JP2003039819A - Ink jet recording sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink jet recording sheet having excellent ozone resistance and glossiness by suppressing occurrence of aging bleeding. SOLUTION: The ink jet recording sheet comprises a color material acceptive layer on a support. In this sheet, the acceptive layer contains a compound represented by formula (1) of an X-Y-S-CH2 -CH2 -S-Y-X and/or a compound represented by formula (2) of an X-Y-S-S-Y-X, a vapor phase process silica, a polyvinyl alcohol, a boron compound, and a mordant, [wherein X is an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxy group and a carboxylate, an acyl group, an amino group, a thiocarbamoyl group, a sulfamoyl group, a sulfoamino group, a group containing other nitrogen atom, or a group containing other sulfur atom, and Y is an alkylene which may have a substituent].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid ink such as a water-based ink (using a dye or a pigment as a coloring material), an oil-based ink, or a solid state which is solid at room temperature and is melted and liquefied for printing. The present invention relates to a recording material suitable for inkjet recording using ink or the like, and more particularly to an inkjet recording sheet having excellent ink receiving performance.

[0002]

2. Description of the Related Art In recent years, along 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 also been developed and put into practical use. Among the above recording methods, the inkjet recording method is capable of recording on various recording materials, hardware (device)
Has been widely used not only in offices but also in so-called home use because it is relatively inexpensive, compact, and excellent in quietness.

Further, with the recent increase in resolution of ink jet printers, it has become possible to obtain so-called photograph-like high quality recorded matter. With the development of such hardware (device), ink jet recording Various recording sheets have been developed. The properties required of the recording sheet for inkjet recording are generally:
(1) quick drying (high ink absorption speed), (2) proper and uniform ink dot diameter (no bleeding), (3) good graininess, (4) High circularity of dots, (5) High color density, (6) High saturation (no dullness), (7) Good light resistance and water resistance of the printed area thing,
(8) The whiteness of the recording sheet is high, (9) the storage stability of the recording sheet is good (no yellowing coloring occurs during long-term storage), (10) deformation is difficult, and dimensional stability is good. (11) The curl is sufficiently small, and (11) the hard running property is good. In addition to the above characteristics, the photo glossy paper used for the purpose of obtaining a so-called photograph-like high-quality recorded matter may have glossiness, surface smoothness, and a photographic paper-like texture similar to silver salt photographs. Required.

In order to improve the above-mentioned properties, an ink jet recording sheet having a porous structure in the coloring material receiving layer has been developed and put into practical use in recent years. Since the inkjet recording sheet has a porous structure, it has excellent ink absorbability (quick drying) and high gloss.

Japanese Unexamined Patent Publication No. 10-119423, 10
JP-A-217601 and the like propose an ink jet recording sheet in which a colorant receiving layer containing fine inorganic pigment particles and a water-soluble resin and having a high porosity is provided on a support. These recording sheets, particularly ink jet recording sheets provided with a coloring material receiving layer having a porous structure using silica as the above-mentioned inorganic pigment fine particles, have excellent ink absorbability due to the constitution and form a high resolution image. It has a high ink-receptive performance and exhibits high gloss. However, after printing, if it is stored in a high temperature and high humidity environment for a long time,
There is a problem that the solvent diffuses together with the dye in the color material receiving layer to cause image blurring with time (so-called “age blurring”).

Trace gases in the air, especially ozone,
This will cause fading of the recorded image over time. Since the recording material having the porous colorant receiving layer has many voids, the recorded image is easily discolored by ozone gas in the air. Therefore, the resistance to ozone in the air (ozone resistance) is very important for the recording material having the above-described porous color material receiving layer.

In order to prevent such fading due to ozone, Japanese Patent Application Laid-Open No. 2000-177235 proposes an ink jet recording medium containing Mg ions and SCN ions in a porous layer containing hydrated alumina. . The inkjet recording medium is composed of Mg ions and SCN.
Light resistance and ozone resistance are improved by incorporating ions and ions into the porous layer. However, although the ink jet recording medium has improved light resistance and ozone resistance,
It is not possible to prevent generation of bleeding over time at the same time.

Further, JP-A-7-314882 contains at least one compound selected from the group consisting of dicarbamate salts, thiuram salts, thiocyanates, thiocyanates and hindered amine compounds. A recording sheet having a porous ink receiving layer is disclosed. Specific examples of the hindered amine compound include those having a structure in which all the hydrogens on the carbons at the 2- and 6-positions of piperidine are substituted with a methyl group. By containing more than one species, fading of recorded images due to trace gases in the air is prevented. However, the above-mentioned recording sheet cannot sufficiently suppress the generation of blurring with time.

For the purpose of suppressing generation of bleeding with time and improving ozone resistance, JP-A-64-36479.
Japanese Patent Application Laid-Open No. 1-97678, Japanese Patent Application Laid-Open No. 1-11
Japanese Patent Laid-Open No. 5677 and Japanese Patent Laid-Open No. 2000-26178 disclose an inkjet recording medium containing a thioether compound. However, since the exemplified compounds of the thioether-based compounds are water-insoluble, it is difficult to mix them in the coating liquid, and they must be added as an emulsion or the like. As described above, when the thioether compound is added as an emulsion, the glossiness of the inkjet recording medium deteriorates due to the large particle size.

[0010]

As described above, the color material receiving layer is strong without cracks and the like, while it has good ink absorbency and can form a high resolution image, and its formation. Image storage performance that allows ink-jet recording images with vivid colors and high density to be stored as they are for a longer period of time while maintaining ink-receptive properties such as light fastness, water fastness, blur resistance over time, and gloss The present situation is that an inkjet recording sheet provided with is not yet provided.

An object of the present invention is to solve the above-mentioned problems in the prior art and achieve the following objects. That is, it is an object of the present invention to provide an inkjet recording sheet that suppresses the occurrence of bleeding over time and is excellent in ozone resistance and glossiness without deteriorating other ink receiving performance. Further, the present invention has an object to provide an inkjet recording sheet that is strong without generation of cracks, has good ink absorbability, is excellent in water resistance and light resistance, and can form a high-resolution image. And

[0012]

Means for solving the problems Means for solving the above problems are as follows. That is,

<1> An ink jet recording sheet having a colorant receiving layer on a support, wherein the colorant receiving layer is a compound represented by the following general formula (1) and / or a general formula (2) ), A vapor phase silica, polyvinyl alcohol, a boron compound, and a mordant, the ink jet recording sheet.

X—Y—S—CH ₂ —CH ₂ —S—Y—X General Formula (1) X—Y—S—S—Y—X General Formula (2) [wherein, X is an alkyl group, Halogen atom, hydroxy group, alkoxyl group, carboxy group and carboxylate salt, acyl group, amino group, thiocarbamoyl group, sulfamoyl group, sulfoamino group, other nitrogen atom-containing group, or other sulfur atom-containing group Represent. In the formula, Y represents an alkylene group which may have a substituent. ]

<2> At least one of the compounds has a molecular weight of 200 or more. <1>
Is a sheet for inkjet recording.

<3> At least one of the above compounds is water-soluble <1> or <2>
Is a sheet for inkjet recording.

<4> The colorant receiving layer is formed by coating a coating solution containing the compound, the vapor grown silica, and the polyvinyl alcohol on the support and simultaneously with the coating or by the coating. In the middle of drying the coating layer, before the coating layer shows a rate-of-reduction drying, after applying a solution containing the boron compound and the mordant to the coating layer, the coating layer is cured. The inkjet recording sheet of <1> to <3>, which is obtained by

<5> The color material receiving layer is obtained by adding the above compound and the above polyvinyl alcohol to an aqueous dispersion of the above fumed silica and a dispersant and having a pH of 4.5 or less and redispersing the coating. A liquid is applied onto the support, simultaneously with the coating, or in the course of drying the coating layer formed by the coating, and before the coating layer shows a rate of reduction drying, the coating layer is The sheet for inkjet recording according to <1> to <3>, which is obtained by applying a solution containing the boron compound and the mordant, and then curing the coating layer.

<6> For the color material receiving layer, a coating solution obtained by adding the polyvinyl alcohol to an aqueous dispersion having a pH of 4.5 or less and comprising gas phase method silica and a dispersant and redispersing the support is used as the support. Applied on top, simultaneously with the coating, or in the course of drying the coating layer formed by the coating,
It is obtained by applying a solution containing the compound, the boron compound and the mordant to the coating layer before the coating layer shows a rate of decrease in drying rate, and then curing the coating layer. The inkjet recording sheet according to <1> to <3>.

<7> The mordant is an ink jet recording sheet of <1> to <6>, which is a polyallylamine having a weight average molecular weight of 100,000 or less and a derivative thereof.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION << Inkjet recording sheet >>
The ink jet recording sheet of the present invention, on a support,
A compound represented by the following general formula (1) and / or a compound represented by the following general formula (2) (hereinafter sometimes referred to as “compound in the present invention”), vapor phase silica, and polyvinyl alcohol. A coloring material receiving layer containing a boron compound and a mordant is provided.

[0022] _{X-Y-S-CH 2} -CH 2 -S-Y-X Formula (1) X-Y-S -S-Y-X Formula (2) wherein, X represents alkyl group, Halogen atom, hydroxy group, alkoxyl group, carboxy group and carboxylate salt, acyl group, amino group, thiocarbamoyl group, sulfamoyl group, sulfoamino group, other nitrogen atom-containing group, or other sulfur atom-containing group Represent. In the formula, Y represents an alkylene group which may have a substituent. ]

In the ink jet recording sheet of the present invention, the compound of the present invention is contained in the coloring material receiving layer, whereby generation of bleeding with time can be suppressed and ozone resistance can be further improved. Furthermore, by using vapor phase silica, polyvinyl alcohol, a boron compound and a mordant together with the colorant receiving layer, the glossiness, ink absorption, bleeding resistance with time, light resistance, print density (maximum density), etc. are improved. be able to.

<Coloring Material Receiving Layer> The coloring material receiving layer in the present invention comprises, as described above, a compound represented by the following general formula (1) and / or a compound represented by the following general formula (2):
It has at least vapor-phase process silica, polyvinyl alcohol, a boron compound, and a mordant, and may further contain various additives.

(Compounds represented by the general formula (1) and the general formula (2)) The following general formula (1) and the following general formula (2)
The compound represented by is a thioether compound.

[0026] _{X-Y-S-CH 2} -CH 2 -S-Y-X Formula (1) X-Y-S -S-Y-X Formula (2)

In the above general formulas (1) and (2),
X is an alkyl group, a halogen atom, a hydroxy group, an alkoxyl group, a carboxy group and a carboxylate, an acyl group, an amino group, a thiocarbamoyl group, a sulfamoyl group, a sulfoamino group, another nitrogen atom-containing group, or other sulfur Represents a group containing an atom. Incidentally, these groups may be substituted with a substituent. Examples of the substituent include the same as those of Y described later.

As the above-mentioned alkyl group, an alkyl group having 1 to 12 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, and methyl group. ,
Ethyl group and propyl group are preferred.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine, with chlorine and bromine being preferred.

The alkoxyl group is a group having an ether bond, and the alkoxyl group has 1 to 4 carbon atoms.
Is preferred, and an alkoxyl group having 1 to 2 carbon atoms is particularly preferred. Specific examples of the alkoxyl group include a methoxy group, an ethoxy group, a propoxy group and a butoxy group, and a methoxy group and an ethoxy group are preferable.

The carboxylic acid salt is sodium,
Examples include potassium and ammonium salts, sodium,
Ammonium salts are preferred.

The above-mentioned acyl group is a group represented by "R-CO-", wherein R includes an alkyl group having 1 to 7 carbon atoms and a hydrogen atom, and an alkyl group having 1 to 3 carbon atoms,
A hydrogen atom is preferred. Specific examples of the acyl group include:
Formyl group, acetyl group, propionyl group and butyryl group can be mentioned.

Further, X may be a group containing another nitrogen atom or another group containing sulfur. The other nitrogen atom-containing group is not particularly limited as long as it is a nitrogen atom-containing group, and examples thereof include a methylamino group, a dimethylamino group, a hydroxyamino group, an acetamide group, a carbamoyl group, an oxamoyl group, and a cyano group. And the like, and a methylamino group, a hydroxyamino group and a cyano group are preferable.

Examples of the other sulfur atom-containing groups include:
There is no particular limitation as long as it is a group containing a sulfur atom, for example,
Examples thereof include thiocyanato group, thioformyl group, thioacetyl group, methylthio group, methylsulfonyl group, and methylsulfinyl group, with thiocyanato group and thioformyl group being preferred.

As X in the above formula, a hydroxy group, a carboxy group, a carboxylate and an amino group are preferable, and a hydroxy group and a carboxy group are particularly preferable.

In the above general formulas (1) and (2),
Y represents an alkylene group which may have a substituent. The carbon number of the alkylene group is preferably 1-10, more preferably 1-5.

As the above-mentioned substituents, an alkyl group; a halogen such as a fluoro group, a chloro group, a bromo group or an iodo group; a hydroxy group; an alkoxyl group such as a methoxy group or an ethoxy group; a carboxy group or a salt thereof; an acyl group;
A group containing nitrogen such as amino group, methylamino group, dimethylamino group, hydroxyamino group, acetamide group, carbamoyl group, oxamoyl group or cyano group; thiocyanato group, thioformyl group, thioacetyl group, methylthio group, methylsulfonyl group or methyl Examples thereof include a sulfur-containing group such as a sulfinyl group; a thiocarbamoyl group; a sulfamoyl group; and a sulfoamino group. The substituent is preferably a hydroxy group, a carboxy group, a carboxylate salt, or an amino group.

The compounds represented by the general formulas (1) and (2) are preferably water-soluble compounds. Here, "water-soluble" refers to one that is soluble in water in an amount of 1% by mass or more. When a compound which is dissolved in water by less than 1% by mass is used as the compound in the present invention, it is difficult to dissolve it in the coating liquid for the colorant receiving layer, so that it is added as an emulsion and the glossiness of the recording sheet is increased. May decrease. Therefore, when the compound in the present invention is a water-soluble compound, it can be easily dissolved in the coating liquid, and the glossiness of the recording sheet can be improved.

The molecular weight of the compounds represented by the general formulas (1) and (2) is preferably 180 or more, and more preferably 200 to 500, and more preferably 200 to 350.
Is particularly preferable. The inkjet recording sheet of the present invention can sufficiently suppress generation of bleeding over time by including the above compound having a molecular weight of 180 or more.

The ink jet recording sheet of the present invention comprises
It suffices that the coloring material receiving layer contains at least one of the compounds represented by the general formulas (1) and (2). Therefore, the compound represented by the general formula (1) or (2) may be contained alone or in combination of two or more, and the compounds represented by the general formulas (1) and (2) may be used in combination. You may. When the compound [x] represented by the general formula (1) and the compound [y] represented by the general formula (2) are used in combination, the mixing ratio (mass ratio; x: y) is not particularly limited. , Preferably 1:10 to 10: 1, and more preferably 1: 5 to 5: 1. Further, the total content of the compounds represented by the general formulas (1) and (2) contained in the colorant receiving layer is preferably 0.1 to 10 g / m ^{2, and} is preferably 0.1 to 10 g / m ² .
It is more preferably 5 to 5 g / m ² . The above total content is 0.1
If it is less than g / m ² , sufficient ozone resistance may not be imparted, and if it exceeds 10 g / m ² , the surface of the ink jet recording sheet may be booked when stored in a low temperature environment (for example, 1 week at 5 ° C.). The compound of the invention may be precipitated, and the image print density may be lowered.

The specific examples of the compounds of the present invention (Compound A to Compound F) are shown below, but the compounds of the present invention are not limited thereto.

[0042]

[Chemical 1]

(Gas phase method silica) As described above, the coloring material receiving layer in the present invention contains the gas phase method silica which is the inorganic pigment fine particles. Silica fine particles are generally roughly classified into wet method particles and dry method (gas phase method) particles depending on the production method. In the above-mentioned wet method, a method in which activated silica is generated by acid decomposition of a silicate, and the activated silica is appropriately polymerized and coagulated and precipitated to obtain hydrous silica is the mainstream. On the other hand, the vapor phase method is a method by high temperature vapor phase hydrolysis of silicon halide (flame hydrolysis method),
The mainstream method is to obtain anhydrous silica by a method in which silica sand and coke are heated and reduced and vaporized by an arc in an electric furnace, and this is oxidized by air (arc method). It means anhydrous silica fine particles obtained by the method.

The vapor-phase process silica is different from the hydrous silica in the density of silanol groups on the surface and the presence or absence of pores.
It has different properties but is suitable for forming three-dimensional structures with high porosity. Although the reason for this is not clear, in the case of hydrous silica, the density of silanol groups on the surface of the fine particles is as high as 5 to 8 / nm ² , and the silica fine particles are likely to be densely aggregated (aggregate). In the case of method silica, the density of silanol groups on the surface of fine particles is 2 to
It is presumed that sparse soft agglomeration (flocculate) occurs due to a small number of 3 / nm ² , resulting in a structure having a high porosity.

Since the above-mentioned vapor grown silica has a particularly large specific surface area, it has a high ink absorption and retention efficiency, and has a low refractive index. Therefore, if it is dispersed to an appropriate particle size, it is transparent to the receiving layer. Is provided, and high color density and good color developability are obtained. The transparency of the receiving layer is not only for applications requiring transparency such as OHP, but also for obtaining high color density and good color forming gloss even when applied to recording sheets such as photo glossy paper. is important.

The average primary particle diameter of the vapor phase silica is preferably 30 nm or less, more preferably 20 nm or less, particularly preferably 10 nm or less, most preferably 3 to 10 nm. In the vapor phase silica, particles are easily attached to each other by hydrogen bonds due to silanol groups, so that a structure having a large porosity can be formed when the average primary particle diameter is 30 nm or less, and the ink absorption characteristics are effectively improved. Can be improved.

Further, other inorganic materials such as hydrous silica fine particles, colloidal silica, titanium dioxide, barium sulfate, calcium silicate, zeolite, kaolinite, halloysite, mica, talc, calcium carbonate, magnesium carbonate, calcium sulfate, boehmite, pseudoboehmite and the like. You may use together pigment fine particles. When the other inorganic pigment fine particles are used in combination with the vapor-phase method silica, the content of the vapor-phase method silica in all the inorganic pigment fine particles is preferably 50% by mass or more, more preferably 70% by mass or more.

(Polyvinyl alcohol) Similarly, the colorant receiving layer in the present invention has polyvinyl alcohol which is a water-soluble resin. The polyvinyl alcohol includes, in addition to polyvinyl alcohol (PVA), cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, and other polyvinyl alcohol derivatives. The above polyvinyl alcohols may be used alone or in combination of two or more.

The PVA has a hydroxyl group in its structural unit, and the hydroxyl group and the silanol group on the surface of the silica fine particles form a hydrogen bond to form a three-dimensional network structure having secondary particles of the silica fine particles as chain units. Make it easier to form. It is considered that the formation of the above-mentioned three-dimensional network structure makes it possible to form a coloring material receiving layer having a porous structure with a high porosity. In inkjet recording, the porous coloring material-receiving layer obtained as described above can rapidly absorb ink by a capillary phenomenon and form dots with good circularity without ink blurring.

The content of the above-mentioned polyvinyl alcohol is such that the film strength is prevented from being lowered and the cracking at the time of drying is prevented due to the excessive content of the polyvinyl alcohol.
From the viewpoint of preventing the ink absorptivity from being reduced due to the fact that the voids are more likely to be blocked by the resin and the void ratio is reduced, 9 to 40% by mass is preferable with respect to the total solid mass of the colorant receiving layer. , 12 to 33 mass% is more preferable.

From the viewpoint of transparency, the saponification degree is 70-9.
9% PVA is more preferable, and PVA having a saponification degree of 80 to 99% is particularly preferable.

Further, polyvinyl acetal, cellulose resin [methyl cellulose (MC), ethyl cellulose (EC), hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC), etc.], chitins,
Chitosans, starch; polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene glycol (PE), which are resins having ether bonds
G), polyvinyl ether (PVE); polyacrylamide (P which is a resin having an amide group or an amide bond)
AAM), polyvinylpyrrolidone (PVP), and
You may use together other water-soluble resin which has a carboxyl group as a dissociative group, such as polyacrylic acid salt, maleic acid resin, alginate, and gelatins. When the other water-soluble resin is used in combination with the polyvinyl alcohol, the content of polyvinyl alcohol in the total water-soluble resin is preferably 50% by mass or more, and more preferably 70% by mass or more.

-Content ratio of vapor-phase method silica and polyvinyl alcohol-Vapor-phase method silica (all inorganic pigment fine particles when used in combination with other inorganic pigment fine particles; i) and polyvinyl alcohol (use in combination with other water-soluble resin) In the case of the total water-soluble resin; p), the content ratio [PB ratio (i: p), mass of vapor phase method silica to 1 part by mass of polyvinyl alcohol] has a great influence on the film structure of the colorant receiving layer. give. That is, PB
The larger the ratio, the larger the porosity, pore volume and surface area (per unit mass). Specifically, the PB ratio (i:
p) is due to the PB ratio being too large,
Prevents deterioration of film strength and cracking during drying, and
If the PB ratio is too small, the voids are more likely to be blocked by the resin, and from the viewpoint of preventing the ink absorbency from decreasing due to the decrease in the void ratio, 1.5: 1.
10: 1 is preferable.

Since the recording sheet may be stressed when passing through the transport system of the ink jet printer, it is necessary that the coloring material receiving layer has sufficient film strength. Further, in the case of cutting into a sheet shape, it is necessary that the coloring material receiving layer has sufficient film strength in order to prevent cracking or peeling of the coloring material receiving layer. In this case, the PB ratio is preferably 5: 1 or less, and is preferably 2: 1 or more from the viewpoint of ensuring high-speed ink absorbency in an inkjet printer.

For example, anhydrous silica fine particles having an average primary particle diameter of 20 nm or less and a water-soluble resin have a PB ratio of 2: 1 to 5:
When the coating solution completely dispersed in an aqueous solution in 1 was coated on a support and the coating layer was dried, a three-dimensional network structure having secondary particles of silica fine particles as chain units was formed, and the average pore diameter was It is possible to easily form a translucent porous film having a thickness of 30 nm or less, a porosity of 50% to 80%, a pore specific volume of 0.5 ml / g or more and a specific surface area of 100 m ² / g or more.

(Boron Compound) The coloring material receiving layer of the ink jet recording sheet of the present invention is a cross-linking agent capable of further cross-linking the above polyvinyl alcohol to the coating layer (porous layer) containing the inorganic pigment fine particles and the water-soluble resin. A layer containing a boron compound and cured by a crosslinking reaction between the boron compound and the polyvinyl alcohol.

The application of the above-mentioned boron compound is carried out at the same time as the coating liquid for forming the above-mentioned porous coloring material receiving layer (coloring material receiving layer coating liquid) is applied, or by applying the coloring material receiving layer coating liquid. It is preferable to be performed before the coating layer thus formed exhibits a decreasing rate of drying. By this operation, it is possible to effectively prevent the occurrence of cracks that occur during the drying of the coating layer. That is, the boron compound solution (crosslinking agent solution) permeates into the coating layer at the same time as the coating liquid is coated, or before the coating layer starts to exhibit the decreasing rate of drying, so that the polyvinyl alcohol in the coating layer and the By reacting with and gelling (curing) polyvinyl alcohol, the film strength of the coating layer is immediately and significantly improved.

In the present invention, a coating solution obtained by adding and redispersing a solution (first solution) containing at least the above polyvinyl alcohol to an aqueous dispersion comprising the above vapor grown silica and a dispersant. Coating the surface of the support, at the same time as the coating, or in the course of drying the coating layer formed by the coating, and before the coating layer exhibits a rate of reduction drying, at least the coating layer is Solution containing mordant (second
It is also possible to preferably use a method of forming a color material-receiving layer by applying the solution). When using this method, the second
It is preferable to add the above-mentioned boron compound to the above solution, and the boron compound may be added to both the above-mentioned aqueous dispersion comprising the vapor-phase grown silica and the dispersing agent, and the second solution to be applied later.

The boron compound can rapidly crosslink the polyvinyl alcohol. Examples of the boron compound include borax, boric acid, borate (eg, orthoborate, InBO ₃ , ScBO ₃ , YBO ₃ , LaB).
_{O 3, Mg 3 (BO 3} ) 2, Co 3 (BO 3) 2, two borates _{(e.g., Mg 2 B 2 O 5,} Co 2 B 2 O 5), metaborate salts (e.g., LiBO _2, Ca (BO ₂ ) ₂ , NaBO ₂ , KB
O ₂ ), tetraborate (eg, Na ₂ B ₄ O ₇ · 10H
₂ O), pentaborate (eg KB ₅ O ₈ .4H ₂ O, Ca _{2
B 6 O 1 1 · 7H 2} O, can be cited CsB ₅ O ₅₎ or the like. Among them, borax, boric acid, and boric acid salts are preferable, and boric acid is more preferable, because they rapidly cause a crosslinking reaction.

The following compounds can be used in combination with the boron compound as a crosslinking agent for the polyvinyl alcohol. 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-triazine, 2,4-dichloro-6-S-
Active halogen compounds such as triazine / sodium salt; divinylsulfonic acid, 1,3-vinylsulfonyl-2-propanol, N, N'-ethylenebis (vinylsulfonylacetamide), 1,3,5-triacryloyl-hexahydro Active vinyl compounds such as -S-triazine; N such as dimethylolurea and methyloldimethylhydantoin
A methylol compound; a melamine resin (eg methylol melamine, alkylated methylol melamine); an epoxy resin;

Isocyanate compounds such as 1,6-hexamethylene diisocyanate; US Pat. No. 301
Nos. 7280 and 2983611; aziridine compounds; carboximide compounds described in U.S. Pat. No. 3,100,704; epoxy compounds such as glycerol triglycidyl ether; 1,6-hexamethylene-N, N '. -Ethyleneimino compounds such as bisethyleneurea; halogenated carboxaldehyde compounds such as mucochloric acid and mucophenoxycyclo acid; dioxane compounds such as 2,3-dihydroxydioxane; chromium alum, potassium alum, zirconium sulfate, Chromium acetate and the like. In this case, when the above-mentioned boron compound and another cross-linking agent for PVA are used in combination, the content of the boron compound in all cross-linking agents is preferably 50% by mass or more, and more preferably 70% by mass or more. The above boron compounds may be used alone or in combination of two or more.

When the above boron compound is applied, the solution is prepared by dissolving the boron compound in water and / or an organic solvent. The concentration of the boron compound in the boron compound solution is 0.
05-10 mass% is preferable and 0.1-7 mass% is especially preferable. As a solvent constituting the boron compound solution,
Water is generally used, and it may be an aqueous mixed solvent containing an organic solvent miscible with the water. Any organic solvent can be used as long as it can dissolve a boron compound, and examples thereof include alcohols such as methanol, ethanol, isopropyl alcohol, and glycerin; ketones such as acetone and methyl ethyl ketone; methyl acetate;
Examples thereof include esters such as ethyl acetate; aromatic solvents such as toluene; ethers such as tetrahydrofuran; and halogenated carbon solvents such as dichloromethane.

(Mordant) In the present invention, a mordant is contained in the colorant-receptive layer in order to further improve the water resistance and bleeding resistance of the formed image. As the mordant, a cationic polymer (cationic mordant) is preferable, and by allowing the mordant to be present in the colorant-receiving layer, the colorant interacts with a liquid ink having an anionic dye as the colorant. It is possible to stabilize and improve water resistance and blurring over time.

However, when this is directly added to the coating solution for forming the colorant-receptive layer, there is a risk of aggregation with the gas phase method silica having an anion charge, but it is prepared as a separate solution. If the coating method is used, there is no need to worry about the aggregation of the inorganic pigment fine particles. Therefore, in the present invention, a solution different from the above vapor phase silica (for example,
It is preferably contained in a crosslinking agent solution) before use.

As the above cationic mordant, a polymer mordant having a primary to tertiary amino group or a quaternary ammonium group as a cationic group is preferably used, but a cationic non-polymer mordant is also used. can do. As the polymer mordant, first to third
A homopolymer of a monomer (mordant monomer) having a primary amino group and a salt thereof, or a quaternary ammonium salt group, and a copolymerization weight of the mordant monomer and another monomer (hereinafter, referred to as "non-mordant monomer"). Those obtained as a polymer or a condensation polymer are preferable. Further, these polymer mordants can be used in the form of either a water-soluble polymer or water-dispersible latex particles.

Examples of the above-mentioned monomer (mordanting monomer) include trimethyl-p-vinylbenzylammonium chloride, trimethyl-m-vinylbenzylammonium chloride, triethyl-p-vinylbenzylammonium chloride, triethyl-m-vinylbenzylammonium. Chloride, N, N-dimethyl-N-ethyl-N-p-vinylbenzylammonium chloride,
N, N-diethyl-N-methyl-N-p-vinylbenzylammonium chloride, N, N-dimethyl-Nn
-Propyl-N-p-vinylbenzyl ammonium chloride, N, N-dimethyl-Nn-octyl-N-p
-Vinylbenzylammonium chloride, N, N-dimethyl-N-benzyl-Np-vinylbenzylammonium chloride, N, N-diethyl-N-benzyl-
N-p-vinylbenzylammonium chloride, N,
N-dimethyl-N- (4-methyl) benzyl-Np-
Vinylbenzylammonium chloride, N, N-dimethyl-N-phenyl-Np-vinylbenzylammonium chloride,

Trimethyl-p-vinylbenzylammonium bromide, trimethyl-m-vinylbenzylammonium bromide, trimethyl-p-vinylbenzylammonium sulfonate, trimethyl-m-vinylbenzylammonium sulfonate, trimethyl-p-vinylbenzylammonium acetate, trimethyl- m
-Vinylbenzyl ammonium 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 acetate,

N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth)
Acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, Methyl chloride of N-diethylaminopropyl (meth) acrylamide,
Examples thereof include ethyl chloride, methyl bromide, ethyl bromide, quaternary compounds of methyl iodide or ethyl iodide, and sulfonates, alkylsulfonates, acetates or alkylcarboxylates of which anions are substituted.

Specifically, for example, trimethyl-2-
(Methacryloyloxy) ethylammonium chloride, triethyl-2- (methacryloyloxy) ethylammonium chloride, trimethyl-2- (acryloyloxy) ethylammonium chloride, triethyl-2- (acryloyloxy) ethylammonium chloride, trimethyl-3- (methacryloyl) Oxy)
Propyl ammonium chloride, triethyl-3-
(Methacryloyloxy) propylammonium chloride, trimethyl-2- (methacryloylamino) ethylammonium chloride, triethyl-2- (methacryloylamino) ethylammonium chloride, trimethyl-2- (acryloylamino) ethylammonium chloride, triethyl-2- (acryloyl) Amino) 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- (acryloylamino) propyl ammonium acetate etc. can be mentioned. In addition, as the copolymerizable monomer, N-vinylimidazole, N-vinyl-2-methylimidazole and the like can also be mentioned.

Further, allylamine, diallylamine, derivatives thereof, salts and the like can be used. Examples of such compounds include allylamine, allylamine hydrochloride, allylamine acetate, allylamine sulfate, diallylamine, diallylamine hydrochloride, diallylamine acetate, diallylamine sulfate, diallylmethylamine and salts thereof (as the salt, for example, Hydrochloride, acetate, sulfate, etc.),
Examples thereof include diallylethylamine and salts thereof (for example, hydrochlorides, acetates, sulfates and the like), diallyldimethylammonium salts (for counter anions of the salts chloride, acetate ion sulfates and the like). Since these allylamine and diallylamine derivatives have poor polymerizability in the form of amine, it is common to polymerize in the form of a salt and desalt as necessary. Further, it is also possible to use a unit such as N-vinylacetamide or N-vinylformamide, which is converted into a vinylamine unit by hydrolysis after polymerization, or a salt thereof.

The non-mordanting monomer does not contain a basic or cationic moiety such as a primary to tertiary amino group and its salt, or a quaternary ammonium salt group, and interacts with the dye in the ink jet ink. A monomer that does not show or has a substantially small interaction. Examples of the non-mordanting monomer include (meth) acrylic acid alkyl ester; (meth) acrylic acid cycloalkyl ester such as cyclohexyl (meth) acrylate; (meth)
(Meth) acrylic acid aryl ester such as phenyl acrylate; aralkyl ester such as benzyl (meth) acrylate; aromatic vinyls such as styrene, vinyltoluene, α-methylstyrene; vinyl acetate, vinyl propionate, vinyl versatate And vinyl esters such as allyl acetate; halogen-containing monomers such as vinylidene chloride and vinyl chloride; vinyl cyanide such as (meth) acrylonitrile; olefins such as ethylene and propylene.

The above-mentioned (meth) acrylic acid alkyl ester has a (meth) alkyl group having 1 to 18 carbon atoms.
Acrylic acid alkyl esters are preferable, for example, methyl (meth) acrylate, ethyl (meth) acrylate,
Propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate,
Examples include hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate. Among them, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate and hydroxyethyl methacrylate are preferable. The non-mordant monomers can be used alone or in combination of two or more.

Further, as a polymer mordant, polydiallyldimethylammonium chloride, polymethacryloyloxyethyl-β-hydroxyethyldimethylammonium chloride, polyethyleneimine, polyallylamine, polyallylamine hydrochloride, polyamide-polyamine resin, cationized starch, dicyandiamide formalin. Condensates, dimethyl-2-hydroxypropylammonium salt polymers, polyamidines, polyvinylamines and the like can also be mentioned as preferable ones.

The molecular weight of the polymer mordant is preferably 1,000 to 100,000 in terms of weight average molecular weight, and more preferably 3000 to 60,000 in terms of weight average molecular weight. When the molecular weight is in the range of 1,000 to 100,000, water resistance will not be insufficient, and it will be possible to prevent the handling suitability from decreasing due to too high viscosity. As the cationic non-polymer mordant, for example, water-soluble metal salts such as aluminum sulfate, aluminum chloride, polyaluminum chloride and magnesium chloride are preferable. As the mordant in the present invention, polyallylamine having a weight average molecular weight of 100,000 or less and derivatives thereof are particularly preferable in terms of water resistance, ozone resistance, ink absorption rate, and glossiness.

(Other Components) The colorant receiving layer may contain the following components, if necessary. For the purpose of suppressing the deterioration of the coloring material, various kinds of ultraviolet absorbers, antioxidants, and fading inhibitors such as singlet oxygen quencher may be contained. Examples of the ultraviolet absorber include cinnamic acid derivatives, benzophenone derivatives, benzotriazolylphenol derivatives and the like. For example, α-cyano-phenyl butyl cinnamate, o
-Benzotriazole phenol, o-benzotriazole-p-chlorophenol, o-benzotriazole-2,4-di-t-butylphenol, o-benzotriazole-2,4-di-t-octylphenol and the like can be 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.

Further, benzotriazole type ultraviolet absorbers, salicylic acid type ultraviolet absorbers, cyanoacrylate type ultraviolet absorbers, oxalic acid anilide type ultraviolet absorbers and the like can also be used. For example, JP-A-47-1053
No. 7, gazette 58-111942 gazette, gazette 58-21.
No. 2844, No. 59-19945, No. 59-
46646, 59-109055, and 6
No. 3-53544, Japanese Patent Publication No. 36-10466, No. 42-26187, No. 48-30492, No. 48-31255, No. 48-41572.
JP-A-48-54965 and JP-A-50-1072.
No. 6, gazettes, US Pat. Nos. 2,719,086, 3,707,375, 3,754,919, 4,220,711, etc. There is.

A fluorescent whitening agent can also be used as an ultraviolet absorber, and examples thereof include a coumarin-based fluorescent whitening agent. Specifically, JP-B-45-4699 and 54-53.
No. 24, etc.

Examples of the above-mentioned antioxidant include European Patent Nos. 223739, 309401, 309402, 310551 and 31.
No. 0552, No. 459416, German Published Patent No. 3435443, and Japanese Patent Laid-Open No. 54-48535.
No. 60-107384 and No. 60-107.
No. 383, No. 60-125470, No. 60-
No. 125471, No. 60-125472, No. 60-287485, No. 60-287486, No. 60-287487, and No. 60-28748.
8 gazette, the same 61-160287 gazette, the same 61-18.
5483, 61-211079 and 62.
No. 146678, No. 62-146680,
62-146679, 62-282885, 62-262047, 63-0511.
74, 63-89877, 63-88.
No. 380, No. 66-88381, No. 63-1.
No. 13536,

63-163351 and 63-2.
No. 03372, No. 63-224989, No. 6
No. 3-251282, No. 63-267594, No. 63-182484, Japanese Patent Laid-Open No. 1-2392.
82, JP-A-2-262654, and 2-7.
No. 1262, No. 3-121449, and No. 4-2.
No. 91685, No. 4-291684, No. 5-
No. 61166, No. 5-119449, No. 5-
No. 188687, No. 5-188686, No. 5
-110490 gazette, the same 5-1108437 gazette,
No. 5-170361, Japanese Patent Publication No. 48-43295, No. 48-33212, and U.S. Pat. No. 4,814.
No. 262, No. 4980275, etc. are mentioned.

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 cyclohexanoate, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -2 -Ethylhexane, 2
-Methyl-4-methoxy-diphenylamine, 1-methyl-2-phenylindole and the like can be mentioned.

The anti-fading agents may be used alone or in combination of two or more kinds. This anti-fading agent is water-soluble,
It may be dispersed or emulsified, or may be contained in microcapsules. The amount of the anti-fading agent added is preferably 0.01 to 10% by mass of the coating material for the colorant receiving layer.

Further, for the purpose of enhancing the dispersibility of the fine particles of the inorganic pigment, various inorganic salts may be contained, and an acid, an alkali or the like may be contained as a pH adjusting agent. Further, metal oxide fine particles having electronic conductivity may be included for the purpose of suppressing frictional electrification and peeling electrification on the surface, and various matting agents may be included for the purpose of reducing the frictional property of the surface.

(Preparation of Inkjet Recording Sheet) As described above, it is preferable that a mordant is introduced into the coloring material receiving layer in the process of applying the above crosslinking agent solution. That is,
The colorant receiving layer contains the compound represented by the general formula (1) and / or
Alternatively, a coating liquid (coating liquid for a colorant receiving layer) containing the compound represented by the general formula (2), vapor-phase method silica and polyvinyl alcohol is coated, and at the same time as the coating, or in the coating layer formed. Before the coating layer shows a decreasing rate of drying in the middle of drying, a solution (crosslinking agent solution) containing a boron compound and a mordant is applied to the coating layer, and then the application of the solution is applied. A method of crosslinking and curing a layer (WOW method; W
It is preferably formed by the et On Wet method). In this method, the pH of the coating material for the colorant receiving layer is 8.
It shows an alkalinity at about 0 to 10.0.

The colorant-receiving layer of the ink jet recording sheet of the present invention comprises a coating liquid for the colorant-receiving layer and a solution of a crosslinking agent, which is a barrier liquid made of a material which does not react with the boron compound (provided that the boron compound is used). A mordant may be contained in at least one of the containing solution and the barrier solution.) It may also be obtained by simultaneously applying the composition on a support while sandwiching it and curing it.

As described above, in the present invention, the water resistance of the colorant receiving layer can be improved by simultaneously applying the mordant together with the boron compound. That is, when the mordant is added to the coating liquid for the colorant receiving layer, the mordant may be aggregated in the coexistence with the gas phase method silica having an anionic charge on the surface, because the mordant is cationic. If a method of separately preparing a solution containing a and a coating solution for a colorant receiving layer and individually coating is adopted, it is not necessary to consider aggregation of vapor phase method silica and the selection range of mordants is expanded. .

In the present invention, a coating material for a colorant receiving layer containing at least the compound represented by the general formula (1) and / or the compound represented by (2), vapor phase method silica and polyvinyl alcohol is, for example, , Can be prepared as follows. That is, by adding vapor phase method silica to water (for example, 1
0 to 20% by mass, using a high-speed rotating wet colloid mill (for example, CLEARMIX (manufactured by M Technique Co., Ltd.)), for example, 10,000 rpm (preferably 5000).
After being dispersed for 20 minutes (preferably 10 to 30 minutes) under the condition of high-speed rotation of up to 20,000 rpm, an aqueous solution of polyvinyl alcohol (for example, PVA having a mass about 1/3 of that of vapor phase silica) is added. It can be prepared by further adding a compound represented by the general formula (1) and / or a compound represented by the general formula (2), and dispersing under the same rotation conditions as above. The obtained coating liquid is a uniform sol, and a porous coloring material-receiving layer having a three-dimensional network structure can be formed by coating and forming this on a support by the coating method described below. The dispersion treatment method includes a high-speed rotation disperser, a medium agitation disperser (ball mill, sand mill, etc.), an ultrasonic disperser,
Although various conventionally known dispersers such as a colloid mill disperser and a high pressure disperser can be used, in the present invention, the lump-shaped fine particles to be formed are efficiently dispersed,
A colloid mill disperser or a high pressure disperser is preferably used.

If necessary, a surfactant, a pH adjuster, an antistatic agent, etc. may be added to the coating material for the color material receiving layer. The coating of the color material receiving layer coating liquid is, for example, an extrusion die coater, an air doctor coater, a bread coater, a rod coater, a knife coater,
It can be performed by a known coating method such as a squeeze coater, a reverse roll coater, or a bar coater.

After applying the coating material for the colorant-receiving layer, the crosslinking agent solution is applied to the coating layer, but the crosslinking agent solution is applied before the coating layer after application has a decreasing rate of drying. May be given to. That is, after the coating liquid for the color material receiving layer is coated, the boron compound and the mordant are preferably introduced while the coating layer shows a constant rate of drying.

Here, "before the coating layer starts to exhibit the decreasing rate of drying" usually means a few minutes immediately after the coating of the coating liquid for the colorant-receptive layer, and during this period, the coating layer coated is applied. The constant drying rate, which is a phenomenon in which the content of the solvent therein decreases in proportion to time, is shown. The time indicating the constant rate of drying is described in Chemical Engineering Handbook (p. 707 to 712, published by Maruzen Co., Ltd., October 25, 1980).

As described above, after applying the coating material for the colorant receiving layer,
The coating layer is dried until it exhibits a rate of dry reduction, which is generally 0.5-10 at 50-180 ° C.
It is performed for a minute (preferably 0.5 to 5 minutes). As the drying time, it naturally depends on the coating amount, but the above range is suitable.

As a method for applying the above-mentioned coating layer before it shows the rate of decrease in drying rate, (1) a method for further coating the coating layer with the crosslinking agent solution, (2) spraying by a method such as spraying Method, (3) a method of immersing the support on which the coating layer is formed in a solution of a crosslinking agent, and the like.

In the above method (1), as a coating method for coating the crosslinking agent solution, for example, 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, A known coating method such as a bar coater can be used. However, it is preferable to use a method such as an extrusion die coater, a curtain flow coater, or a bar coater in which the coater does not directly contact the already-formed coating layer.

The coating amount of the crosslinking agent solution containing at least the boron compound and the mordant applied on the color material receiving layer is generally 0.01 to 10 g / m ^{2 in} terms of boron compound. 05-5 g / m ² is preferable.

After the application of the crosslinking agent solution, it is generally 40 to 1
It is heated at 80 ° C. for 0.5 to 30 minutes to be dried and cured. Above all, it is preferable to heat at 40 to 150 ° C. for 1 to 20 minutes. For example, when borax or boric acid is used as the boron compound contained in the cross-linking agent solution, heating at 60 to 100 ° C is preferably performed for 5 to 20 minutes.

Further, the above-mentioned crosslinking agent solution may be applied at the same time when the coloring material receiving layer coating solution is applied. In this case, the color material-receptive layer coating solution and the cross-linking agent solution are simultaneously coated on the support so that the color material-receptive layer coating solution is in contact with the support (multi-layer coating), and then dried and cured to obtain the color. A material receiving layer can be formed.

The simultaneous coating (multilayer coating) can be carried out by a coating method using an extrusion die coater or a curtain flow coater. After the simultaneous coating, the formed coating layer is dried, and the drying in this case is generally performed by heating the coating layer at 40 to 150 ° C. for 0.5 to 10 minutes, preferably 40 to 150 ° C.
It is carried out by heating at 100 ° C. for 0.5 to 5 minutes. For example, when borax or boric acid is used as the boron compound contained in the cross-linking agent solution, the borax or boric acid is used at 60 to 100 ° C.
It is preferable to heat for 20 minutes.

When the above-mentioned simultaneous coating (multilayer coating) is carried out, for example, by an extrusion die coater, the two kinds of coating liquids discharged at the same time are in the vicinity of the discharge port of the extrusion die coater, that is, before being transferred onto the support. Is formed in multiple layers, and in that state, multiple layers are applied on the support. Since the two-layer coating solution that has been overlaid before coating tends to cause a cross-linking reaction at the interface between the two solutions when it is transferred to the support, the two solutions to be discharged are mixed near the discharge port of the extrusion die coater. May increase the viscosity, which may hinder the coating operation. Therefore, in the simultaneous coating as described above, the coating liquid for the colorant-receiving layer and the coating liquid for the cross-linking agent as well as the barrier layer liquid (intermediate layer liquid) made of a material that does not react with the boron compound are interposed between the two liquids. It is preferable that the coating is carried out at the same time and the three layers are simultaneously coated.

The barrier layer liquid can be selected without particular limitation as long as it can form a liquid film without reacting with the boron compound. For example, an aqueous solution containing a trace amount of a water-soluble resin that does not react with a boron compound, water, and the like can be given. The above-mentioned water-soluble resin is used in consideration of coatability for the purpose of a thickener and the like, and examples thereof include hydroxypropylmethylcellulose, methylcellulose, hydroxyethylmethylcellulose, polyvinylpyrrolidone, gelatin. And the like. The mordant may be contained in the barrier layer liquid.

Further, the colorant receiving layer in the present invention is a solution (first solution) containing at least the above polyvinyl alcohol in an aqueous dispersion comprising the above fumed silica and a dispersant.
Is added and redispersed to obtain a coating liquid, which is applied to the surface of the support, simultaneously with the coating, or while the coating layer formed by the coating is being dried, and the coating layer has a decreasing rate of drying. Before showing, the coating layer may be formed by a method of curing the coating layer after applying a solution (second solution) containing at least the boron compound and the mordant to the coating layer. In this method, the pH of the aqueous dispersion is 4.
It is 5 or less and shows acidity. At this time, the compound represented by the general formula (1) and / or (2) is added to at least either the first solution or the second solution, or may be added to both. The use of this method is preferable because the glossiness and the print density are improved.

As the dispersant, a cationic polymer can be used. As the cationic polymer, a homopolymer of a monomer having a primary to tertiary amino group and a salt thereof, or a quaternary ammonium base, which is mentioned as an example of the mordant, or a homopolymer of the monomer, Those obtained as a copolymer or a condensation polymer with another monomer can be preferably used. Also, these dispersants are preferably used in the form of water-soluble polymers.

The molecular weight of the dispersant is preferably 1,000 to 200,000, and more preferably 3,000 to 600, in terms of weight average molecular weight.
00 is more preferable. If the molecular weight is less than 1000, the dispersibility may be poor, and if it exceeds 200,000, the viscosity of the aqueous dispersion may be high. The amount of the dispersant added to the fumed silica is preferably 1% to 30%,
3% to 20% is more preferable. If the addition amount is less than 1%, the dispersibility may be poor, and if it exceeds 30%, the color density may decrease when printed on an inkjet recording sheet, which is not preferable.

The preparation of the aqueous dispersant comprising the vapor phase silica and the dispersant may be carried out by preparing an aqueous dispersion of the vapor phase silica in advance and adding the aqueous dispersion to the aqueous dispersant solution. The aqueous dispersant solution may be added to the vapor-phase silica aqueous dispersion, or may be mixed at the same time. Further, instead of an aqueous dispersion of vapor-phase method silica, powdery vapor-phase method silica may be added to the dispersant aqueous solution as described above. After mixing the vapor phase silica and the dispersant described above, the mixture is atomized using a disperser to obtain an aqueous dispersion having an average particle diameter of 50 to 300 nm. As the disperser used to obtain the aqueous dispersion, various types of conventionally known ones such as a high-speed rotation disperser, a medium stirring type disperser (ball mill, sand mill, etc.), an ultrasonic disperser, a colloid mill disperser, a high-pressure disperser, etc. Although a disperser can be used, a colloid mill disperser or a high-pressure disperser is preferable from the viewpoint of efficiently dispersing the lump-shaped fine particles to be formed.

Further, water, an organic solvent, or a mixed solvent thereof can be used as a solvent in each step.
Examples of the organic solvent that can be used for this 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, toluene and the like. To be

After the color material receiving layer is formed on the support, the surface of the color material receiving layer is smoothed by subjecting the color material receiving layer to calendering through a roll nip under heat and pressure using, for example, a super calender or a gloss calender. It is possible to improve properties, glossiness, transparency and coating film strength. However, the calendering process may cause a decrease in the porosity (that is, the ink absorbency may decrease), and therefore, it is necessary to set conditions under which the decrease in the porosity is small.

The roll temperature for calendering treatment is preferably 30 to 150 ° C., and 40 to 100 ° C.
C is more preferred. Further, the linear pressure between the rolls during the calendar treatment is preferably 50 to 400 kg / cm,
100 to 200 kg / cm is more preferable.

In the case of ink jet recording, the layer thickness of the color material receiving layer needs to be determined in relation to the porosity in the layer, because it is necessary to have an absorption capacity enough to absorb all the droplets. is there. For example, if the ink amount is 8 nL / mm ²
If the porosity is 60%, the layer thickness is about 15 μm.
The above film is required. Considering this point, in the case of inkjet recording, the layer thickness of the colorant receiving layer is 1
0 to 50 μm is preferable.

The pore diameter of the color material receiving layer is preferably 0.005 to 0.030 μm in terms of median diameter, and 0.01 to
0.025 μm is more preferable. The porosity and the median pore diameter can be measured using a mercury porosimeter (trade name: Boasizer 9320-PC2, manufactured by Shimadzu Corporation).

The colorant receiving layer preferably has excellent transparency, and as a guideline, the haze value when the colorant receiving layer is formed on a transparent film support is 30.
% Or less, and more preferably 20% or less. The haze value is a haze meter (HG
M-2DP: It can be measured using Suga Test Instruments Co., Ltd.

(Support) As the support, 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 order to make the most of the transparency of the colorant receiving layer, it is preferable to use a transparent support or a highly glossy opaque support.

As a material that can be used for the transparent support, a material that is transparent and has a property of withstanding radiant heat when used in an OHP or a backlight display is preferable. Examples of the material include polyesters such as polyethylene terephthalate (PET); polysulfone,
Examples thereof include polyphenylene oxide, polyimide, polycarbonate and polyamide. Among them, polyesters are preferable, and polyethylene terephthalate is particularly preferable. The thickness of the transparent support is not particularly limited, but is preferably 50 to 200 μm from the viewpoint of handleability.

As the highly glossy opaque support, one having a glossiness of 40% or more on the surface on which the colorant receiving layer is provided is preferable. The glossiness is JIS P-814.
It is a value determined according to the method described in 2 (75 degree specular gloss test method for paper and board). Specific examples include the following supports.

For example, high gloss paper supports such as art paper, coated paper, cast coated paper, baryta paper used for silver salt photographic supports, polyesters such as polyethylene terephthalate (PET), nitrocellulose. Cellulose esters such as cellulose acetate and cellulose acetate butyrate, and plastic films such as polysulfone, polyphenylene oxide, polyimide, polycarbonate and polyamide are made opaque by containing a white pigment and the like (may be subjected to surface calendering treatment). High-gloss film; or a high-gloss film containing the above various paper supports, the above-mentioned transparent supports, or white pigments, etc., provided with a polyolefin coating layer containing or not containing a white pigment. Support. A white pigment-containing expanded polyester film (for example, expanded PET in which polyolefin fine particles are contained and voids are formed by stretching) can also be preferably mentioned. Further, resin coated paper used for silver salt photographic printing paper is also suitable.

The thickness of the opaque support is not particularly limited, but it is preferably 50 to 300 μm from the viewpoint of handleability.

Further, a corona discharge treatment,
Those subjected to glow discharge treatment, flame treatment, ultraviolet irradiation treatment and the like may be used.

Next, the base paper used for the resin coated paper will be described in detail. The base paper is made from wood pulp as a main raw material, and if necessary, synthetic paper such as polypropylene, or synthetic fiber such as nylon or polyester is used in addition to wood pulp. Examples of the wood pulp include LBKP, LBSP, NBKP, NBS
Any of P, LDP, NDP, LUKP and NUKP can be used, but LBKP and NBS with a large amount of short fibers
It is preferable to use more P, LBSP, NDP, and LDP. However, the ratio of LBSP and / or LDP is preferably 10% by mass or more and 70% by mass or less.

As the above pulp, a chemical pulp containing few impurities (sulfate pulp or sulfite pulp) is preferably used,
Pulp that has been bleached to improve its whiteness 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 strengthening agents such as starch, polyacrylamide and polyvinyl alcohol, fluorescent whitening agents, A water retention agent such as polyethylene glycol, a dispersant, and a softening agent such as quaternary ammonium can be appropriately added.

The freeness of the pulp used for papermaking is as follows.
According to CSF regulations, 200 to 500 ml is preferable, and
The fiber length after beating is preferably 30 to 70% of the sum of the 24% mesh residual mass% and the 42 mesh residual mass% defined by JIS P-8207. The mass% of the 4-mesh residue is preferably 20 mass% or less.

The basis weight of the base paper is preferably 30 to 250 g, 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 papermaking stage or after the papermaking. The base paper density is 0.7 to 1.2 g / m ² (J
ISP-8118) is common. Furthermore, the stiffness of the base paper is 2 under the conditions specified in JIS P-8143.
0 to 200 g is preferable.

A surface sizing agent may be applied to the surface of the base paper, and as the surface sizing agent, the same sizing agent as that which can be added to the base paper can be used. The pH of the base paper is JI
It is preferably 5 to 9 when measured by the hot water extraction method specified in SP-8113.

The polyethylene for covering the front and back surfaces of the base paper is mainly low-density polyethylene (LDPE) and / or high-density polyethylene (HDPE), but other LLDPE, polypropylene or the like can be partially used.

In particular, the polyethylene layer on the side for forming the colorant-receiving layer contains rutile or anatase type titanium oxide, a fluorescent brightening agent, and ultramarine blue added to polyethylene, as is widely used in photographic printing paper. However, those having improved opacity, whiteness and hue are preferred. Here, the content of titanium oxide is generally 3 to 3 with respect to polyethylene.
20 mass% is preferable and 4-13 mass% is more preferable. The thickness of the polyethylene layer is not particularly limited, but 10 to 50 μm is suitable for both the front and back layers. Further, an undercoat layer may be provided on the polyethylene layer in order to impart adhesion to the coloring material receiving layer. As the undercoat layer, aqueous polyester, gelatin and PVA are preferable. Further, the thickness of the undercoat layer is preferably 0.01 to 5 μm.

The polyethylene-coated paper can be used as a glossy paper, or when a polyethylene is melt-extruded on the surface of a base paper for coating, a so-called patterning treatment is performed to obtain a matte surface or a matte surface obtained by ordinary photographic printing paper. It is also possible to use those having a silk surface.

As described above, a compound represented by the general formula (1) and / or a compound represented by the general formula (2):
By having vapor phase method silica, polyvinyl alcohol, a boron compound, and a mordant in the colorant receiving layer, it suppresses the generation of bleeding with time without deteriorating other ink receiving performance, and has ozone resistance and gloss. It is possible to improve the sex. Moreover, when the colorant receiving layer has a three-dimensional network structure containing vapor-phase grown silica and having a porosity of 50 to 80%, good ink absorbability is exhibited and a high-resolution and high-density image can be formed, and high temperature It is also possible to simultaneously secure excellent ink receiving performance such that bleeding with time in a humid environment is suppressed and the formed image also has high light resistance and water resistance.
The inkjet recording sheet obtained by the present invention can exhibit a glossiness of 30% or more at 60 °. The glossiness is measured by a digital variable angle glossiness meter (UGV-5
It can be measured by 0DP, manufactured by Suga Test Instruments Co., Ltd., or the like.

[0126]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. still,
All "parts" and "%" in the examples mean "parts by mass" and "% by mass".

—Preparation of Support— Wood pulp consisting of 100 parts of LBKP was processed with a double disc refiner to obtain Canadian freeness of 300 ml.
Beaten to 0.5 parts of epoxidized behenic acid amide, 1.0 part of anionic polyacrylamide, 0.1 part of polyamide polyamine epichlorohydrin, and 0.5 parts of cationic polyacrylamide, all in an absolutely dry mass ratio to pulp. Then, it was weighed with a Fourdrinier paper machine to make 170 g / m ² of base paper.

In order to adjust the surface size of the above-mentioned base paper, a 4% aqueous solution of polyvinyl alcohol was added to an optical brightener (Whit
ex BB, manufactured by Sumitomo Chemical Co., Ltd.) was added 0.04%, and the above base paper was impregnated with this so as to have an absolute dry weight of 0.5 g / m ² , dried and then calendered. Then, a base paper having a density adjusted to 1.05 was obtained.

The wire surface (back surface) side of the obtained base paper was subjected to corona discharge treatment, and then high density polyethylene was coated to a thickness of 19 μm using a melt extruder, and a resin layer composed of a matte surface was formed. Was formed (hereinafter, the resin layer surface is referred to as “back surface”). The resin layer on the back side is further subjected to corona discharge treatment, and thereafter, aluminum oxide (alumina sol 100, manufactured by Nissan Chemical Industries, Ltd.) and silicon dioxide (Snowtex O, manufactured by Nissan Chemical Industries, Ltd.) are used as antistatic agents. And (2) were dispersed in water in a ratio of 1: 2 (mass ratio), and the dispersion was applied so that the dry mass would be 0.2 g / m ² .

Furthermore, after the corona discharge treatment was applied to the felt surface (front surface) side where the resin layer was not provided, anatase type titanium dioxide 10%, a trace amount of ultramarine blue, and an optical brightening agent 0.01% ( To polyethylene), MFR
(Melt flow rate) 3.8 low-density polyethylene was melt-extruded using a melt extruder to a thickness of 29 μm to form a high-gloss thermoplastic resin layer on the front surface side of the base paper (hereinafter, This high-gloss surface is referred to as the "front surface"), and was used as a support.

[Example 1] -Preparation of coating liquid for coloring material receiving layer- (1) Fine particles of vapor-phase method silica in the following composition and (2) Ion-exchanged water were mixed, and a high-speed rotating colloid mill (Clearmix) was used. , M Technique Co., Ltd.)
After dispersing at 0000 rpm for 20 minutes, the following (3) polyoxyethylene lauryl ether, (4) ammonia water, (5) polyvinyl alcohol 9% aqueous solution, and (6) the above compound A were added, and further under the same conditions as above. Dispersion was performed to prepare a coating material A for the color material receiving layer. Mass ratio of silica fine particles and water-soluble resin (PB ratio / (1):
(5)) is 3.5: 1 and is the coating liquid A for the colorant receiving layer.
Had a pH of 9.5 and was alkaline.

[0132] [Composition of coating liquid A for colorant receiving layer] (1) Gas phase method silica fine particles (inorganic pigment fine particles) 9.9 parts     (Average primary particle diameter 7 nm; Aerosil 300, manufactured by Nippon Aerosil Co., Ltd.) (2) Deionized water 72.6 parts (3) Polyoxyethylene lauryl ether (surfactant) 7.2 parts     (Emulgen 109P (10%), manufactured by Kao Corporation, HLB value 13.6) (4) 17 g / l aqueous ammonia solution (pH adjuster) 5.3 parts (5) Polyvinyl alcohol 9% aqueous solution (water-soluble resin) 31.4 parts   (PVA420, manufactured by Kuraray Co., Ltd., saponification degree 81.8%, polymerization degree 2000) (6) 1.0 part of the above compound A     (Compound represented by the general formula (1); molecular weight 182)

—Preparation of Inkjet Recording Sheet— After the front surface of the support was subjected to corona discharge treatment, the colorant receiving layer coating solution A obtained above was applied to the front surface of the support by an extrusion die coater. Using 20
A coating amount of 0 ml / m ² was applied (coating step), followed by drying with a hot air dryer at 80 ° C. (air velocity 3 to 8 m / sec) until the solid concentration of the coating layer reached 20%. The coating layer showed a constant drying rate during this period. Immediately after that, it was immersed in a cross-linking agent solution A having the following composition for 30 seconds, and 20 g / m
² is attached (step of applying a cross-linking agent solution), and further 80
It was dried at 0 ° C. for 10 minutes (drying step). From this, an inkjet recording sheet (1) of the present invention provided with a color material receiving layer having a dry film thickness of 32 μm was produced.

[0134] [Composition of Crosslinking Agent Solution A] ・ Boric acid (6%; crosslinking agent) 25 parts -PAS-F5000 (20%) aqueous solution 7.15 parts   (Mordant; Nittobo Co., Ltd.) ・ Ion-exchanged water 63.98 parts ・ Ammonium chloride (surface pH adjuster) 0.2 parts Aqueous ammonia solution (25%; pH adjuster) 1.67 parts ・ Polyoxyethylene lauryl ether (surfactant) 2.0 parts (Emulgen 109P (10%), manufactured by Kao Corporation, HLB value 13.6)

Example 2 The compound A in the coating solution A for the colorant receiving layer of Example 1 was replaced by the compound B (general formula (1)
An ink jet recording sheet (2) of the present invention was produced in the same manner as in Example 1 except that the compound represented by the formula; The pH of the coating liquid for the colorant receiving layer
Showed 9.5.

[Example 3] The compound A in the coating material A for the colorant receiving layer of Example 1 was replaced by the compound C (general formula (1)).
The ink jet recording sheet (3) of the present invention was produced in the same manner as in Example 1 except that the compound represented by the formula; The pH of the coating liquid for the colorant receiving layer
Showed 9.4.

[Example 4] -Preparation of coating liquid B for colorant receiving layer- (1) to (3) in the following composition were mixed, and a high-speed rotating colloid mill (Clearmix, M Technique Co., Ltd.) was mixed.
Manufactured), and dispersed for 20 minutes at a rotation speed of 10,000 rpm, then a solution containing the following (4) to (7) is added, and redispersion is performed at a rotation speed of 10,000 rpm for 20 minutes.
A coating liquid B for a color material receiving layer was prepared. The mass ratio of the silica fine particles to the water-soluble resin (PB ratio / (1) :( 4)) is 4.
It was 5: 1, and the pH of the coating material B for the colorant receiving layer was 3.5, showing acidity.

[0138] [Composition of coating liquid B for colorant receiving layer] (1) Fine particles of vapor phase silica (inorganic pigment fine particles) 10.0 parts     (Average primary particle diameter 7 nm; Leosir QS30, manufactured by Tokuyama Corp.) (2) Deionized water 51.7 parts (3) PAS-M-1 (dispersant; Nittobo Co., Ltd.) 5.0 parts (4) Polyvinyl alcohol 8% aqueous solution (water-soluble resin) 27.8 parts   (PVA124, manufactured by Kuraray Co., saponification degree 98.5%, polymerization degree 2400) (5) 1.0 part of the above compound A     (Compound represented by the general formula (1); molecular weight 182) (6) Polyoxyethylene lauryl ether (surfactant) 1.2 parts     (Emulgen 109P (10%), manufactured by Kao Corporation, HLB value 13.6) (7) Deionized water 30.74 parts

—Preparation of Inkjet Recording Sheet— After the front surface of the support is subjected to corona discharge treatment, the colorant-receptive layer coating liquid B obtained above is applied to the front surface of the support by an extrusion die coater. Using 20
A coating amount of 0 ml / m ² was applied (coating step), followed by drying with a hot air dryer at 80 ° C. (air velocity 3 to 8 m / sec) until the solid concentration of the coating layer reached 20%. The coating layer showed a constant drying rate during this period. Immediately after that, it was dipped in a cross-linking agent solution B having the following composition for 30 seconds to obtain 20 g / m of the coating layer.
² is attached (step of applying a cross-linking agent solution), and further 80
It was dried at 0 ° C. for 10 minutes (drying step). From this, an inkjet recording sheet (4) of the present invention provided with a coloring material receiving layer having a dry film thickness of 32 μm was prepared.

[0140] [Composition of Crosslinking Agent Solution B] ・ Boric acid (6%; crosslinking agent) 25 parts -PAA-10C (10%) aqueous solution 20 parts   (Mordant; Nittobo Co., Ltd.) ・ Ion-exchanged water 52.8 parts ・ Ammonium chloride (surface pH adjuster) 0.2 parts ・ Polyoxyethylene lauryl ether (surfactant) 2 parts (Emulgen 109P (10%), manufactured by Kao Corporation, HLB value 13.6)

Example 5 The compound A in the coating material B for the colorant receiving layer of Example 4 was replaced by the compound D (general formula (2)).
An inkjet recording sheet (5) of the present invention was produced in the same manner as in Example 4 except that the compound represented by the formula; The pH of the coating liquid for the colorant receiving layer
Showed 3.5.

[Example 6] The compound A in the coating material B for the colorant receiving layer of Example 4 was replaced by the compound E (general formula (1)).
An ink jet recording sheet (6) of the present invention was produced in the same manner as in Example 4 except that the compound represented by the formula; The pH of the coating liquid for the colorant receiving layer
Showed 3.6.

Example 7 The compound A in the coating solution B for the colorant receiving layer of Example 4 was replaced by the compound F (general formula (1)).
An ink jet recording sheet (7) of the present invention was produced in the same manner as in Example 4 except that the compound represented by the formula; The pH of the coating liquid for the colorant receiving layer
Showed 3.4.

Example 8 In Example 4, the compound A was not added to the coating material B for the colorant-receiving layer, and the crosslinking agent solution B was added to the compound C (compound represented by the general formula (1); molecular weight 242). ) An ink jet recording sheet (8) of the present invention was produced in the same manner as in Example 4 except that 1.0 part was added. The pH of the coating material for the colorant receiving layer was 3.5.

Comparative Example 1 A comparative inkjet recording sheet (1) was prepared in the same manner as in Example 4 except that the compound A was not added to the coating material B for the colorant receiving layer of Example 4. . The pH of the coating material for the colorant receiving layer was 3.5.

Comparative Example 2 A comparative inkjet recording sheet (2) was prepared in the same manner as in Example 4 except that the compound A in the coating material B for the colorant receiving layer of Example 4 was changed to the following comparative compound. Was produced. The pH of the coating material for the colorant receiving layer was 3.5.

[0147]

[Chemical 2]

<Performance Evaluation> The following evaluation was made for each of the inkjet recording sheets (1) to (8) of the present invention and the comparative inkjet recording sheets (1) to (2) obtained above. I did it. The evaluation result is
The results are shown in Table 1 below.

(Glossiness) The 60 ° glossiness on the surface of the color material receiving layer of the recording sheet before printing was measured with a digital variable angle glossiness meter (UGV-50DP, manufactured by Suga Test Instruments Co., Ltd.).

(Ink Absorption Speed) Using an ink jet printer (PM-900C, manufactured by Seiko Epson Corp.), Y (yellow), M (magenta), C (cyan) on the color material receiving layer of each recording sheet. , K (black), B (blue), G
Solid images of (green) and R (red) were printed, and then (after about 10 seconds), a paper was contact-pressed on the image, and the degree of transfer of the ink to the paper was evaluated according to the following criteria. [Standard] AA: No transfer of ink onto the paper was observed. BB: Partial transfer of the ink onto the paper was observed. CC: A large amount of ink transfer was observed on the paper.

(Water resistance) Similar to the evaluation of the ink absorption rate, Y (yellow), M (magenta), C (cyan),
Solid images of K (black), B (blue), G (green) and R (red) are printed, left for 3 hours, and then immersed in water for 1 minute,
The outflow degree of the ink into water was visually evaluated according to the following criteria. [Standard] AA: No dye outflow was observed. BB: The dye outflow was recognized as a whole, and the color density of the image gradually decreased. CC: The dye has almost completely flowed out into the water.

(Bluing with time) A grid-like linear pattern (line width 0.28 mm) in which magenta ink and black ink are adjacent to each other was formed on each ink jet recording sheet using the same printer for measuring the ink absorption speed. Printed. After leaving for 3 hours after printing, 40 ℃, relative humidity 90%
Was stored in a constant temperature and humidity chamber for 3 days, and the line width of the black portion was measured and evaluated according to the following criteria. [Criteria] AA: Almost no generation of bleeding with time was observed, which was good. (Line width: 0.28 to 0.30 mm) BB: Some bleeding with time was observed, but it was at a level where there was no practical problem. (Line width: 0.31-0.35m
m) CC: Remarkable bleeding with time was observed, which was a level of practical problem. (Line width: 0.35 mm or more)

(Light resistance) In the same manner as the evaluation of the ink absorbency, Y (yellow), M (magenta), C (cyan), K
After printing solid images of (black), B (blue), G (green) and R (red), Xenonweather is passed through a film that blocks ultraviolet rays in the wavelength region of 365 nm or less.
Using -ometer Ci65A (manufactured by ATLAS), the lamp was turned on for 3.8 hours under an environmental condition of 25 ° C. and a relative humidity of 32%, and then the lamp was turned off for 20 hours.
A cycle of standing for 1 hour under environmental conditions of ° C and 91% relative humidity was performed for 96 hours, and the degree of fading of each color density of the image was visually evaluated according to the following criteria. [Standard] A: Almost no fading was observed. O: Slight fading was observed. Δ: A considerable amount of fading was observed. X: The degree of fading was remarkable.

(Printing Density) A solid image of K (black) was printed on an inkjet recording sheet with an inkjet printer (PM-900C, manufactured by Seiko Epson Corporation), and after leaving it for 3 hours, the reflection density of the printed screen was measured. Was measured with a Macbeth reflection densitometer.

(Ozone resistance) A solid image of cyan was printed on an inkjet recording sheet with an inkjet printer (PM-900C, manufactured by Seiko Epson Corp.), and the sheet was stored for 2 hours in an environment with an ozone concentration of 3 ppm. The cyan density before and after storage was measured, and the residual ratio of the cyan density was calculated.

[0156]

[Table 1]

From the results shown in Table 1 above, when the compound represented by the general formula (1) or the compound represented by the general formula (2) is used, good ink absorption is exhibited, and a high resolution and high density image is obtained. Was formed, the bleeding with time in a high temperature and high humidity environment was suppressed, and the formed image also showed high light resistance, water resistance, glossiness, and excellent ozone resistance. Especially the molecular weight is 200
The inkjet recording sheets of Examples 2 to 3 and 5 to 8 described above were excellent in the effect of suppressing blurring over time. Also,
The inkjet recording sheets of Examples 4 to 8 using the acidic coloring material-receptive layer coating liquids were excellent in glossiness and print density.

On the other hand, the comparative inkjet recording sheet (1) which did not use the compound of the present invention had low ozone resistance and could not sufficiently suppress generation of bleeding with time. Further, a comparative inkjet recording sheet (2) using a comparative compound instead of the compound in the present invention
Had a low glossiness and was insufficient for photographic image quality.

[0159]

According to the present invention, the present invention provides an ink jet recording sheet which suppresses the generation of bleeding over time and is excellent in ozone resistance and glossiness without deteriorating other ink receiving performance. With the goal. Further, the present invention has an object to provide an inkjet recording sheet that is strong without generation of cracks, has good ink absorbability, is excellent in water resistance and light resistance, and can form a high-resolution image. And

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2C056 EA13 FC06                 2H086 BA01 BA15 BA33 BA35 BA37                       BA41                 4D075 BB64Z CA35 DA03 DB18                       DC27 EA05 EB11 EB19 EC01                       EC03 EC30

Claims (7)

[Claims] 1. An ink jet recording sheet having a colorant receiving layer on a support, wherein the colorant receiving layer is a compound represented by the following general formula (1) and / or a general formula (2) below. An ink jet recording sheet comprising a compound represented by the formula, a fumed silica, polyvinyl alcohol, a boron compound, and a mordant. _{X-Y-S-CH 2} -CH 2 -S-Y-X Formula (1) X-Y-S -S-Y-X Formula (2) wherein, X represents alkyl group, a halogen atom, It represents a hydroxy group, an alkoxyl group, a carboxy group and a carboxylate, an acyl group, an amino group, a thiocarbamoyl group, a sulfamoyl group, a sulfoamino group, other nitrogen atom-containing groups, or other sulfur atom-containing groups. In the formula, Y represents an alkylene group which may have a substituent. ] 2. The ink jet recording sheet according to claim 1, wherein the compound has a molecular weight of 200 or more. 3. The inkjet recording sheet according to claim 1, wherein the compound is water-soluble. 4. The color material receiving layer is formed by coating a coating solution containing the compound, the vapor grown silica and the polyvinyl alcohol on the support, simultaneously with the coating, or by the coating. During the drying of the coating layer
2. The coating layer is obtained by applying a solution containing the boron compound and the mordant to the coating layer before the coating layer shows a rate of decrease in drying rate, and then curing the coating layer. 4. The inkjet recording sheet according to any one of 3 to 3. 5. A coating liquid obtained by adding the compound and the polyvinyl alcohol to an aqueous dispersion having a pH of 4.5 or less, which comprises the vapor phase silica and a dispersant, and re-dispersing the coloring material receiving layer. Is coated on the support, simultaneously with the coating, or in the course of drying the coating layer formed by the coating, and before the coating layer shows a decreasing rate of drying, the coating layer is The inkjet recording sheet according to claim 1, which is obtained by applying a solution containing a boron compound and the mordant and then curing the coating layer. 6. The coloring material-receiving layer comprises a coating liquid obtained by adding the polyvinyl alcohol to an aqueous dispersion of pH 4.5 or less containing a vapor-phase method silica and a dispersant and re-dispersing it on the support. The coating layer is coated with the compound and the boron compound at the same time as the coating, or in the course of drying the coating layer formed by the coating, and before the coating layer exhibits a rate of reduction drying. The inkjet recording sheet according to any one of claims 1 to 3, which is obtained by applying a solution containing: and a mordant, and then curing the coating layer. 7. The ink jet recording sheet according to claim 1, wherein the mordant is polyallylamine having a weight average molecular weight of 100,000 or less and a derivative thereof.