JPH08318672A - Ink jet recording sheet and recording method - Google Patents

Abstract

PURPOSE: To provide a recording sheet excellent in ink fixing properties immediately after printing, short in drying and fixing time and forming an image excellent in resolving power and uniformity by adding gelatin and a cationic water-soluble polymer to a base material or the ink receiving layer provided on the base material. CONSTITUTION: An ink jet recording sheet is obtained by adding gelation and a cationic water-soluble polymer to a base material or the ink receiving layer on the base material. The cationic water-soluble polymer is a polymer having a quaternary ammonium group represented by formulae I, II, III. In the formula I, R<1> is a hydrogen atom or a methyl group, Q is an oxygen atom or -NH-, R<2> , R<3> and R<4> are a methyl group or an ethyl group, X<-> is a halogen ion and n is 2 or 3. In the formula II, R<5> , R<6> and R<7> are a methyl group or an ethyl group and, in the formula III, R<8> , R<9> and R<10> are a methyl group or an ethyl group.

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 sheet and a recording method using a water-based ink,
In particular, the present invention relates to an ink jet recording sheet and a recording method which have excellent ink fixability immediately after printing and also have excellent image resolution and uniformity.

[0002]

2. Description of the Related Art Ink-jet recording has no noise, high-speed printing is possible, and it is easy to perform multicolor recording by using a plurality of ink nozzles. In recent years, it has rapidly spread as an information output device. Also, in the field of use, transparent films and glossy resin-coated paper are used as recording media, and the content of the output image is a color composition or design that requires image quality similar to photographs due to characters and figures. It is expanding to the image etc.

By the way, as the ink for ink jet recording, a water-based ink mainly containing water and a water-soluble organic solvent is used from the viewpoint of safety and recording characteristics, to prevent clogging of the ink and improve ejection characteristics. Etc. are planned. Further, as the recording sheet, conventionally, a recording sheet, which is referred to as ordinary paper or ink jet recording paper, provided with a porous ink absorbing layer on a support has been used.

However, these conventional recording sheets cannot meet the recent demands for high image quality because of large ink bleeding and low gloss. Furthermore, when a conventional porous ink absorbing layer is used for a transparent film or glossy resin-coated paper, the porous ink absorbing layer has a low light transmittance, so that the transparency and glossiness are lost. .
Further, when the ink absorption layer is non-porous, the light transmittance is improved, but since the water-based ink receptivity is poor, the ink remains on the sheet surface for a long time after image recording and printing, and the dry fixing time is long. There was a problem that

In order to solve these problems, as an ink absorbing layer having high light transmittance and excellent water-based ink receptivity,
It has been proposed to use gelatin. For example, in JP-A-62-263084, a receiving layer formed from an aqueous gelatin solution having a specific pH is used, and in JP-A-1-146784, the use of a mixture of gelatin and a surfactant is disclosed.
No. 64306 proposes a recording sheet obtained by temporarily converting a coated gelatin into a gel state and then drying it by a cold dry method.

Certainly, the receptive layer using these gelatins has excellent ink receptivity and high light transmittance. However, it takes several minutes to tens of minutes in terms of the dry fixing time of the ink, and if it is touched with a hand or other paper immediately after the image recording and printing, these may be stained with the ink or the image itself may be soiled. There is a problem. Further, in the ink receiving layer using gelatin, the ink droplets are easily aggregated on the surface or inside of the receiving layer and the image is liable to become lumpy, which is a cause of hindering the improvement of the image resolution. Further, in recent years, as the performance of printers has been improved, since ink droplets are further miniaturized, the content of the water-soluble organic solvent in the ink tends to be increased for the purpose of preventing clogging, but such an ink was used. In these cases, these problems become more serious.

Further, JP-A-57-36692 discloses an ink jet recording sheet containing a basic latex polymer. However, this is a technique for making recorded images highly water resistant, and its purpose is different from that of the present invention. Further, the basic latex polymer used is basically insoluble in water, and even if it is used, it has no effect on shortening the drying and fixing time of the ink and preventing the aggregation of ink droplets, which is the object of the present invention. found.

[0008]

SUMMARY OF THE INVENTION Therefore, the first object of the present invention is to provide an ink jet recording sheet which has excellent ink fixability immediately after printing, short dry fixing time, and excellent image resolution and uniformity. In offer. Secondly, there is provided an ink jet recording sheet having an ink receiving layer which is excellent in ink fixability, image resolution and uniformity, and is also excellent in light transmittance. Thirdly, it is to provide an ink jet recording sheet excellent in ink fixability, image resolution and uniformity even when an ink having a low water content in the ink is used.

[0009]

The above objects of the present invention are as follows: (1) Gelatin and at least one cationic water-soluble polymer are contained in a substrate or in an ink receiving layer provided on the substrate. An inkjet recording sheet characterized by:

(2) The above-mentioned (1), wherein the mixture of gelatin and at least one cationic water-soluble polymer is contained in the substrate or in the ink receiving layer provided on the substrate. Inkjet recording sheet.

(3) The cationic water-soluble polymer is represented by the following general formula [1], [2] or [3].
At least one selected from polymers having a quaternary ammonium group, polyallylamine, dicyandiamide condensate, polyethyleneimine, cation-modified PVA, cation-modified PVP, epichlorohydrin derivative, amino group-substituted nylon and cationic polyaluminum hydroxide.
The inkjet recording sheet according to (1) or (2) above, which is a seed.

[0012]

[Chemical 4]

In the formula, R ¹ represents a hydrogen atom or a methyl group, and Q represents an oxygen atom or --NH--. R ² , R ³ and R
Each of ⁴ represents a methyl group or an ethyl group, and may be the same or different. X ⁻ represents a halogen ion, a sulfonate anion, an alkylsulfonate anion, an acetate anion or an alkylcarboxylic acid anion. n represents 2 or 3.

[0014]

Embedded image

In the formula, R ⁵ , R ⁶ and R ⁷ each represent a methyl group or an ethyl group, and may be the same or different. X ⁻ represents a halogen ion, a sulfonate anion, an alkylsulfonate anion, an acetate anion or an alkylcarboxylic acid anion. n represents 2 or 3.

[0016]

[Chemical 6]

In the formula, R ⁸ , R ⁹ and R ¹⁰ each represent a methyl group or an ethyl group, and may be the same or different. X ⁻ represents a halogen ion, a sulfonate anion, an alkylsulfonate anion, an acetate anion or an alkylcarboxylic acid anion. n represents 2 or 3.

(4) The cationic water-soluble polymer is at least one selected from polyallylamine compounds, dicyandiamide condensates, cation-modified PVP, epichlorohydride derivatives and cationic polyaluminum hydroxide. (1), (2) or (3)
The ink jet recording sheet according to [1].

(5) Gelatin and at least one cationic water-soluble polymer are contained in an ink receiving layer provided on a hydrophobic substrate, and the above (1) to (1)
The inkjet recording sheet according to any one of (4).

(6) The ink jet recording sheet according to (5) above, wherein the hydrophobic substrate is a resin-coated paper obtained by coating both sides of paper with a resin.

(7) The ink jet recording sheet according to the above (6), wherein the resin is a polyolefin resin.

(8) The ink jet recording sheet according to (7) above, wherein the polyolefin resin is a polyethylene resin.

(9) The ink jet recording sheet according to the above (5), wherein the hydrophobic substrate is a transparent polyester resin film.

(10) The inkjet recording sheet described in (9) above, wherein the transparent polyester resin film is a polyethylene terephthalate film.

(11) The presence ratio of the cationic water-soluble polymer to gelatin in the ink receiving layer is 0.1 to 70 wt% with respect to gelatin (1).
The inkjet recording sheet according to any one of (1) to (10).

(12) The ink jet recording sheet described in any one of (1) to (11) above, wherein the ratio of the cationic water-soluble polymer to gelatin is 1 to 50 wt%. .

(13) For ink jet recording according to any one of the above (1) to (12), the existence ratio of the cationic water-soluble polymer to gelatin is 3 to 20 wt%. Sheet.

(14) Gelatin in the ink receiving layer,
(1) to (1), which contains a cationic water-soluble polymer and at least one water-soluble polymer
The ink jet recording sheet according to any one of (13).

(15) The ink jet recording sheet according to (14) above, wherein the water-soluble polymer is at least one polymer selected from polyvinylpyrrolidone, polyvinyl alcohol and polyethylene glycol.

(16) The ink jet recording sheet as described in (14) or (15) above, wherein the content of the water-soluble polymer in the ink receiving layer is 5 to 80 wt%.

(17) The ink jet recording sheet as described in (14), (15) or (16) above, wherein the content of the water-soluble polymer in the ink receiving layer is 20 to 60 wt%. .

(18) The ink jet recording sheet described in any one of (1) to (17) above, wherein the gelatin is acid-treated gelatin.

(19) The above-mentioned (1) to (1) wherein the gelatin is amino group inactivated gelatin.
7. The inkjet recording sheet according to any one of 7).

(20) The ink receiving layer is composed of two or more layers, and at least the uppermost layer of the ink receiving layer contains a fluorinated surfactant.
The inkjet recording sheet according to any one of (19).

(21) Any of the above (1) to (20), wherein the fluorine-based surfactant has at least one anionic surfactant and at least one cationic surfactant. 2. The inkjet recording sheet according to item 1.

(22) In the above (1) to (21), the ink receiving layer is composed of two or more layers, and the cationic water-soluble polymer is contained in at least a lower layer adjacent to the uppermost layer. The ink jet recording sheet according to any one of items.

(23) In the ink jet recording sheet described in any one of (1) to (22) above, the solvent for dissolving the dye has a composition of water / organic solvent = 3/7 to / 3. An ink jet recording method, wherein recording is performed using a functional ink.

(24) The ink jet recording method as described in (23) above, wherein the organic solvent is at least one selected from glycols and pyrrolidones.

Was achieved by

The present invention will be described in detail below.

The ink jet recording sheet of the present invention comprises
Gelatin is contained in the substrate or in the ink receiving layer provided on the substrate.

As the gelatin used in the present invention, any gelatin made from animal collagen can be used, but gelatin made from pig skin, cow hide and cow bone collagen is preferable. Further, the type of gelatin is not particularly limited, but lime-processed gelatin, acid-processed gelatin, gelatin derivatives (for example, Japanese Patent Publication No. 38-48).
No. 54, No. 39-5514, No. 40-12237.
U.S. Pat. No. 2,525,753 and U.S. Pat. No. 2,594,29.
No. 3, No. 2,614,928, No. 2,763,6
No. 39, No. 3,118,766, No. 31294
5, No. 3186846, No. 3312553,
British Patent Nos. 861,414 and 1,033,189
Gelatin derivatives) described in No. 1 or the like can be used alone or in combination.

By using acid-treated gelatin or amino group-inert gelatin in the present invention, not only the effect of the present invention can be better exhibited but also another effect of improving the glossiness of the surface of the ink receiving layer can be obtained. it can. It is one of the preferred embodiments that the gelatin is present at least in the outermost layer of the ink receiving layer.

The acid-processed gelatin preferably used in the present invention is gelatin produced by decalcifying collagen and then acid-treating with hydrochloric acid or the like, and is an acid-processed gelatin.

In the present invention, the amino group inactivated gelatin is preferably gelatin in which 50% or more, preferably 80% or more, and more preferably 90% or more of the amino groups in gelatin are inactivated. . The above gelatin can be produced by a known acylation method, and examples thereof include acetylated gelatin, phthalated gelatin, malenoylated gelatin, benzoylated gelatin, succinoylated gelatin, methylurea gelatin, phenylcarbamoylated gelatin, and carboxy modified gelatin. Can be mentioned.

The jelly strength of the gelatin used in the present invention (by the PAGI method, by the plume type jelly strength meter) is preferably 150 g or more, and particularly preferably 200 to 300 g.

In the present invention, the coating amount of gelatin contained in the ink receiving layer is 3 to 50 g / solid matter.
m ² is preferable, and more preferably 5 to 30 g / m ² .

When the ink receiving layer is less than 3 g / m ² , the ink receiving property is poor and the ink overflows from the receiving layer after printing. Further, when the amount is more than 50 g / m ² , the ink receptivity is improved but problems such as cracking and curling occur.

The ink jet recording sheet of the present invention contains at least one cationic water-soluble polymer together with gelatin in the base material or in the ink receiving layer provided on the base material. The cationic water-soluble polymer referred to in the present invention means a polymer whose main constituent is cationic in an aqueous solution, and typical examples thereof are described in JP-A-5-104848 and JP-A-5-124329. Examples thereof include polymers containing a primary, secondary or tertiary amino group or a quaternary ammonium salt, and polymers containing a water-soluble metal salt such as aluminum. Any such water-soluble cationic polymer can be used, and the type thereof is not particularly limited, but the cationic polymers preferably used in the present invention include the following.

A) polyallylamine b) dicyandiamide condensate c) polyethyleneimine d) cation-modified PVA e) cation-modified PVP f) epichlorohydrin derivative g) amino group-substituted nylon h) cationic polyaluminum hydroxide i) the above Polymer having quaternary ammonium group represented by general formula [1] j) Polymer having quaternary ammonium group represented by general formula [2] k) Quaternary ammonium represented by general formula [3] Group-containing polymer The polyallylamines referred to in the present invention include polyallylamine represented by the following general formula [4] and the following general formula [5-
1] or [5-2], a polydiallylamine derivative represented by the following general formula [6-1] or [6-2], or a polymer thereof.

[0051]

[Chemical 7]

In the general formula [4], n is 5 to 1000.
An integer of 0, X ⁻ represents a residue of an inorganic acid or an organic acid.

[0053]

Embedded image

General formulas [5-1], [5-2], [6-
1] and [6-2], R ₁ and R ₂ each represent a hydrogen atom, a methyl group, an ethyl group or a hydroxyethyl group, X ₂ ⁻ represents an inorganic acid residue or an organic acid residue, and Y Represents a divalent linking group. Also, n / m = 9/1 to 2/8, l =
It is 5 to 10000.

Specific examples of the polydiallylamine derivative represented by the general formula [6-1] or [6-2] include SO represented by the general formula described in JP-A-60-83882.
Those containing _two groups as repeating units, copolymers with acrylamide described on page 2 of JP-A No. 1-9776, and represented by the general formula [6-1] or [6-2] of the present invention. Examples thereof include copolymers with polydiallylamine.

Specific examples of the dicyandiamide type condensate used in the present invention include a dicyandiamide formalin condensate and a polyalkylenepolyamine dicyandiamide ammonium salt condensate. These are Sunfix 70 manufactured by Sanyo Kasei Co. and Nikafloc manufactured by Nippon Carbide Co. D
-1000, Nichia Kagaku Co., Ltd. Neofix F, Neofix RP-70Y and the like are commercially available.

The polyethyleneimines referred to in the present invention are
It is a polymer obtained by polymerizing ethyleneimine or a derivative thereof, and a polyethyleneimine quaternary ammonium compound is particularly preferable. Specifically, JP-A-60-727
85 and 60-76386 are mentioned.

The cation-modified PVA referred to in the present invention is a copolymer of vinyl alcohol and a monomer unit having a cationic group, and specifically, it is disclosed in JP-A-62-138280.
Those described on pages 3 and 4 of the publication can be used.

The cation-modified PVP referred to in the present invention is a copolymer of vinylpyrrolidone and a monomer unit having a cationic group. Specific examples of the monomer unit having a cationic group include quaternized vinylimidazole, quaternized dialkylaminoethyl methacrylate, and methacrylamidopropyltrialkylammonium salt.

Specific examples of the epichlorohydrin derivative used in the present invention include polyamide epichlorohydrin resins, reaction products of epichlorohydrin and tertiary amines described on page 2 of JP-A-61-252189, and JP-A- Examples thereof include compounds of the general formula (II) described on page 4 of JP-A No. 62-259882.

These can be synthesized by a known method. Further, as commercially available products, there are Nalpoli-607 (manufactured by Nalco Chemical Co., Ltd.) and Polyfix 601 (manufactured by Showa High Polymer Co., Ltd.).

Specific examples of the amino group-substituted nylon used in the present invention are described on page 2 of JP-A-59-33179, and commercially available products include AQ nylon (trade name:
Made by Toray).

As the cationic polyaluminum hydroxide used in the present invention, those described in item 2 of JP-A-60-257286 can be used.

Preferred compounds among the monomers represented by the general formula [1] include, for example, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate and N, N-dimethylamino. Propyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth ) Acrylamide and N, N
-Diethylaminopropyl (meth) acrylamide methyl chloride, ethyl chloride, methyl bromide, ethyl bromide, quaternary compounds of methyl iodide or ethyl iodide, or sulfonates, alkyl sulfonates, and acetates substituted with their anions. Alternatively, an alkylcarboxylic acid salt may be mentioned.
Of these, particularly preferable compounds include, for example, trimethyl-2- (methacryloyloxy) ethylammonium chloride, triethyl-2- (methacryloyloxy) ethylammonium chloride, trimethyl-2-
(Acryloyloxy) ethylammonium chloride, triethyl-2- (acryloyloxy) ethylammonium chloride, trimethyl-3- (methacryloyloxy) propylammonium chloride, triethyl-3- (methacryloyloxy) propylammonium chloride, trimethyl-2- (methacryloyl) Amino) ethylammonium chloride, triethyl-2
-(Methacryloylamino) ethylammonium chloride, trimethyl-2- (acryloylamino) ethylammonium chloride, triethyl-2- (acryloylamino) ethylammonium chloride, trimethyl-3- (methacryloylamino) propylammonium chloride, triethyl-3- ( Methacryloylamino) propyl ammonium 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)
Propyl ammonium bromide, trimethyl-2-
Examples thereof include (methacryloyloxy) ethylammonium sulfonate and trimethyl-3- (acryloylamino) propylammonium acetate.

Preferred examples of the monomer represented by the general formula [2] include trimethyl-p-vinylbenzylammonium chloride, trimethyl-m-vinylbenzylammonium chloride, triethyl-p-vinylbenzylammonium chloride and triethyl-m-vinyl. Benzyl ammonium chloride, N, N-dimethyl-N
-Ethyl-p-vinylbenzylammonium chloride, N, N-diethyl-N-methyl-p-vinylbenzylammonium chloride, trimethyl-p-vinylbenzylammonium bromide, trimethyl-m-vinylbenzylammonium bromide, trimethyl-p-
Vinylbenzyl ammonium sulfonate, trimethyl-m-vinyl benzyl ammonium sulfonate, trimethyl-p-vinyl benzyl ammonium acetate,
Examples thereof include trimethyl-m-vinylbenzylammonium acetate.

Preferred examples of the monomer represented by the general formula [3] include diallyldimethylammonium chloride, diallyldiethylammonium chloride, diallyldimethylammonium bromide, diallyldimethylammonium sulphonate and diallyldimethylammonium acetate.

In addition to these monomer units, acrylamide, methacrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide, diacetone acrylamide, N-methylol acrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth). By copolymerizing a monomer selected from acrylate and N-vinylpyrrolidone in the range of 20 to 80 parts by weight, the ink absorption capacity and the ink absorption rate of the polymer having the quaternary ammonium salt group are increased, and the ink dot diameter is further increased. It is possible to impart extremely preferable properties such as adjusting to an appropriate size and eliminating uneven printing on the solid portion.

Among these cationic polymers, polyallylamines, dicyandiamide type condensates, cation-modified PVP, epichlorohydrin derivatives and cationic polyaluminum hydroxides are particularly preferable.

The abundance ratio of these cationic polymers to gelatin is preferably 0.1 to 70 wt%, more preferably 1 to 50 wt%, and further preferably 3 to 20 w.
t%. If it exceeds 70%, the ink receptivity of gelatin is lowered, and if it is less than 0.1%, the resolution and dry fixing time of the present invention cannot be obtained.

The ink receiving layer of the present invention may be provided as a separate layer by coating it on the substrate even if it is provided in the substrate by mixing the material constituting the ink receiving layer with pulp slurry during paper making. However, the latter is preferable from the viewpoint of gloss and texture of the recording sheet. Any conventionally known base material can be used. Examples of the transparent substrate include films or plates of polyester resin, diacetate resin, triacetate resin, acrylic resin, polycarbonate resin, polyvinyl chloride, polyimide resin, cellophane, celluloid, and glass plates.
Such a transparent substrate preferably has a thickness of about 10 to 200 μm. As the opaque substrate, paper, coated paper, synthetic paper, resin-coated paper, opaque film containing pigment, foamed film and the like can be used.

The base material used in the present invention is a transparent or opaque film made of various resins, a resin-coated paper, or the like. It is preferable from the viewpoint of quality when it is provided in a layered structure. Particularly preferred is a polyester resin for a transparent substrate, and a resin-coated paper similar to a photographic paper support for an opaque substrate,
The most preferred embodiment of the present invention is to provide an ink receiving layer in the form of a coating layer on the surface of such a substrate.

In the present invention, it is a preferred embodiment from the viewpoint of the effect of the present invention that the gelatin and the cationic water-soluble polymer are contained in the same layer.

In the present invention, the following nonionic or anionic water-soluble polymer is used in combination with gelatin and a cationic water-soluble polymer as a binder in the ink receiving layer for the purpose of improving ink receptivity and dot reproducibility. You can Examples of the water-soluble polymer used in combination include, for example, polyvinyl formal such as polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl pyridinium halide, and various modified polyvinyl alcohols and their derivatives (JP-A-60-145879 and 60-220750).
No. 61-143177, No. 61-235182
No. 61-235183, No. 61-237681
No. 61-261089), polyacrylamide, polydimethylacrylamide, polydimethylaminoacrylate, sodium polyacrylate, acrylic acid methacrylic acid copolymer salt, polymethacrylic acid sodium salt, acrylic acid vinyl alcohol copolymer salt, etc. Polymers containing an acrylic group (JP-A-60-168651 and JP-A-62-99)
88), starch, oxidized starch, carboxyl starch, dialdehyde starch, cationized starch, dextrin, sodium alginate, gum arabic, casein, pullulan, dextran, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose, or other natural polymers or Derivatives thereof (JP 59-17
No. 4382, No. 60-262685, No. 61-143.
No. 177, No. 61-181679, No. 61-1938.
79, 61-287782), polyethylene glycol, polypropylene glycol, polyvinyl ether, polyglycerin, maleic acid alkyl vinyl ether copolymer, maleic acid N-vinyl pyrrole copolymer, styrene maleic anhydride copolymer, polyethylene. Synthetic polymers such as imines (see JP-A Nos. 61-32787, 61-237680, 61-277483).
Etc. can be mentioned.

Of these, polyvinylpyrrolidones, polyvinyl alcohols and polyethylene glycols are particularly preferable. The proportion of these water-soluble polymers in the ink receiving layer is preferably 5 to 80 wt%,
More preferably, it is 20 to 60 wt%.

For the purpose of preventing adhesion failure such as blocking, a matting agent is added in an amount of about 0.005 to 0.1 g / m ² ,
It can be contained in the front and / or back layers.

Matting agents are well known in the photographic art and can be defined as discrete solid particles of an inorganic or organic material dispersible in a hydrophilic organic colloid binder. Examples of inorganic matting agents include oxides (eg, silicon dioxide, titanium oxide, magnesium oxide, aluminum oxide, etc.), alkaline earth metal salts (eg, sulfates and carbonates, such as barium sulfate and carbonate). Examples thereof include calcium, magnesium sulfate, calcium carbonate, etc., silver halide grains that do not form an image (such as silver chloride and silver bromide, and a small amount of iodine atoms may be added as a halogen component) and glass.

Besides this, West German Patent 2,529,321
No., British Patent Nos. 760,775 and 1,260,77
No. 2, US Pat. Nos. 1,201,905 and 2,19.
No. 2,241, No. 3,053,661, No. 3,06
No. 2,649, No. 3,257,206, No. 3,32
No. 2,555, No. 3,353,958, No. 3,37
0,951, 3,411,907, 3,43
7,484, 3,523,022, 3,61
No. 5,554, No. 3,635,714, No. 3,76
9,020, 4,021,245, 4,02
Inorganic matting agents described in No. 9,504 and the like can also be used.

Examples of organic matting agents include starch, cellulose ester (eg, cellulose acetate propionate, etc.), cellulose ether (eg, ethyl cellulose, etc.), synthetic resin and the like. Examples of synthetic resins are water-insoluble or sparingly soluble synthetic polymers, such as alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate,
(Meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin (for example, ethylene), styrene, benzoguanamine formaldehyde condensate, etc., alone or in combination, or with these, acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid It is possible to use a polymer having a polymer component of a combination of styrene, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrene sulfonic acid, etc. Other epoxy resin, nylon, polycarbonate, phenol resin, polyvinylcarbazole, polychlorinated Vinylidene or the like can also be used.

Besides this, British Patent No. 1,055,713
No. 1,933,213, 2,221,
873, 2,268,662, 2,322,0
No. 37, No. 2,376,005, No. 2,391,18
No. 1, No. 2,701,245, No. 2,992,101
No. 3,079,257, No. 3,262,782
No. 3,443,946 No. 3,516,832
No. 3,539,344, No. 3,591,379
Issue 3, Issue 3,754,924, Issue 3,767,448
JP-A-49-106821 and JP-A-57-14835.
The organic matting agents described in the above publications can be used.

Among them, polymethylmethacrylate, benzoguanamine formaldehyde condensation polymer (benzoguanamine resin, specifically a product represented by the following formula, for example, trade name Eposter: Nippon Shokubai Kagaku Kogyo KK: existing chemical substance 7-31, etc.) , Polyolefin (for example, trade name Flow Beads LE-1080, CL-2080, HE-5
023: Chemistry Pearl V-10 manufactured by Iron Chemicals or trade name
0: Mitsui Petrochemical)

[0081]

[Chemical 9]

Polystyrene beads (manufactured by Moritex), nylon beads (manufactured by Moritex), AS resin beads (manufactured by Moritex), epoxy resin beads (manufactured by Moritex), polycarbonate resin (manufactured by Moritex) and the like are preferable.

These matting agents may be used in combination.

As the method for forming the ink receiving layer of the present invention, in the case of forming a coating layer on a substrate, a size press method, a roll coater method, a blade coater method, an air knife coater method, a gate roll coater method, A commonly used coating method such as a rod bar coater method, a curtain method or an extrusion method is used. Further, as described above, it is also possible to provide the ink receiving layer in the base material by the internal addition method of mixing the materials constituting the ink receiving layer into the pulp slurry to make the paper.

The drying method after coating is not particularly limited, but the cold drying method described on page 4 of JP-A-6-64306 is a preferable drying method for obtaining a recording sheet having a high quality impression. .

In the present invention, a surfactant may be added to the ink receiving layer in addition to the binder for the purpose of improving dot reproducibility. The surfactant used may be any of anionic, cationic, nonionic and betaine types, and may be low molecular weight or high molecular weight. The amount of the surfactant added is preferably 0.001 to 5 g, and more preferably 0.01 to 3 g, based on 100 g of the binder constituting the ink receiving layer.

In the present invention, the ink receiving layer preferably contains a fluorine-containing surfactant, and when the ink receiving layer is composed of two or more layers, it is preferably contained in the uppermost layer. The fluorochemical surfactant is preferably an anionic and / or cationic surfactant.

Examples of the anionic fluorochemical surfactant preferably used in the present invention include those represented by the following general formula (FA).

In the general formula (FA) (Cf)-(Y) _n , Cf is an n-valent group containing at least 3 fluorine atoms and at least 2 carbon atoms, and Y is -COO.
_{M, -SO 3 M, -OSO 3} M or -P (= O) (OM)
Represents ₂ . M is a hydrogen atom or an alkali metal or a fourth
Represents a cation such as a primary ammonium salt, and n is 1 or 2
Is.

The more preferable anionic fluorochemical surfactant is one represented by the following general formula (FA ').

General formula (FA ') Rf- (D) _t -Y In the formula, Rf represents a fluorine-substituted alkyl group having 3 to 30 carbon atoms or an aryl group, and D represents -O-, -COO-,-.
It represents a divalent group having 1 to 12 carbon atoms and containing at least one bond of CON (R ₁ )-or —SO ₂ N (R ₁ )-. R ₁ represents an alkyl group having 1 to 5 carbon atoms, t is 1 or 2, and Y is —COOM—, —SO ₃ M, —O.
SO ₃ M or —P (═O) (OM) ₂ is represented, and M is a hydrogen atom or an alkali metal or a cation such as a quaternary ammonium salt.

Specific examples of the compound represented by formula (FA) are shown below, but the invention is not limited thereto.

[0093]

[Chemical 10]

[0094]

[Chemical 11]

[0095]

[Chemical 12]

[0096]

[Chemical 13]

[0097]

Embedded image

It is particularly preferable to use an anionic fluorochemical surfactant containing at least one bond of —SO ₂ N (R ₁ ) —.

The cationic fluorosurfactant preferably used in the present invention is a compound represented by the following general formula (FK).

General formula (FK) Rf'-LX ⁺ Z ^{-In the} formula, Rf 'represents a hydrocarbon group having 1 to 20 carbon atoms, and at least one hydrogen atom is substituted with a fluorine atom. L represents a chemical bond or a divalent group. X is a cation,
Z represents a counter anion.

As an example of Rf ', -C _k F _{k + 1} (k = 1
20, particularly 3 to 12 is _{preferred), - C m F 2m,} -C m
_F2m-1 (m = 2 to 20, particularly preferably 3 to 12) and the like can be mentioned.

As an example of L, --SO ₂ N (R ¹ ) (CH
_{2) p -, - CON (} R 1) (CH 2) p -, - OASO 2 N
_{^{(R 1) (CH 2)}} p -, - OACON (R 1) (CH 2) p
_{-, - OAO (CH 2)} p -, - OA (CH 2) p -, - O
_{(CH 2 CH 2 O) q} (CH 2) p -, - O (CH 2) p-,
_{^{-N (R 1) (CH 2}} ) p -, - SO 2 N (R 1) (CH 2)
_{p O (CH 2) r -} , - CON (R 1) (CH 2) p O (CH
_{2) r -, - OASO 2} N (R 1) (CHR 1) p OA -, -
_{(CH 2) p (CHOH)} s (CH 2) r - , and the like.

As an example of X ⁺ , -N ⁺ (R ¹ ) ₃ , -N ⁺
_{(CH 2 CH 2 OCH 3)} 3, -N + C 4 H 8 O (R 1). -N
^{+ (R 1) (R 2} ) (CH 2 CH 2 OCH 3), - N + C
^{_{5 H 5, -N + (R}} 1) (R 2) (CH 2) p C 6 H 5, -N
⁺ (R ¹ ) (R ² ) (R ² ) and the like can be mentioned. Here, R ¹ and R ² each represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (which may have a substituent), p, r,
s is 0 to 6, and q is 1 to 20, respectively.

Examples of Y ⁻ include I ⁻ , Cl ⁻ , Br ⁻ , C
_{^{H 3 SO 3 -, CH 3}} -C 6 H 4 -SO 3 - , and the like.

Specific examples of the cationic fluorosurfactant preferably used in the present invention are shown below, but the invention is not limited thereto.

[0106]

[Chemical 15]

[0107]

Embedded image

Examples of the anionic fluorine-containing surfactant or the cationic fluorine-containing surfactant according to the present invention include those disclosed in US Pat. Nos. 2,559,751 and 2,567,011,
No. 2,732,398, No. 2,764,602,
2,806,866, 2,809,998, 2,915,376, 2,915,528, 2,918,501, 2,934,450, 2 , 937,098, 2,957,031, 3,472,894, 3,555,089, British Patents 1,143,927, 1,130,822,
JP-B-45-37304, JP-A-47-9613,
49-134614, 50-117705, 50-117727, 50-121243, 5
2-41182 and 51-12392, Journal of the British Chemical Society (J. Chem. Soc.) 1950 2789.
Pp. 1957, pages 2574 and 2640, Journal of American Chemical Society (J. Amer. Chem. Soc.) 79, 25.
49 (1957), Oil Chemistry (J. Japan Oi
l Chemists Soc. ) 12: 653, Journal of Organic Chemistry (J. Org. Chem.) 30: 3524
It can be synthesized by the method described on page (1965) and the like. Some of these fluorine-based surfactants are trade names of Megafac F from Dainippon Ink and Chemicals, Inc., and Fluorad FC from Minnesota Mining and Manufacturing Company. Under the trade name of Imperial Chemical Industry under the name of Monflor, under the trade name of E. I. DuPont Nemeras & Company under the name of Zonyls, or under the name of Farbeberke Hoechst. Licovet V
It is marketed under the trade name PF.

In the present invention, the effect of the present invention can be more excellently achieved by using at least one of the anionic fluorochemical surfactant and the cationic fluorochemical surfactant.

The total amount of the cationic fluorinated surfactant and the anionic fluorinated surfactant preferably used in the present invention is 0.1 to 1000 mg per 1 m ² .
Preferably 0.5 to 300 mg, more preferably 1.0
~ 150 mg is good. When used in combination, two or more of each may be used in combination. In addition, a nonionic fluorine-based surfactant, a betaine-type fluorine-based surfactant, and a hydrocarbon-based surfactant may be used in combination.

The addition ratio of the anionic fluorosurfactant and the cationic fluorosurfactant is preferably 1:10 to 10: 1 in molar ratio, and more preferably 3: 7 to 7: 3.
Is preferred.

In the present invention, the ink receiving layer can be hardened with an appropriate hardener for the purpose of improving water resistance and dot reproducibility. Specific examples of the hardener include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and chloropentanedione, and bis (2-chloroethylurea) -2-hydroxy-4,6-dichloro-1. , 3,5 triazine, a compound having a reactive halogen as described in US Pat. No. 3,288,775, divinyl sulfone, a compound having a reactive olefin as described in US Pat. No. 3,635,718, US N-methylol compounds as described in US Pat. No. 2,732,316, US Pat. No. 3,103,43
Isocyanates such as those described in US Pat.
No. 7,280, 298,3611, aziridine compounds, US Pat. No. 3,100,704, carbodiimide compounds, US Pat. No. 3,093.
There are epoxy compounds such as 1,537, halogen carboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane, inorganic hardeners such as chromium alum, potassium alum, zirconium sulfate, etc. Alternatively, two or more kinds can be used in combination. The amount of the hardener added is preferably 0.01 to 10 g, and more preferably 0.1 to 5 g, with respect to 100 g of the binder constituting the ink receiving layer.

In the present invention, the ink receiving layer further comprises an inorganic pigment, a coloring dye, a coloring pigment, an ink dye fixing agent, an ultraviolet absorber, an antioxidant and a pigment in addition to the above-mentioned surfactant and hardener. Various known additives such as a dispersant, a defoaming agent, a leveling agent, a preservative, a fluorescent whitening agent, a viscosity stabilizer, and a pH adjusting agent can also be added.

The base paper constituting the resin wrapping paper, which is preferably used in the present invention, is not particularly limited, and commonly used paper can be used, but more preferably it is used as a photographic support. A smooth and smooth base paper is preferred. As the pulp constituting the raw paper, one kind or a mixture of two or more kinds of natural pulp, recycled pulp, synthetic pulp and the like is used. This base paper has a sizing agent, a paper strengthening agent, a filler, an antistatic agent, an optical brightening agent, which is generally used in papermaking,
Additives such as dyes are blended.

Further, a surface sizing agent, a surface paper strength agent, a fluorescent whitening agent, an antistatic agent, a dye, an anchoring agent or the like may be applied on the surface.

The thickness of the base paper is not particularly limited, but it is preferable that the paper has good surface smoothness such as compression by applying pressure with a calender during or after the paper making, and its basis weight is 30 to 250 g / m ² is preferable.

As the resin for the resin covering paper, a polyolefin resin or a resin curable by an electron beam can be used.
The polyolefin resin is a homopolymer of olefins such as low-density polyethylene, high-density polyethylene, polypropylene, polybutene, and polypentene, or a copolymer of two or more olefins such as ethylene-propylene copolymer and a mixture thereof. Various densities,
Those having a melt viscosity index (melt index) can be used alone or as a mixture thereof.

In the resin of the resin covering paper, white pigments such as titanium oxide, zinc oxide, talc and calcium carbonate, fatty acid amides such as stearic acid amide and arachidic acid amide, zinc stearate, calcium stearate and stearin. Fatty acid metal salts such as aluminum acid salt and magnesium stearate, antioxidants such as Irganox 1010 and Irganottas 1076, blue pigments and dyes such as cobalt blue, ultramarine blue, cesianian blue and phthalocyanine blue, cobalt violet, fast violet, manganese purple It is preferable to add various additives such as magenta pigments and dyes, fluorescent whitening agents, and ultraviolet absorbers in an appropriate combination.

The resin wrapping paper, which is a base material preferably used in the present invention, is produced by a so-called extrusion coating method in which a resin melted by heating is cast in the case of a polyolefin resin on a running base paper, and its screen is displayed. Covered with resin. In the case of a resin that is cured by an electron beam, the resin is applied by a commonly used coater such as a gravure coater or a blade coater, and then the resin is irradiated with an electron beam to cure and coat the resin. Further, it is preferable to perform activation treatment such as corona discharge treatment or flame treatment on the base paper before coating the base paper with the resin. The surface of the base material to which the ink receiving layer is applied (surface) is a glossy surface, depending on the application.
It has a matte surface, and glossy images are used predominantly.
It is not necessary to cover the back surface with resin, but it is preferable to cover the resin from the viewpoint of preventing curling. The back surface is usually a matte surface, and the front surface or both front and back surfaces can be subjected to an activation treatment such as corona discharge treatment or flame treatment as required. The thickness of the covering resin layer is not particularly limited, but it is generally 5 to 50 μm on both the front surface and the back surface.

Various back coat layers can be applied to the substrate of the present invention for antistatic property, transport property, curl preventive property and the like. The back coat layer may contain an inorganic antistatic agent, an organic antistatic agent, a hydrophilic binder, a latex, a curing agent, a pigment, a surfactant and the like in an appropriate combination.

The aqueous ink referred to in the present invention is a recording liquid containing the following colorant, liquid medium and other additives. Examples of the colorant include water-soluble dyes such as direct dyes, acid dyes, basic dyes, reactive dyes and food dyes.

As the solvent of the water-based ink, water and various water-soluble organic solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, C1-C4 alkyl alcohols such as isobutyl alcohol; amides such as dimethylformamide and dimethylacetamide;
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,
Alkylene glycols having 2 to 6 alkylene groups such as diethylene glycol; lower alkyl ethers of polyhydric alcohols such as glycerin, ethylene glycol methyl ether, diethylene glycol methyl (or ethyl) ether, triethylene glycol and monomethyl ether; 2H-pyrrolidinone And the like; pyrrolidones such as 1-methyl-2-pyrrolidone and 2-pyrrolidone. Among these many water-soluble organic solvents, polyhydric alcohols such as diethylene glycol, lower alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl ether and triethylene glycol monoethyl ether, and pyrrolidones are preferable.

In the present invention, the ink solvent is preferably a mixed solvent of water and the organic solvent from the viewpoint of preventing clogging of the ink head nozzles.
The mixing ratio of water and the organic solvent is 30/70 / to 70 by weight.
/ 30 is preferable, and more preferably 40/60 to 70 /
Thirty.

Other additives include, for example, a pH adjusting agent, a sequestering agent, an antifungal agent, a viscosity adjusting agent, a surface tension adjusting agent, a wetting agent, a surfactant, and a chain preventing agent.

[0125]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
In the following description, "part" means "part by weight".

Example 1 The following were prepared as the cationic water-soluble polymer of the present invention.

A) Polyallylamines a) -1 PAA-HCl (polyallylamine hydrochloride Nitto Boseki) a) -2 PAS-H (polydimethyldiallylammonium chloride Nitto Boseki) a) -3 PAS-J (diallyl) Dimethyl ammonium chloride-acrylamide copolymer Nitto Bo) b) Dicyandiamide condensate b) -1 Sunfix 70 (dicyandiamide formalin condensate Sanyo Kasei) b) -2 Neofix RP-70 (polyalkylene polyamine dicyandiamide formalin condensation) Product Nichika) c) Polyethyleneimines c) -1 Epomin PK (strong cationic polyethyleneimine manufactured by Nippon Shokubai) d) Cation-modified PVA d) -1 Gohsenol CM-318 (cation-modified P)
VA Nippon Synthetic Chemical Industry) e) Cation-modified PVP e) -1 GAFQUAT HS-100 (Cation-modified PVP ISP) f) Epichlorohydrin derivative f) -1 Nalpoly-607 (Epichlorohydrin-)
Tertiary amine reaction product Nalco Chemical) f) -2 Polyfix 601 (Showa Polymer Co., Ltd.) g) Amino group substituted nylon g) -1 AQ nylon A-90 (modified 6-nylon Toray) h) Cationic Polyaluminum hydroxide h) -1 Paho # 2S (polyaluminum hydroxide manufactured by Asada Chemical Co., Ltd.) Next, an ink receiving layer coating liquid was prepared so that the composition of the dry solid content was as shown in Table 1, and this was applied to a bar. An ink jet recording sheet was obtained by coating a resin-coated paper having both sides coated with polyethylene with a coater so that the weight after drying was 8 g / m ² , and drying. By using an inkjet printer (Design Jet 650C, manufactured by Hewlett-Packard Co.), the maximum colors of yellow (Y), magenta (M), cyan (C), blue (B), green (G), and red (R) can be obtained. Printed at density and 50% density. In addition, each color of B, G, R is M
And C, Y and C, and Y and M inks were obtained by overlapping and printing from different nozzles.

The composition of each ink at this time is as follows.

Y: Direct Yellow 50 (CI.29052) 6 parts Diethylene glycol 47 parts Water 47 parts M: Xylene Red B (CI.45100) 6 parts Diethylene glycol 47 parts Water 47 parts C: Light Green SF Yellowish 6 parts Diethylene glycol 47 Part water 47 parts This print sample was used to evaluate the uniformity of the maximum density part of the green and the fixing and drying time of the ink. The uniformity of the maximum density portion was evaluated by visually observing whether or not the cod was observed, and the dry fixing time was evaluated by the time required until the fine paper was brought into close contact with the maximum density portion of the green and transfer was not observed. Table 1 shows the results.

[0130]

[Table 1]

[0131]

[Chemical 17]

In Table 1 and the following tables, the meanings of the symbols in the column of uniformity of maximum density part are as follows.

⊚: No coddle-shaped density unevenness is observed with the naked eye. O: Coddy-shaped density unevenness is present, but cannot be recognized without staring. Δ: Presence of cod-like unevenness can be recognized at a glance. It is at an acceptable level for practical use. X: Cod-like unevenness is severe and is a problem for practical use.

From Table 1, it can be seen that according to the present invention, the uniformity of the image and the dry fixing time when the ink-jet printing using gelatin is carried out can be greatly improved. Further, it is found that polyallylamines, dicyandiamide condensate, cation-modified PVP, epichlorohydrin derivative and cationic polyaluminum hydroxide are particularly excellent as the cationic polymer used. Further, it is found that even with the same cationic polymer, the effect of the present invention cannot be obtained with a water-insoluble latex polymer.

Example 2 The same procedure as in Example 1 was carried out except that a transparent polyethylene terephthalate film having a thickness of 100 μm was used as the base material to which the coating liquid for the ink receiving layer was applied. As a result, Example 1
The same evaluation result as was obtained.

Example 3 The same procedure as in Example 1 was carried out except that the ink jet printer and ink were replaced with Mach Jet 700V2C and a dedicated ink (manufactured by Seiko Epson Corporation).
As a result, the same evaluation results as in Example 1 were obtained.

Example 4 An ink jet recording sheet was obtained in the same manner as in Example 1 except that a) -1 was used as the cationic polymer and the composition of the dry solid content of the ink receiving layer was as shown in Table 2. . These were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0138]

[Table 2]

From Table 2, if the ratio of the cationic polymer to gelatin is too small, the effect of improving both the dry fixing time and the uniformity of the image is small, and if it is too large, the uniformity of the image is improved, but the dry fixing time It can be seen that the improvement effect is lost. Further, it is found that the ratio of the cationic polymer to gelatin is most preferably 3 to 20%.

Example 5 The procedure of Example 3 was repeated except that e) -1 was used as the cationic polymer. The results are shown in Table 3.

[0141]

[Table 3]

From Table 3, when e) -1 is used, a)-
Although it is preferable to use a little more than 1
It can be seen that almost the same evaluation results as in Example 3 are obtained.

Example 6 An ink jet recording sheet was obtained in the same manner as in Example 1 so that the dry solid content of the ink receiving layer was as shown in Table 4. These samples were evaluated for the magenta (M) and cyan (C) dot diameters and the dry fixing time. The dot diameter was measured by observing the 50% density portion with a microscope equipped with a ruler. Table 4 shows the results.

[0144]

[Table 4]

From Table 4, it can be seen that the dot diameter can be reduced by using the nonionic or anionic water-soluble polymer in combination, which is advantageous for obtaining an image with high resolution. Further, it is understood that the dry fixing time can be further shortened by appropriately adjusting the content of the nonionic or anionic water-soluble polymer.

Example 7 The procedure of Example 5 was repeated, except that the nonionic or anionic water-soluble polymer was changed to polyvinyl alcohol (PVAGL05 (Nippon Gosei Kagaku)). As a result, the same evaluation results as in Example 5 were obtained.

Example 8 On the polyethylene resin-coated paper used in Example 1, the coating liquid was applied by the bar coating method so as to have the following constitution, to obtain a recording sheet.

First layer (ink receiving layer, bottom layer) Lime-treated gelatin 1.2 g / m ² PVP-K90 0.8 g / m ² Second layer (ink receiving layer) Gelatin (described in Table 5) 3.5 g / m ² PVP-K90 3.5 g / m ² Cationic water-soluble polymer (described in Table 5) 0.35 g / m ² Third layer (ink receiving layer / top layer) Gelatin (described in Table 5) 0.8 g / m ² PVP-K90 0.32 g / m ² polyethylene glycol (molecular weight 150,000, manufactured by Meisei Chemical) 0.48 g / m ² sodium di-2-ethylhexyl sulfosuccinate 16 mg / m ² matting agent (polymethacrylic acid methyl ester, average particle size) Diameter 10 μm) 0.05 g / m ^{2 The} obtained sample was subjected to the same print test as in Example 3,
At the same time, the glossiness of the unprinted portion at 60 ° C. was measured using a gloss meter VG-1D type (manufactured by Nippon Denshoku Industries Co., Ltd.). The gloss level evaluation criteria are as follows.

⊚: 80 ° or more, extremely good glossiness ◯: 70 to 80 °, good glossiness Δ: 50 to 70 °, glossy but practically acceptable lower limit x: less than 40 ° There is no gloss.

The results are shown in Table 5.

[0151]

[Table 5]

From Table 5, by using acid-treated gelatin or amino group-inactive gelatin in the present invention, not only the image quality and ink drying property are improved, but also the glossiness of the surface is improved and the print quality is further improved. I understand.

Example 9 Sample No. 8 of Example 8 was used. 8-4 was prepared in the same manner as the sample except that the coating liquid was adjusted so that each of the exemplified compounds FA-1 and FK-1 of the above-mentioned surfactant was 3 mg / m ² in the uppermost layer. The same evaluation as in 8 was performed. As a result, the ink drying properties and glossiness were the same, but the uniformity of the maximum density part was further improved. Image quality equivalent to 8-7 was obtained.

From the above results, it is understood that the effect of the present invention can be better achieved by using the fluorine-containing surfactant in the uppermost layer of the ink receiving layer.

Example 10 An ink jet recording sheet was obtained in the same manner as in Example 1 such that the composition of the dry solid content of the ink receiving layer was as shown in Table 6. Further, the ink shown in Example 1 had a solvent composition of water / diethylene glycol = 50/50, but an ink was prepared by changing the solvent composition as shown in Table 6. Using these in the combinations shown in Table 6, the dry fixing time was evaluated in the same manner as in Example 1. The results are shown in Table 6.

[0156]

[Table 6]

From Table 6, when the cationic water-soluble polymer of the present invention is not used, the drying and fixing time is relatively short when an ink containing a large proportion of water is used, whereas it is necessary for high-definition printing. It can be seen that the dry fixing time becomes long when the ink having a high ratio of the organic solvent is used. On the other hand, the ink jet recording sheet of the present invention has a short dry fixing time regardless of the water / organic solvent ratio of the ink solvent, which is advantageous for high-definition printing.

[0158]

According to the present invention, it is possible to provide an ink jet recording sheet which has an excellent ink fixability immediately after printing, a short dry fixing time, and an excellent image resolution and uniformity. Further, according to the present invention, it is possible to provide an inkjet recording sheet having an ink receiving layer which is excellent in ink fixability, image resolution and uniformity, and is also excellent in light transmittance. Further, according to the present invention, it is possible to provide an inkjet recording sheet excellent in ink fixability, image resolution and uniformity even when an ink having a low water content in the ink is used.

Claims (24)

[Claims] 1. An inkjet recording sheet comprising gelatin and at least one cationic water-soluble polymer in a substrate or in an ink receiving layer provided on the substrate. 2. A mixture of gelatin and at least one cationic water-soluble polymer is contained in the substrate or in the ink receiving layer provided on the substrate.
The inkjet recording sheet described above. 3. The cationic water-soluble polymer has a quaternary ammonium group represented by the following general formula [1], [2] or [3], a polyallylamine, a dicyandiamide condensate, and polyethylene. The ink jet recording sheet according to claim 1 or 2, which is at least one selected from imines, cation-modified PVA, cation-modified PVP, epichlorohydrin derivative, amino group-substituted nylon, and cationic polyaluminum hydroxide. Embedded image [In the formula, R ¹ represents a hydrogen atom or a methyl group, and Q represents an oxygen atom or —NH—. R ² , R ³ and R ⁴ each represent a methyl group or an ethyl group, and may be the same or different. X ⁻ is a halogen ion, a sulfonate anion,
It represents an alkyl sulfonate anion, an acetate anion or an alkyl carboxylate anion. n represents 2 or 3. ] [Chemical 2] [In the formula, R ⁵ , R ⁶ and R ⁷ each represent a methyl group or an ethyl group, and may be the same or different. X ⁻ represents a halogen ion, a sulfonate anion, an alkylsulfonate anion, an acetate anion or an alkylcarboxylic acid anion. n represents 2 or 3. ] [Chemical 3] [In the formula, R ⁸ , R ⁹ and R ¹⁰ each represent a methyl group or an ethyl group, and may be the same or different. X ⁻ represents a halogen ion, a sulfonate anion, an alkylsulfonate anion, an acetate anion or an alkylcarboxylic acid anion. n represents 2 or 3. ] 4. The cationic water-soluble polymer is at least one selected from polyallylamine, dicyandiamide condensate, cation-modified PVP, epichlorohydrin derivative and cationic polyaluminum hydroxide. The ink jet recording sheet according to 1, 2, or 3. 5. Gelatin and at least one cationic water-soluble polymer are contained in an ink receiving layer provided on a hydrophobic substrate.
Ink jet recording sheet according to the item. 6. The ink jet recording sheet according to claim 5, wherein the hydrophobic substrate is a resin-coated paper in which both surfaces of the paper are coated with a resin. 7. The ink jet recording sheet according to claim 6, wherein the resin is a polyolefin resin. 8. The ink jet recording sheet according to claim 7, wherein the polyolefin resin is a polyethylene resin. 9. The inkjet recording sheet according to claim 5, wherein the hydrophobic substrate is a transparent polyester resin film. 10. The ink jet recording sheet according to claim 9, wherein the transparent polyester resin film is a polyethylene terephthalate film. 11. The abundance ratio of the cationic water-soluble polymer to gelatin in the ink receiving layer is 0.1.
The ink-jet recording sheet according to any one of claims 1 to 10, wherein the content is from 70 to 70 wt%. 12. The ink jet recording sheet according to claim 1, wherein the ratio of the cationic water-soluble polymer to gelatin is 1 to 50 wt%. 13. The ink jet recording sheet according to claim 1, wherein the presence ratio of the cationic water-soluble polymer to gelatin is 3 to 20 wt%. 14. The ink jet recording according to any one of claims 1 to 13, wherein the ink receiving layer contains gelatin, a cationic water-soluble polymer and at least one water-soluble polymer. Sheet. 15. The inkjet recording sheet according to claim 14, wherein the water-soluble polymer is at least one polymer selected from polyvinylpyrrolidone, polyvinyl alcohol and polyethylene glycol. 16. The ink jet recording sheet according to claim 14, wherein the content of the water-soluble polymer in the ink receiving layer is 5 to 80 wt%. 17. The ink jet recording sheet according to claim 14, 15 or 16, wherein the content of the water-soluble polymer in the ink receiving layer is 20 to 60 wt%. 18. The ink jet recording sheet according to claim 1, wherein the gelatin is acid-treated gelatin. 19. The gelatin according to claim 1, wherein the gelatin is amino group inactivated gelatin.
Ink jet recording sheet according to the item. 20. The ink receiving layer is composed of two or more layers, and at least the uppermost layer of the ink receiving layer contains a fluorine-based surfactant. The inkjet recording sheet described above. 21. The fluorine-containing surfactant comprises at least one anionic surfactant and at least one cationic surfactant.
5. The inkjet recording sheet according to any one of 1. 22. The ink receiving layer comprises two or more layers, and the cationic water-soluble polymer is contained in at least a lower layer adjacent to the uppermost layer. The ink jet recording sheet according to [1]. 23. An ink jet recording sheet according to any one of claims 1 to 22, wherein a water-soluble ink having a dye-dissolving solvent composition of water / organic solvent = 3/7 to / 3 is used. An ink jet recording method characterized by performing recording by means of recording. 24. The inkjet recording method according to claim 23, wherein the organic solvent is at least one selected from glycols and pyrrolidones.