JP2002301860A - Ink-jet recording paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink-jet recording paper in which light-resistance is improved when ink-jet recording is performed with a water-based ink containing a water-based dye and blotting after printing is remarkably suppressed. SOLUTION: The ink-jet recording paper characterized by providing a porous ink absorbing layer comprising a polyalkylene-polyamine-dicyandiamide polycondensate and a zirconium atom-containing compound (however, zirconium oxide is excluded) on a non-water-absorbing substrate is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet recording paper, and more particularly, to a paper having a porous ink absorbing layer,
The present invention relates to an ink jet recording paper having improved light fastness and image bleeding.

[0002]

2. Description of the Related Art In recent years, the image quality obtained by ink-jet recording has been rapidly improving, and the image quality is approaching that of silver halide photography. As means for achieving such image quality equivalent to silver halide photography (hereinafter, referred to as photographic image quality) by ink jet recording, quality improvement has also been advanced in ink jet recording paper (hereinafter, also simply referred to as recording paper), Among them, recording paper provided with an ink absorbing layer having fine voids on a highly smooth support is becoming one of the closest to photographic quality because of its high ink absorbing property and high drying property. is there.

[0003] The characteristics required for recording paper have been further increased with the above-mentioned high image quality. In particular, a support is a non-water-absorbing support, and a void-type ink absorbing layer is provided thereon. With the provided ink jet recording paper, the support maintains high smoothness during ink jet recording, so that high quality prints can be obtained, which is preferable.

In ink-jet recording, a water-soluble dye is usually used as a coloring material in many cases. However, when the ink-absorbing layer is a void layer, a uniform image having a high ink-absorbing property and no unevenness during ink-jet recording is obtained. On the other hand, it was found that oxygen permeability was high because of the porous film, and light resistance after recording was apt to be lowered.

[0005] In particular, many compounds which have been effective when added to ink jet recording papers have a relatively sufficient anti-fading effect in the initial stage, but their effects are gradually lost after long-term storage. However, as a result of intensive studies on a technique for solving photobleaching involving oxygen for a relatively long period of time, Japanese Patent Laid-Open
It has been found that the ink-jet recording paper having a porous ink absorbing layer containing a polyalkylenepolyamine / dicyandiamide-based polycondensate on a non-water-absorbing support, which is the invention described in US Pat.

[0006] The invention described in JP-A-2000-263928
According to the polyalkylene polyamine dicyandiamine
The effect of maintaining the anti-fading effect by
The effect is especially great when stored for a long time in a high humidity atmosphere.
On the other hand, polyalkylene polyamine dicyandi
If an amide-based polycondensate is contained, the
When stored in a highly humid atmosphere, bleeding may worsen.
In order to prevent the bleeding from becoming worse, the ink absorbing layer
It is effective to include water-soluble polyvalent metal ions
I found something. Here, the water-soluble polyvalent metal ion and
Is a polyvalent metal ion having 2 to 4 valences.
Ca²⁺, Mg²⁺, Zn²⁺, Cu²⁺, Fe ³⁺, Ni²⁺, C
o²⁺, Al³⁺Etc., but in particular Ca²⁺, Mg²⁺,
Zn²⁺, Al³⁺Is preferred, but its effect
Is still inadequate and achieves a quality approaching that of silver halide photography.
Therefore, the development of further improved technology is eagerly desired.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an ink jet recording paper having a porous ink absorbing layer containing a polyalkylene polyamine / dicyandiamide polycondensate on a non-water-absorbing support. An object of the present invention is to provide an ink jet recording sheet which has improved light fastness when ink jet recording is carried out by using the method described above and in which bleeding after printing is remarkably suppressed.

[0008]

The above object of the present invention has been attained by the following constitutions.

1. Compound containing a polyalkylene polyamine / dicyandiamide-based polycondensate and a zirconium atom on a non-water-absorbing support (excluding zirconium oxide)
An ink jet recording paper comprising a porous ink absorbing layer containing:

[0010] 2. Polyalkylene polyamine / dicyandiamide polycondensate, compound containing zirconium atom on non-water-absorbing support (excluding zirconium oxide)
And a cationic polymer having a quaternary ammonium salt group.

3. 3. The ink jet recording paper according to claim 1, wherein the compound containing a zirconium atom is at least one selected from zirconyl ammonium carbonate, zirconyl acetate, and zirconyl oxychloride.

4. 0.01 to 5 g / m ^{2 of the} polyalkylenepolyamine / dicyandiamide-based polycondensate, and 0.01% of the compound containing the zirconium atom.
4. The ink jet recording sheet according to any one of the above items 1 to 3, wherein the content of the ink is from 5 to 5 g / m ² .

Hereinafter, the present invention will be described in detail. In the invention according to the first aspect, a polyalkylene polyamine is formed on a non-water-absorbing support as an inkjet recording sheet.
It is characterized by having a porous ink absorbing layer containing a dicyandiamide-based polycondensate and a compound containing a zirconium atom (excluding zirconium oxide). In the present invention, in order to improve the light resistance of an ink jet recording paper provided with a void-type ink absorbing layer on a non-water-absorbing support, it is a point to be noted when using a polyalkylene polyamine / dicyandiamide-based polycondensate, Among the polyvalent metal ions, as a means to suppress the deterioration of later bleeding,
A compound containing a zirconium atom can exert its effect remarkably.

In the present invention, the polyalkylenepolyamine
The dicyandiamide-based polycondensate is a polycondensate of a polyalkylene polyamine and dicyandiamide.

Examples of the polyalkylene polyamine include diethylene triamine, triethylene tetramine,
Examples include tetraethylenepentamine, iminobispropylamine and their hydrochlorides, lead sulfate, acetate and the like.

As the polyalkylene polyamine / dicyandiamide-based polycondensate, various products are commercially available. For example, Neofix RP-70, Neofix PNF-70, Neofix E-117, (Nichika Chemical Co., Ltd.) ), Parafix EP (manufactured by Ohara Palladium Chemical Co.), Diazine Fix 400 (manufactured by Nissei Chemicals), Fastgen P-708 (manufactured by Tokai Oil Industries), Jet Fix 20 (manufactured by Kuroda Kako), Kayafix M (manufactured by Nippon Kayaku Co., Ltd.), PAP-1 (manufactured by Nippon Senka Kogyo Co., Ltd.), Sunfix 414 (Sanyo Chemical Co., Ltd.), and the like, and derivatives thereof. Among these, Sunfix 414 and Parafix EP are particularly preferably used. The average molecular weight of the polyalkylene polyamine / dicyandiamide-based polycondensate is from 2,000 to 20.
000 is preferred.

The compound containing a zirconium atom used in the present invention excludes zirconium oxide. Specific examples thereof include zirconium difluoride, zirconium trifluoride, zirconium tetrafluoride, and hexafluorozirconate. (Eg, potassium salt), heptafluorozirconate (eg, sodium salt, potassium salt or ammonium salt), octafluorozirconate (eg, lithium salt), zirconium fluoride oxide, zirconium dichloride, zirconium trichloride, Zirconium tetrachloride, hexachlorozirconate (eg, sodium salt or potassium salt), zirconium oxychloride (zirconyl chloride), zirconium dibromide, zirconium tribromide, zirconium tetrabromide, zirconium bromide, zirconium triiodide , Zirconium iodide, peroxide, zirconium hydroxide, sulfide, zirconium sulfate, p- toluenesulfonic acid zirconium, zirconyl sulfate, zirconyl sodium sulfate, acidic zirconyl sulfate trihydrate, potassium zirconium sulfate,
Zirconium selenate, zirconium nitrate, zirconyl nitrate, zirconium phosphate, zirconyl carbonate, zirconyl ammonium carbonate, zirconium acetate, zirconyl acetate, zirconyl ammonium acetate, zirconyl lactate, zirconyl citrate, zirconyl stearate, zirconyl phosphate, zirconium oxalate, Examples include zirconium isopropylate, zirconium butyrate, zirconium acetylacetonate, acetylacetone zirconium butyrate, zirconium butyrate stearate, zirconium acetate, bis (acetylacetonato) dichlorozirconium, and tris (acetylacetonato) chlorozirconium.

Among these compounds, zirconyl carbonate, zirconyl ammonium carbonate, zirconyl acetate, zirconyl nitrate, zirconyl oxychloride, zirconyl lactate, zirconyl carbonate, zirconyl carbonate, zirconyl carbonate, zirconyl carbonate, zirconyl lactate, zirconyl lactate Zirconyl citrate is preferred, with zirconyl ammonium carbonate, zirconyl acid chloride and zirconyl acetate being particularly preferred. Specific product names of the compounds include zirconyl acetate ZA (trade name) manufactured by Daiichi Rare Earth Element Chemical Industry Co., Ltd., and zirconyl oxychloride (trade name) manufactured by Daiichi Rare Earth Element Chemical Co., Ltd.

The compound containing a zirconium atom may be used alone, or two or more different compounds may be used in combination. When two or more kinds are used, there is an advantage that bronzing (a phenomenon of promoting the crystallization of the dye in the ink to give a metallic luster) which is likely to occur when a compound containing a zirconium atom is used can be suppressed. .

The compound containing a zirconium atom may be added to the coating liquid for forming the ink absorbing layer, or may be applied to the ink absorbing layer after the porous layer is applied and dried, and then applied to the ink absorbing layer by an overcoating method. Is also good. When the former compound containing a zirconium atom is added to the coating liquid for forming the ink absorbing layer, a method of uniformly dissolving the compound in water, an organic solvent or a mixed solvent thereof, or a wet milling method such as a sand mill or emulsification A method of dispersing and adding to fine particles by a method such as dispersion can be used. When the ink absorbing layer is composed of a plurality of layers, only one layer may be added, or two or more layers or all the constituent layers may be added.

When the latter porous ink absorbing layer is formed once and then added by an overcoating method, it is preferable that the zirconium compound is uniformly dissolved in a solvent and then supplied to the ink absorbing layer.

The compound containing a zirconium atom is a polymer
Uses polyalkylene polyamine / dicyandiamide polycondensate
To use to solve problems that arise when
From the point of view, there is a particularly preferable range for the use amount of both.
You. In the present invention, the polyalkylene polyamine dicyan
The diamide-based polycondensate is 1m in inkjet recording paper ^Two
It is preferable to use 0.01 to 5 g, more preferably
Preferably, it is used in the range of 0.1 to 2 g. one
On the other hand, compounds containing zirconium atoms are
Recording paper 1m^TwoIt is preferable to use 0.01 to 5 g per unit.
More preferably, it is more preferably used in the range of 0.05 to 2 g.
And particularly preferably in the range of 0.1 to 1 g.
is there. In particular, if each amount is within this range,
The effects of the invention are remarkably exhibited and are preferable.

According to the second aspect of the present invention, the ink jet recording paper comprises a polyalkylene polyamine / dicyandiamide polycondensate, a compound containing a zirconium atom (excluding zirconium oxide) and a fourth It is characterized by having a porous ink absorbing layer containing a cationic polymer having a quaternary ammonium base.

In the present invention, a cationic polymer containing a quaternary ammonium base is used in combination with the constitution according to the first aspect. This is because, in order to impart water resistance to the porous ink absorbing layer, alumina fine particles whose surface is cationic are generally used as inorganic fine particles, or silica fine particles whose surface is anionic and quaternary ammonium base are used. When a polyalkylene polyamine / dicyandiamide-based polycondensate according to the present invention is added to such an ink absorbing layer, bleeding tends to worsen after printing. In particular, when a cationic polymer having a quaternary ammonium base and a polyalkylene polyamine / dicyandiamide-based polycondensate are used, water resistance and light resistance are remarkably improved. At this time, the compound containing a zirconium atom according to the present invention is used. It has been found that the combined use of the above significantly improves bleeding after printing caused by the polyalkylenepolyamine / dicyandiamide-based polycondensate, and is preferable.

The cationic polymer containing a quaternary ammonium base according to the present invention is a polymer having a quaternary ammonium base in the polymer main chain or side chain. Also,
These polymers are preferably substantially water-soluble from the viewpoint of easy production of the ink jet recording paper.

Examples of the cationic polymer containing a quaternary ammonium base according to the present invention include, for example, those described in
No. 64591, cationic polymers having a guanidyl group, dimethyldiallylammonium chloride described in JP-A-59-20696, JP-A-59-3317
No. 6, polyamine sulfones described in JP-A-63-11
No. 5780, a quaternary ammonium salt of an alkyl (meth) acrylate or a quaternary ammonium salt of a (meth) acrylamidoalkyl quaternary ammonium salt;
No. 9776 and 64-75281, copolymers of dimethylallylammonium chloride and acrylamide described in JP-A-3-133686, and cationic polymers containing two or more quaternary nitrogen atoms in the repeating unit described in JP-A-3-133686. JP-A-4-288286 describes a polyvinylpyrrolidone having a quaternary ammonium salt group.
Nos. 92010 and 6-234268, cationic polymers obtained by reacting a secondary amine with epihalohydrin, polystyrene-type cationic polymers described in International Patent Publication No. 99-64248,
And a cationic polymer comprising a repeating unit having two or more cationic groups described in 348409.

Specific examples of the repeating unit containing a quaternary ammonium base are shown below, but the present invention is not limited thereto.

The cationic polymer containing a quaternary ammonium salt according to the present invention may be a homopolymer or a condensate of a repeating unit containing a quaternary ammonium salt, or may contain a quaternary ammonium salt. And a copolymer with another copolymerizable repeating unit. The copolymerizable repeating unit has one copolymerizable unsaturated bond.
Or is derived from a monomer having two or more, and specific examples of such a monomer include, for example, styrene,
Vinyl chloride, vinylidene chloride, (meth) acrylic acid,
(Meth) acrylic acid ester (for example, methyl (meth)
Acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate,
Octyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, etc.), (meth) acrylamide, butadiene,
Examples thereof include ethylene, vinyl acetate, vinyl methyl ether, acrylonitrile, N-vinyl-2-pyrrolidone, maleic acid, and divinylbenzene. When the cationic polymer containing a quaternary ammonium base is the above-mentioned copolymer, the proportion of the repeating unit having a quaternary ammonium base is preferably at least 10 mol%, particularly preferably at least 20 mol%.

Specific examples of the cationic polymer containing a quaternary ammonium base according to the present invention include the following polymers.

The CMs shown in Table 1 below represent repeating units having a quaternary ammonium base, and Q1 and Q
2 and Q3 each represent a repeating unit containing no quaternary ammonium base, and are represented by the following abbreviations. The ratio of each copolymer described in parentheses represents mol%.

MMA: methyl methacrylate EMA: ethyl methacrylate NPMA: N-propyl methacrylate NBA: N-butyl methacrylate HEMA: hydroxyethyl methacrylate AA: acrylamide VP: N-vinyl-2-pyrrolidone

[0032]

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[0033]

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[0034]

[Table 1]

The cationic polymer containing a quaternary ammonium base according to the present invention can be used in combination of two or more kinds.

Particularly preferred as the cationic polymer containing a quaternary ammonium base according to the present invention are a cationic polymer represented by the following general formula (1) and a cation represented by the following general formula (2) Polymer.

[0037]

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In the general formula (1), R represents a hydrogen atom or an alkyl group. R ₁ , R ₂ and R ₃ each represent an alkyl group or a benzyl group. J represents a simple bond or a divalent organic group. X ^- represents an anionic group. A represents a repeating unit having no quaternary ammonium base in the molecule. p represents a positive number of 0 to 6. x is 5 to 100, y
Represents 0 to 95 (all in a molar ratio).

In the general formula (2), Q represents a repeating unit represented by the following general formula (2A), (2B) or (2C).

A has the same meaning as A in the general formula (1). x1 represents 5 to 100, and y1 represents 0 to 95 (all in a molar ratio).

[0041]

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In the general formula (2A), R, R ₁ , R ₂ ,
R ₃ and X ⁻ are R, R ₁ , R ₂ , R _{3 in the} general formula (1).
And X ^- as synonymous. J ₁ represents a simple bond or a divalent organic group. The B -O- or -NR ₅ - (R ₅ represents a hydrogen atom, an alkyl group, an allyl group or a benzyl group). m represents an integer of 1 to 6.

[0043] In the general formula (2B), R and X ^- is R and X in the general formula (1) ^- synonymous. J ₁ has the same meaning as J _{1 in} formula (2A), and R ₄ represents an alkyl group.

[0044] In the general formula (2C), R and X ^- is R and X in the general formula (1) ^- synonymous. R ₄ has the same meaning as R _{4 in} formula (2B).

Next, the porous ink absorbing layer according to the present invention will be described. The ink jet recording paper of the present invention is provided with a porous ink-absorbing layer on a non-water-absorbing support. As a method for forming the porous ink-absorbing layer, there have been conventionally known many methods. However, in the present invention, it is preferable that a void layer is formed from inorganic fine particles and a small amount of a hydrophilic binder.

As the inorganic fine particles which can be used in the present invention, fine particles having a smaller particle size are preferred from the viewpoint of providing higher image density. Examples of such inorganic fine particles include, for example, light calcium carbonate, heavy calcium carbonate, magnesium carbonate, kaolin, clay, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc hydroxide, zinc sulfide, carbonate Zinc, hydrotalcite, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, alumina, colloidal alumina, pseudoboehmite, aluminum hydroxide, lithopone, zeolite,
Examples include white inorganic pigments such as magnesium hydroxide.

The shape of the above-mentioned inorganic fine particles is not particularly limited in the present invention, and may be any of a spherical shape, a rod shape, a needle shape, a flat plate shape, and a bead shape.

The inorganic fine particles may be used in a state of being uniformly dispersed in a hydrophilic binder as primary particles, or in a state of forming secondary aggregated particles and being dispersed in a hydrophilic binder. Although it may be used, the latter is more preferable from the viewpoint of achieving high gloss and fast ink absorption. From the same viewpoint,
It is preferable to use inorganic fine particles having an average particle size of 3 to 200 nm. When the thickness is 200 nm or less, the glossiness of the recording paper is good, and irregular reflection on the surface hardly occurs, so that the maximum density is high and a clear image can be obtained. Further, in the present invention, the lower limit of the average particle size is not particularly limited, but from the viewpoint of production of the inorganic fine particles, the lower limit is approximately 3%.
nm or more, particularly preferably 6 nm or more. From these viewpoints, particularly preferred inorganic fine particles have an average particle size of 2
0-100 nm.

The average particle size of the inorganic fine particles referred to in the present invention can be determined by observing the fine particles themselves or the cross section or surface of the void-type ink absorbing layer with an electron microscope and measuring the particle size of a large number of arbitrary fine particles. It is obtained as a simple average (number average). Each particle size in the present invention is represented by a diameter assuming a circle equal to the projected area.

In the present invention, composite particles composed of inorganic fine particles and a small amount of an organic substance (either a low molecular compound or a high molecular compound) are regarded as inorganic fine particles. Also in this case, the particle size of the highest order particles in the dry film measured by the above method is defined as the particle size of the inorganic fine particles.

In the composite particles of the above-mentioned inorganic fine particles and a small amount of organic substance, the mass ratio of organic substance / inorganic fine particles is approximately 1 /.
100 to 1/4.

In the present invention, the inorganic fine particles having an anionic surface are silica or silica synthesized by a gas phase method because of their low cost and low refractive index fine particles capable of obtaining a high reflection density. Colloidal silica is preferred.
As the inorganic fine particles having a cationic surface, fumed silica treated with a cationic surface, colloidal silica treated with a cationic surface, alumina, colloidal alumina, pseudo boehmite, and the like can also be used.

The amount of the inorganic fine particles used in the porous layer greatly depends on the required ink absorption capacity, the porosity of the void amount, the type of the inorganic fine particles, and the type of the hydrophilic binder. Usually ^{2 to} 30 per ²
g, preferably 5 to 25 g. The ratio between the inorganic fine particles and the hydrophilic binder used in the void-type ink absorbing layer is usually from 2: 1 to 20: 1 by mass, and especially 3: 1.
It is preferably from 10 to 10. Although the ink absorption capacity increases as the amount of the inorganic fine particles increases, curling, cracking, and the like are liable to deteriorate. Therefore, a method of increasing the ink absorption capacity by controlling the porosity is preferable. In terms of ink absorption capacity, curl, cracks, etc.,
Preferred porosity is 40-75%. The porosity can be set to a desired value depending on the type of the selected inorganic fine particles and hydrophilic binder, or the mixing ratio thereof, or by appropriately adjusting the amount of other additives. The porosity in the present invention is the ratio of the total volume of the voids to the volume of the void layer, and can be calculated from the total volume of the components of the layer and the thickness of the layer. Also,
The total volume of the voids can be easily obtained also by measuring a saturated transition amount by Bristow measurement, a water absorption amount, or the like.

Next, the hydrophilic binder that can be used for the ink jet recording paper of the present invention will be described.

The term “hydrophilic” as used in the present invention means, in addition to the case where the compound is simply soluble in water, a mixture of water and a water-miscible organic solvent such as methanol, isopropyl alcohol, acetone and ethyl acetate. Polymers soluble in solvents are also included. In this case, the amount of the water-miscible organic solvent is usually 50% by mass or less based on the total amount of the solvent.

The term "hydrophilic" means that the binder usually dissolves in the solvent in an amount of 1% by mass or more at room temperature, more preferably 3% by mass or more.

The hydrophilic binder used in the present invention includes, for example, polyvinyl alcohol, gelatin, polyethylene oxide, polyvinylpyrrolidone, casein,
Starch, agar, carrageenan, polyacrylic acid, polymethacrylic acid, polyacrylamide, polymethacrylamide, polystyrenesulfonic acid, cellulose, hydroxylethylcellulose, carboxymethylcellulose,
Examples include hydrophilic polymers such as hydroxylethylcellulose, dextran, dextrin, pullulan, and water-soluble polyvinyl butyral. These hydrophilic polymers can be used in combination of two or more.

The hydrophilic polymer preferably used in the present invention is polyvinyl alcohol. The polyvinyl alcohol includes, in addition to ordinary polyvinyl alcohol obtained by hydrolyzing polyvinyl acetate, modified polyvinyl alcohol such as polyvinyl alcohol having a cation-modified terminal and anion-modified polyvinyl alcohol having an anionic group. As the polyvinyl alcohol obtained by hydrolyzing vinyl acetate, those having an average degree of polymerization of 1000 or more are preferably used.
000 are preferably used, and the degree of saponification is 7
0-100% is preferable, and 80-99.5% is particularly preferable.

The cation-modified polyvinyl alcohol is
For example, a polyvinyl alcohol having a primary to tertiary amino group or a quaternary ammonium group in the main chain or side chain of the polyvinyl alcohol as described in JP-A-61-10483, It is obtained by saponifying a copolymer of an ethylenically unsaturated monomer having a group and vinyl acetate.

Examples of the ethylenically unsaturated monomer having a cationic group include trimethyl- (2-acrylamido-2,2-dimethylethyl) ammonium chloride and trimethyl- (3-acrylamido-3,3-dimethylpropyl). ) Ammonium chloride, N-vinylimidazole, N-vinyl-2-methylimidazole, N
-(3-dimethylaminopropyl) methacrylamide,
Hydroxylethyltrimethylammonium chloride, trimethyl- (2-methacrylamidopropyl) ammonium chloride, N- (1,1-dimethyl-3-
Dimethylaminopropyl) acrylamide and the like.

The ratio of the cation-modified group-containing monomer in the cation-modified polyvinyl alcohol is 0.1 to 10 mol%, preferably 0.2 to 5 mol%, based on vinyl acetate.

As the anion-modified polyvinyl alcohol, for example, polyvinyl alcohol having an anionic group as described in JP-A-1-206088,
JP-A-61-237681 and JP-A-63-307979
And copolymers of vinyl alcohol and a vinyl compound having a water-soluble group as described in
Modified polyvinyl alcohol having a water-soluble group as described in JP-A-285265.

Examples of the nonionic modified polyvinyl alcohol include polyvinyl alcohol derivatives having a polyalkylene oxide group added to a part of vinyl alcohol as described in JP-A-7-9758, and JP-A-8-25795. And a block copolymer of a vinyl compound having a hydrophobic group and a vinyl alcohol. Further, as the modified polyvinyl alcohol, a polyvinyl alcohol modified with a silyl group is also included in the polyvinyl alcohol referred to in the present invention. Further, as the polyvinyl alcohol, two or more kinds of different kinds such as a degree of polymerization, a degree of saponification and a modification may be used in combination.

Further, gelatin, polyethylene oxide, or polyvinylpyrrolidone can be used in combination with polyvinyl alcohol. These hydrophilic binders are preferably used in combination with polyvinyl alcohol.
To 50% by mass, particularly preferably in the range of 0 to 20% by mass.

The non-water-absorbing support according to the present invention may be a plastic resin film support or a support having both sides of paper covered with a plastic resin film.

Examples of the plastic resin film support include a polyester film, a polyvinyl chloride film, a polypropylene film, a cellulose triacetate film, a polystyrene film, and a laminated film support thereof. As the plastic resin film, a transparent or translucent one can also be used.A particularly preferred support is a support in which both sides of the paper are coated with a plastic resin, and the most preferable is a support in which both sides of the paper are coated with a polyolefin resin. It is a support.

A support in which both surfaces of paper, which is a non-water-absorbing support particularly preferred in the present invention, are coated with a polyolefin resin will be described below.

The paper used for the non-water-absorbing support according to the present invention is made of wood pulp as a main material, and if necessary, in addition to wood pulp, synthetic pulp such as polypropylene or synthetic fiber such as nylon or polyester. Paper making. As wood pulp, for example, LBKP, LBS
P, NBKP, NBSP, LDP, NP, LUKP, N
Although any of UKP can be used, it is preferable to use LBKP, NBSP, LBSP, NDP, and LDP which have a large amount of short fibers. However, LBSP, LDP
Is preferably in the range of 10 to 70%.

In the pulp, a chemical pulp containing less impurities (sulfate pulp or sulfite pulp) is preferably used, and pulp having improved whiteness by performing a bleaching treatment is also useful. Also, in the paper, higher fatty acids, sizing agents such as alkyl ketene dimer, calcium carbonate,
Talc, white pigments such as titanium oxide, paper strength enhancers such as starch, polyacrylamide, and polyvinyl alcohol, fluorescent whitening agents, water retention agents such as polyethylene glycols,
A dispersant, a softening agent such as quaternary ammonium, or the like can be appropriately added.

The freeness of pulp used for papermaking is determined by CSF
It is preferable that the fiber length after beating is 30 to 40 ml, which is the sum of the remaining 24 mesh residue and 42 mesh residue specified in JIS P 8207.
Preferably, it is 70%. In addition, it is preferable that 4 mesh residue is 20% or less.

The basis weight of the paper is preferably from 50 to 250 g, and particularly preferably from 70 to 200 g.
The thickness of the paper is preferably 50 to 210 μm.

The paper may be calendered at the papermaking stage or after the papermaking to give high smoothness. Paper density is 0.7
１．２1.2 g · m ² (JIS P 8118) is common. Further, the stiffness of the base paper is preferably 20 to 200 g under the conditions specified in JIS P 8143.
Further, a surface sizing agent may be applied to the paper surface.

The pH of the paper is preferably 5 to 9 as measured by the hot water extraction method specified in JIS P 8113.

Next, the polyolefin resin covering both sides of the paper will be described. Examples of the polyolefin resin that can be used in the present invention include polyethylene, polypropylene, polyisobutylene, and polyethylene. Polyolefins such as a copolymer mainly composed of propylene are preferable, and polyethylene is particularly preferable.

Hereinafter, particularly preferred polyethylene will be described. As the polyethylene for covering the front and back surfaces of the paper, mainly low-density polyethylene (LDPE) or high-density polyethylene (HDPE) is preferable, but other LLDPE, polypropylene, and the like can be partially used.

In particular, it is preferable that the polyolefin layer on the coating layer side has improved opacity and whiteness by adding rutile or anatase type titanium oxide therein. The content of titanium oxide is about 1-2 with respect to polyolefin.
0%, preferably 2 to 15%. Ultraviolet, navy blue, cobalt blue, phthalocyanine blue, manganese blue, cerulean, tungsten blue, molybdenum blue, anthraquinone blue and the like are included in the polyolefin layer. Examples of the fluorescent whitening agent include dialkylaminocoumarin, bisdimethylaminostilbene, bismethylaminostilbene, 4-alkoxy-1,8-naphthalenedicarboxylic acid-N-alkylimide, bisbenzoxazolylethylene, and dialkylstilbene. Is mentioned.

The amount of polyethylene used on the front and back of the paper is selected so as to optimize the thickness of the ink absorbing layer and the curl under low and high humidity after the back layer is provided.
Generally, the thickness of the polyethylene layer is 1 on the ink absorbing layer side.
It is in the range of 5 to 50 μm and 10 to 40 μm on the back layer side. The ratio of the front and back polyethylene is preferably set so as to adjust the curl that changes depending on the type and thickness of the ink receiving layer, the thickness of the inner paper, and the like. It is approximately 3: 1 to 1: 3.

Further, the paper support coated with the polyethylene preferably has the following characteristics (1) to (8).

(1) Tensile strength: JIS P 811
The strength specified in 3 and the vertical direction is 20-300N (2-
30kg), 10-200N (1-20kg) in the horizontal direction
(2) Tear strength: 20-30 g in the longitudinal direction and 10-250 in the horizontal direction at a strength specified by JIS P 8116.
g is preferable. (3) Compression elastic modulus: 9.8 kN / cm ² is preferable. (4) Opacity: 80% or more, particularly 85 to 98%, is preferable when measured by a method specified in JIS P 8138. ) Whiteness: L ^* defined by JIS Z 8727,
a ^* and b ^* are L ^* = 80 to 96, a ^* = − 3 to +5, b ^*
= -7 is preferably + 2 (6) Clark stiffness: support Clark stiffness in the carrying direction is 50~300cm ^3/100 of the recording sheet is preferably (7) the moisture of the base paper: the bookblock (8) Gloss (75-degree specular gloss) on the side provided with the ink receiving layer: preferably 10 to 90%.

In the ink jet recording paper of the present invention, the void type ink absorbing layer contains a hydrophilic binder represented by polyvinyl alcohol, and the ink absorbing layer preferably contains boric acid or a salt thereof. Polyvinyl alcohol is presumed to be cross-linked by boric acid or a salt thereof, but boric acid or a salt thereof that can be used in the present invention indicates an oxygen acid having a boron atom as a central atom or a salt thereof, Specifically, orthoboric acid, diboric acid, metaboric acid, tetraboric acid, pentaboric acid, octaboric acid and salts thereof are included.

The amount of boric acid or a salt thereof varies depending on the kind of the hydrophilic binder, the kind of the inorganic fine particles, the ratio to the hydrophilic binder, and the like. When polyvinyl alcohol is used, it is usually 5 to 500 per gram of the binder.
mg, preferably 10-300 mg.

The boric acid or a salt thereof may be added to a coating solution for forming a porous layer used for preparing recording paper, or a water-soluble coating solution for forming a porous layer containing no hardener may be used. After applying and drying the coating solution, the solution can be supplied by overcoating.

The ink jet recording paper of the present invention may contain a known hardener in addition to boric acid or a salt thereof.

The hardener which can be used is generally a compound having a group capable of reacting with a hydrophilic binder or a compound which promotes the reaction between substituents contained in the hydrophilic binder. When, for example, polyvinyl alcohol is used as the hydrophilic binder, epoxy hardeners (eg, diglycidyl ethyl ether, ethylene glycol diglycidyl ether,
1,4-butanediol diglycidyl ether, 1,6
-Diglycidylcyclohexane, N, N-diglycidyl-4-glycidyloxyaniline, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, etc., aldehyde-based curing agents (eg, formaldehyde, glyoxal, etc.), active halogen-based hardening agents (eg, , 2,4-Dichloro-4-hydroxy-1,3,5-
s-triazine and the like), active vinyl compounds (for example,
1,3,5-trisacryloyl-hexahydro-s-
Triazine, bisvinylsulfonylmethyl ether, etc.), aluminum alum, isocyanate compounds and the like.

Various additives other than those described above can be added to the ink receiving layer and other optional layers of the ink jet recording paper of the present invention, for example, polystyrene, polyacrylates and the like. , Polymethacrylic esters, polyacrylamides, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, or copolymers thereof, organic latex fine particles such as urea resin or melamine resin, various cationic or nonionic surfactants And JP-A-57-74193.
Ultraviolet absorbers described in JP-A-57-87988 and JP-A-62-261476; JP-A-57-74192; JP-A-57-87989; JP-A-60-72785;
No. 146591, JP-A-1-95091 and 3-1
No. 3376, etc .;
-42993, 59-52689, 62-28
0069, 61-242871 and JP-A-4-24-2
No. 19266, a fluorescent whitening agent, a pH adjuster such as sulfuric acid, phosphoric acid, citric acid, sodium hydroxide, potassium hydroxide, potassium carbonate, an antifoaming agent, a preservative, a thickener,
Various known additives such as an antistatic agent and a matting agent can be contained.

In the ink jet recording paper of the present invention, a method for applying various hydrophilic layers, which are optionally provided, such as a porous ink receiving layer and an undercoat layer, on a support is appropriately selected from known methods. You can do it.
A preferable method is obtained by applying a coating solution constituting each layer on a support and drying the coating solution. In this case, each constituent layer is 1
A method of sequentially applying layers one by one or a method of simultaneously coating two or more layers may be used. In particular, a so-called simultaneous multilayer coating method in which all the hydrophilic binder layers are applied in one application is preferable.

As the coating method, for example, a roll coating method, a rod bar coating method, an air knife coating method, a spray coating method, a curtain coating method, or an extrusion method using a hopper described in US Pat. No. 2,681,294. The method is preferably used.

The recording surface pH of the recording surface of the ink jet recording paper of the present invention is preferably 3.5 to 7.5. When the film surface pH is 3.5 or more, precipitation of the dye at the time of recording by inkjet is suppressed, and a change in metallic gloss, that is, so-called bronzing, is hardly caused. The compound containing a zirconium atom according to the present invention tends to cause bronzing, but it is easy to prevent this by setting the film surface pH to 3.5 or more. When the film surface pH is 7.5 or less, the effect of suppressing bleeding by the compound containing a zirconium atom can be more remarkably exhibited. Recording surface pH
Is measured according to J. TAPPI paper pulp test method No. 4
According to the method described in No. 9, the value was measured after 30 seconds using distilled water. In the present invention, the film surface pH of the recording surface
Can be adjusted to a predetermined film surface pH by appropriately adjusting the pH of the coating solution for forming the recording surface. Alternatively, a predetermined value can be obtained by overcoating a suitable pH adjuster after forming the recording surface. p
As the H adjustor, a suitable acid or alkali water-soluble agent can be used. In this case, the type and concentration of the acid or alkali to be used can be appropriately selected depending on the pH range to be adjusted.

In the recording paper of the present invention, by adding a polyalkylenepolyamine / dicyandiamide-based polycondensate to the ink-absorbing layer on the non-absorbing support, the light resistance of the phthalocyanine-based dye is particularly improved. This discoloration preventing effect is preferable since the effect can be maintained by further adding a sulfur-containing compound or the like. The effect of maintaining the anti-fading effect is particularly remarkable when stored at high humidity.

Examples of the above sulfur-containing compounds that can be used in the present invention include, for example, JP-A-61-1772.
No. 79, No. 61-163886, No. 64-36479
JP-A-7-314883, JP-A-7-314882
No. 1-1115677, and the like, for example, thiocyanate, thiourea, 2-mercaptobenzimidazole, 2-mercaptobenzthiazole, 2-mercaptobenzthiazole,
Mercaptobenzoxazole, 5-mercapto-1-
Methyltetrazole, 2,5-dimercapto-1,3,
4-triazole, 2,4,6-trimercaptocyanuric acid, thiosalicylic acid, thiouracil, 1,2-bis (2-hydroxyethylthio) ethane and the like.

In the image recording using the inkjet recording paper of the present invention, a recording method using an aqueous ink is preferable.

The aqueous ink in the present invention means a recording liquid comprising the following colorant, liquid medium, and other additives.

As the colorant that can be used in the present invention, a water-soluble dye or a water-dispersible pigment such as a direct dye, an acid dye, a basic dye, a reactive dye, and a food colorant known by ink jet can be used. Can be. Among them, a particularly preferred coloring agent is an ink using a phthalocyanine dye as a cyan dye. Phthalocyanine dyes are particularly widely known and used among cyan dyes.

Examples of the solvent for the aqueous ink include water and various water-soluble organic solvents, for example, alcohols such as methyl alcohol, i-propyl alcohol, butyl alcohol, t-butyl alcohol and i-butyl alcohol; dimethylformamide, dimethyl alcohol Amides such as acetamide;
Ketones or ketone alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2, 6-hexanetriol, thiodiglycol, hexylene glycol,
Polyhydric alcohols such as diethylene glycol, glycerin and triethanolamine; ethylene glycol methyl ether, diethylene glycol methyl (or ethyl)
And lower alkyl ethers of polyhydric alcohols such as ether and triethylene glycol monobutyl ether.

Among these water-soluble organic solvents, polyhydric alcohols such as diethylene glycol, triethanolamine and glycerin, and lower alkyl ethers of polyhydric alcohols such as triethylene glycol monobutyl ether are preferred.

Examples of other water-based ink additives include a pH adjuster, a metal sequestering agent, a fungicide, a viscosity adjuster, and the like.
Examples include surface tension modifiers, wetting agents, surfactants, and rust inhibitors.

The aqueous ink liquid has a thickness of 250 to 600 μm at 20 ° C. in order to improve the wettability on the recording paper.
It is preferred to have a surface tension in the range of N, preferably 300-500 μN.

The printer that can be used in the present invention is not particularly limited as long as it has, for example, a recording medium storage section, a transport section, an ink cartridge, and an ink jet print head, as are commercially available printers. At least a roll-shaped recording medium storage unit, a transport unit,
It is preferable that the printer is a series of printer sets including an ink jet print head, a cutting unit, and, if necessary, a heating unit, a pressing unit, and a recording print storage unit. The ink jet print head to be used may be an on-demand type or a continuous type. In addition, as a discharge method, an electro-mechanical conversion method (for example, a single cavity type, a double cavity type, a bender type, a piston type, a shared mode type, a shared wall type, etc.), and an electro-thermal conversion method (for example, thermal Examples thereof include an ink jet type, a bubble jet (registered trademark) type, an electrostatic suction type (for example, an electric field control type, a slit jet type, and the like), and a discharge type (for example, a spark jet type). Although the electro-mechanical conversion method is preferable, any discharge method may be used.

[0099]

EXAMPLES The present invention will be described below with reference to examples, but embodiments of the present invention are not limited thereto. In the examples, "%" means absolute dry mass% unless otherwise specified.
Represents

Example 1 << Preparation of Support >> A basis weight of 200 g / m 2 having a water content of 6% by mass.
A low-density polyethylene having a density of 0.92 was applied to the back surface of the photographic base paper of No. ² by an extrusion coating method at a thickness of 33 μm. Next, a low-density polyethylene containing 5.5% by mass of anatase type titanium oxide and having a density of 0.92 was applied to the front side with a thickness of 38 μm by an extrusion coating method to prepare a support having both surfaces coated with polyethylene. did. Perform a corona discharge on the front side to form an undercoat layer of polyvinyl alcohol of 0.0
After performing corona discharge on the back side at ² g / m ² , a latex layer was applied at 0.15 g / m ² .

<< Preparation of Dispersion >> (Preparation of Silica Dispersion-1) The average particle size of the primary particles is about 1
2 nm fumed silica (QS-20 manufactured by Tokuyama) 1
Using a jet stream inductor mixer TDS manufactured by Mitamura Riken Kogyo Co., Ltd., 60 kg of 500 kg of pure water (ethanol 1) adjusted to pH 3.0 with nitric acid.
Then, the dispersion was suction-dispersed at room temperature into a total volume of 600 liters with pure water.

(Preparation of Silica Dispersion-2) An aqueous solution (pH = 4.0) containing 2.0 kg of a cationic polymer (exemplified compound CP-12), 2.2 liters of ethanol and 1.1 liters of propanol was prepared. To 15 liters, 60.0 liters of the silica dispersion-1 was added with stirring, and then an aqueous solution 8 containing 75 g of borax (Na ₂ B ₄ O ₇ .10H ₂ O: molecular weight = 381.4). Then, 200 ml of an aqueous solution containing 2 g of an antifoaming agent (SN381 manufactured by Sannobuco) was added. This mixed solution was dispersed with a high-pressure homogenizer manufactured by Sanwa Kogyo Co., Ltd., and the whole amount was adjusted to 85 liters with pure water to prepare a silica dispersion liquid-2.

(Preparation of Silica Dispersion-3) An aqueous solution (pH = 4.0) containing 2.0 kg of a cationic polymer (exemplified compound CP-15), 4.2 liters of ethanol and 1.1 liters of propanol was prepared. To 15 liters, 60.0 liters of the silica dispersion-1 was added with stirring, and then 8.0 liters of an aqueous solution containing 75 g of borax was added, and an anionic fluorescent brightener UVITEX was added.
5 g of NFW LIQUID (manufactured by Ciba Specialty Chemicals) was added. This mixed solution was dispersed with a high-pressure homogenizer manufactured by Sanwa Kogyo Co., Ltd., and the whole amount was adjusted to 85 liters with pure water to prepare silica dispersion-3.

(Preparation of Oil Dispersion-1) 8400 g of the following light fastness improver ST-1 and diisodecyl phthalate 9
000 g and 18 liters of ethyl acetate.
It melted by heating at ° C. 3500 g of this acid-treated gelatin,
The cationic polymer (exemplified compound CP-12) and saponin were added to and mixed with 75 liters of an aqueous solution containing 6000 ml of a 50% aqueous solution, and emulsified and dispersed using a high-pressure homogenizer manufactured by Sanwa Kogyo Co., Ltd. to remove ethyl acetate under reduced pressure. After that, the total volume was finished to 110 liters, and the oil dispersion-
1 was prepared.

[0105]

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<< Preparation of Coating Solution >> First Layer, Second Layer, Third Layer
The coating solution for the layer and the fourth layer was prepared by the following procedure.

(Preparation of Coating Solution for First Layer) The following additives were sequentially mixed with 600 ml of the silica dispersion liquid 2 at 40 ° C. while stirring to prepare a coating solution for first layer.

6% of a 10% aqueous solution of polyvinyl alcohol (manufactured by Kuraray Industries: PVA203) 5 ml of a 5% aqueous solution of polyvinyl alcohol (manufactured by Kuraray Industries: a mixture of 7/3 of PVA235 and PVA245) 290 ml Oil dispersion-1 40 ml Daiichi Kogyo Co., Ltd .: Latex emulsion AE-803 18 ml The total amount was adjusted to 1000 ml with pure water.

(Preparation of Coating Solution for Second Layer) The following additives were sequentially mixed with 640 ml of the above-mentioned silica dispersion liquid 2 at 40 ° C. while stirring to prepare a coating solution for second layer.

6% 10% aqueous solution of polyvinyl alcohol (Kuraray Industries: PVA203) 5% aqueous solution of polyvinyl alcohol (mixture of 7/3 of PVA235 and PVA245 from Kuraray Industries) 245 ml Oil dispersion-1 55 ml Thioether-based oxidation 30% of a 20% aqueous solution of inhibitor-1 (* 1) was made up to 1000 ml with pure water.

* 1 Thioether antioxidant-1; HO
C ₂ H ₄ 64 of _{S-C 2 H 4 S-} C 2 H 4 OH ( Preparation of third layer coating solution) The silica dispersion -3
The following additives were sequentially mixed with 0 ml while stirring at 40 ° C. to prepare a third layer coating solution.

6 ml of a 10% aqueous solution of polyvinyl alcohol (manufactured by Kuraray Industries: PVA203) 5 ml of a 5% aqueous solution of polyvinyl alcohol (manufactured by Kuraray Industries: a mixture of 7/3 of PVA235 and PVA245) 245 ml oil dispersion-1 25 ml polyalkylenepolyamine Dicyandiamide-based polycondensate The amount shown in Table 2 (the numerical value is the mass per 1 m ² of the recording paper).

(Preparation of Coating Solution for Fourth Layer) Silica Dispersion
The following additives were sequentially mixed with 650 ml of No. 3 while stirring at 40 ° C. to prepare a coating solution for the fourth layer.

6% of a 10% aqueous solution of polyvinyl alcohol (manufactured by Kuraray Industries: PVA203) 5 ml of a 5% aqueous solution of polyvinyl alcohol (manufactured by Kuraray Industries: a mixture of 7/3 of PVA235 and PVA245) 225 ml 50% aqueous solution of saponin 4 ml betaine surfactant Agent-1 (5% solution) 3 ml The total amount was made up to 1000 ml with pure water.

[0115]

Embedded image

Each coating solution prepared as described above was filtered with the following filter. First to third layers: Two-stage structure of TCP10 manufactured by Toyo Filter Paper Co., Ltd. Fourth layer: Two-stage structure of TCP30 manufactured by Toyo Filter Paper Co., Ltd. << Preparation of recording paper >> The first layer (45 μm) and the second layer (45 μm) were placed on the front side of the coated support containing titanium oxide.
μm), a third layer (45 μm), and a fourth layer (45 μm). The numerical values in parentheses indicate the respective wet film thicknesses, and the first to fourth layers were simultaneously applied.

Each coating solution was applied at 40 ° C. by a slide type curtain coating method. Immediately after coating, the coating solution was cooled in a cooling zone maintained at 5 ° C. for 10 seconds, and then blown at a temperature of 20 to 30 ° C. for 30 seconds. , 70 ° C for 60 seconds, 50 ° C for 60 seconds
The recording papers 101 to 114 of the present invention and the comparative examples 121 to 128 were produced by drying sequentially for 50 seconds at 50 ° C. for 30 seconds. The film surface pH on the recording surface side of any recording paper,
It was in the range of 3.5 to 7.5.

Incidentally, the zirconium compounds shown in Table 2 were
The zirconium compounds added to the third layer coating solution and added are zirconyl acetate (abbreviated as G-1), zirconyl oxychloride (abbreviated as G-2), and zirconyl ammonium carbonate (G).
In the case of zirconyl sulfate (abbreviated as G-4), the solution was in-line mixed as a 20% aqueous solution of a zirconium compound immediately before coating. When no zirconium compound was added, the same volume of water was added.

However, when the zirconium compound was zirconium acetylacetonate bisethylacetoacetate (abbreviated as G-5), an ink absorbing layer was formed once, dried, and then overcoated as an aqueous solution.

[0120]

[Table 2]

In Table 2, Parafix EP was manufactured by Ohara Palladium Chemical Co., Ltd., and Sunfix 414 was manufactured by Sanyo Chemical Co., Ltd.

<< Evaluation of Recording Paper >> Each recording paper produced as described above was evaluated for light resistance and bleeding of a printed image according to the following method.

(Evaluation of Light Resistance) Using an aqueous ink containing 2% by mass of a phthalocyanine cyan dye, 6% by mass of glycerin, and 20% by mass of ethylene glycol, the discharge amount was changed stepwise by an ink jet printer, and A cyan image was printed on recording paper.

The obtained print image was subjected to a fluorescent lamp fading tester under the condition that the print surface was about 2200 Lux, in an atmosphere at a temperature and humidity of 35 ° C. and 50% RH, at 35 ° C. and 75% RH.
Light irradiation was performed for 25 days and 90 days under two conditions in an atmosphere of% RH.

The reflection density after the fluorescent lamp irradiation at the point where the reflection density before the fluorescent lamp irradiation becomes 1.0 was measured as the dye residual ratio.
It was a measure of light fastness.

(Evaluation of bleeding) A line of cyan (line width: about 300 μm) was printed on each recording paper with the ink used in the light fastness test and an ink jet printer, and the recording was performed at 45 ° C. and 85% R.
Stored under an atmosphere of H for 7 days.

Next, the line width (μm) of the portion having a reflection density of 50% of the maximum density before and after storage was measured with a microdensitometer, and bleeding was determined according to the following equation. The smaller the value, the better the bleeding.

Bleed = [line width after storage (μm) −line width before storage (μm)] / line width before storage (μm) The results obtained above are also shown in Table 2.

As is clear from the results shown in Table 2, comparative recording paper 121 using no polyalkylenepolyamine / dicyandiamide polycondensate and a compound containing a zirconium atom, or comparative recording paper using only a compound containing a zirconium atom In the case of 123, in particular, the problem of bleeding is not so large, but it is inferior in light resistance. Further, in the comparative recording paper 122 which uses a polyalkylene polyamine / dicyandiamide-based polycondensate to improve light resistance and does not use a compound containing a zirconium atom, the light resistance is improved, but bleeding occurs as a new problem. are doing. In order to solve the problem of bleeding, the comparative recording papers 124 to 128 using a compound containing a polyvalent metal other than the compound containing a zirconium atom have improved light resistance and slightly improved bleeding.

On the other hand, the recording papers 101 to 101 of the present invention were used.
114 shows that the use of a compound containing a zirconium atom, after improving the light resistance with a polyalkylenepolyamine / dicyandiamide-based polycondensate, remarkably shows the effect of solving the problem of bleeding.
In particular, it can be seen that the use of zirconyl acetate and zirconyl oxychloride has a remarkable effect of suppressing bleeding.

Further, the recording paper of the present invention uses a polyalkyl
The amount of lenpolyamine-dicyandiamide-based polycondensate
0.4g / m which is the optimum point^Two, 0.6 g / m^TwoIn any of
If any, and also the weight of the compound containing a zirconium atom
0.1g / m which is the optimal point of ^Two, 0.2 g / m^TwoAny of
However, it can be seen that the effects of the present invention are remarkably exhibited.

Example 2 (Preparation of coating solution) A 15% aqueous solution of a cationic polymer containing each quaternary ammonium base shown in Table 3 (pH =
3.2) The average primary particle size is about 12 nm per 100 g.
25% of fine particle silica (QS-20 manufactured by Tokuyama Corporation)
500 g of the aqueous dispersion, then 2.5 g of boric acid and 1.0 g of borax were added and dispersed by a high-speed homogenizer.
Next, 5 ml of a 10% aqueous solution of polyvinyl alcohol (Kuraray PVA203) and 6% of polyvinyl alcohol (Kuraray PVA245) were added to the aqueous dispersion.
The aqueous solution was 280 ml, and the polyalkylene polyamine / dicyandiamide-based polycondensate shown in Table 3 (Sunfix 414 manufactured by Sanyo Chemical Co., Ltd.) was weighed at 0.6 g / m2.
² was added. Finally, the volume of the whole liquid is 10
Pure water is added to make the coating solution to a volume of 00 ml and the coating solution 2 is translucent.
01-210 were prepared.

In the preparation of the coating solution, 100 g of water was added instead to the coating solution 205 which did not use a cationic polymer containing a quaternary ammonium base.
In the case of a coating solution using thioether-based antioxidant-1, 30 ml of a 20% aqueous solution was added to the coating solution, and then finished to 1000 ml.

[0134]

[Table 3]

(Preparation of Recording Paper) Each of the coating liquids prepared as described above was applied to the recording surface side of the support prepared in Example 1 so that the wet film thickness was 180 μm.
After cooling at 10 ° C for 10 seconds, wind at 30 ° C for 60 seconds at 50 ° C
After drying for 60 seconds in a wind of 70 ° C. and 60 seconds in a wind of 70 ° C.,
The humidity was adjusted at 5 ° C. and a relative humidity of 50% to prepare inkjet recording papers 201 to 210. In addition, in any of the recording papers, the film surface pH of the recording surface was in the range of 3.5 to 7.5.

The zirconium compounds shown in Table 3 were zirconyl acetate (G-1) and zirconyl acid chloride (G
-2) In the case of zirconyl sulfate (G-4), it was in-line mixed as a 20% aqueous solution of a zirconium compound immediately before coating.

However, when the zirconium compound was zirconium acetylacetonate bisethylacetoacetate (G-5), an ink absorbing layer was formed once, dried, and then overcoated as an aqueous solution.

(Evaluation of Recording Paper) With respect to each recording paper produced as described above, the light resistance and bleeding of the printed image were evaluated by the method described in Example 1, and the obtained results are also shown in Table 3. Show.

As is clear from the results in Table 3, it was found that all the recording papers of the present invention had good light fastness and good bleeding. Among them, the recording paper containing a cationic polymer containing a quaternary ammonium base was able to effectively suppress bleeding on the recording paper 205 not using the same.

Further, among these recording papers, it was confirmed that the recording paper using a thioether-based antioxidant had better light resistance than the recording paper not using the same. Therefore, it was found that the recording paper using a cationic polymer containing a quaternary ammonium base and a thioether-based antioxidant remarkably exerts the effects of the present invention.

[0141]

According to the present invention, a water-based ink containing a water-based dye can be used on an ink-jet recording sheet having a porous ink-absorbing layer containing a polyalkylenepolyamine / dicyandiamide-based polycondensate on a non-water-absorbing support. It was possible to provide an ink jet recording paper having improved light fastness during ink jet recording and significantly suppressing bleeding after printing.

Claims (4)

[Claims] 1. A non-water-absorbing support having a porous ink-absorbing layer containing a polyalkylenepolyamine / dicyandiamide-based polycondensate and a compound containing a zirconium atom (excluding zirconium oxide). Characteristic inkjet recording paper. 2. A polyalkylene polyamine / dicyandiamide-based polycondensate, a compound containing a zirconium atom (excluding zirconium oxide), and a cationic polymer having a quaternary ammonium base, on a non-water-absorbing support. An ink jet recording sheet comprising a porous ink absorbing layer. 3. The compound containing a zirconium atom,
3. The ink jet recording paper according to claim 1, wherein the ink jet recording paper is at least one selected from zirconyl ammonium carbonate, zirconyl acetate, and zirconyl oxychloride. 4. The polyalkylene polyamine / dicyandiamide polycondensate is contained in an amount of 0.01 to 5 g / m ² ,
And the compound containing a zirconium atom in an amount of 0.01 to 5
ink-jet recording sheet according to any one of claims 1 to 3, characterized in that g / m ² containing.