JP2006231904A - Composition for ink jet image receiving layer and ink jet recording medium - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink jet recording medium which is little in oozing out with the passage of time of an image, and to provide a composition for the ink jet image receiving layer used therefor. <P>SOLUTION: The composition for an ink jet image receiving layer contains at least an inorganic fine particle, a water soluble binder and a cationic cellulose and the ink jet recording medium having the ink jet image receiving layer contains at least the inorganic fine particle, the water soluble binder and the cationic cellulose on a base material. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a composition for an ink jet image-receiving layer and an ink jet recording medium, and in particular, an ink jet using a liquid ink such as a water-based ink or an oil-based ink, or a solid ink that is solid at room temperature and melted and liquefied for printing. The present invention relates to an ink jet recording medium suitable for recording and an ink jet image receiving layer composition used therefor.

In recent years, with the rapid development of the information industry, various information processing systems have been developed, and recording methods and apparatuses suitable for the information systems have been developed and put into practical use.
Among the above recording methods, the inkjet recording method is capable of recording on a variety of recording materials, the hardware (device) is relatively inexpensive, compact, and excellent in quietness. Of course, it has been widely used in so-called home use.

In addition, with the recent increase in resolution of inkjet printers, it has become possible to obtain so-called photographic-like high-quality recorded matter. Furthermore, with the development of hardware (device), various recording sheets for ink jet recording have been developed.
The characteristics required for the recording sheet for ink jet recording are generally (1) fast drying (high ink absorption speed), and (2) ink dot diameter is appropriate and uniform. (No blur), (3) good graininess, (4) high dot roundness, (5) high color density, (6) high chroma (dullness) (7) The light resistance, gas resistance and water resistance of the printed portion are good, (8) the whiteness of the recording sheet is high, and (9) the preservability of the recording sheet is good ( (No long-term storage, yellowing coloration, long-term storage does not cause image blur), (10) Stable deformation, good dimensional stability (curl is sufficiently small), (11) Hard running performance Is good. Furthermore, in addition to the above properties, glossy, surface smoothness, texture of photographic paper-like texture similar to silver salt photography, etc. are used for photo glossy paper used for the purpose of obtaining so-called photographic-like high-quality recorded matter. Required.

  As an ink jet recording medium satisfying the above requirements, a sheet is formed from a paper stock mainly composed of raw pulp and a compound having a cationic group so that the surface becomes an ink jet recording surface using an anionic pigment ink. And an ink jet recording medium obtained by adjusting the zeta potential of the surface at pH 7 to 9 to a positive potential (for example, see Patent Document 1). However, the ink jet recording medium described in Patent Document 1 does not have sufficient gloss.

The paper is made from a pulp slurry containing at least a filler, a sizing agent, a sulfuric acid band, and a cationic resin, the ash content in the paper is 5 to 40% by weight, and the water absorption by the Cobb method is 16 to 100 g / m ^2. Inkjet recording paper characterized by the above is known (for example, see Patent Document 2). However, the inkjet recording paper described in Patent Document 2 does not have sufficient gloss.

Furthermore, an ink jet recording sheet characterized by having a layer containing cationized cellulose and microfibrillated cellulose on a supporting substrate is known (for example, see Patent Document 3). However, the ink jet recording sheet described in Patent Document 3 is inferior in ink absorbability.
Japanese Patent Laid-Open No. 2003-21833 JP-A-8-292094 Japanese Patent Laid-Open No. 9-20067

  The present invention has been made in view of the above problems, and an object of the present invention is to provide an ink jet recording medium having a high image color density and little image aging, and an ink jet image receiving layer composition used therefor.

That is, the present invention
<1> A composition for an ink jet image-receiving layer containing at least inorganic fine particles, a water-soluble binder, and cationized cellulose.

  <2> The inkjet image-receiving layer composition according to <1>, wherein the inorganic fine particles are vapor-phase-process silica.

  <3> The composition for inkjet image-receiving layer according to <2>, wherein an average primary particle diameter of the vapor phase method silica is 50 nm or less.

  <4> An inkjet recording medium having an inkjet image-receiving layer containing at least inorganic fine particles, a water-soluble binder and cationized cellulose on a support.

  <5> The inkjet recording medium according to <4>, wherein the inorganic fine particles are vapor phase silica.

  <6> The inkjet recording medium according to <5>, wherein the gas phase method silica has an average primary particle size of 50 nm or less.

  According to the present invention, it is possible to provide an inkjet recording medium having a high color density of an image and less blurring of the image over time, and an inkjet image receiving layer composition used therefor.

Hereinafter, the composition for an ink jet image-receiving layer and the ink jet recording medium of the present invention will be described in detail.
The composition for inkjet image-receiving layer of the present invention contains at least inorganic fine particles, a water-soluble binder and cationized cellulose. A coating liquid for forming an ink jet image receiving layer is preferred as the composition for the ink jet image receiving layer.
The ink jet recording medium of the present invention has an ink jet image receiving layer containing at least inorganic fine particles, a water-soluble binder and cationized cellulose on a support.
Since the inkjet image-receiving layer contains cationized cellulose, the inkjet recording medium of the present invention has a high image color density and little blurring of the image over time.

The inkjet image-receiving layer according to the present invention is a layer obtained by crosslinking and curing a coating layer in which the coating liquid for forming an inkjet image-receiving layer according to the present invention (hereinafter sometimes referred to as “first liquid”) is applied on a support. Preferably there is. In addition, the crosslinking and curing may be performed (1) at the same time as the first liquid is applied, or (2) during the drying of the coating layer formed by applying the first liquid, and the coating layer is dried at a reduced rate. At any time before showing, it can be carried out by applying a solution containing a metal compound (hereinafter sometimes referred to as “second liquid”) to the coating layer or coating film.
Although the cationized cellulose is contained in the coating liquid for forming an inkjet image-receiving layer according to the present invention, the cationized cellulose may be further contained in the second liquid.

Each material contained in the inkjet image receiving layer will be described. The inkjet image-receiving layer contains at least inorganic fine particles, a water-soluble binder, and cationized cellulose, and contains a crosslinking agent, a metal compound, a mordant, a surfactant, a high-boiling organic solvent, and the like as necessary.
(Cationized cellulose)
Examples of the cationized cellulose used in the present invention include cellulose cationized by introducing a cation group such as an ammonium group or an amino group into the cellulose by a conventional method. Such a cationized cellulose can be easily obtained, for example, as Gelna-QH-300 manufactured by Daicel Chemical Industries. It is preferable to use cationized cellulose as an aqueous solution of about 3% in relation to viscosity.
The addition amount of the cationized cellulose is preferably 0.3 to 10% by mass and more preferably 1 to 5% by mass with respect to the total solid mass of the ink-jet image receiving layer. Further, preferably 0.05 to 2 g / m ² as a coating amount of cationic cellulose, more preferably ^{0.1~1g / m 2, 0.2~0.7g / m} 2 is particularly preferred. If the amount of cationized cellulose applied is less than 0.05 g / m ² , the effect of improving bleeding is small. On the other hand, when the coating amount of cationized cellulose exceeds ² g / m ² , the viscosity of the coating solution becomes high and handling may be difficult.

(Inorganic fine particles)
Examples of the inorganic fine particles used in the present invention include silica fine particles such as gas phase method silica and hydrous silica fine particles, colloidal silica, alumina, titanium dioxide, barium sulfate, calcium silicate, zeolite, kaolinite, halloysite, mica, talc, Examples thereof include calcium carbonate, magnesium carbonate, calcium sulfate, boehmite, pseudoboehmite and the like. These can be used alone or in combination of two or more. These inorganic fine particles are preferably dispersed and used with a cationic resin.

  Among the inorganic fine particles, gas phase method silica is particularly preferable, and the gas phase method silica and the other inorganic fine particles can be used in combination. The amount of the vapor phase silica in the total mass of the inorganic fine particles when used in combination is preferably 90% by mass or more, and more preferably 95% by mass or more.

  Silica fine particles are generally roughly classified into wet method particles and dry method (gas phase method) particles according to the production method. In the wet method, a method in which activated silica is produced by acid decomposition of a silicate, which is appropriately polymerized and coagulated and precipitated to obtain hydrous silica is the mainstream. On the other hand, in the vapor phase method, a method by high-temperature vapor phase hydrolysis of silicon halide (flame hydrolysis method), a method in which silica sand and coke are heated and reduced by an arc in an electric furnace and oxidized with air. The method of obtaining anhydrous silica by the (arc method) is the mainstream, and the “gas phase method silica” means anhydrous silica fine particles obtained by the gas phase method.

Vapor phase silica is different from hydrous silica in terms of the density of silanol groups on the surface, the presence or absence of vacancies, etc., and exhibits different properties, but is suitable for forming a three-dimensional structure with a high porosity. The reason for this is not clear, but in the case of hydrous silica, the density of silanol groups on the surface of the fine particles is large at 5 to 8 / nm ² , and the silica fine particles tend to aggregate closely (aggregate). In the case of the method silica, the density of silanol groups on the surface of the fine particles is 2 to 3 / nm ² , so that it is sparse soft agglomeration (flocculate), resulting in a structure with a high porosity. Is done.

  Vapor phase silica has a particularly large specific surface area, so it has high ink absorption and retention efficiency, and its refractive index is low, so it provides transparency to the inkjet image receiving layer when dispersed to an appropriate particle size. And high color density and good color development can be obtained. The transparency of the inkjet image-receiving layer is important from the viewpoint of obtaining a high color density and good color development gloss even when applied to uses such as photo glossy paper.

The average primary particle size of the vapor phase silica is preferably 50 nm or less, more preferably 10 nm or less, and particularly preferably 3 to 10 nm. Vapor phase silica is easy to adhere to each other due to hydrogen bonds with silanol groups, so that when the average primary particle size is 50 nm or less, it can form a structure with a large porosity, effectively improving ink absorption characteristics. In addition, the transparency and surface gloss of the inkjet image-receiving layer can be enhanced. In addition, the vapor phase method silica may be used as primary particles or may be contained in a state where secondary particles are formed.
The average primary particle diameter of the vapor phase silica can be measured using a scanning electron microscope.

Vapor phase silica is preferably used in a dispersed state. Vapor phase silica can be dispersed by using a cationic resin as a dispersant (flocculation inhibitor) and can be used as a vapor phase silica dispersion. The cationic resin is not particularly limited, but a cationic polymer having primary to tertiary amino groups and salts thereof, and a quaternary ammonium base, such as examples of other mordant components described later, is preferable. It is also preferable to use a silane coupling agent as the dispersant. Specifically, a water-soluble or aqueous emulsion type can be suitably used. For example, a dicyan cation resin represented by a dicyandiamide-formalin polycondensate, a polyamine cation resin represented by a dicyanamide-diethylenetriamine polycondensate, epichlorohydrin - dimethylamine addition polymers, dimethyldiallylammonium chloride -SO ₂ copolymer, diallylamine salt -SO ₂ copolymer, dimethyl diallyl ammonium chloride polymer, polymer of allylamine salt, dialkylaminoethyl (meth) acrylate quaternary Examples thereof include polycationic cation resins such as salt polymers and acrylamide-diallylamine salt copolymers.

Among these, gas phase method silica having a specific surface area of 200 m ² / g or more by BET method is preferable. By containing vapor-phase process silica, a porous structure can be obtained and the ink absorption performance can be improved. Further, when the specific surface area is 200 m ² / g or more, the ink absorbability is improved and the speed is increased. The dryness and ink bleeding are improved, and the image quality and print density can be increased.

  Here, the BET method is one of the powder surface area measurement methods by the vapor phase adsorption method, and is a method for obtaining the total surface area, that is, the specific surface area of a 1 g sample from the adsorption isotherm. Usually, nitrogen gas is used as the adsorbed gas, and a method of measuring the amount of adsorption from the change in pressure or volume of the gas to be adsorbed is common. A prominent expression of the isotherm of multimolecular adsorption is the Brunauer Emmett and Teller equation (BET equation). Based on this, the amount of adsorption is obtained, and the surface area is obtained by multiplying the area occupied by one adsorbed molecule on the surface. .

(Water-soluble binder)
Examples of the water-soluble binder used in the present invention include polyvinyl alcohol (PVA), polyvinyl acetal, cellulose resin [methyl cellulose (MC), ethyl cellulose (EC), hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC) and the like], Chitins, chitosans, starches: Polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene glycol (PEG), polyvinyl ether (PVE), which are resins having an ether bond; Polyamide, which is a resin having an amide group or an amide bond Acrylamide (PAAM), polyvinylpyrrolidone (PVP), and polyacrylates, maleic resins, alginates, gelatins, etc. having carboxyl groups as dissociative groups, etc. And the like. These can be used alone or in combination of two or more.

  Among the above, polyvinyl alcohol is preferable, and the polyvinyl alcohol and the other water-soluble binder can be used in combination. The amount of polyvinyl alcohol in the total mass of the water-soluble binder when used in combination is preferably 90% by mass or more, and more preferably 95% by mass or more.

  In addition to polyvinyl alcohol (PVA), the polyvinyl alcohol includes cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, and other polyvinyl alcohol derivatives. Polyvinyl alcohol can be used alone or in combination of two or more.

The polyvinyl alcohol (PVA) has a hydroxyl group in its structural unit, and this hydroxyl group and a silanol group on the surface of the silica fine particle form a hydrogen bond, and a three-dimensional network structure having secondary particles of the silica fine particle as a chain unit. Make it easier to form. It is considered that this can form an ink-jet image receiving layer having a porous structure with a high porosity by forming a three-dimensional network structure.
The ink jet image-receiving layer having a porous structure as described above can absorb ink rapidly by capillary action during ink jet recording, and can form dots having good roundness without ink bleeding.

  As the content of the water-soluble binder (particularly polyvinyl alcohol), the film strength is prevented from being reduced due to an insufficient amount and cracking at the time of drying is prevented. From the viewpoint of preventing a decrease in ink absorbency due to a decrease, the amount is preferably 9 to 40% by mass, and 12 to 33% by mass with respect to the total solid mass of the layer when the ink jet image receiving layer is formed. More preferred.

  As a number average polymerization degree of the said polyvinyl alcohol (PVA), 1800 or more are preferable from a viewpoint of crack prevention, and 2000 or more are more preferable. Further, from the viewpoint of transparency and the viscosity of the coating liquid for forming an inkjet image receiving layer, PVA having a saponification degree of 88% or more is preferable, and PVA having a saponification degree of 95% or more is particularly preferable.

-Content ratio of inorganic fine particles and water-soluble binder-
The content ratio of the inorganic fine particles (i) to the water-soluble binder (p) [PB ratio (i: p); the mass of the inorganic fine particles relative to 1 part by mass of the water-soluble binder] has a great influence on the film structure when the layer is formed. give. That is, as the PB ratio increases, the porosity, pore volume, and surface area (per unit mass) increase. Specifically, as the PB ratio, it is possible to prevent a decrease in film strength due to the PB ratio being too large and cracking at the time of drying, and the PB ratio is too small so that the voids are easily blocked by the resin. From the viewpoint of preventing the ink absorbency from being lowered due to the decrease in the porosity, 1.5: 1 to 10: 1 is preferable.

  Since stress may be applied when the ink jet recording medium passes through the transport system of the ink jet printer, the ink jet image receiving layer needs to have sufficient film strength. Further, when cutting into a sheet shape, the ink jet image receiving layer needs to have sufficient film strength in order to prevent cracking or peeling of the ink jet image receiving layer. From this viewpoint, the PB ratio is preferably 5: 1 or less, and preferably 2: 1 or more from the viewpoint of securing high-speed ink absorbability with an inkjet printer.

For example, a coating solution in which a vapor phase method silica having an average primary particle diameter of 20 nm or less and a water-soluble binder are completely dispersed in an aqueous solution at a PB ratio of 2: 1 to 5: 1 is coated on a support, and the coating layer Is dried, a three-dimensional network structure is formed in which the secondary particles of silica fine particles are chain units, the average pore diameter is 30 nm or less, the porosity is 50% to 80%, and the pore specific volume is 0.5 ml / g. As described above, a translucent porous film having a specific surface area of 100 m ² / g or more can be easily formed.

(Crosslinking agent)
The inkjet image-receiving layer according to the inkjet recording medium of the present invention includes a coating layer containing fine particles and a water-soluble binder, and further includes a crosslinking agent capable of crosslinking the water-soluble binder, and a crosslinking reaction between the crosslinking agent and the water-soluble binder. The aspect which is the porous layer hardened | cured by is preferable.

Boron compounds are preferred for crosslinking the above water-soluble binder, particularly polyvinyl alcohol resins. Examples of the boron compound include borax, boric acid, borates (for example, orthoborate, InBO ₃ , ScBO ₃ , YBO ₃ , LaBO ₃ , Mg ₃ (BO ₃ ) ₂ , Co ₃ (BO ₃ ) ₂ , two Borate (eg, Mg ₂ B ₂ O ₅ , Co ₂ B ₂ O ₅ ), metaborate (eg, LiBO ₂ , Ca (BO ₂ ) ₂ , NaBO ₂ , KBO ₂ ), tetraborate (eg, Na _{2 B 4 O 7 · 10H 2} O), can be mentioned five borate _{(e.g., KB 5 O 8 · 4H 2} O, Ca 2 B 6 O 11 · 7H 2 O, CsB 5 O 5) or the like. Among them, Of these, borax, boric acid, and borate are preferable, and boric acid is particularly preferable in that a crosslinking reaction can be promptly caused.

  Moreover, the following compounds other than a boron compound can also be used. For example, aldehyde compounds such as formaldehyde, glyoxal, and glutaraldehyde; ketone compounds such as diacetyl and cyclopentanedione; bis (2-chloroethylurea) -2-hydroxy-4,6-dichloro-1,3,5- Active halogen compounds such as triazine and 2,4-dichloro-6-S-triazine sodium salt; divinylsulfonic acid, 1,3-vinylsulfonyl-2-propanol, N, N′-ethylenebis (vinylsulfonylacetamide) ), Active vinyl compounds such as 1,3,5-triacryloyl-hexahydro-S-triazine; N-methylol compounds such as dimethylolurea and methyloldimethylhydantoin; melamine resins (for example, methylolmelamine, alkylated methylolmelamine) ;Epoxy resin;

Isocyanate compounds such as 1,6-hexamethylene diisocyanate; aziridine compounds described in US Pat. Nos. 3,017,280 and 2,983611; carboximide compounds described in US Pat. No. 3,100,704; glycerol triglycidyl Epoxy compounds such as ether; Ethyleneimino compounds such as 1,6-hexamethylene-N, N′-bisethyleneurea; Halogenated carboxaldehyde compounds such as mucochloric acid and mucophenoxycyclolic acid; 2,3-dihydroxy Dioxane-based compounds such as dioxane; titanium-containing aluminum sulfate, chromium alum, potassium alum, metal-containing compounds such as zirconyl acetate, chromium acetate, polyamine compounds such as tetraethylenepentamine, hydrazide compounds such as adipic acid dihydrazide, A low molecule or polymer containing two or more oxazoline groups. The above crosslinking agents may be used singly or in combination of two or more.

  The crosslinking agent may be added to the first liquid and / or the second liquid, or the first liquid is applied onto a support on which a coating liquid containing a crosslinking agent has been applied in advance. The cross-linking agent can be supplied to the ink jet image-receiving layer by, for example, overcoating a second liquid (for example, a cross-linking agent solution) after applying and drying the first liquid not containing an agent.

  For example, the crosslinking agent can be suitably applied as follows. Here, a boron compound will be described as an example. That is, when the inkjet image-receiving layer is a layer obtained by crosslinking and curing the coating layer coated with the first liquid, the crosslinking curing is performed simultaneously with (1) forming the coating layer by coating the first liquid. When the coating layer formed by applying the first liquid is being dried and before the coating layer exhibits reduced-rate drying, the second liquid described above is applied to the coating layer. However, the boron compound as the crosslinking agent may be contained in either the first liquid or the second liquid, or may be contained in both of these liquids. When the inkjet image receiving layer is composed of two or more layers, two or more coating liquids can be applied in multiple layers, and the second liquid may be applied from the layer formed.

  1-50 mass% is preferable with respect to the mass of a water-soluble binder, and, as for the usage-amount of a crosslinking agent, 5-40 mass% is more preferable.

(Metal compound)
The ink jet image receiving layer preferably contains a metal compound. A metal compound (and other mordant components) acts as a mordant, and an ink, particularly a dye, is sufficiently mordanted to obtain an ink jet recording medium excellent in image printing density and glossiness and less bleed over time.
In the present invention, a coating layer composed of the first liquid containing a metal compound (hereinafter, the metal compound added to the first liquid may be referred to as “first metal compound”) is provided in advance. In addition, by applying the second liquid further containing a metal compound (hereinafter, the metal compound added to the second liquid may be referred to as a “second metal compound”) to the coating layer. Good film-forming properties that can be sufficiently hardened are obtained.

  As said 1st metal compound, an acidic metal compound is preferable and a polyvalent water-soluble metal salt and a hydrophobic metal salt compound are mentioned. Specific examples include magnesium, aluminum, calcium, scandium, titanium, vanadium, manganese, iron, nickel, zirconium, copper, zinc, gallium, germanium, strontium, yttrium, molybdenum, indium, barium, lanthanum, cerium, praseodymium, neodymium. And salts or complexes of metals selected from samarium, europium, gadolinium, dysproprosium, erbium, ytterbium, hafnium, tungsten, bismuth.

  Specifically, for example, calcium acetate, calcium chloride, calcium formate, zirconium acetate, zirconium tetrachloride, calcium sulfate, barium acetate, barium sulfate, barium phosphate, manganese chloride, manganese acetate, manganese formate dihydrate, manganese ammonium sulfate Hexahydrate, cupric chloride, ammonium copper (II) chloride dihydrate, copper sulfate, cobalt chloride, cobalt thiocyanate, cobalt sulfate, nickel sulfate hexahydrate, nickel chloride hexahydrate, nickel acetate Tetrahydrate, nickel ammonium sulfate hexahydrate, nickel amidosulfate tetrahydrate, aluminum sulfate, aluminum alum, basic polyaluminum hydroxide, aluminum sulfite, aluminum thiosulfate, polyaluminum chloride, aluminum nitrate nonahydrate , Aluminum chloride hexahydrate Ferrous bromide, ferrous chloride, ferric chloride, ferrous sulfate, ferric sulfate, zinc phenolsulfonate, zinc bromide, zinc chloride, zinc nitrate hexahydrate, zinc sulfate, zinc acetate Ammonium, zinc ammonium carbonate, titanium tetrachloride, tetraisopropyl titanate, titanium acetylacetonate, titanium lactate, chromium acetate, chromium sulfate, magnesium sulfate, magnesium chloride hexahydrate, magnesium citrate nonahydrate, sodium phosphotungstate , Sodium tungsten citrate, 12 tungstophosphoric acid n hydrate, 12 tungstosilicic acid 26 hydrate, molybdenum chloride, 12 molybdophosphoric acid n hydrate, gallium nitrate, germanium nitrate, strontium nitrate, yttrium acetate, yttrium chloride , Yttrium nitrate, indium nitrate, orchid nitrate Tan, lanthanum chloride, lanthanum acetate, lanthanum benzoate, cerium chloride, cerium sulfate, cerium octylate, praseodymium nitrate, neodymium nitrate, samarium nitrate, europium nitrate, gadolinium nitrate, dysprosium nitrate, erbium nitrate, ytterbium nitrate, hafnium chloride, nitric acid Bismuth etc. are mentioned. Among these, aluminum sulfate, aluminum alum, basic polyaluminum hydroxide, aluminum sulfite, aluminum thiosulfate, polyaluminum chloride, aluminum nitrate nonahydrate, aluminum chloride hexahydrate, zirconium nitrate, and zirconium tetrachloride are preferable.

  It is preferable that two or more kinds of the first metal compounds are contained in the first liquid. Since the metal compound has a different mordanting dye depending on the type, the mordanting ability can be enhanced by using two or more types of the first metal compound. Therefore, more specifically, it is preferable to contain a metal compound corresponding to two or more dyes to be mordanted. Various combinations are conceivable as the metal compound corresponding to the dye. For example, a zirconium compound is effective for a black dye of a general ink.

  As content in the 1st liquid of a said 1st metal compound, 0.01-1 mass% is preferable with respect to the total mass of a 1st liquid, More preferably, it is 0.05-0.8 mass%. . By setting the content of the first metal compound in the above-described range, an ink jet recording medium having little bleeding with time of an image can be produced without deteriorating curling under low humidity conditions. In addition, when using together the other mordant component mentioned later, total amount is in the said range, Comprising: It can contain in the range which does not impair the effect of this invention.

  As the second metal compound contained in the second liquid, those which are stable under basic conditions can be used without limitation. The metal compound may be a metal salt, a metal complex compound, an inorganic oligomer, or an inorganic polymer. . As said metal compound, what is mentioned as an inorganic mordant mentioned later is used preferably. Of these, zirconium compounds, aluminum compounds and zinc compounds are preferable, and zirconium compounds are particularly preferable. Examples include ammonium zirconium carbonate, ammonium zirconium nitrate, potassium potassium carbonate, zirconium ammonium citrate, zirconyl stearate, zirconyl octylate, zirconyl nitrate, zirconium oxychloride, and zirconium zirconium hydroxy chloride, with zirconium ammonium carbonate being particularly preferred. Moreover, you may use together the other mordant component mentioned later for the 2nd liquid as needed.

  In addition, as the metal complex compound, the metal complex described in “Chemical Review No. 32 1981” edited by the Chemical Society of Japan and “Coordination Chemistry Review”, Vol. 84, pages 85-277 (1988). And transition metal complexes containing a transition metal such as ruthenium described in JP-A-2-182701 can be used.

  The content of the second metal compound in the second liquid is preferably 0.1 to 0.8 mass%, more preferably 0.2 to 0.5 mass%, based on the total mass of the second liquid. It is. By setting the content of the second metal compound in the above range, the gloss can be improved without deteriorating bronzing. In addition, when using together the other mordant component mentioned later, total amount is in the said range, Comprising: It can contain in the range which does not impair the effect of this invention.

  Next, the basic compound contained in the second liquid will be described. Basic compounds include ammonium salts of weak acids, alkali metal salts of weak acids (lithium carbonate, sodium carbonate, potassium carbonate, lithium acetate, sodium acetate, potassium acetate, etc.), alkaline earth metal salts of weak acids (magnesium carbonate, barium carbonate) , Magnesium acetate, barium acetate, etc.), alkali metal or alkaline earth metal hydroxide, hydroxyammonium, ammonia, primary to tertiary amines (ethylamine, dimethylamine, triethylamine, polyallylamine, tripropylamine, tributylamine, Hexylamine, dibutylamine, butylamine, N-ethyl-N-methylbutylamine, etc.), primary to tertiary anilines (diethylaniline, dibutylaniline, ethylaniline, aniline, etc.), pyridine optionally having a substituent (2 Aminopyridine, 3-aminopyridine, 4-aminopyridine, 4- (2-hydroxyethyl) -, etc. aminopyridine) but the like, ammonium salts of weak acids are particularly preferred.

  The weak acid is an inorganic acid or an organic acid described in Chemical Handbook Fundamentals II (Maruzen Co., Ltd.) or the like and having an pKa of 2 or more. Examples of the weak acid ammonium salt include ammonium carbonate, ammonium hydrogen carbonate, ammonium borate, and ammonium acetate. However, it is not limited to these. Among these, ammonium carbonate, ammonium hydrogen carbonate, and ammonium carbamate are preferable, and they are effective in that they do not remain in the layer after drying and ink bleeding can be reduced. Two or more basic compounds may be used in combination.

  As content in the 2nd liquid of the said basic compound, 0.5-10 mass% is preferable with respect to the total mass of a 2nd liquid, More preferably, it is 1-5 mass%. When the content of the basic compound is particularly in the above range, a sufficient degree of curing can be obtained, and the ammonia concentration becomes too high and the working environment is not impaired.

(mordant)
A mordant can be contained together with the above-described metal compound for the purpose of further improving the bleeding and water resistance of the image of the inkjet image-receiving layer.
Examples of the mordant include organic mordants such as cationic polymers (cationic mordants) and inorganic mordants such as water-soluble metal compounds. The cationic mordant is preferably a polymer mordant having a primary to tertiary amino group or a quaternary ammonium base as a cationic functional group, but a cationic non-polymer mordant can also be used.

  As the polymer mordant, a homopolymer of a monomer having a primary to tertiary amino group and a salt thereof, or a quaternary ammonium base (a mordant monomer), or the mordant monomer and other monomers (non-mordant) Those obtained as copolymers or condensation polymers with mordant monomers) are preferred. Moreover, these polymer mordants can be used in any form of a water-soluble polymer or water-dispersible latex particles.

  Examples of the mordant monomer include trimethyl-p-vinylbenzylammonium chloride, trimethyl-m-vinylbenzylammonium chloride, triethyl-p-vinylbenzylammonium chloride, triethyl-m-vinylbenzylammonium chloride, N, N-dimethyl- N-ethyl-Np-vinylbenzylammonium chloride, N, N-diethyl-N-methyl-Np-vinylbenzylammonium chloride, N, N-dimethyl-Nn-propyl-Np-vinylbenzyl Ammonium chloride, N, N-dimethyl-Nn-octyl-Np-vinylbenzylammonium chloride, N, N-dimethyl-N-benzyl-Np-vinylbenzylammonium chloride, N, N-diethyl-N Benzyl-Np-vinylbenzylammonium chloride, N, N-dimethyl-N- (4-methyl) benzyl-Np-vinylbenzylammonium chloride, N, N-dimethyl-N-phenyl-Np-vinyl Benzylammonium chloride;

Trimethyl-p-vinylbenzylammonium bromide, trimethyl-m-vinylbenzylammonium bromide, trimethyl-p-vinylbenzylammonium sulfonate, trimethyl-m-vinylbenzylammonium sulfonate, trimethyl-p-vinylbenzylammonium acetate, trimethyl-m-vinyl Benzylammonium acetate, N, N, N-triethyl-N-2- (4-vinylphenyl) ethylammonium chloride, N, N, N-triethyl-N-2- (3-vinylphenyl) ethylammonium chloride, N, N-diethyl-N-methyl-N-2- (4-vinylphenyl) ethylammonium chloride, N, N-diethyl-N-methyl-N-2- (4-vinylphenyl) ethylammonium chloride Tate;

N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N- Methyl chloride, ethyl chloride, methyl bromide of dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide , Quaternized products of ethyl bromide, methyl iodide or ethyl iodide, or sulfonates, alkyl sulfonates, acetates or alkyl carboxylates substituted with their anions.

  Specific examples of the compound include monomethyl diallylammonium chloride, trimethyl-2- (methacryloyloxy) ethylammonium chloride, triethyl-2- (methacryloyloxy) ethylammonium chloride, trimethyl-2- (acryloyloxy) ethylammonium chloride, Triethyl-2- (acryloyloxy) ethylammonium chloride, trimethyl-3- (methacryloyloxy) propylammonium chloride, triethyl-3- (methacryloyloxy) propylammonium chloride, trimethyl-2- (methacryloylamino) ethylammonium chloride, triethyl- 2- (methacryloylamino) ethylammonium chloride, trimethyl-2- (acryloylua) C) ethylammonium chloride, triethyl-2- (acryloylamino) ethylammonium chloride, trimethyl-3- (methacryloylamino) propylammonium chloride, triethyl-3- (methacryloylamino) propylammonium chloride, trimethyl-3- (acryloylamino) Propylammonium chloride, triethyl-3- (acryloylamino) propylammonium chloride;

N, N-dimethyl-N-ethyl-2- (methacryloyloxy) ethylammonium chloride, N, N-diethyl-N-methyl-2- (methacryloyloxy) ethylammonium chloride, N, N-dimethyl-N-ethyl- 3- (acryloylamino) propylammonium chloride, trimethyl-2- (methacryloyloxy) ethylammonium bromide, trimethyl-3- (acryloylamino) propylammonium bromide, trimethyl-2- (methacryloyloxy) ethylammonium sulfonate, trimethyl-3- And (acryloylamino) propylammonium acetate. In addition, examples of copolymerizable monomers include N-vinylimidazole and N-vinyl-2-methylimidazole. Moreover, what used polymerization units, such as N-vinylacetamide and N-vinylformamide, and converted into the vinylamine unit by hydrolysis after superposition | polymerization, and the thing which made this a salt can also be utilized.

The non-mordant monomer does not contain a basic or cationic moiety such as a primary to tertiary amino group and a salt thereof, or a quaternary ammonium base, and does not interact with a dye in an inkjet ink. Or a monomer having a substantially small interaction.
For example, (meth) acrylic acid alkyl ester; (meth) acrylic acid cycloalkyl ester such as cyclohexyl (meth) acrylic acid; (meth) acrylic acid aryl ester such as phenyl (meth) acrylate; benzyl (meth) acrylic acid Aralkyl esters of styrene; vinyl aromatics such as styrene, vinyl toluene and α-methyl styrene; vinyl esters such as vinyl acetate, vinyl propionate and vinyl versatate; allyl esters such as allyl acetate; vinylidene chloride, vinyl chloride, etc. Halogen-containing monomers, vinyl cyanides such as (meth) acrylonitrile, olefins such as ethylene and propylene, and the like.

  The (meth) acrylic acid alkyl ester is preferably a (meth) acrylic acid alkyl ester having 1 to 18 carbon atoms in the alkyl moiety, specifically, for example, methyl (meth) acrylate or ethyl (meth) acrylate. Propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, (meth) Examples include octyl acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and the like. Among these, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, and hydroxyethyl methacrylate are preferable. The non-mordant monomer can also be used alone or in combination of two or more.

  Further, as the polymer mordant, polydiallyldimethylammonium chloride, polymethacryloyloxyethyl-β-hydroxyethyldimethylammonium chloride, polyethyleneimine, polyallylamine and a modified product thereof, polyallylamine hydrochloride, polyamide-polyamine resin, cationized starch, Dicyandiamide formalin condensate, dimethyl-2-hydroxypropylammonium salt polymer, polyamidine, polyvinylamine, cationic polyurethane resin described in JP-A-10-86505, and the like are also preferred.

  The modified polyallylamine is obtained by adding 2 to 50 mol% of acrylonitrile, chloromethylstyrene, TEMPO, epoxy hexane, sorbic acid or the like to polyallylamine, and preferably 5 to 5 of acrylonitrile, chloromethylstyrene, and TEMPO. It is a 10 mol% adduct, and 5 to 10 mol% TEMPO adduct of polyallylamine is particularly preferable from the viewpoint of exhibiting an effect of preventing ozone fading.

  The molecular weight of the mordant is preferably 2000 to 300000 in terms of weight average molecular weight. When the molecular weight is in the above range, water resistance and aging resistance can be improved.

(Surfactant)
The first liquid preferably contains a surfactant. As the surfactant, any of cationic, anionic, nonionic, amphoteric, fluorine and silicone surfactants can be used. These surfactants may be used alone or in combination of two or more.

  Examples of the nonionic surfactant include polyoxyalkylene alkyl ethers and polyoxyalkylene alkyl phenyl ethers (for example, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyalkylene ether) Ethylene nonylphenyl ether), oxyethylene / oxypropylene block copolymer, sorbitan fatty acid esters (for example, sorbitan monolaurate, sorbitan monooleate, sorbitan trioleate, etc.), polyoxyethylene sorbitan fatty acid esters (for example, polyoxyethylene) Sorbitan monolaurate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitant Oleate, etc.), polyoxyethylene sorbitol fatty acid esters (eg, polyoxyethylene sorbitol tetraoleate), glycerin fatty acid esters (eg, glycerol monooleate), polyoxyethylene glycerin fatty acid esters (polyoxymonostearate) Ethylene glycerol, monooleic acid polyoxyethylene glycerin, etc.), polyoxyethylene fatty acid esters (polyethylene glycol monolaurate, polyethylene glycol monooleate, etc.), polyoxyethylene alkylamine, acetylene glycols (eg, 2, 4, 7) , 9-tetramethyl-5-decyne-4,7-diol, and ethylene oxide adducts and propylene oxide adducts of the diols), and the like. Sharp emission alkyl ethers are preferable.

  Examples of the amphoteric surfactant include amino acid type, carboxyammonium betaine type, sulfoammonium betaine type, ammonium sulfate betaine type, imidazolium betaine type, and the like, for example, US Pat. No. 3,843,368, Those described in JP-A-59-49535, JP-A-63-236546, JP-A-5-303205, JP-A-8-262742, and JP-A-10-282619 can be suitably used. As the amphoteric surfactant, an amino acid type amphoteric surfactant is preferable, and as the amino acid type amphoteric surfactant, as described in JP-A-5-303205, for example, an amino acid (glycine, glutamic acid, Histidine acid etc.) and N-aminoacyl acids and salts thereof into which long chain acyl groups have been introduced.

Examples of the anionic surfactant include fatty acid salts (for example, sodium stearate, potassium oleate), alkyl sulfate esters (for example, sodium lauryl sulfate, triethanolamine lauryl sulfate), and sulfonates (for example, sodium dodecylbenzenesulfonate). Alkyl sulfosuccinate (for example, sodium dioctyl sulfosuccinate), alkyl diphenyl ether disulfonate, alkyl phosphate, and the like.
Examples of the cationic surfactant include alkylamine salts, quaternary ammonium salts, pyridinium salts, imidazolium salts, and the like.

  Examples of the fluorosurfactant include compounds derived via an intermediate having a perfluoroalkyl group using a method such as electrolytic fluorination, telomerization, or oligomerization. Examples thereof include perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl trialkyl ammonium salts, perfluoroalkyl group-containing oligomers, and perfluoroalkyl phosphate esters.

  The silicone surfactant is preferably a silicone oil modified with an organic group, and can have a structure in which a side chain of a siloxane structure is modified with an organic group, a structure in which both ends are modified, or a structure in which one end is modified. Examples of the organic group modification include amino modification, polyether modification, epoxy modification, carboxyl modification, carbinol modification, alkyl modification, aralkyl modification, phenol modification, and fluorine modification.

  As content of the said surfactant, 0.001-2.0 mass% is preferable in the said 1st liquid, and 0.01-1.0 mass% is more preferable.

(Other ingredients)
Further, the inkjet image receiving layer is configured to contain the following components as required.
For the purpose of suppressing deterioration of the coloring material, various kinds of ultraviolet absorbers, surfactants, antioxidants, and anti-fading agents such as singlet oxygen quenchers may be included.
Examples of the ultraviolet absorber include cinnamic acid derivatives, benzophenone derivatives, benzotriazolylphenol derivatives, and the like. For example, α-cyano-phenyl cinnamate butyl, o-benzotriazole phenol, o-benzotriazole-p-chlorophenol, o-benzotriazole-2,4-di-t-butylphenol, o-benzotriazole-2,4 -Di-t-octylphenol etc. are mentioned. A hindered phenol compound can also be used as an ultraviolet absorber, and specifically, a phenol derivative in which at least one of 2-position or 6-position is substituted with a branched alkyl group is preferable.

  Moreover, a benzotriazole type ultraviolet absorber, a salicylic acid type ultraviolet absorber, a cyanoacrylate type ultraviolet absorber, an oxalic acid anilide type ultraviolet absorber, etc. can be used. For example, JP-A-47-10537, 58-111942, 58-21284, 59-19945, 59-46646, 59-109055, 63-53544. No. 36, Japanese Patent Publication No. 36-10466, No. 42-26187, No. 48-30492, No. 48-31255, No. 48-41572, No. 48-54965, No. 50-10726. No. 2,719,086, US Pat. No. 3,707,375, US Pat. No. 3,754,919, US Pat. No. 4,220,711, and the like. .

  A fluorescent brightening agent can also be used as an ultraviolet absorber, and examples thereof include a coumarin fluorescent brightening agent. Specifically, it is described in Japanese Patent Publication Nos. 45-4699 and 54-5324.

  Examples of the antioxidant include European Patent Publication No. 223739, Publication No. 309401, Publication No. 309402, Publication No. 310551, Publication No. 310552, Publication No. 4594416, Publication of German Patent No. 3435443, JP-A-54-48535, JP-A-60-107384, JP-A-60-107383, JP-A-60-125470, JP-A-60-125471, JP-A-60-125472, JP-A-60-287485. 60-287486, 60-287487, 60-287488, 61-160287, 61-185483, 61-2111079, 62-146678, 62-146680, 62-146679, 62-282885, JP same 62-262047, JP-same 63-051174, JP-same 63-89877, JP-same 63-88380, JP-same 66-88381, JP-same 63-113536, JP-

JP-A-63-163351, JP-A-63-203372, JP-A-63-224989, JP-A-63-251282, JP-A-63-267594, JP-A-63-182484, JP-A-1-239282, JP-A-2-262654, JP-A-2-71262, JP-A-3-121449, JP-A-4-29185, JP-A-4-291684, JP-A-5-61166, JP-A-5-119449, 5-188687, 5-188686, 5-110490, 5-110437, 5-170361, JP 48-43295, 48-33212, Examples thereof include those described in U.S. Pat. Nos. 4,814,262 and 4,980,275.

  Specifically, 6-ethoxy-1-phenyl-2,2,4-trimethyl-1,2-dihydroquinoline, 6-ethoxy-1-octyl-2,2,4-trimethyl-1,2-dihydroquinoline 6-ethoxy-1-phenyl-2,2,4-trimethyl-1,2,3,4-tetrahydroquinoline, 6-ethoxy-1-octyl-2,2,4-trimethyl-1,2,3 4, -tetrahydroquinoline, nickel cyclohexane acid, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -2-ethylhexane, 2-methyl-4-methoxy-diphenylamine, Examples include 1-methyl-2-phenylindole.

  These anti-fading agents may be used alone or in combination of two or more. The anti-fading agent may be water-solubilized, dispersed, emulsified, or included in microcapsules. The addition amount of the antifading agent is preferably 0.01 to 10% by mass in the first liquid.

  The ink jet image-receiving layer may contain various inorganic salts and acids, alkalis and the like as pH adjusting agents for the purpose of enhancing the dispersibility of the inorganic fine particles. Furthermore, it may contain metal oxide fine particles having electronic conductivity for the purpose of suppressing surface frictional charge or peeling charge, and may contain various matting agents for the purpose of reducing surface frictional characteristics. .

  The inkjet image receiving layer may contain an acid. By adding an acid, the surface pH of the inkjet image-receiving layer is adjusted to 3 to 6, preferably 3 to 5. This is preferable because yellowing resistance of the white background portion is improved. The surface pH is measured by the A method (coating method) of the surface pH measurement determined by the Japan Paper Pulp Technology Association (J.TAPPI). For example, the measurement can be performed by using a paper PH measurement set “Type MPC” manufactured by Kyoritsu Riken Co., Ltd. corresponding to the method A.

Specific examples of acids include formic acid, acetic acid, glycolic acid, oxalic acid, propionic acid, malonic acid, succinic acid, adipic acid, maleic acid, malic acid, tartaric acid, citric acid, benzoic acid, phthalic acid, isophthalic acid , Glutaric acid, gluconic acid, lactic acid, aspartic acid, glutamic acid, salicylic acid, salicylic acid metal salts (salts such as Zn, Al, Ca, Mg), methanesulfonic acid, itaconic acid, benzenesulfonic acid, toluenesulfonic acid, trifluoromethanesulfone Acid, styrenesulfonic acid, trifluoroacetic acid, barbituric acid, acrylic acid, methacrylic acid, cinnamic acid, 4-hydroxybenzoic acid, aminobenzoic acid, naphthalenedisulfonic acid, hydroxybenzenesulfonic acid, toluenesulfinic acid, benzenesulfinic acid, Sulfanilic acid, sulfamic acid, α-le Examples include ricinic acid, β-resorcinic acid, γ-resorcinic acid, gallic acid, phloroglicin, sulfosalicylic acid, ascorbic acid, erythorbic acid, bisphenolic acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, boric acid, boronic acid, etc. It is done. What is necessary is just to determine the addition amount of these acids so that the surface pH of an inkjet image receiving layer may be set to 3-6.
The above acids can be metal salts (eg sodium, potassium, calcium, cesium, zinc, copper, iron, aluminum, zirconium, lanthanum, yttrium, magnesium, strontium, cerium, etc.) or amine salts (eg ammonia, triethylamine, tri Butylamine, piperazine, 2-methylpiperazine, polyallylamine, etc.).

(High boiling point organic solvent)
By including the nonionic or amphoteric surfactant and the high boiling point organic solvent in the first liquid, it is possible to keep the curl of the ink jet recording medium flat.
The high-boiling organic solvent is preferably water-soluble, and examples of the water-soluble high-boiling organic solvent include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, glycerin, diethylene glycol monobutyl ether (DEGMBE), and triethylene glycol. Monobutyl ether, glycerin monomethyl ether, 1,2,3-butanetriol, 1,2,4-butanetriol, 1,2,4-pentanetriol, 1,2,6-hexanetriol, thiodiglycol, triethanolamine And alcohols such as polyethylene glycol (weight average molecular weight of 400 or less), and preferably diethylene glycol monobutyl ether (DEGMBE).

  As content in the said 1st liquid of the said high boiling point organic solvent, 0.05-1 mass% is preferable, Most preferably, it is 0.1-0.6 mass%.

  The composition for inkjet image-receiving layer of the present invention comprises, in addition to the inorganic fine particles, water-soluble binder and cationized cellulose, each component contained in the above-described inkjet image-receiving layer and the coating liquid for forming the inkjet image-receiving layer as necessary. May be included. Preferred specific examples and preferred ranges of the respective components are the same as those of the above-described inkjet image-receiving layer and the coating liquid for forming an inkjet image-receiving layer. Moreover, when the composition for inkjet image receiving layers of this invention contains the solvent mentioned later, it can be used as a coating liquid for inkjet image receiving layer formation.

-Support-
As the support usable in the present invention, any of a transparent support made of a transparent material such as plastic and an opaque support made of an opaque material such as paper can be used. In particular, in order to make use of the transparency of the ink jet image receiving layer, it is preferable to use a transparent support or a highly glossy opaque support. Further, a read-only optical disc such as a CD-ROM or DVD-ROM, a write-once optical disc such as a CD-R or DVD-R, or a rewritable optical disc can be used as a support, and ink jet image receiving layers can be provided on both sides of the label. .

The material that can be used for the transparent support is preferably a material that has transparency and can withstand radiant heat when used in an OHP or a backlight display. Examples of the material include polyesters such as polyethylene terephthalate (PET); polysulfone, polyphenylene oxide, polyimide, polycarbonate, polyamide and the like. Of these, polyesters are preferable, and polyethylene terephthalate is particularly preferable.
Although there is no restriction | limiting in particular as thickness of the said transparent support body, 50-200 micrometers is preferable at the point which is easy to handle.

  As the highly glossy opaque support, one having a glossiness of 40% or more on the surface on which the ink jet image receiving layer is provided is preferable. The glossiness is a value determined according to the method described in JIS P-8142 (75-degree specular gloss test method for paper and paperboard). Specifically, the following supports are mentioned.

  For example, high gloss paper support such as art paper, coated paper, cast coated paper, baryta paper used for silver salt photographic support, etc .; polyesters such as polyethylene terephthalate (PET), nitrocellulose, cellulose acetate , Cellulose esters such as cellulose acetate butyrate, and plastic films such as polysulfone, polyphenylene oxide, polyimide, polycarbonate, and polyamide are made opaque by adding a white pigment or the like (surface calendering may be applied). Glossy film; or a support in which a polyolefin coating layer containing or not containing a white pigment is provided on the surface of a highly glossy film containing the various paper supports, the transparent support or the white pigment. Etc. A white pigment-containing foamed polyester film (for example, foamed PET containing polyolefin fine particles and forming voids by stretching) can also be suitably exemplified.

  Although there is no restriction | limiting in particular also about the thickness of the said opaque support body, 50-300 micrometers is preferable at the point of handleability.

  The surface of the support may be subjected to corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment, etc. in order to improve wettability and adhesion.

Next, the base paper used for the paper support will be described in detail.
As the base paper, wood pulp is used as a main raw material, and paper is made using synthetic pulp such as polypropylene or synthetic fiber such as nylon or polyester in addition to wood pulp as necessary. As the wood pulp, any of LBKP, LBSP, NBKP, NBSP, LDP, NDP, LUKP, NUKP can be used, but it is preferable to use more LBKP, NBSP, LBSP, NDP, LDP with a lot of short fibers. preferable. However, the ratio of LBSP and / or LDP is preferably 10% by mass or more and 70% by mass or less. The pulp is preferably a chemical pulp (sulfate pulp or sulfite pulp) with few impurities, and a pulp having a whiteness improved by bleaching is also useful.

  In the base paper, sizing agents such as higher fatty acids and alkyl ketene dimers, white pigments such as calcium carbonate, talc and titanium oxide, paper strength enhancing agents such as starch, polyacrylamide and polyvinyl alcohol, fluorescent whitening agents, polyethylene glycols A water retaining agent such as a dispersant, a softening agent such as a quaternary ammonium, and the like can be appropriately added.

The freeness of the pulp used for papermaking is preferably 200 to 500 ml as defined by CSF, and the fiber length after beating is a 24 mesh residual mass% and a 42 mesh residual as defined in JIS P-8207. 30-70 mass% of the sum with the mass% of is preferable. In addition, it is preferable that the mass% of 4 mesh remainder is 20 mass% or less. The basis weight of the base paper is preferably 30 to 250 g, and particularly preferably 50 to 200 g. The thickness of the base paper is preferably 40 to 250 μm. The base paper can be given a high smoothness by calendering at the paper making stage or after paper making. The density of the base paper is generally 0.7 to 1.2 g / m ² (JIS P-8118). Furthermore, the base paper stiffness is preferably 20 to 200 g under the conditions specified in JIS P-8143.

  A surface sizing agent may be applied to the surface of the base paper. As the surface sizing agent, a sizing agent similar to the size that can be added to the base paper can be used. The pH of the base paper is preferably 5 to 9 when measured by a hot water extraction method defined in JIS P-8113.

  The surfaces on both sides of the base paper can generally be coated with polyethylene. The polyethylene is mainly low-density polyethylene (LDPE) and / or high-density polyethylene (HDPE), but other LLDPE, polypropylene and the like can also be used in part.

  In particular, the polyethylene layer on the side on which the ink jet image-receiving layer is formed is obtained by adding rutile or anatase type titanium oxide, fluorescent whitening agent, ultramarine blue to polyethylene, as is widely done in photographic paper, Those having improved whiteness and hue are preferred. Here, as a titanium oxide content, about 3-20 mass% is preferable with respect to polyethylene, and 4-13 mass% is more preferable. Although the thickness of a polyethylene layer does not have limitation in particular, 10-50 micrometers is suitable for both front and back layers. Further, an undercoat layer may be provided on the polyethylene layer in order to provide adhesion with the ink jet image receiving layer. As the undercoat layer, aqueous polyester, gelatin and PVA are preferable. Moreover, as thickness of this undercoat layer, 0.01-5 micrometers is preferable.

  Polyethylene-coated paper can be used as glossy paper, or when it is coated by melt-extruding polyethylene onto the surface of the base paper, a matte or silky surface that can be obtained with ordinary photographic printing paper by performing a so-called molding process. Can also be used.

-Method for forming inkjet image-receiving layer-
The ink jet image receiving layer according to the present invention is preferably a layer obtained by crosslinking and curing a coating layer obtained by coating the first liquid on a support. In addition, the crosslinking and curing may be performed (1) at the same time as the first liquid is applied, or (2) during the drying of the coating layer formed by applying the first liquid, and the coating layer is dried at a reduced rate At any time before showing, it can be carried out by applying a second liquid containing a metal compound to the coating layer or coating film.
For example, a coating liquid for forming an inkjet image receiving layer containing vapor phase silica, polyvinyl alcohol (PVA), cationized cellulose, boric acid, a cationic resin, a nonionic or amphoteric surfactant and a high boiling point organic solvent as the first liquid is Can be prepared as follows.
That is, after adding vapor phase method silica in water and further adding a cationic resin and dispersing with a high pressure homogenizer, a sand mill or the like, boric acid is added thereto, and an aqueous PVA solution (for example, the amount of PVA is 1 / of that of vapor phase method silica). 3) and cationized cellulose, and a nonionic or amphoteric surfactant and a high-boiling organic solvent can be added and stirred. The obtained coating liquid is a uniform sol, and a coating layer can be obtained by coating this on a support by the following coating method to form a porous inkjet image receiving layer having a three-dimensional network structure. it can. At this time, as described above, partial gelation of PVA can be prevented by adding PVA after diluting boric acid.

  The first liquid can be made into an aqueous dispersion having an average particle diameter of 10 to 300 nm by refining using a disperser. As a disperser used for obtaining the aqueous dispersion, various types of conventionally known dispersers such as a high-speed rotary disperser, a medium agitating disperser (ball mill, sand mill, etc.), an ultrasonic disperser, a colloid mill disperser, and a high pressure disperser. Although a disperser can be used, a medium stirring type disperser, a colloid mill disperser, or a high-pressure disperser is preferable from the viewpoint that the formed fine particles are efficiently dispersed.

  The first liquid is preferably an acidic solution, and preferably has a pH of 6.0 or less, more preferably 5.0 or less, and even more preferably 4.0 or less. This pH can be adjusted by appropriately selecting the type and addition amount of the cationic resin. Moreover, you may adjust by adding an organic or inorganic acid. When the pH of the first liquid is 6.0 or less, the crosslinking reaction of the water-soluble resin by the crosslinking agent (particularly the boron compound) can be more sufficiently suppressed.

  The first liquid can be applied by a known application method using, for example, an extrusion die coater, an air doctor coater, a bread coater, a rod coater, a knife coater, a squeeze coater, a reverse roll coater, a bar coater, or the like. .

  The second liquid (basic solution) can be applied after the application of the first liquid, but the application is preferably carried out before the coating layer exhibits reduced-rate drying. That is, after the application of the first liquid, the second liquid is preferably introduced while the coating layer exhibits constant rate drying.

  The second liquid may contain a crosslinking agent and a mordant as necessary. The second liquid can be used as an alkaline solution to promote hardening, and is preferably adjusted to pH 7.1 or higher, more preferably pH 7.5 or higher, and particularly preferably pH 7.9 or higher. If the pH is too close to the acidic side, the cross-linking reaction of the water-soluble polymer contained in the first liquid is not sufficiently performed by the cross-linking agent, resulting in the occurrence of bronzing and defects such as cracks in the inkjet image receiving layer. is there.

  The second liquid is, for example, ion-exchanged water, a metal compound (for example, 1 to 5% by mass), a basic compound (for example, 1 to 5% by mass), and, if necessary, p-toluenesulfonic acid (for example, 0.5% by mass). ˜3 mass%) and can be prepared by sufficiently stirring.

  Moreover, water, an organic solvent, or these mixed solvents can be used for the solvent used for preparation of each liquid. Examples of the organic solvent that can be used for coating include alcohols such as methanol, ethanol, n-propanol, i-propanol, and methoxypropanol, ketones such as acetone and methyl ethyl ketone, tetrahydrofuran, acetonitrile, ethyl acetate, and toluene. .

  Here, “before the coating layer comes to show reduced-rate drying” usually refers to a process for several minutes immediately after the application of the first liquid, and during this time, the solvent (dispersion in the applied coating layer) The phenomenon of “constant rate drying” in which the content of the medium) decreases in proportion to time. About the time which shows this "constant rate drying", it describes in chemical engineering handbook (pages 707-712, Maruzen Co., Ltd. issue, October 25, 1980), for example.

  As described above, after the application of the first liquid, it is dried until the coating layer of the first liquid shows reduced-rate drying. This drying is generally performed at 40 to 180 ° C. (preferably 50 to 120 ° C.). It is performed for 0.5 to 10 minutes (preferably 0.5 to 5 minutes). The drying time naturally varies depending on the coating amount, but usually the above range is appropriate.

  As a method of applying the second liquid before the coating layer shows reduced-rate drying, (1) a method of further coating the second liquid on the coating layer, (2) spraying by a method such as spraying. And (3) a method of immersing the support on which the coating layer is formed in the second liquid.

  In the method (1), examples of the application method for applying the second liquid include a curtain flow coater, an extrusion die coater, an air doctor coater, a bread coater, a rod coater, a knife coater, a squeeze coater, a reverse roll coater, and a bar. A known coating method such as a coater can be used. However, it is preferable to use a method in which the coater does not directly contact an already formed coating layer, such as an extrusion die coater, a curtain flow coater, a bar coater or the like.

  After application of the second liquid, it is generally heated at 40 to 180 ° C. for 0.5 to 30 minutes to be dried and cured. Especially, it is preferable to heat at 40-150 degreeC for 1 to 20 minutes.

  The second liquid (basic solution) can also be preferably applied simultaneously with the application of the first liquid. In such a case, the first liquid and the second liquid are brought into contact with the support. Thus, an inkjet image-receiving layer can be formed by simultaneous application (multilayer application) on the support, followed by drying and curing.

  The simultaneous coating (multilayer coating) can be performed by a coating method using, for example, an extrusion die coater or a curtain flow coater. After the simultaneous application, the formed application layer is dried. In this case, the drying is generally performed by heating the application layer at 15 to 150 ° C. for 0.5 to 10 minutes, preferably 40 to 100. It is carried out by heating at a temperature of 0.5 to 5 minutes.

  When the simultaneous coating (multilayer coating) is performed by, for example, an extrusion die coater, the two types of coating liquid discharged simultaneously are in the vicinity of the discharge port of the extrusion die coater, that is, before moving onto the support. In that state, it is coated on the support in multiple layers. Since the two-layer coating liquid layered before coating is likely to cause a cross-linking reaction at the interface between the two liquids when transferred to the support, the two liquids to be ejected are mixed in the vicinity of the discharge port of the extrusion die coater. As a result, thickening is likely to occur, which may hinder the application operation. Therefore, at the time of simultaneous application as described above, it is preferable to apply the simultaneous triple layer application with the barrier liquid (intermediate liquid) interposed between the two liquids together with the application of the first liquid and the second liquid.

  The barrier layer solution can be selected without particular limitation. For example, an aqueous solution containing a trace amount of water-soluble resin, water, or the like can be given. The water-soluble resin is used in consideration of applicability for the purpose of a thickener and the like. For example, cellulose resin (for example, hydroxypropylmethylcellulose, methylcellulose, hydroxyethylmethylcellulose) And polymers such as polyvinylpyrrolidone and gelatin. The barrier layer liquid may contain a mordant.

  After forming the inkjet image-receiving layer on the support, the inkjet image-receiving layer is subjected to, for example, super calendering, gloss calendering, etc., and calendering through the roll nip under heat and pressure, so that surface smoothness, glossiness, It is possible to improve transparency and coating strength. However, the calendar process may cause a decrease in the porosity (that is, the ink absorbability may be decreased), so it is necessary to set the conditions under which the decrease in the porosity is small.

  As roll temperature in the case of performing a calendar process, 30-150 degreeC is preferable and 40-100 degreeC is more preferable. Moreover, as a linear pressure between rolls at the time of a calendar process, 50-400 kg / cm is preferable and 100-200 kg / cm is more preferable.

The thickness of the ink-jet image receiving layer needs to be determined in relation to the porosity in the layer because it is necessary to have an absorption capacity that can absorb all droplets in the case of ink-jet recording. For example, if the ink amount is 8 nL / mm ² and the porosity is 60%, a film having a layer thickness of about 15 μm or more is required. Considering this point, in the case of inkjet recording, the thickness of the inkjet image receiving layer is preferably 10 to 50 μm.

Further, the pore diameter of the ink jet image receiving layer is preferably 0.005 to 0.030 μm, more preferably 0.01 to 0.025 μm in terms of median diameter.
The porosity and the median diameter of the pores can be measured using a mercury porosimeter (trade name: Bore Sizer 9320-PC2, manufactured by Shimadzu Corporation).

  In addition, the ink-jet image receiving layer is preferably excellent in transparency, but as a guide, the haze value when the ink-jet image receiving layer is formed on a transparent film is preferably 30% or less, and 20% or less. It is more preferable. The haze value can be measured with a haze meter (HGM-2DP: manufactured by Suga Test Instruments Co., Ltd.).

    EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. In the examples, an inkjet recording sheet is prepared as an example of an inkjet recording medium, and “parts” and “%” in the examples represent mass standards unless otherwise specified.

[Example 1]
(Production of support)
50 parts of LBKP made of acacia and 50 parts of LBKP made of aspen were beaten to 300 ml of Canadian freeness by a disc refiner to prepare a pulp slurry.

  Next, the pulp slurry obtained above was charged with 1.3% cationic starch (CATO 304L manufactured by NSC Japan), 0.15% anionic polyacrylamide (DA4104 manufactured by Seiko PMC Co., Ltd.), and alkyl ketene dimer. (Arakawa Chemical Size Pine K) 0.29%, epoxidized behenamide 0.29%, polyamide polyamine epichlorohydrin (Arakawa Chemical Co., Ltd .: Arafix 100) 0.32%, then added antifoaming agent 0.12% was added.

In the process of making the pulp slurry prepared as described above with a long paper machine and pressing the felt surface of the web against the drum dryer cylinder through the dryer canvas, the tensile force of the dryer canvas is 1.6 kg / After drying at a setting of cm, 1 g / m ² of polyvinyl alcohol (manufactured by Kuraray Co., Ltd .: KL-118) was applied to both sides of the base paper with a size press and dried to perform calendar treatment. The base paper was made with a basis weight of 166 g / m ² to obtain a base paper (base paper) having a thickness of 160 μm.

After the corona discharge treatment was performed on the wire surface (back surface) side of the obtained base paper, high-density polyethylene was coated to a thickness of 25 μm using a melt extruder, and a thermoplastic resin layer comprising a mat surface was formed. (Hereinafter, this thermoplastic resin layer surface is referred to as “back surface”). The thermoplastic resin layer on the back side is further subjected to corona discharge treatment, and then, as an antistatic agent, aluminum oxide (“Alumina Sol 100” manufactured by Nissan Chemical Industries, Ltd.) and silicon dioxide (manufactured by Nissan Chemical Industries, Ltd.) Of “Snowtex O”) was dispersed in water at a mass ratio of 1: 2 so that the dry mass was 0.2 g / m ² .

  Further, after the corona discharge treatment is performed on the felt surface (surface) side where the thermoplastic resin layer is not provided, 10% of anatase-type titanium dioxide and 0.3% of ultramarine manufactured by Tokyo Ink Co., Ltd. are contained. Low density of MFR (melt flow rate) 3.8, adjusted to a content of 0.08% with a whitening agent “Whitefloor PSN conc” manufactured by Nippon Chemical Industry Co., Ltd. Polyethylene is extruded using a melt extruder so as to have a thickness of 25 μm, and a high gloss thermoplastic resin layer is formed on the surface side of the base paper (hereinafter, this high gloss surface is referred to as “front side”). A support was prepared. This support was made into a long roll body with a width of 1.5 m and a winding length of 3000 m.

(Preparation of first liquid (inkjet image-receiving layer forming coating liquid A))
(1) Vapor phase silica fine particles, (2) ion-exchanged water, (3) “Charol DC-902P” and (4) “ZA-30” in the following composition are mixed, and a bead mill (KD-P (( After dispersion using Shinmaru Enterprises)), the dispersion was heated to 45 ° C. and held for 20 hours. Thereafter, the following (5) boric acid, (6) polyvinyl alcohol solution, (7) “Superflex 600”, (8) polyoxyethylene lauryl ether, (9) ethanol, and (10) Gerner QH-200 It added at 30 degreeC and prepared the coating liquid A for inkjet image receiving layer formation.
The mass ratio between the silica fine particles and the water-soluble resin (PB ratio = (1) :( 6)) is 4.5: 1, and the pH of the coating liquid A for forming an inkjet image-receiving layer is 3.9, which is acidic. Indicated.

<Composition of Coating Liquid A for Forming Inkjet Image Receiving Layer>
(1) Gas phase method silica fine particles (inorganic fine particles) 10.0 parts (AEROSIL300SF75 manufactured by Nippon Aerosil Co., Ltd.)
(2) Ion-exchanged water 64.8 parts (3) "Charol DC-902P" (51.5% aqueous solution) 0.87 parts (dispersant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
(4) 0.54 parts “ZA-30” (Daiichi Rare Element Chemical Industries, Ltd.)
(5) Boric acid (crosslinking agent) 0.37 parts (6) Polyvinyl alcohol (water-soluble resin) solution of the following composition 29.4 parts (7) "Superflex 600" 1.24 parts (Daiichi Kogyo Seiyaku ( Made by Co., Ltd.)
(8) 0.49 part of polyoxyethylene lauryl ether (surfactant) (“Emulgen 109P” (10% aqueous solution), HLB value 13.6, manufactured by Kao Corporation)
(9) Ethanol 2.49 parts (10) Gelner QH-200 (Daicel Chemicals cationized cellulose)
0.31 parts

<Composition of polyvinyl alcohol solution>
・ "PVA235" manufactured by Kuraray Co., Ltd., saponification degree 88%, polymerization degree 3500
2.03 parts ・ Polyoxyethylene lauryl ether (surfactant) 0.03 parts ・ Diethylene glycol monobutyl ether 0.68 parts (Butisenol 20P, manufactured by Kyowa Hakko Co., Ltd.)
・ Ion exchange water 26.6 parts

(Preparation of inkjet recording medium)
A 5-fold diluted polyaluminum chloride aqueous solution (polyaluminum chloride is alpha-in 83 (manufactured by Daimei Chemical Industry Co., Ltd.)) was applied inline at a rate of 7.7 cc / min to the first solution that was flowed to 184 cc / m ² ( Application process). It dried with the hot air dryer at 80 degreeC (wind speed 3-8 m / sec) until the solid content density | concentration of the application layer became 20%. This coating layer exhibited a constant rate of drying during this period. Immediately after that, it was immersed in a second liquid having the following composition for 3 seconds to deposit 13 g / m ² on the coating layer (step of applying a mordant solution) and further dried at 80 ° C. for 10 minutes (drying step). ). Thus, an inkjet recording medium 1 of the present invention provided with an inkjet image receiving layer having a dry film thickness of 32 μm was produced.

<Composition of the second liquid>
(1) Boric acid 0.65 parts (2) Zirconyl ammonium carbonate 2.5 parts (Zircozol AC-7 (28% aqueous solution); manufactured by Daiichi Rare Element Chemical Co., Ltd.)
(3) Ammonium carbonate 3.5 parts (1st grade: manufactured by Kanto Chemical Co., Inc.)
(4) Ion-exchanged water 63.3 parts (5) Polyoxyethylene lauryl ether (surfactant) 30.0 parts ("Emulgen 109P" (2% aqueous solution) manufactured by Kao Corporation, HLB value 13.6)

[Comparative Example 1]
In Example 1, except that (10) Gelner QH-200 of coating liquid A for forming an inkjet image-receiving layer was changed to “SM-4 (methyl cellulose manufactured by Shin-Etsu Chemical Co., Ltd.)”, inkjet was performed in the same manner as Example 1. Recording medium 2 was produced.

[Comparative Example 2]
In Example 1, except that (10) Gelner QH-200 of the coating liquid A for forming an inkjet image-receiving layer was changed to “HPC-SSL (hydroxypropylcellulose manufactured by Nippon Soda Co., Ltd.)”, the same as in Example 1. Thus, an inkjet recording medium 3 was produced.

[Comparative Example 3]
An inkjet recording medium 4 was produced in the same manner as in Example 1 except that (10) Gelner QH-200 of the coating liquid A for forming an inkjet image-receiving layer was omitted.

The obtained inkjet recording medium was used to evaluate gloss, color density and blur.
<Glossiness evaluation method>
A solid black image was printed on each inkjet recording medium using an inkjet printer (“PM-G800” manufactured by Seiko Epson Corporation). Thereafter, the glossiness of the black solid image portion was measured at an incident angle of 60 degrees and a received light intensity of 60 degrees using a digital variable angle glossimeter (Suga Test Instruments Co., Ltd. UGV-5D measuring hole 8 mm). The obtained results are shown in Table 1.

<Color density evaluation method>
A solid image of yellow, magenta, cyan, and black is printed on each inkjet recording medium using an inkjet printer (“Seiko Epson Corporation,“ PM-G800 ”), and stored in an environment of 23 ° C. and 60% RH for 24 hours. Thereafter, the color density of each ink jet recording medium was measured with a reflection density meter (X-rite 938, manufactured by X-rite), and Table 1 shows the result of black density having a large color density change.

<Smudge evaluation method>
Using an inkjet printer (“PM-970C” manufactured by Seiko Epson Corporation), a grid-like linear pattern (line width 0.28 mm) in which magenta ink and black ink are adjacent to each other on each inkjet recording medium. Printed. Immediately after printing, the printed inkjet recording medium was inserted into a transparent PP file, and stored for 3 days in an environment of 35 ° C. and a relative humidity of 80%. Thereafter, the width of the black line of the linear pattern was measured, and the bleeding (%) with time was calculated from the measured value and the width of the black line immediately after printing, which was separately obtained, by the following formula. The obtained results are shown in Table 1.
Bleeding with time (%) = (width of black line of linear pattern stored at 35 ° C. and 80% for 3 days) / (width of black line immediately after printing) × 100

  From Table 1, it can be seen that the introduction of cationized cellulose can suppress the decrease in color density and improve bleeding.

Claims (4)

  A composition for an ink jet image-receiving layer, comprising at least inorganic fine particles, a water-soluble binder, and cationized cellulose.   The composition for ink-jet image receiving layer according to claim 1, wherein the inorganic fine particles are vapor phase silica.   The composition for an inkjet image receiving layer according to claim 2, wherein an average primary particle diameter of the vapor phase method silica is 50 nm or less.   An ink jet recording medium having an ink jet image-receiving layer containing at least inorganic fine particles, a water-soluble binder and cationized cellulose on a support.