemical 18] (X ⁻ is halogen ion, nitrate ion, nitrite ion,
Anion such as acetate ion, n is an integer indicating the degree of polymerization)

To improve the image quality by reacting with an anionic compound such as a dispersant for a dye or a pigment in a recording material,
Most preferably, a cationic polymer compound as described above is used. However, it is also effective to add a monomer compound which reacts with the following anionic compound to reduce the solubility and dispersibility to the treatment liquid, and in particular,
Use in combination with a cationic polymer compound is preferable in that the reaction between the cationic polymer compound and the anionic compound in the recording material is promoted.

[Chemical 19] (X ⁻ is halogen ion, nitrate ion, nitrite ion,
Anion such as acetate ion, R ₁ , R ₂ , and R ₃ are alkyl groups whose total carbon number is 5 to 32)

In the above cationic compound, R₂, R₃
Are both methyl groups, and R ₁Has 10 to 2 carbon atoms
A compound of 0 has a high solubility and has a high solubility in the recording liquid.
The effect of reducing the solubility and dispersibility by reacting with anion compounds
It is preferable because it has both sides of high fruit. Carbon number
If it is larger than this, it lacks solubility in the processing solution and can be stored.
And environmental changes may cause problems such as precipitation.
It Compounds with low carbon numbers have excellent dissolution stability
However, it is soluble by reaction with anionic compounds in the recording liquid
And the ability to reduce dispersibility are small, improving image quality
The effect of doing is small.

As a more specific example of the cationic compound represented by the above general formula (19), the following structural compounds can be exemplified. These cationic compounds may be used alone or in combination in the treatment liquid of the present invention.

[Chemical 20]

As these cationic compounds, commercially available compounds can be used. Specifically, the trade names are as follows: Cation S, Cation SK, Cation M, Cation G-50.
(Above, Sanyo Kasei Co., Ltd.), cation F2-35R, cation F2-40E, cation M2-100, cation S2.
-100 (above, manufactured by NOF CORPORATION), SANNIZAR C, SANISOL B-50 (above, manufactured by Kao) and the like.

As described above, it is preferable to use the cationic polymer compound and the compound represented by the above formula in combination in the treatment liquid.
It is presumed that it has an appropriate surface activity and makes the wettability of the processing liquid to the recording material uniform. When a general recording liquid is applied to high-quality paper, which is a typical recording material, microscopically there are areas that are easily wetted and areas that are difficult to wet depending on the distribution of the surface sizing agent. Is presumed to cause image quality deterioration such as blurring and uneven density in a solid image portion. Since the treatment liquid is applied “uniformly” to the recording material such as plain paper and then the recording liquid is attached to the recording material, irregular wetting is reduced, resulting in less feathering and excellent reproducibility of fine lines. It is possible to obtain an image with high image quality and high image density without blurring of color boundaries.

Further, the monomer / cationic compound represented by the above formula has a high compatibility with the above-mentioned cationic polymer compound, does not cause precipitation or separation in the treatment liquid, and can be uniformly mixed easily. Therefore, it is possible to provide a highly reliable treatment liquid which is excellent in storage stability and coating amount stability.

As the compound which lowers the solubility and dispersion stability in the recording liquid, a treatment liquid in which cationic particles are dispersed and suspended is used in addition to the above-mentioned cationic polymer compound which is soluble in water. Is also effective. However, in the cationic emulsion, the cation concentration in the processing liquid tends to be low, and in order to sufficiently improve the image quality, a water-soluble cationic polymer compound, a cationic surfactant having a higher alkyl group, etc. It is preferable to use it together with other cation compounds.

Examples of the liquid in which the cationic particles are dispersed and suspended include a cationic resin emulsion and a cationic white or light pigment dispersion. Examples of the cationic emulsion include, for example, Akrit UW319-SX, Akrit RKW-460, Akrit RKW-400SX, Akrit RKW-450.
Styrene-acrylic cationic emulsions such as SX and ACRYT RKW-450 (all manufactured by Taisei Kako Co., Ltd.) are commercially available.

By adding the cationic resin emulsion to the treatment liquid, a glossy image can be obtained and high water resistance of the image can be obtained as compared with the case of using the water-soluble cationic polymer compound alone. , It can have abrasion resistance. Further, the light resistance of an image can be enhanced by incorporating an ultraviolet absorber, an antioxidant, a quencher, etc. in the emulsion.

As an example of the liquid in which the cationic particles are dispersed and suspended, a dispersion of silica having a cationic property can be exemplified. Examples of the cationic silica include Snowtex AK (manufactured by Nissan Chemical Industries, Ltd.) and SMR.
8-17-109 SMSG3CS (manufactured by Grace Japan Co., Ltd.), CEP10AK97002 (manufactured by CABOT Co.) and the like are commercially available. However,
Even when a cationic silica is used, the cationic silica alone tends to have a low cation concentration in the treatment liquid, as in the case of the cationic resin emulsion, and in order to sufficiently enhance the image quality, the water-soluble cationic It is preferable to use together with other cationic compounds such as a polymer compound and a cationic surfactant having a higher alkyl group. By adding the cationic resin silica to the treatment liquid, the sticky feeling immediately after the image printing can be reduced as compared with the case of using the water-soluble cationic polymer compound alone.

It is also effective to use a polyvalent metal salt such as aluminum chloride, calcium chloride, aluminum nitrate, magnesium nitrate, magnesium chloride or calcium nitrate in the processing liquid as a compound that reduces the solubility and dispersibility of the recording liquid. Is. However, the polyvalent metal salt generally has a slightly weaker ability to reduce the dissolution stability or dispersion stability of the recording liquid, as compared with the cationic polymer compound,
When using a polyvalent metal salt, what kind of anionic compound is used in the recording liquid is important. When using a polyvalent metal salt, it is preferable to use a dye having two or more, preferably three carboxyl groups or sulfonic acid groups in one molecule.

In the case of a recording liquid using a pigment, it is preferable to use a polymer compound having a carboxyl group as a dispersant or a pigment having a carboxyl group introduced by a covalent bond. When a polyvalent metal salt is used in the treatment liquid, if a dye is used in the recording liquid, a complex is formed between the dye and the metal, and the light resistance of the recorded image is improved.

For the treatment liquid of the present invention, it is preferable to use a water-soluble solvent having a boiling point higher than that of water in an amount of 20 to 80% by weight. Further, if the viscosity changes due to evaporation of a solvent component such as water in the treatment liquid, the amount applied to the recording material also changes, and it is not possible to secure a certain image quality.
In addition to preventing drying, in order to make the processing liquid have the desired physical properties, to improve the dissolution stability of compounds and other additives that insolubilize the colorant in the recording liquid, and to stabilize the coating properties of the processing liquid. The following water-soluble organic solvents can be used for such purposes.

The content of the water-soluble organic solvent is preferably 20 to 80% by weight. If it is less than 20% by weight, the effect of suppressing the evaporation of water from the treatment liquid is small, the change in the viscosity of the treatment liquid due to the evaporation of water is large, and the stability of the applied amount is lacking. Also, due to water evaporation, the dissolution stability of the cationic polymer compound deteriorates and the treatment liquid gels,
Insoluble matter may be generated.

As the water-soluble organic solvent used in the treatment liquid of the present invention, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,5-pentanediol, 1,6-hexanediol, glycerin, 1,
Polyhydric alcohols such as 2,6-hexanetriol, 1,2,4-butanetriol, 1,2,3-butanetriol and petriol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, Polyhydric alcohol alkyl ethers such as diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether and propylene glycol monoethyl ether, polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether, N -Methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethylimidazolidino , Nitrogen-containing heterocyclic compounds such as ε-caprolactam, amines such as monoethanolamine, diethanolamine and triethanolamine, sulfur-containing compounds such as sulfolane and thiodiethanol, propylene carbonate, ethylene carbonate, γ-butyrolactone Etc. can be used.

These solvents may be used alone or in combination with water together. The optimum type and composition ratio of the water-soluble organic solvent used in the treatment liquid of the present invention should be selected according to other materials used in the treatment liquid. In the present invention, since a compound such as a cationic polymer compound that reduces the solubility or dispersibility of the recording liquid is used at a high concentration, it is important to ensure the solubility of the compound.

Of these, particularly preferred are diethylene glycol, thiodiethanol, polyethylene glycol 200 to 600, triethylene glycol, glycerin, 1,2,6-hexanetriol, 1,2,4-.
Butanetriol, petriol, 1,5-pentanediol, N-methyl-2-pyrrolidone, N-hydroxyethylpyrrolidone, 2-pyrrolidone, and 1,3-dimethylimidazolidinone, which are highly cationic. The solubility of insolubilizing compounds such as molecular compounds can be maintained, and the treatment liquid can be applied to the recording material with high reliability.

Further, the treatment liquid can contain a monohydric alcohol such as ethanol, whereby it is possible to prevent the occurrence of coating unevenness due to foaming of the treatment liquid, and to apply the treatment liquid to the recording material. Can be performed uniformly.

Water can be added to the treatment liquid of the present invention. However, if the amount of water added is smaller than that of the conventional treatment liquid, the stability of application of the liquid to the recording material can be maintained. preferable. In addition, the composition ratio of water is set to be less than the water ratio absorbed by the composition obtained by removing water from the treatment liquid in the equilibrium state with the atmospheric humidity (relative humidity, for example, 20 to 70%) in the operating environment of the recording apparatus. By setting the composition ratio at or near that, it is possible not only to prevent the evaporation of water during application of the treatment liquid to the recording material or during the standing period of the application device, but also to apply the treatment liquid to the recording material. Even if the time from application to recording of an image is long, for example, about 5 minutes, it is possible to obtain the same image quality improvement effect as when image recording is performed immediately after application.

The water content is preferably 0 to 40% by weight. A particularly preferred range is 10 to 30% by weight. If the water content exceeds 40% by weight, the viscosity of the liquid may increase or gelation may occur due to the evaporation of water during application of the treatment liquid to the recording material or during the standing period of the applicator. Problems such as precipitation of insoluble matter tend to occur. Also,
In the time from the application of the processing liquid to the recording of the image, the water evaporates, the processing liquid loses its fluidity, the reaction with the recording liquid becomes slow, and a sufficient image quality improvement effect is obtained. It will be difficult. In addition, when there is a time lag between the application of the treatment liquid and the image recording at the leading edge or the trailing edge of the image, there arises a problem that a difference in image quality occurs. Water content is 10
Even if it is less than wt%, the solubility of the cationic compound tends to be insufficient, and problems such as gelation and formation of insoluble matter are likely to occur.

The treatment liquid of the present invention preferably contains water and a water-soluble liquid compound in an amount of 20 to 80% by weight. Two
If it is less than 0% by weight, the stability of dissolution of the cationic polymer compound is poor and the treatment liquid is gelated or insoluble matter is generated.

The processing liquid of the present invention has a surface tension adjusted to 40 mN / m or less by adding a surfactant and / or a wetting promoter, and is used as an application means for applying the recording material or the processing liquid. It is preferable to improve the wettability of. By increasing the wettability, the treatment liquid uniformly adheres to the recording material, so that it is possible to enhance the image quality with a small application amount.

Further, by increasing the wettability to the liquid applying means such as the rubber roller and the metal roller, the uniform application to the recording material becomes easy. The surfactant that can be used in the treatment liquid of the present invention is not particularly limited, but examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, lauryl sulfate, and polyoxyethylene alkyl ether sulfate. And non-ionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl. Examples include, but are not limited to, amines and polyoxyethylene alkylamides.

The above surfactants can be used alone or in admixture of two or more.

A wetting promoter other than the surfactant may be added for the purpose of adjusting the surface tension, and examples of such a compound include diethylene glycol monophenyl ether, ethylene glycol monophenyl ether, ethylene glycol monoallyl ether and diethylene glycol. Alkyl and aryl ethers of polyhydric alcohols such as monophenyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, tetraethylene glycol chlorophenyl ether, 1,6-hexanediol, 1,5-pentanediol, 2,2,4- Polyhydric alcohols such as trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, polyoxyethylene polyoxypropylene block copolymer , Ethanol, lower alcohols such as 2-propanol.

Further, it is preferable to add an antiseptic / antifungal agent to the treatment liquid in the present invention in order to prevent alteration of the liquid due to bacterial growth. Examples of preservatives and fungicides that can be added include sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, 1,2-dibenzisothiazoline- 3-on etc. are mentioned.

The pH value of the treatment liquid is preferably kept substantially neutral. When stainless steel or nickel is used as the liquid applying member, it is preferable to keep the pH value in the range of 8 to 11 in order to suppress its corrosiveness, but the solubility of the cationic resin is generally in the range of relatively low pH value. Is high, and a region close to neutral is preferable in view of the balance between the two. In order to adjust the pH value of the treatment liquid to a desired value, the treatment liquid contains amines such as diethanolamine and triethanolamine,
Hydroxides of alkali metal elements such as lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide,
Quaternary ammonium hydroxide, quaternary phosphonium hydroxide, carbonates of alkali metals such as lithium carbonate, sodium carbonate, potassium carbonate and the like can be added.

In addition, in order to improve the light resistance of the image,
An ultraviolet absorber, an antioxidant and the like can be added to the treatment liquid. As the ultraviolet absorber, various benzotriazole-based, salicylic acid ester-based, benzophenone-based, cyanoacrylate-based, benzofuran derivative, substituted acrylonitrile-based, substituted-N-phenylaminoethylene-based, pyrone-based, methylenemalonic acid ester, cinnamic acid Preferable examples thereof include esters, phenyl salicylates, hindered amines and the like.

As the antioxidant, various phenol-based, sulfur-based, phosphoric acid-based, naphthol-based, hindered phenols, paraphenylenediamines, hydroquinones, organic sulfur compounds, organic phosphorus compounds, hindered amines Preferable examples include coumarone type, spiroindane type, hydrazine and the like. These ultraviolet absorbers and antioxidants may be added as an emulsion in order to improve dispersibility.

Next, the intermediate transfer member of the present invention will be described. The intermediate transfer member used in the present invention can have various shapes such as a roller shape, a drum shape, and a belt shape. The surface of the intermediate transfer member is preferably macroscopically smooth so that the transfer is performed uniformly. However, it is not preferable that the treatment liquid and the recording liquid attached to the surface of the intermediate transfer member easily move, so that microscopic unevenness can be formed on the surface of the intermediate transfer member. For repeated use, it is preferably a surface on which neither the recording liquid nor the treatment liquid penetrates. This is because the penetration of the liquid into the intermediate transfer member means that the surface is easily contaminated with the recording liquid or the processing liquid, and conversely it is extremely difficult to clean the surface. In addition, it is not preferable that the surface of the intermediate transfer body is dissolved or corroded with respect to the recording liquid or the processing liquid. Furthermore, the properties required of the intermediate transfer member are those widely applicable to the intermediate transfer member, but they also have a suitable wettability with respect to the processing liquid and the recording liquid and an appropriate releasing property with respect to the mixture of the processing liquid and the recording liquid. It is preferable. If the wetness is poor, the image is deteriorated on the transfer body, and if the releasability is insufficient, the image is lost. Specifically, as a material forming the intermediate transfer member, various resins such as silicone resins and acrylic resins can be used. It is also possible to control the surface characteristics by subjecting these resin surfaces to a chemical or physical surface treatment.

The configuration and form of the image recording apparatus will be described below. FIG. 1 is a configuration diagram of an image recording apparatus that uses an inkjet to apply a treatment liquid to an intermediate transfer member. Treatment liquid applying means 2 (inkjet head) on the intermediate transfer body 1.
Thus, the treatment liquid is applied. Recording is performed by the inkjet head 3 on the intermediate transfer body 1 coated with the treatment liquid, and an image is formed on the intermediate transfer body 1. The ink reacts with the treatment liquid and becomes highly viscous. The recording medium 4 is conveyed between the pressure roller 6 and the intermediate transfer body 1, and at this time, the image on the intermediate transfer body 1 is transferred to the recording medium 4. A cleaning unit 5 that cleans the intermediate transfer member 1 is provided between the transfer unit and the processing liquid applying unit 2.

FIG. 2 is a block diagram of an image recording apparatus using an application roller to apply the treatment liquid to the intermediate transfer member.
The processing liquid is applied to the intermediate transfer member 1 by the processing liquid applying unit 7 (application roller). Intermediate transfer member 1 coated with treatment liquid
Then, recording is performed by the inkjet head 3 and an image is formed on the intermediate transfer body 1. The ink reacts with the treatment liquid and becomes a highly viscous state. The recording medium 4 is conveyed between the pressure roller 6 and the intermediate transfer body 1, and at this time, the image on the intermediate transfer body 1 is transferred to the recording medium 4. A cleaning unit 5 for cleaning the intermediate transfer member 1 is provided between the transfer unit and the processing liquid applying unit 7.

FIG. 3 is a block diagram of an image recording apparatus using a spray nozzle to apply the treatment liquid to the intermediate transfer member. The treatment liquid is applied to the intermediate transfer member 1 by the treatment liquid applying unit 8 (spray nozzle). Recording is performed by the inkjet head 3 on the intermediate transfer body 1 coated with the treatment liquid, and an image is formed on the intermediate transfer body 1. The ink reacts with the treatment liquid and becomes highly viscous. The recording medium 4 is conveyed between the pressure roller 6 and the intermediate transfer body 1, and at this time, the image on the intermediate transfer body 1 is transferred to the recording medium 4. Intermediate transfer body 1
A cleaning unit 5 for cleaning the above is provided between the transfer section and the processing liquid applying unit 8.

FIG. 4, FIG. 5, and FIG. 6 are explanatory views showing the adhesion range of the processing liquid on the intermediate transfer member. FIG. 4 shows an example in which the treatment liquid is deposited on the intermediate transfer body in an area corresponding to almost the entire surface of the recording medium. The treatment liquid is treated with an inkjet head, a coating roller, or a spray nozzle.
The toner is adhered onto the intermediate transfer member in a range corresponding to almost the entire surface of the recording medium.

FIG. 5 shows an example in which the treatment liquid is attached to an area on the intermediate transfer member corresponding to the image forming area of the recording medium. The treatment liquid is deposited on the intermediate transfer member in a range corresponding to the image forming area (a range excluding white information) of the recording medium by an inkjet head or a spray nozzle.

FIG. 6 shows an example in which the treatment liquid is adhered to an area on the intermediate transfer member corresponding to the image information on the recording medium. The treatment liquid is made to adhere to the intermediate transfer body by the inkjet head based on the same information as the image information.

[0152]

EXAMPLES Examples and comparative examples of the present invention will be shown below, but the present invention is not limited thereto. In addition,
The amount (%) of each component described in the examples is% by weight unless otherwise specified.

Example 1 Preparation of Recording Liquid After mixing and stirring according to the following recording liquid formulation, the pH was adjusted to 10.5 with sodium hydroxide. Then, filtration was performed with a membrane filter having an average pore diameter of 0.1 μm to obtain a recording liquid composition. [Yellow recording liquid 1] C.I. I. Acid Yellow 23 2% by weight N-methyl-2-pyrrolidone 10% by weight Polyethylene glycol 200 15% by weight Diethylene glycol monobutyl ether 12% by weight 1,5-Pentanediol 3% by weight Sodium alginate 0.2% by weight Sodium benzoate 0.4 Weight% Ion-exchanged water Remaining amount

[0154] [Magenta recording liquid 1]     C. I. Acid Red 52 1.5% by weight     C. I. Acid Red 254 1.5% by weight     N-methyl-2-pyrrolidone 10% by weight     Polyethylene glycol 200 15% by weight     Diethylene glycol monobutyl ether 12% by weight     1,5-pentanediol 3% by weight     Sodium alginate 0.2% by weight     Sodium benzoate 0.4% by weight     Deionized water remaining

[0155] [Cyan recording liquid 1]     C. I. Acid Blue 9 1.5% by weight     Projet Fast Cyan 2 (manufactured by Avicia) 1.5% by weight     N-methyl-2-pyrrolidone 10% by weight     Polyethylene glycol 200 15% by weight     Diethylene glycol monobutyl ether 12% by weight     1,5-pentanediol 3% by weight     Sodium alginate 0.2% by weight     Sodium benzoate 0.4% by weight     Deionized water remaining

[0156] [Black recording liquid 1]     C. I. Food Black 25% by weight     N-methyl-2-pyrrolidone 10% by weight     Polyethylene glycol 200 15% by weight     Diethylene glycol monobutyl ether 12% by weight     1,5-pentanediol 3% by weight     Sodium alginate 0.2% by weight     Sodium benzoate 0.4% by weight     Deionized water remaining

Preparation of Treatment Liquid The following composition was stirred and mixed to prepare Treatment Liquid Example 1 having a pH of 7
Was adjusted with triethanolamine. [Treatment liquid example 1] Polyallylamine 5% by weight Cationic surfactant 3% by weight Glycerin 5% by weight Ethylene glycol 20% by weight Sodium benzoate 0.5% by weight Ion-exchanged water Remaining amount

Image recording evaluation Image recording evaluation was performed as follows. The treatment liquid 1 is filled in the treatment liquid coating inkjet head 2 of the image recording apparatus shown in FIG. 1, and the yellow recording liquid 1, the magenta recording liquid 1, the cyan recording liquid 1, and the black recording liquid 1 are transferred to the image recording inkjet head. It was filled so that it could be discharged from No. 3. For each inkjet head, an on-demand type ink jet head using PZT is used.
The maximum frequency was 16 KHz, the recording liquid droplet volume was 14 pl, the treatment liquid droplet volume was 5 pl, the pixel density was 600 dpi, and the treatment liquid was also applied to the intermediate transfer member 1 according to the image to perform image recording. Commercially available copy paper (NBS) is used as the recording material.
Ricoh: My paper) was used. The evaluation results are shown in Table 1.

(1) Black Image Density A solid image of a black recording liquid is printed, and after drying, the density of the solid image of the black recording liquid is measured by a reflection color spectrophotometric densitometer (X
-Rite). 1.45 or above is ◎,
A value of 1.2 to less than 1.45 was evaluated as O, and a value of less than 1.2 was evaluated as X.

(2) Color boundary bleeding On the recording material, magenta, cyan, and
Line images each having a black 10-dot line width were formed, and the occurrence of color boundary bleeding was visually observed. Similarly, when a line image having a line width of 10 dots of magenta, yellow, and black is formed in a solid image of cyan,
The occurrence of color boundary bleeding was also observed when a line image having a line width of 10 dots of cyan, yellow, and black was formed in a solid image of magenta. When no color boundary bleeding can be visually confirmed, ◎, when almost no color boundary bleeding can be visually confirmed, △ when there is some color boundary bleeding visually, and visually When there was bleeding on the color boundary, it was evaluated as x.

(3) One of magenta, cyan, yellow, and black on the feathering recording medium
A line image having a line width of 0 dots was formed on each recording material, and the presence or absence of feathering was observed. When it is observed with a 10x loupe, it is almost not observed. It can be confirmed when observed with a 10x loupe, but it is a level that can not be visually confirmed, if there is no problem in practical use, and if there is a slight occurrence with visual observation. Δ: Poor when clearly visible can be confirmed.

(4) See-through solid image was visually observed from the back side. When the boundary between the solid image and the white background is completely unclear and does not interfere with the reading of the double-sided print, ◎, the boundary between the solid image and the white background is almost unclear, and there is almost no problem with the reading of the double-sided print. ○: If the boundary between the solid image and the white background is observed, but you do not mind reading the double-sided print, △: The colorant of the solid image is missing to the back side, which hinders the reading of the double-sided print. The case was judged as x.

(5) Cockling The presence or absence of cockling in the solid portion was observed. Two
When almost no cockling is observed in the secondary color, ⊙ A slight occurrence is observed in the secondary color, but when almost no occurrence is observed in the single color, ○, some cockling is observed in the single color. When the color was clear, it was marked with Δ, and when it was clear that it was a single color, it was marked with x.

Comparative Example 1 The same recording material as that used in Example 1 was attached to the intermediate transfer member 1, and the recording liquid used in Example 1 was used without applying the treatment liquid. An image was formed in the same manner as in Example 1. The obtained image was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Comparative Example 2 A recording material similar to that used in Example 1 was attached to the intermediate transfer member 1, and the treatment liquid was applied in the same manner as in Example 1, that is, directly applied to the recording material. An image was formed in the same manner as in Example 1 using the recording liquid used in Example 1. The obtained image was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results
Shown in.

Comparative Example 3 In order to compare with the image recording method according to the present invention, in addition to the head for ejecting the recording liquid to the apparatus of FIG. 1 for recording an image, a supply system and recording for applying the processing liquid are also provided. A head and a driver having the same structure as those for ejecting the liquid were provided.
The signal processing / driving system was also changed so that the treatment liquid was applied only to the portion where the image was recorded. The treatment liquid 1 is filled in a cassette that supplies the treatment liquid ejecting head of the apparatus after the change, and the treatment liquid is not applied by the roller in FIG. 2, and the treatment liquid is applied only to a portion where an image is formed. Image recording was performed with the same recording liquid as that used in Example 1 while being applied by the treatment liquid ejection head. At this time, the applied amount of the treatment liquid 1 was 10.5 g / m 2 in the image part.
^{Was 2} . The evaluation results are shown in Table 1.

Reference Example 1 In the present invention, evaluation was carried out when the amount of treatment liquid applied was at the same level as in the conventional case. Example 1 in the apparatus of FIG.
The same treatment liquid as in (1) was placed in the container of the applying device, and the amount of the treatment liquid applied was adjusted to be larger than that in Example 1 by controlling the rotation of the applying amount control roller and the pressure with the other rollers. Images were recorded in the same manner as in Example, except that the amount of the treatment liquid applied was increased. At this time, the applied amount of the treatment liquid 1 was 10.3 g / m ² . When the applied amount exceeds 10.0 g / m ² , remarkable cockling occurs on the paper, but when image recording (application of the treatment liquid) is performed on only one side at the same time, the image is marked on the paper. Curls have also occurred. The evaluation results are shown in Reference Example 1 of Table 1.

Example 2 Preparation of Treatment Liquid The following composition was stirred and mixed to prepare Treatment Liquid Example 2 having a pH of 7
Was adjusted with lithium hydroxide. [Treatment liquid example 2] Dicyandiamide / diethylenetriamine polycondensate 40 wt% Cationic surfactant 1 wt% Glycerin 10 wt% Triethanolamine Appropriate amount Ion-exchanged water Remaining viscosity of this treatment liquid is manufactured by Tokyo Keiki Co., Ltd. 850 mPas · sec (25 ° C) when measured with a B-type rotational viscometer
Met.

Application of Treatment Liquid and Evaluation of Image Recording As in Example 1, the treatment liquid 2 was filled in the treatment liquid container 2 of the image recording apparatus shown in FIG. 1, and the linear velocity was 60 mm / sec.
When it was applied to commercially available copy paper and bond paper at a speed of ¹ , the adhesion amount was 2.6 to 3.2 g / m ² . After applying the treatment liquid, the same recording liquid as that used in Example 1 was used and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 3 Preparation of Pigment Dispersion A dispersion composition of each color pigment was mixed and stirred according to the following dispersion formulation, and then dispersed using a bead mill for 8 hours using zirconia beads having a diameter of 2 mm to disperse the pigment. A liquid was prepared. [Yellow Pigment Dispersion Liquid 1] C.I. I. Pigment Yellow 74 15% by weight Formalin condensate of naphthalene sulfonate 3% by weight Diethylene glycol 15% by weight Ion-exchanged water Remaining amount (particle size mode after dispersion 120 nm)

[0171] [Magenta pigment dispersion 1]     C. I. Pigment Red 122 15% by weight     Styrene-hexyl acrylate-methacrylic acid       Copolymer diethanolamine salt 5% by weight     Ethylene glycol 13% by weight     Deionized water remaining (Mode of particle size after dispersion 110 nm)

[0172] [Cyan pigment dispersion 1]     C. I. Pigment Blue 15: 3 15% by weight     Styrene-hexyl acrylate-methacrylic acid       Copolymer diethanolamine salt 4% by weight     Ethylene glycol 15% by weight     Deionized water remaining (Mode value of particle size after dispersion is 85 nm)

[0173] [Black pigment dispersion 1]     Carbon black 15% by weight     Formalin condensate of naphthalene sulfonate 3% by weight     Diethylene glycol 15% by weight     Deionized water remaining (Mode of particle size after dispersion is 115 nm)

Preparation of Recording Liquid After mixing and stirring according to the following recording liquid formulation, a recording liquid was prepared by adjusting the pH to 9 with a 10% aqueous solution of lithium hydroxide. Then, filtration was performed with a membrane filter having an average pore size of 1.0 μm to obtain a recording liquid composition. [Yellow recording liquid 2] Yellow pigment dispersion liquid 1 6.7% by weight (pigment 4% by weight) Glycerin 10% by weight 2-pyrrolidone 10% by weight Dihexylsulfosuccinate (anionic surfactant) 1% by weight 2-ethyl -1,3-Hexanediol (penetrant) 2% by weight 2-pyridinethiol-1-oxide sodium (preservative) 0.2% by weight Ion-exchanged water Remaining amount

[0175] [Magenta Recording Liquid 2]     Magenta pigment dispersion 1 26.7% by weight (pigment 4% by weight)     Glycerin 10% by weight     2-pyrrolidone 10% by weight     Dihexyl sulfosuccinate (anionic surfactant) 1% by weight     2-ethyl-1,3-hexanediol (penetrant) 2% by weight     2-pyridinethiol-1-oxide       Sodium (preservative) 0.2% by weight     Deionized water remaining

[0176] [Cyan recording liquid 2]     Cyan pigment dispersion 1 20% by weight (pigment 3% by weight)     Glycerin 10% by weight     2-pyrrolidone 10% by weight     Dihexyl sulfosuccinate (anionic surfactant) 1% by weight     2-ethyl-1,3-hexanediol (penetrant) 2% by weight     2-pyridinethiol-1-oxide       Sodium (preservative) 0.2% by weight     Deionized water remaining

[0177] [Black recording liquid 2]     Black pigment dispersion 1 33.3 wt% (pigment 5 wt%)     Glycerin 10% by weight     2-pyrrolidone 10% by weight     Dihexyl sulfosuccinate (anionic surfactant) 1% by weight     2-ethyl-1,3-hexanediol (penetrant) 2% by weight     2-pyridinethiol-1-oxide       Sodium (preservative) 0.2% by weight     Deionized water remaining

Preparation of Treatment Liquid The following composition was stirred and mixed, and triethanolamine was added to adjust the pH to 7, whereby Treatment Liquid Example 3 was prepared. [Treatment liquid example 3] Cellopol YM-500 (dicyandiamide resin manufactured by Sanyo Kasei Co., Ltd.) 20% by weight Surfactant of the general formula (2) 1% by weight glycerin 10% by weight triethanolamine appropriate amount ion-exchanged water residual amount When the viscosity of the treatment liquid was measured with a B-type rotational viscometer manufactured by Tokyo Keiki Co., Ltd., it was 530 mPas · sec (25 ° C.).
Met.

Application of treatment liquid and image recording evaluation Treatment liquid example 3 was filled in the treatment liquid container 2 of the image recording apparatus shown in FIG. 1 and applied to commercially available copy paper or bond paper at a linear velocity of 30 mm / sec. 1.8-2.0 g /
It was the attached amount of m ² . After applying the treatment liquid, a print head 9 using a laminated PZT having a nozzle of 22 μm diameter for each color head using yellow recording liquid 2, magenta recording liquid 2, cyan recording liquid 2, and black recording liquid 2 is used. Frequency of 25 KHzk, drop weight 10 ng
Image formation with a pixel density of 1200 dpi by
Image quality and cockling were evaluated in the same manner as in.
The results are shown in Table 1.

The evaluation results are shown in Table 1.

[Table 1]

[0181]

As described above, according to claim 1,
A step (A) of forming an image by applying a recording liquid containing at least a colorant to the intermediate transfer body as droplets according to an image signal, and containing a component capable of reacting with at least one component in the recording liquid. A step (B) of applying the treatment liquid to the intermediate transfer member, a step (C) of contact-mixing the recording liquid and the treatment liquid on the intermediate transfer member, and a step of transferring the mixture to a recording material. (D) a treatment liquid used in the image forming method, which comprises a cationic polymer compound as a component capable of reacting with at least one component in the recording liquid. , When the recording liquid and the treatment liquid are mixed on the intermediate transfer member, the compatibility with the aqueous recording liquid is high, the reaction occurs efficiently, the mixed liquid easily thickens, and the polymer is Remarkable migration of colorant after transfer to recording material Win therefore less likely deterioration of image quality caused by the movement of the colorant of the recording liquid such as bleeding bleeding or boundaries. In addition, a high transfer rate can be obtained when transferred to the recording material. Further, the water resistance of the image is improved.

According to a second aspect of the present invention, the cationic polymer compound is a dicyandiamide resin, and the treatment liquid according to the first aspect provides a processing liquid containing a dicyandiamide resin, which serves as a coloring agent for a recording liquid. When a dye is used, the blur suppression effect and the image density are particularly excellent.

According to the third aspect, the cationic polymer compound is contained in an amount of 10 to 80% by weight, and the viscosity of the treatment liquid is 20 to 1
When it is set to 0000 mPas · sec, it can be applied onto the intermediate transfer member, and the effects described in claims 1 and 2 are easily exhibited.

According to the fourth aspect, the treatment liquid is a compound which contains 20 to 80% by weight of water and a water-soluble liquid compound to reduce the solubility or the dispersibility of the recording liquid. Even though the treatment liquid contains a high concentration of compound, it is possible to apply the treatment liquid with high reliability to the intermediate transfer member.

According to claim 5, the content of water is 0 to 40.
The content of the water-soluble liquid compound is 20 to 80% by weight.
Since the treatment liquid is characterized by its weight percentage, the content of water is relatively small, and the content of the water-soluble liquid compound having a higher boiling point than that of water is large. A compound that can reduce the amount of water vaporized from the pretreatment liquid even when used in an open state to the atmosphere, and can reduce the solubility or dispersibility of a recording liquid having strong hydrophilicity Since the solubility of the treatment liquid can be maintained by the water-soluble liquid compound, the physical properties of the treatment liquid are stable, and the treatment liquid having high reliability can be applied to the intermediate transfer member.

According to the sixth aspect, the treatment liquid contains a surfactant and / or a wetting promoter and has a surface tension of 40 m.
Since it is adjusted to N / m or less, when the treatment liquid is applied to the recording material, the recording material can be uniformly wetted even when the amount of the treatment liquid applied per unit area is small. The effect of improving the image quality is large even when the number is small.

According to the seventh aspect, a step (A) of forming an image by applying a recording liquid containing at least a colorant to the intermediate transfer body as a droplet in accordance with an image signal, and at least the recording liquid. A step (B) of applying a treatment liquid containing a component capable of reacting with one component to the intermediate transfer member, and a step (C) of contact-mixing the recording liquid and the treatment liquid on the intermediate transfer member, A step (D) of transferring the mixture onto a recording material,
In an image forming method comprising: a treatment liquid containing any one of the above cationic polymer compounds is used as the treatment liquid. It contains a cationic polymer compound as a component capable of reacting with the material to be treated, and when the recording liquid and the processing liquid are mixed on the intermediate transfer member, the compatibility with the aqueous recording liquid is high and the reaction is efficient. Since the viscosity of the mixed liquid is high and the polymer is high, migration of the colorant after it is transferred to the recording material is significantly suppressed. Image quality deterioration due to movement is unlikely to occur. In addition, a high transfer rate can be obtained when transferred to the recording material. Further, the water resistance of the image is improved.

[Brief description of drawings]

FIG. 1 is a configuration diagram of a recording apparatus that applies a treatment liquid to an intermediate transfer member of the present invention by inkjet.

FIG. 2 is a configuration diagram of a recording apparatus that applies a treatment liquid to an intermediate transfer member of the present invention with an application roller.

FIG. 3 is a configuration diagram of a recording apparatus that applies a treatment liquid to an intermediate transfer member of the present invention with a spray nozzle.

FIG. 4 is an explanatory diagram in which the treatment liquid on the intermediate transfer member of the present invention is attached to the entire surface of the recording medium.

FIG. 5 is an explanatory diagram when the treatment liquid on the intermediate transfer member of the present invention is attached to the image forming area of the recording medium.

FIG. 6 is an explanatory diagram of a case where the treatment liquid on the intermediate transfer member of the present invention is attached based on the same information as image information.

[0188]

[Explanation of symbols]

1 Intermediate transfer body 2 Inkjet head for pretreatment liquid application 3 Inkjet head for image recording 4 recording media 5 Cleaning device 6 pressure roller 7 Pretreatment liquid application roller device 8 Spray nozzle for pretreatment liquid application 9 Conveyor rollers

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Takesada Hirose             1-3-3 Nakamagome, Ota-ku, Tokyo Stocks             Company Ricoh (72) Inventor Tetsuya Kaneko             1-3-3 Nakamagome, Ota-ku, Tokyo Stocks             Company Ricoh (72) Inventor Masayuki Oyano             1-3-3 Nakamagome, Ota-ku, Tokyo Stocks             Company Ricoh F-term (reference) 2C056 EA05 EA13 EA25 EC21 EC43                       FC02                 2H086 BA01 BA02 BA05 BA26 BA59                       BA60 BA61 BA62                 4J039 AB01 AD10 AD12 AE13 BE12                       BE22 BE28 CA06 EA38 EA42

Claims (7)

[Claims] 1. A treatment liquid for image formation comprising a cationic polymer compound. 2. The image forming treatment liquid according to claim 1, wherein the cationic polymer compound is a dicyandiamide resin. 3. A cationic polymer compound is contained in an amount of 10 to 80% by weight and has a viscosity of 20 to 10000 mPas · sec.
The image forming treatment liquid according to claim 1 or 2, wherein 4. Water and a water-soluble liquid compound are added in an amount of 20 to 80.
The image forming treatment liquid according to any one of claims 1 to 3, wherein the treatment liquid is contained in an amount of wt%. 5. The content of water is 0 to 40% by weight, and the content of the water-soluble liquid compound is 20 to 80% by weight, according to any one of claims 1 to 4. Image forming treatment liquid. 6. The image forming treatment liquid according to claim 1, which contains a surfactant and / or a wetting promoter and has a surface tension of 40 mN / m or less. . 7. A step (A) of forming an image by applying a recording liquid containing at least a colorant to the intermediate transfer member as a droplet according to an image signal, and reacting with at least one component in the recording liquid. A step (B) of applying the image forming treatment liquid according to any one of claims 1 to 6 to the intermediate transfer member, and the recording liquid and the treatment liquid on the intermediate transfer member. An image forming method comprising a step (C) of contact mixing and a step (D) of transferring the mixture to a recording material.