JP4040416B2 - Image forming method using recording medium - Google Patents

Description

【００６２】
【発明の効果】
以上説明したように、本発明において利用される記録媒体の製造方法によれば、記録媒体の有するインク受容層中の多価金属イオンの量を効果的に制御し、優れた光沢感、インク吸収性を有する記録媒体を提供することが可能となり、インク受容層中に含有させた多価金属イオンの作用により画像が形成されたインク受容層に付与された液体組成物中の高分子を不溶化させて画像保護用の被覆層を形成する記録画像の形成方法に好適に利用される記録媒体を提供することができる。更に、この記録媒体の製造方法を利用した画像記録物の形成方法によれば、被覆層形成用の液体組成物の画像への付与手段としてのインクジェット装置におけるプリントヘッドにおけるノズルの目詰まりや液体組成物塗布ローラー表面における固形物の固着を発生することなく、被覆層形成後のべとつきもなく、画像の品位、耐ガス性及び耐擦性に優れた画像記録物を提供することができる。また、本発明によれば、画像記録物の形成に使用する装置の小型化も容易となる。[0001]
BACKGROUND OF THE INVENTION
  The present invention is an inkjetrecoding mediaThe present invention relates to a method for manufacturing an image recorded material using the.
[0002]
[Prior art]
The ink jet recording method is a method in which micro droplets of ink are ejected by various operating principles and attached to a recording medium such as paper to record images, characters, etc. In other words, it has features such as a large flexibility in recording patterns, no need for development and fixing, and in recent years, it has been rapidly spread in various applications including information equipment as a recording apparatus for various images. Furthermore, it is possible to obtain images that are comparable to multi-color printing by the plate-making method and printing by the color photographic method for images formed by the multi-color inkjet method. Since it is cheaper than multi-color printing and printing, it is being widely applied to the field of full-color image recording. In recent years, a recording medium having a coating layer using an alumina hydrate having a boehmite structure has been proposed, and disclosed in, for example, Patent Document 1 and the like.
[0003]
In these recording media using alumina hydrate, since the alumina hydrate has a positive charge, the ink dye is well fixed and an image with good color can be obtained. Furthermore, there has been proposed a recording medium having glossiness and image quality comparable to a silver salt photograph by glossing the ink receiving layer containing alumina hydrate. For example, Patent Document 2 is disclosed. Recording media using these alumina hydrates have advantages such as being preferable to conventional recording media in terms of image quality, particularly in full-color images and glossiness.
[0004]
However, although the recording medium using the dye-based ink and the alumina hydrate as described above has an image quality comparable to or surpassing that of the silver salt print, the formed high-quality image is maintained for a long time. In particular, the present situation is that, in particular, resistance to deterioration (gas resistance) due to substances such as ozone gas in the air does not have satisfactory performance.
[0005]
As a technique aiming at improving image durability comparable to silver salt photography, a method of providing a protective layer on the surface of a recording material after image formation is disclosed. For example, Patent Document 3 discloses a method of laminating various plastic films as a protective film on an image record.
[0006]
Further, in Patent Document 4 and the like, fine particles made of a thermoplastic polymer are contained in the ink receiving layer of a recording medium, and after performing printing in a state where ink absorbability is maintained, the fine particles are removed with heat or a solvent. A method is described in which a protective film is formed by melting and dissolving to form a resin film on the surface. As an example of using the same method as the image forming method as a means for forming a coating layer, Patent Document 5 discloses a method of forming a coating layer by discharging a liquid composition containing a resin having a film forming function such as an emulsion by an inkjet method. It is disclosed.
[0007]
On the other hand, Patent Document 6 and the like are disclosed as examples in which an alkaline earth metal salt is contained in a recording medium produced by a casting method.
[0008]
[Patent Document 1]
Japanese Unexamined Patent Publication No. 7-232475
[Patent Document 2]
Japanese Unexamined Patent Publication No. 06-79967
[Patent Document 3]
Japanese Patent Laid-Open No. 2001-158092
[Patent Document 4]
JP-A-10-315448
[Patent Document 5]
JP 2000-225695 A
[Patent Document 6]
JP-A-9-104165
[0009]
[Problems to be solved by the invention]
However, in the method described in Patent Document 4 and the like, although the gas resistance is surely good, it is necessary to separately provide a laminating apparatus and a melting / dissolving apparatus for fine particles made of a thermoplastic polymer in addition to the image recording apparatus. In some cases, the device becomes large. Further, in the method of Patent Document 5, the use of a resin having a self-forming film such as an emulsion for the ink jet recording liquid may cause solidification due to long-term standing at a fine nozzle tip.
[0010]
On the other hand, in the method described in Patent Document 6, there is a problem that the pigment and polyvalent metal ions are aggregated during coating, and castability is deteriorated, resulting in a decrease in print density and poor gloss. is there.
[0011]
  The present invention has been made for the purpose of solving the above-mentioned problems, and it is possible to fix solid matter on a coating roller for applying a liquid composition for forming a coating layer to an image or to clog a nozzle in an ink jet apparatus. A protective coating layer can be formed without generation, and there is no stickiness after the coating layer is formed, and even with a miniaturized device, the image is highly glossy, excellent in image quality, gas resistance, and abrasion resistance. INK JET RECORDING MEDIUM MANUFACTURING METHOD APPLICABLE TO FORMATION METHOD OF IMAGE RECORDED MATERIAL FORMABLEImage forming method using inkjet recording medium manufactured byIt is to provide.
[0012]
Another object of the present invention is to provide a method for forming an image recording material that is capable of obtaining an image recording material having high gloss and excellent image quality, gas resistance and abrasion resistance.
[0013]
[Means for Solving the Problems]
  The above object is achieved by the present invention described below. That is, the present inventionThe method for forming an image recorded matter is a method for forming an image recorded matter having a coating layer on at least a part of an image,
The following general formula (1):
-COOA (1)
(However, A in the general formula (1) represents an alkali metal, ammonium or organic ammonium.)
A step of preparing an aqueous liquid composition containing in a dissolved state a polymer having a group having a structure represented by:
Preparing an image recording material having an image formed by an ink jet recording method in an ink receiving layer containing a polyvalent metal ion of an ink jet recording medium;
The liquid composition is applied to at least a part of an image formed on the ink jet recording medium, and the polymer contained in the liquid composition is added to the polyvalent ink in the ink receiving layer of the ink jet recording medium. Forming a coating layer by insolubilization with metal ions;
Have
The inkjet recording medium has an ink receiving layer in which one or more layers are laminated on a substrate, and a layer containing alumina hydrate is formed as an outermost layer, and the alumina hydrate is After forming the ink receiving layer containing on the substrate as the outermost layer, the ink receiving layer is swollen again using a treatment liquid containing polyvalent metal ions, and the surface thereof is pressure-bonded to a heated mirror drum, It is manufactured by a method for manufacturing an inkjet recording medium to be dried.
It is characterized by that.
[0014]
  In the present invention,The polymer contained in the liquid composition applied to at least a part of the image formed on the recording medium is insolubilized by the action of polyvalent metal ions in the ink receiving layer of the recording medium. Thus, a coating layer is formed. According to this coating layer, it is possible to have an effect of improving the image quality, and it is possible to impart gas resistance and abrasion resistance to the image. In addition, the formation position of the coating layer on the image is not limited to a colored portion by a coloring material such as a dye, and may be only a non-colored portion.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail below.
[0016]
  The present inventionUsed inThe recording medium is formed by ejecting a recording liquid containing a coloring material by an ink jet recording method to form an image on the recording medium, and then applying a liquid composition onto at least the image of the recording medium to form a coating layer. It is suitably used for the method.
[0017]
This liquid composition for forming a coating layer contains a polymer having a carboxylate. This polymer is dissolved in an aqueous medium, and the insolubilization is performed by the action of polyvalent metal ions in the ink receiving layer of the recording medium to which the liquid composition is applied. As a preferred embodiment, the polymer is instantaneously insolubilized on a recording medium having an ink receiving layer adjusted to a polyvalent metal ion concentration capable of insolubilizing the polymer in the liquid composition. Examples thereof include a method of separating and absorbing the solvent component in the recording medium to form a coating layer made of a polymer on the recording medium.
[0018]
Further, the means for applying the liquid composition for forming the coating layer onto the recording medium is not particularly limited, as in a general coating method such as a roll coater and a reverse coater, and a recording liquid containing a color material. An ink jet recording method can be used, and it can be applied on the ink receiving layer of a recording medium on which an image has already been formed using these applying means. In addition, when the ink jet recording method is used, the coating layer forming part of the polymer in the liquid composition may be only the colored part of the image on the recording medium or the entire surface. Further, it is not always necessary to cover the entire image portion. In some cases, the coloring portion of the color material is not covered, and the purpose may be to protect the surface of the image in the blank portion and to prevent the stain. In particular, by using an ink jet recording method, it is easy to make the coating layer thin and uniform, and further, by adding the nozzle for the liquid composition to the ink jet recording head by the same method as the image forming method. Since it is not necessary to separately provide a unit for forming the coating layer, the size can be reduced.
[0019]
In order to form such a coating layer, the polyvalent metal ion concentration in the ink receiving layer of the recording medium must be controlled to a value that can insolubilize the polymer of the liquid composition. The specific polyvalent metal ion concentration may be appropriately selected depending on the polymer used in the liquid composition for forming the coating layer. A preferable range is that the polyvalent metal ion concentration in the ink receiving layer is 0.01 to The range is 1.0 (mol / l), more preferably 0.04 to 0.8 (mol / l). When the polyvalent metal ion concentration in the ink receiving layer is less than 0.01 (mol / l), insolubilization of the polymer on the recording medium may be difficult to occur, and a sufficient coating layer may be formed. It may not be possible. Further, when the polyvalent metal ion concentration in the ink receiving layer exceeds 1.0 (mol / l), the color of the recorded image may be deteriorated.
[0020]
In the present invention, the polyvalent metal ion concentration in the ink receiving layer is determined by the following formula.
Formula: Multivalent metal ion concentration (mol / L) = W × V_P
W and V in the above formula_PRepresents the polyvalent metal ion content (g / g) per 1 g of the ink receiving layer and the void volume (mL / g) in 1 g of the ink receiving layer, respectively.
[0021]
  The above W can be measured using a fluorescent X-ray measuring apparatus after appropriately taking out the ink receiving layer from the recording medium. Also, V_PIs the volume of the ink receiving layer (V) per unit area on the recording medium.₁(Ml / m²)), The mass of the ink receiving layer per unit area on the recording medium (H₁(G / m²)), And the true density (D1 (ml / g)) of the ink receiving layer, V_P= V₁/ H₁-D₁As required. The true density of the ink receiving layer can be measured by, for example, a dry automatic densimeter (manufactured by Shimadzu Corporation; Accupic 1330) after the ink receiving layer is appropriately removed from the recording medium. In addition, the present inventionUsed inThe ink receiving layer of the recording medium may have a single layer structure or a multilayer structure, but in any structure, at least a layer containing alumina hydrate is used as the outermost layer constituting the ink receiving surface. In the case of a single layer configuration, the multivalent metal ion concentration is determined by the above formula for the entire single-layer ink receiving layer in the case of a single layer configuration, and the above formula for the outermost layer in the case of a multilayer configuration. To obtain the polyvalent metal ion concentration.
[0022]
In the present invention, in order to contain polyvalent metal ions in the ink receiving layer of the recording medium, a coating liquid is applied and dried on a substrate to form an ink receiving layer, and then a treatment liquid containing polyvalent metal ions. Is re-swelled, and the surface is pressed against a heated mirror surface and dried.
[0023]
Any polyvalent metal ion may be used as long as it can insolubilize the polymer in the liquid composition for forming the coating layer. For example, alkaline earth metals such as magnesium and calcium, and rare earth metals such as yttrium, lanthanum, and cerium. And multivalent ions such as transition metals such as zirconium. At least one selected from these polyvalent metal ions can be used. Preferably, calcium can be used from the viewpoint of re-swellability and cohesiveness of the alumina hydrate used in the ink receiving layer.
[0024]
The concentration of polyvalent metal ions in the treatment liquid for imparting polyvalent metal ions to the ink receiving layer is preferably in the range of 0.03 to 2.0 (mol / L), more preferably 0.03 to 0.03. The range is 1.0 (mol / L), more preferably 0.03 to 0.5 (mol / L). If the concentration of the metal salt in the treatment liquid exceeds this range, the re-swellability of the receiving layer may deteriorate and a good glossy surface may not be obtained. In addition, when the concentration of the polyvalent metal ion is less than this range, there may be a case where a sufficient content of the polyvalent metal ion cannot be supplied to the ink receiving layer. Formation of the coating layer may not be achieved.
[0025]
Further, the temperature of the mirror drum to be bonded is preferably 60 ° C. to 150 ° C., more preferably 70 ° C. to 120 ° C. If the drum temperature is less than this range, drying may be insufficient or it may be difficult to obtain excellent gloss. When the temperature exceeds this range, it may be difficult to obtain excellent glossiness due to rapid drying of the rewetting liquid.
[0026]
The press pressure at the time of pressure bonding is preferably in the range of 10 kg / cm to 100 kg / cm, more preferably in the range of 15 kg / cm to 80 kg / cm. When the press pressure is less than this range, it may be difficult to obtain excellent glossiness.When the press pressure exceeds this range, the pores are crushed and sufficient absorption of ink and auxiliary liquid is obtained. It may be difficult. Temporarily, when forming the ink receiving layer by applying and drying the coating liquid on the base material, if the coating liquid contains polyvalent metal ions together with alumina hydrate, the alumina hydrate Tends to agglomerate, causing problems in stability during a long run, and rewetting is deteriorated unlike when it is contained in the treatment liquid, and it may be difficult to obtain a good glossy surface.
[0027]
In the present invention, the pH of the ink receiving layer coating solution is preferably adjusted to 4.0 to 6.5. By controlling the pH within this range, the dispersibility of the alumina hydrate in the coating solution can be excellent, and excellent gloss can be obtained.
[0028]
As the substrate, papers such as appropriately sized paper and non-size paper can be used. In particular, the surface pH of the substrate is preferably the same as or lower than the surface pH of the recording medium from the viewpoint of storage stability of the recording medium.
[0029]
Furthermore, in consideration of gas intrusion from the back side of the recording medium, it is also preferable to use a gas-sealed back side by laminating or the like after performing a glossing process by a process with a mirror drum.
[0030]
The ink receiving layer of the recording medium in the present invention is preferably formed so that the total pore volume is in the range of 0.35 to 1.0 ml / g, more preferably 0.4 to 0.9 ml / g. When the pore volume of the ink receiving layer is larger than the above range, the ink receiving layer is cracked and powdered off. There are cases where ink overflows from the ink receiving layer and bleeding tends to occur in the image.
[0031]
The BET specific surface area of the ink receiving layer is 50 to 300 m.²/ g range is preferred, more preferably 100-300m²/ g. If it is smaller than this range, the glossiness of the ink receiving layer is lost, and haze increases, so that the image may appear white. On the other hand, if it is larger than the above range, the ink receiving layer may be easily cracked.
[0032]
The BET specific surface area and pore volume can be determined by a nitrogen adsorption / desorption method after deaeration treatment at 120 ° C. for 24 hours.
[0033]
The ink receiving layer is formed as a layer whose outermost layer contains alumina hydrate. Preferred examples of the alumina hydrate for forming an ink receiving layer exhibiting physical properties relating to the pore volume and the BET specific surface area include an alumina hydrate represented by the following general formula (2).
[0034]
On the other hand, as the alumina hydrate used for forming the ink receiving layer provided on the substrate, for example,
1) The ink absorption speed is fast and there is no more blur than necessary.
2) High print density and color development,
3) Excellent weather resistance
A material that satisfies the desired characteristics such as the above and that can form the above-described ink receiving layer having the predetermined gloss is used. As such an alumina hydrate, what is represented by the following general formula (2) can be mentioned as a suitable thing.
General formula (2):
Al₂O_3-n(OH)_2n・ MH₂O
In the formula, n represents an integer of 0, 1, 2, or 3, and m represents a value of 0 to 10, preferably 0 to 5. mH₂Since O represents a detachable water phase that is not involved in the formation of crystal lattice in many cases, m can take a non-integer value. Moreover, when this type of alumina hydrate is calcined, m may reach a value of zero. Note that m and n are not 0 at the same time.
[0035]
The alumina hydrate is adjusted in pore properties during the production process. In order to satisfy the desired BET specific surface area and pore volume of the ink receiving layer, the pore volume is 0.3 to 1.0 ml / g. It is preferable to use an alumina hydrate which is more preferably 0.35 to 0.9 ml / g. Alumina hydrate having a pore volume in this range is more suitable for keeping the pore volume of the ink receiving layer within the specified range. Moreover, about BET specific surface area, it is 50-350m.²/ g alumina hydrate is preferably used, more preferably 100 to 250 m²/ g. Alumina hydrate having a BET specific surface area within this range is more suitable for setting the specific surface area of the ink receiving layer within the specified range.
[0036]
The coating amount of the dispersion for forming the ink receiving layer is 0.5 to 60 g / m in terms of dry solid content.², More preferably 5 to 45 g / m²The thickness of the ink receiving layer is, for example, 15 μm to 60 μm, preferably 20 μm to 55 μm, particularly preferably 25 μm to 50 μm, in order to obtain good ink absorbability and resolution. Can do.
[0037]
Next, the liquid composition for forming a coating layer in the present invention will be described. The polymer as a carboxylate in the liquid composition is stably dissolved in the liquid composition and insolubilized by the action of polyvalent metal ions in the ink receiving layer of the recording medium to form a stable layer. Anything is possible. For example, a vinyl copolymer obtained by using one or more acrylic monomers such as acrylic acid, methacrylic acid, maleic acid, maleic acid half ester, and itaconic acid can be added by adding a basic substance. A solubilized one is preferred.
[0038]
The basic substance in this case is not particularly limited, and alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonia water, monoethanolamine, diethanolamine, triethanolamine, Examples thereof include monoisopropanolamine diisopropanolamine, triisopropanolamine, morpholine, aminomethylpropanol, aminomethylpropanediol and aminoethylpropanediol, and at least one of them can be used.
[0039]
The monomer that can be copolymerized with the acrylic acid-based monomer is not particularly limited as long as it can form a polymer having the desired characteristics. At least one kind can be used. That is, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, n- (Meth) acrylate monomers such as hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, further, styrene monomer, Benzyl (meth) acrylate, 2-anthryl (meth) acrylate, 2- (benzoyloxy) ethyl (meth) acrylate, 2- (5-ethyl-2-pyridyl) ethyl (meth) acrylate, [1,1′-biphenyl ] -4-yl ( ) Acrylate, 7-oxo-1,3,5-cycloheptatrien-1-yl (meth) acrylate, 8-quinolyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, 1-methyl Hexyl (meth) acrylate, 1-methylheptyl (meth) acrylate, 2-methylpentyl (meth) acrylate, 1-cyclohexyl-3-azetidinyl (meth) acrylate, 9-carbazolylmethyl (meth) acrylate, tetrahydro-2H -Pyran-2-yl (meth) acrylate, 3-nitrophenyl (meth) acrylate, 1- (3-perylenyl) ethyl (meth) acrylate, (3-methyloxiranyl) methyl (meth) acrylate, etc. And at least selected from these It can be used alone.
[0040]
Examples of the counter ion (A in the general formula (1)) in the present invention include alkali metals, ammonium and organic ammonium, and at least one selected from these can be used. Examples of the alkali metal include lithium, sodium, potassium, rubidium and the like, and examples of the organic ammonium include monoethanolammonium, diethanolammonium, triethanolammonium, monoisopropanolammonium, diisopropanolammonium, triisopropanolammonium, Examples thereof include alkylammonium such as monomethylammonium, dimethylammonium, trimethylammonium, monoethylammonium, diethylammonium and triethylammonium, and alkanolammonium.
[0041]
  Also,CarboxylateThe acid value of the polymer as is preferably from 50 to 300. If it is less than 50, a problem may occur in terms of adhesion. In particular, when a thermal ink jet is used, it may cause scorching on the heater, and stable ejection properties may not be obtained. On the other hand, if it exceeds 300, insolubilization of the copolymer on the paper surface becomes difficult to occur, the surface pH of the recording medium for forming the coating layer must be extremely lowered, and there is a problem with color and bronze of the image. It may become.
[0042]
The preferred content ratio of the polymer as the carboxylate, the water-soluble organic solvent and water in the liquid composition in the state before the addition of the basic substance for solubilization to the liquid composition is about the polymer Can be selected from the range of 1 to 15% by mass, from 0 to 90% by mass for water-soluble organic solvents, more preferably from the range of 5 to 70% by mass, and from 9 to 99% by mass for water. .
[0043]
  In addition, the present inventionInIn the liquid composition, for example, a coloring material may be included for the purpose of decoration (logo putting with light blue etc.). In this case, since the coloring material is present in the coating layer, Gas resistance (such as a logo) tends to be slightly inferior to existing colorants. Accordingly, the color material concentration in the liquid composition is preferably 0.5% by mass or less, more preferably 0.2% by mass or less.
[0044]
Next, the recording liquid containing the color material in the present invention will be described.
[0045]
In the present invention, the components of the coloring material may be known per se, and examples thereof include water-soluble dyes represented by direct dyes, acid dyes, basic dyes, reactive dyes, food dyes and the like. Such a water-soluble dye is generally used in a ratio of about 0.1 to 20% by mass in the recording liquid.
[0046]
The solvent used for the recording liquid used in the present invention is water or a mixed solvent of water and a water-soluble organic solvent, and those listed above as the liquid composition for forming a coating layer are preferably used. The content of the water-soluble organic solvent in the recording liquid is generally in the range of 0 to 95% by mass, preferably 10 to 80% by mass, more preferably 20 to 50% by mass with respect to the total mass of the ink. is there.
[0047]
Further, the recording liquid used in the present invention may include a surfactant, a viscosity adjuster, a surface tension adjuster, a pH adjuster, a fungicide, a rust preventive, and the like as necessary in addition to the above components.
[0048]
【Example】
EXAMPLES Hereinafter, although a manufacture example and an Example demonstrate this invention further, this invention is not limited to these. The physical property values were measured by the following methods.
[0049]
(Glossiness)
The 20 ° glossiness on the ink receiving side was measured based on JIS-Z-8741 using a digital variable gloss meter (manufactured by Suga Test Instruments Co., Ltd.).
[0050]
(Printing)
Using an inkjet recording apparatus (BJF660 manufactured by Canon Inc.) having an on-demand type multi-recording head that discharges ink by applying thermal energy corresponding to the recording signal to the ink, single color printing (100%) of color ink having the following composition Thereafter, the liquid composition was solid-printed (200%) by the same method so as to completely cover the portion where the solid-print of each color ink was performed.
[0051]
(Ink composition)
・ Ink dye (Y, M, C or Bk): 5 parts
・ Ethylene glycol: 10 parts
・ Polyethylene glycol: 10 parts
・ Water: 75 parts
Ink dye
Y: C.I. Acid Yellow 23
M: C.I. Acid Red 52
C: C.I. Direct Blue 199
Bk: C.I. Food Black 2
[0052]
(Gas resistance test)
After forming a black monochromatic image part (100%) on the prepared recording medium by an ink jet recording method, a liquid composition for forming a coating layer containing a water-soluble polymer is ejected by the ink jet recording method, and then a test sample is formed. Was put in an ozone exposure tester (manufactured by Suga Test Instruments Co., Ltd.) and exposed to ozone at a concentration of 3.0ppm for 6 hours under conditions of 23 ° C and 60% RH, and the gas resistance was exposed to ozone. Evaluation was based on the percent change in image density after the test.
Gas resistance (%) = (Image density after ozone exposure test / Image density before ozone exposure test) x 100 (%)
[0053]
(Manufacture of liquid composition)
{Liquid composition A}
A liquid composition A having the following composition was prepared using a styrene-acrylic copolymer A (acid value 200, molecular weight: 10,000) synthesized by a solution polymerization method using a radical initiator. In addition, potassium hydroxide was used as a basic substance, and the addition amount was adjusted so that the pH of the liquid composition was 8.0.
・ Styrene-acrylic copolymer A: 3 parts
・ Glycerin: 7 parts
・ Diethylene glycol: 5 parts
・ Water: 85 parts
[0054]
[Production example]
Disperal HP15 (trade name: manufactured by SASOL) was mixed with pure water as an alumina hydrate to obtain a dispersion having a solid content of 22% by mass. Next, 2% of a mixed solution of acetic acid / nitric acid = 1.4 / 0.6 with respect to the solid content was added thereto and stirred for a while. Thereafter, the dispersion was heated to 90 ° C. with stirring, and held at that temperature for 2 hours. Thereafter, the temperature of the dispersion was returned to room temperature, and the coarse particles were separated by a filter to obtain an alumina dispersion A. When this alumina dispersion A was dried and measured by X-ray diffraction, it had a pseudo boehmite structure.
[0055]
Polyvinyl alcohol PVA117 (trade name: manufactured by Kuraray Co., Ltd.) was dissolved in pure water to obtain a 9% by mass solution. The alumina dispersion A and the polyvinyl alcohol solution were mixed and stirred so that the alumina hydrate solid content and the polyvinyl alcohol solid content were 100: 9 in mass ratio, and dispersion B (pH 5. 0) was obtained.
[0056]
[Example 1]
Base material (basis weight 150g / m²5% sodium tetraborate aqueous solution in advance by a knife knife coater at 10g / m²After coating, Dispersion B is die coated to a dry thickness of 35g / m²Then, using a rewetting cast coater on the surface of the ink receiving layer, rewetting treatment was performed using a 0.2 mol / l calcium chloride aqueous solution as a treatment liquid. Furthermore, 20g / m of polyethylene²The recording medium 1 was obtained by bonding to the back surface by extrusion lamination.
[0057]
[Example 2]
Base material (basis weight 150g / m²5% by weight sodium tetraborate aqueous solution in advance with a knife knife coater at a surface pH of 6.8).²After coating, Dispersion B is die coated to a dry thickness of 35g / m²Then, the surface of the ink receiving layer was subjected to a rewet cast treatment using a 0.03 mol / l calcium chloride aqueous solution as a treatment liquid using a rewet cast coater. Furthermore, 20g / m of polyethylene²The recording medium 2 was obtained by bonding to the back surface by extrusion lamination.
[0058]
[Example 3]
A recording medium 3 was obtained in the same manner as in Example 2 except that the treatment liquid in Example 2 was changed to a 0.5 mol / l calcium chloride aqueous solution.
[0059]
[Comparative Example 1]
A recording medium 5 was obtained in the same manner as in Example 2 except that the treatment liquid in Example 2 was changed to a 0.5 mol / l sodium chloride aqueous solution. The obtained recording medium 5 had excellent glossiness, but when the liquid composition was applied, the coating layer was not formed and the gas property was inferior.
[0060]
(Evaluation)
For the recording media obtained in the above Examples and Comparative Examples, the 20 ° glossiness on the ink receiving layer side was measured based on JIS-Z-8741 using a digital variable glossiness meter (manufactured by Suga Test Instruments Co., Ltd.). The results are shown in Table 1. Further, the surface pH value of the glossy surface of the recording medium having the ink receiving layer was measured using a pH measurement set for paper (manufactured by Kyoritsu Riken; model MPC) and the results are shown in Table 1. Further, when an image such as a photograph was printed on a glossy surface having an ink receiving layer of this recording medium using an ink jet printer (trade name: manufactured by BJF-870 Canon Inc.), a silver salt-based image was printed. An image having the texture and image quality of a photograph could be formed. In addition, after discharging the liquid composition A for forming a coating layer containing a water-soluble polymer on the glossy surface of the recording medium on which printing has been performed by the above method by the inkjet recording method, A test was conducted. The results are shown in Table 1.
[0061]
[Table 1]

[0062]
【The invention's effect】
  As explained above, the present inventionUsed inAccording to the method for producing a recording medium, it is possible to effectively control the amount of polyvalent metal ions in the ink receiving layer of the recording medium, and to provide a recording medium having excellent gloss and ink absorption. A recording image for forming a coating layer for image protection by insolubilizing a polymer in a liquid composition applied to an ink receiving layer on which an image is formed by the action of polyvalent metal ions contained in the ink receiving layer It is possible to provide a recording medium that is suitably used in the forming method. Furthermore, according to the method for forming an image recording material using the method for producing a recording medium, nozzle clogging or liquid composition in a print head in an ink jet apparatus as a means for applying an image of a liquid composition for forming a coating layer to an image It is possible to provide an image recorded matter excellent in image quality, gas resistance and abrasion resistance without causing solid matter sticking on the surface of the material application roller and without stickiness after the coating layer is formed. In addition, according to the present invention, it is easy to reduce the size of an apparatus used for forming an image recording.

Claims (5)

A method of forming an image recorded matter having a coating layer on at least a part of an image,
The following general formula (1):
-COOA (1)
(However, A in the general formula (1) represents an alkali metal, ammonium or organic ammonium.)
A step of preparing an aqueous liquid composition containing in a dissolved state a polymer having a group having a structure represented by:
Preparing an image recording material having an image formed by an ink jet recording method in an ink receiving layer containing a polyvalent metal ion of an ink jet recording medium;
The liquid composition is applied to at least a part of an image formed on the ink jet recording medium, and the polymer contained in the liquid composition is added to the polyvalent ink in the ink receiving layer of the ink jet recording medium. Forming a coating layer by insolubilization with metal ions;
Have
The inkjet recording medium has an ink receiving layer in which one or more layers are laminated on a substrate, and a layer containing alumina hydrate is formed as an outermost layer, and the alumina hydrate is After forming the ink receiving layer containing on the substrate as the outermost layer, the ink receiving layer is swollen again using a treatment liquid containing polyvalent metal ions, and the surface thereof is pressure-bonded to a heated mirror drum, A method for forming an image recording product , which is produced by a method for producing an inkjet recording medium to be dried . 2. The method for forming an image recorded matter according to claim 1, wherein the concentration of polyvalent metal ions in the treatment liquid is in the range of 0.03 to 0.5 mol / l. The image-recorded material according to claim 1, wherein the polyvalent metal ion in the treatment liquid is at least one selected from magnesium, calcium, yttrium, lanthanum, cerium, and zirconium . Forming method . The method for forming an image recorded matter according to any one of claims 1 to 4, wherein the concentration of polyvalent metal ions in the ink receiving layer is 0.01 to 1.0 mol / l. The method for forming an image recorded matter according to any one of claims 1 to 4, wherein the pH of the coating solution containing the alumina hydrate is 4.0 to 6.5.