JP4911269B1 - Ink jet receiving agent, ink jet recording medium and printed matter using the same - Google Patents

Abstract

The problem to be solved by the present invention is to provide an ink jet receiving agent and an ink jet recording medium capable of forming an ink receiving layer having excellent water resistance and scratch resistance.
The present invention relates to a urethane resin (A) having a hydrophilic group, polyvinyl alcohol (B), a zirconium compound (C), a water-soluble polyvalent metal salt (D) other than the zirconium compound (C), and an aqueous system. Medium (E), and the zirconium compound (C) comprises the urethane resin (A), the polyvinyl alcohol (B), the zirconium compound (C), and the water-soluble polyvalent metal salt (D). The present invention relates to an ink jet receiving agent that is contained in a range of 0.2% by mass to 15% by mass with respect to the total mass.
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Description

  The present invention relates to an inkjet recording medium that can be used in various scenes such as the manufacture of large signboards that can be installed indoors and outdoors, and photo printing at home and the like, and an inkjet receiver that can be used in the manufacture thereof.

  In recent years, in the industry related to ink-jet printing, where the growth is remarkable, the performance of ink-jet printers and the improvement of ink have advanced dramatically, making it possible to easily obtain high-definition and clear images similar to silver halide photographs even in ordinary households. It's getting on. For this reason, inkjet printers are beginning to be considered for use not only in home use but also in the production of large advertising signs and the like.

  In addition, the improvement in image quality of ink-jet printed materials is largely due to improvements in printing ink as well as higher performance of the printer. Specifically, the use of pigment inks, which are known to be capable of forming printed images having high colorability comparable to dye inks and superior in durability compared to conventional dye inks, has become the mainstream in recent years. It's getting on.

  As the pigment ink, water-based pigment ink and solvent-based pigment ink are mainly known. The water-based pigment ink is obtained by dispersing a pigment in an aqueous medium, and with this ink, it is possible to form a printed image that hardly causes discoloration or cracks during printing.

  However, since the water-based pigment ink is hydrophilic in itself, for example, when rainwater or the like adheres to it, the printed image may be smeared or discolored due to rubbing between papers. In some cases, the scratch resistance was not sufficient.

  In addition, examples of the ink jet receiving agent that can be used in combination with the pigment ink include an ink jet receiving agent containing a water-soluble magnesium salt and an aqueous polyurethane. It is known that an ink receiving layer capable of forming an excellent printed image can be formed (see, for example, Patent Document 1).

  However, the ink-jet printed matter formed on the ink receiving layer still causes color fading or the like when used in a harsh environment such as an outdoor advertising medium that is frequently contacted with rainwater or the like. When a strong force is applied locally on the surface, there may be a case where the pigment ink or the like is lost.

JP 2002-317116 A

  The problem to be solved by the present invention is that it has excellent water resistance at a level that does not cause bleeding or discoloration even when water or the like comes into contact with the surface of the printed image, and is strong against the surface of the printed image. Ink jet receiving agent and ink jet capable of forming a printed image with high color density and excellent printability having excellent scratch resistance at a level that does not cause color fading due to ink loss even when force is applied It is to provide a recording medium.

  In examining the above-mentioned problems, the present inventors have studied using various additives in combination based on a conventionally known aqueous urethane resin-based inkjet receiver.

  Specifically, the use of a zirconium compound in the swelling type ink jet receiving agent of the present invention was examined.

  Although it was possible to form a printed image with a certain level of good water resistance by using the inkjet acceptor, a very high level of water resistance, etc. was required, and it was one step further to the practical level. It wasn't. Moreover, there existed problems, such as the printability of the printed image formed falling.

  Therefore, further investigations proceeded based on the use of the zirconium compound, and when a specific amount of the zirconium compound was used and a sulfonic acid group or a sulfonate group was used as a hydrophilic group to be introduced into the urethane resin, the present invention. I found that I could solve the problem.

  Further, the inventors have further studied and found that when a urethane resin having a carbonate bond is used as the urethane resin, it is possible to form a printed image particularly excellent in printability.

That is, the present invention relates to a urethane resin (A) having a sulfonic acid group or a sulfonate group, polyvinyl alcohol (B), a zirconium compound (C), and a water-soluble polyvalent metal salt other than the zirconium compound (C) ( D) and an aqueous medium (E), and the zirconium compound (C) is the urethane resin (A), the polyvinyl alcohol (B), the zirconium compound (C), and the water-soluble polyvalent metal salt. It is contained in the range of 0.2% by mass to 15% by mass with respect to the total mass with (D) , and the water-soluble polyvalent metal salt (D) is a magnesium salt or a calcium salt. It relates to an ink jet receiving agent.

  In addition, the present invention provides an ink jet recording in which an ink receiving layer is formed on the base material, which is obtained by coating or impregnating the base material with the ink jet receiving agent and then removing the aqueous medium (E). The present invention provides a medium and a printed matter on which printing is performed using an aqueous pigment ink for the ink receiving layer.

  The ink jet receiving agent of the present invention has a very high level of water resistance that does not cause discoloration or bleeding even when water or the like comes into contact with the surface of the printed image, and the surface of the printed image Even if a strong force is applied, it is possible to form a printed image with excellent printability and excellent scratch resistance at a level that does not cause missing ink, etc. It can be used in various scenes such as signage, billboards, advertising flags, and photo printing at home. In particular, even when printing is performed using a printer with a large amount of ink discharged, it is possible to form a printed image that hardly causes bleeding or the like and has excellent printability and water resistance.

  The inkjet acceptor of the present invention includes a urethane resin (A) having a sulfonic acid group or a sulfonate group, a polyvinyl alcohol (B), a zirconium compound (C), and a water-soluble polyvalent metal other than the zirconium compound (C). It contains a salt (D), an aqueous medium (E), and other additives as necessary, and the zirconium compound (C) contains the urethane resin (A), the polyvinyl alcohol (B), and the zirconium. The urethane resin (A) itself is contained in the range of 0.2% by mass to 15% by mass with respect to the total mass of the compound (C) and the water-soluble polyvalent metal salt (D). It can form an ink receiving layer generally called a swelling type that absorbs a solvent in the ink and fixes the ink.

  The urethane resin (A) used in the inkjet receiver of the present invention can be dissolved or dispersed in the aqueous medium (E). Therefore, the urethane resin (A) has a hydrophilic group in an amount that can be dissolved or dispersed in the aqueous medium (E).

  In the present invention, the use of a sulfonic acid group or a sulfonate group formed by neutralizing a part or all of the hydrophilic group with a basic compound as the hydrophilic group is a problem to be solved by the present invention. It is important to solve.

  That is, the ink jet receiving agent of the present invention is not simply a combination of a specific amount of zirconium compound (C), other water-soluble polyvalent metal salt (D), polyvinyl alcohol (B), etc. In combination with a urethane resin (A) having a sulfonic acid group or a sulfonate group is essential for imparting excellent water resistance and scratch resistance and preventing a decrease in color density of a printed image. is there.

  Here, instead of the urethane resin (A) having a sulfonic acid group or a sulfonate group, when a urethane resin having a carboxyl group or a carboxylate group is used, the zirconium compound (C) or the like may be used in combination. In some cases, excellent water resistance and scratch resistance cannot be maintained over a long period of time, or the color density of a printed image may be lowered.

  Examples of basic compounds that can be used for neutralizing the sulfonic acid group include organic amines such as ammonia, triethylamine, pyridine, and morpholine, alkanolamines such as monoethanolamine, Na, K, Li, and Ca. A metal base compound etc. are mentioned.

  The sulfonic acid group and the sulfonate group are present in a total range of 10 mmol / kg to 1000 mmol / kg with respect to the entire urethane resin (A), so that the urethane resin (A) in the aqueous medium (E) is good. It is preferable for imparting water dispersion stability, achieving both excellent water resistance and scratch resistance over a long period of time, and maintaining high printability.

  The urethane resin (A) used in the present invention is particularly preferable to have a carbonate bond in order to form a printed image having excellent printability with high color density and excellent durability such as water resistance and scratch resistance. .

  The carbonate bond can be introduced into the urethane resin (A) by using the polycarbonate polyol (a1-1) as the polyol (a1) used when the urethane resin (A) is produced.

  The urethane resin (A) may have an ester bond together with the carbonate bond. The ester bond is effective in improving the adhesion between the substrate and the ink receiving layer.

  The ester bond can be introduced into the urethane resin (A) by using a polyester polyol as the polyol (a1) used when the urethane resin (A) is produced.

  Moreover, it is preferable to use what has a urea bond as said urethane resin (A), since the abrasion resistance obtained from a high cohesion force can be provided. As said urethane resin (A), it is preferable to use what has the said urea bond in the range of 50-1000 mmol / kg.

  As the urethane resin (A), it is preferable to use a resin having a weight average molecular weight in the range of 10,000 to 200,000 in order to form a printed image having excellent durability such as scratch resistance.

  The urethane resin (A) can be produced, for example, by reacting a polyol (a1) with a polyisocyanate (a2). The urethane resin (A) can be produced by reacting the polyol (a1) and the polyisocyanate (a2) with the polyamine (a3) from the viewpoint of introducing a urea bond.

  As the polyol (a1), conventionally known ones can be used. From the viewpoint of introducing a carbonate bond or a hydrophilic group into the obtained urethane resin (A), the polycarbonate polyol (a1-1), It is preferable to use a sulfonic acid group- or sulfonate group-containing polyol (a1-2).

  As said polycarbonate polyol (a1-1), what is obtained by making carbonate ester and a polyol react, for example, and what is obtained by making phosgene, bisphenol A, etc. react can be used. The polycarbonate polyol may or may not have a hydrophilic group.

  As the carbonate ester, methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like can be used.

  Examples of the polyol capable of reacting with the carbonate ester include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3- Butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptane Diol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 3-methyl-1,5-pentanediol, 2- Ethyl-1,3-hexanediol, 2-methyl-1,3-propa Diol, 2-methyl-1,8-octanediol, 2-butyl-2-ethylpropanediol, 2-methyl-1,8-octanediol, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexane Relatively low molecular weight dihydroxy compounds such as dimethanol, hydroquinone, resorcin, bisphenol-A, bisphenol-F, 4,4′-biphenol, polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, Polyester polyols such as hexamethylene adipate, polyhexamethylene succinate, and polycaprolactone can be used.

  As the polycarbonate polyol (a1-1), use of a product obtained by reacting the carbonate ester with the 1,6-hexanediol increases the strength of the ink-receiving layer and improves the water resistance and scratch resistance. It is preferable for forming a printed image having excellent properties.

  Moreover, as said polycarbonate polyol (a1-1), it is preferable to use what has a number average molecular weight of the range of 500-3000.

  The said polycarbonate polyol (a1-1) should be used in 30 mass%-85 mass% with respect to the whole quantity of the polyol (a1) and polyisocyanate (a2) used for manufacture of the said urethane resin (A). However, it is preferable for forming a printed image having excellent water resistance and scratch resistance.

  The sulfonic acid group- or sulfonate group-containing polyol (a1-2) is other than the polycarbonate polyol (a1-1), for example, 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 5 [ 4-sulfophenoxy] isophthalic acid, their ester derivatives and salts thereof, and a sulfonic acid group or sulfonate group-containing polyol obtained by reacting with a low molecular weight polyol can also be used.

  As the sulfonic acid group or sulfonate group-containing polyol, it is preferable to use a sulfonic acid group or sulfonate group-containing polyester polyol obtained by reacting the 5-sulfoisophthalic acid or the like with a low molecular weight polyol.

  Examples of the low molecular weight polyol that can react with the 5-sulfoisophthalic acid and ester derivatives thereof include, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1 , 6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 3- Methyl-1,5-pentanediol, 2-ethyl-1,3 Hexanediol, 2-methyl-1,3-propanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethylpropanediol, 2-methyl-1,8-octanediol, neopentyl glycol, Relatively low molecular weight dihydroxy compounds such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydroquinone, resorcin, bisphenol-A, bisphenol-F, 4,4′-biphenol, polyethylene glycol, polypropylene glycol, Polyether polyols such as polytetramethylene glycol, polyester polyols such as polyhexamethylene adipate, polyhexamethylene succinate, and polycaprolactone can be used.

  Moreover, as said polyol (a1), other polyols other than the said polycarbonate polyol (a1-1) and the said sulfonic acid group or sulfonate group containing polyol (a1-2) can also be used.

  As said other polyol, a polyester polyol can be used from a viewpoint which introduce | transduces an ester bond into the said urethane resin (A), and improves the adhesiveness of a base material and an ink receiving layer, for example.

  Examples of the polyester polyol include a ring-opening polymerization reaction of a cyclic ester compound such as an aliphatic polyester polyol, an aromatic polyester polyol, or ε-caprolactone obtained by esterifying a low molecular weight polyol and a polycarboxylic acid. Polyesters, copolymerized polyesters thereof, and the like can be used.

  Examples of the low molecular weight polyol include ethylene glycol and propylene glycol.

  Examples of the polycarboxylic acid that can be used include succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, and anhydrides or ester-forming derivatives thereof.

  In addition, as the other polyols, polyether polyols can also be used.

  As the polyether polyol, for example, one obtained by addition polymerization of alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator can be used.

  Examples of the initiator include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, Trimethylolethane, trimethylolpropane and the like can be used.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran.

  Examples of the polyisocyanate (a2) that can react with the polyol (a1) include aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, and isophorone. Aliphatic or aliphatic cyclic structure-containing diisocyanates such as diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate can be used alone or in combination of two or more.

  An ink jet recording medium having an ink receiving layer formed using the ink jet receiving agent of the present invention may be used outdoors, for example, as an advertising banner. In such a case, light resistance and weather resistance may be required in addition to water resistance and scratch resistance.

  In that case, from the viewpoint of preventing deterioration of the surface appearance due to heat discoloration and light discoloration, an alicyclic polyisocyanate and / or an aliphatic polyisocyanate generally called non-yellowing type may be used as the polyisocyanate (a2). preferable.

  Examples of the polyamine (a3) that can be used for the production of the urethane resin (A) include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, and isophorone. Diamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N- Hydroxypropylaminopropylamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, N-ethylaminoethylamine, N-methylaminopropylamine, hydrazine, N, N'-dimethylhydrazine, 1,6-hex Methylenebishydrazine, succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide, β-semicarbazide propionic acid hydrazide, 3-semicarbazide-propyl-carbazic acid ester, semicarbazide-3-semicarbazide Methyl-3,5,5-trimethylcyclohexane and the like can be used.

  As the polyamine (a3), in addition to those described above, sulfonate group or sulfonate group-containing polyamine (a3-1) such as N- (2-aminoethyl) -2-aminoethanesulfonic acid and its sodium salt is used. can do. By using the sulfonic acid group or sulfonate group-containing polyamine (a3-1), a sulfonic acid group or a sulfonate group can be introduced into the urethane resin (A) to be obtained. When the sulfonic acid group or sulfonate group-containing polyamine (a3-1) is used, the sulfonic acid group or sulfonate group-containing polyol (a1-2) is not necessarily used.

  The hydrophilic group-containing compounds such as the hydrophilic group-containing polyamine (a3-1) and the hydrophilic group-containing polyol (a1-2) are polyol (a1) and polyisocyanate used for the production of the urethane resin (A). Use in the range of 0.5% by mass to 30% by mass with respect to the total mass of (a2) and polyamine (a3) is preferable in order to achieve both good water dispersibility and water resistance.

  The urethane resin (A) is obtained by reacting the polyol (a1), the polyisocyanate (a2), and, if necessary, the polyamine (a3) in the absence of a solvent or in the presence of an organic solvent. The aqueous dispersion in which the urethane resin (A) is dissolved or dispersed in the aqueous medium (E) can be produced by producing and then phase inversion emulsifying in the aqueous medium (E).

  When manufacturing the said urethane resin (A), you may use a chain extender as needed. The chain extender may be performed before or after phase inversion emulsification of a urethane resin in an organic solvent solution and then phase inversion emulsification of the urethane resin to the aqueous medium (E).

  Examples of the chain extender include those exemplified as the polyamine (a3), ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1, Glycols such as 4-butanediol and hexamethylene glycol; bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenylsulfone, hydrogenated bisphenol A, hydroquinone, etc. Phenols and their alkylene oxide adducts, polyhydroxy compounds such as glycerin, trimethylolpropane, sorbitol, and water can be used.

  Moreover, when manufacturing the said urethane resin (A), a part or all of the hydrophilic group in the said urethane resin (A) is neutralized from a viewpoint of improving the dispersion stability in an aqueous medium (E). May be. For the neutralization, for example, when the hydrophilic group is an anionic group, it is preferable to use the basic compound described above.

  The reaction of the polyol (a1), the polyisocyanate (a2), and the polyamine (a3) that can be used as necessary includes, for example, the hydroxyl group of the polyol (a1) and the amino group of the polyamine (a3). It is preferable that the equivalent ratio of the isocyanate group which the said polyisocyanate (a2) has with respect to the total amount with the group is in the range of 0.8 to 1.1. Moreover, when using the chain extender mentioned above, it is preferable that the said equivalent ratio is the range of 1.1-1.5.

  Examples of the organic solvent that can be used in producing the urethane resin (A) include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; acetates such as ethyl acetate and butyl acetate; Nitriles: Amides such as dimethylformamide and N-methylpyrrolidone can be used alone or in combination of two or more.

  In the aqueous dispersion of the urethane resin (A) obtained by the above method, the organic solvent used in the production process may remain. The organic solvent is preferably removed by a method such as heating under reduced pressure, for example, during the reaction or after the completion of the reaction, if necessary.

  The urethane resin (A) obtained above is based on the total mass of the urethane resin (A), the polyvinyl alcohol (B), the zirconium compound (C), and the water-soluble polyvalent metal salt (D). It is preferably used in the range of 5% by mass to 60% by mass, and more preferably in the range of 5% by mass to 30% by mass.

  Next, the polyvinyl alcohol (B) used in the present invention will be described.

  Polyvinyl alcohol (B) is a kind of water-soluble resin, and is widely used in the ink-jet receiving agent industry. The reason is that the resin has physical properties necessary for an ink jet receiving agent, such as transparency, film strength, and binder strength against pigments, is easily available, and there are many types of modified products. Is mentioned.

  Polyvinyl alcohol (B) is generally obtained by hydrolyzing an acetyl group portion of a vinyl acetate polymer with a strong base such as sodium hydroxide to form a hydroxyl group (saponification). As polyvinyl alcohol, those having various saponification ratios (saponification degree) and those having various polymerization degrees are commercially available. In the present invention, from the viewpoint of providing an ink-jet receiving agent that provides an ink-jet receiving layer that is excellent in printability and absorbability with respect to the target pigment ink and that has good water resistance of a printed image in both pigment ink and dye ink. Polyvinyl alcohol having a saponification degree in the range of 70 mol% to 99 mol% is preferably used, and more preferably polyvinyl alcohol having a saponification degree in the range of 87 mol% to 99 mol%. The saponification degree is a percentage of the number of hydroxyl groups to the total number of acetic acid groups and hydroxyl groups of polyvinyl alcohol.

  As the polyvinyl alcohol (B), those having any degree of polymerization can be used. From the viewpoint of improving ink absorbency, color density of printed images, and water resistance, the degree of polymerization is in the range of 500 to 4000. It is preferable to use what has.

  Specific examples of the polyvinyl alcohol having a saponification degree of 70 mol% to 99 mol% include Kuraray Poval PVA224, PVA235 (manufactured by Kuraray Co., Ltd.), Gohsenol GL-05, GH-17, GH-20, GH- 23 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) can be used.

  Further, as the polyvinyl alcohol (B), modified polyvinyl alcohol having various modifying groups may be used. Examples of the modifying group include acetoacetyl group, silyl group, quaternary ammonium base, carboxylic acid group, carboxylic acid group, sulfonic acid group, sulfonic acid group, ketone group, mercapto group, amino group, ethylene group, and the like. Can be mentioned. These can be introduced into polyvinyl alcohol by copolymerizing vinyl acetate and the monomer having the modifying group.

  As the polyvinyl alcohol (B), it is more preferable to use acetoacetylated polyvinyl alcohol for further improving printability.

  As the acetoacetylated polyvinyl alcohol, generally, a solution or powder of polyvinyl alcohol obtained by adding and reacting a liquid or gaseous diketene can be used.

  As a commercially available product of the acetoacetylated polyvinyl alcohol, “Gosefimer Z series” (trade name) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. can be used.

  The polyvinyl alcohol (B) is 10% by mass to the total mass of the urethane resin (A), the polyvinyl alcohol (B), the zirconium compound (C), and the water-soluble polyvalent metal salt (D). It is preferably used in the range of 80% by mass, and more preferably in the range of 30% by mass to 75% by mass.

Next, the zirconium compound (C) used in the present invention will be described.
The zirconium compound (C) imparts excellent water resistance and scratch resistance to an ink receiving layer formed using the ink jet receiving agent of the present invention, and prevents a decrease in color density of a printed image. It is an essential ingredient. Here, even if a carbodiimide-based crosslinking agent or an epoxy-based crosslinking agent is used instead of the zirconium compound (C), excellent water resistance or scratch resistance cannot be imparted, or printability may be significantly reduced. is there.

  Further, the zirconium compound (C) is added to the total mass of the urethane resin (A), the polyvinyl alcohol (B), the zirconium compound (C), and the water-soluble polyvalent metal salt (D). It is essential to use in the range of 2% by mass to 15% by mass. When the amount of the zirconium compound (C) used is less than 0.2% by mass, an ink receiving layer having excellent water resistance and scratch resistance may not be formed. Further, when the amount of the zirconium compound (C) used exceeds 15% by mass, the ink absorbability is lowered, which may cause a decrease in water resistance and scratch resistance and a significant decrease in printability.

  The zirconium compound (C) imparts excellent water resistance and scratch resistance to the ink receiving layer, and also prevents the printability from deteriorating. The urethane resin (A) and the polyvinyl alcohol (B) It is particularly preferable to use the zirconium compound (C) and the water-soluble polyvalent metal salt (D) in a range of 0.5% by mass to 10% by mass with respect to the total mass.

  Examples of the zirconium compound (C) include zirconium acetate, zirconium sulfate, zirconium fluoride, zirconium oxychloride, zirconium chloride, zirconium bromide, zirconium acid, zirconate, zirconyl sulfate, zirconyl nitrate, zirconyl carbonate, and ammonium zirconium carbonate. , Potassium zirconium carbonate, zirconyl acetate, zirconyl stearate, zirconyl octylate, zirconyl citrate, zirconyl lactate, zirconyl oxalate, zirconyl phosphate, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium bisacetylacetonate, zirconium Monoethyl acetoacetate, zirconium acetate or the like can be used.

  Among these, it is preferable to use one or more selected from the group consisting of zirconium acetate, ammonium zirconium carbonate, zirconium oxychloride, zirconium nitrate, and zirconium sulfate. It is preferable because it can form an ink-receiving layer having excellent water resistance and scratch resistance, high color density and excellent printability.

  In addition, the zirconium compound (C) is excellent in water resistance and scratch resistance, and has a high color density and excellent printability, so that the zirconium compound (C) is 0 with respect to the mass of the polyvinyl alcohol (B). More preferably, it is used in the range of 5% by mass to 30% by mass.

Next, the water-soluble polyvalent metal salt (D) will be described.
The water-soluble polyvalent metal salt (D) refers to a polyvalent metal salt having solubility in water other than the zirconium compound (C). Specifically, when a saturated aqueous solution of a polyvalent metal salt is prepared using water at 20 ° C., the amount of the polyvalent metal salt contained in 100 g of the saturated aqueous solution is 1 g or more, except for the zirconium salt. is there.

  The water-soluble polyvalent metal salt (D) contains a metal ion which is a polyvalent cation and can bind to an anionic group in a dye or pigment molecule which is a color material in the ink. Contributes to improving the water resistance and scratch resistance of the receiving layer.

  Examples of the water-soluble polyvalent metal salt (D) include divalent metal salts such as magnesium salt, calcium salt, barium salt, iron (II) salt, copper (II) salt, zinc salt, aluminum salt, Trivalent metal salts such as chromium salts can be used. Of these, the use of a magnesium salt or a calcium salt is preferable in terms of improving water resistance, scratch resistance, ink absorbability, and the like.

  As said magnesium salt, magnesium chloride, magnesium acetate, magnesium nitrate, magnesium sulfate, magnesium chlorate etc. can be used individually or in combination of 2 or more types, for example.

  As the calcium salt, calcium chloride, calcium acetate, etc. can be used.

  The water-soluble polyvalent metal salt (D) forms a printed image with a high color density and gives the urethane resin (A) and the polyvinyl alcohol (B) from the viewpoint of imparting excellent water resistance and scratch resistance. ), The zirconium compound (C) and the water-soluble polyvalent metal salt (D) are preferably used in the range of 0.01% by mass to 30% by mass.

  Moreover, as an aqueous medium (E) which comprises the inkjet receptive agent of this invention, the organic solvent mixed with water and water can be used. Examples of organic solvents miscible with water include alcohols such as methanol, ethanol, n- and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; Alkyl ethers; lactams such as N-methyl-2-pyrrolidone, etc. can be used. In the present invention, only water may be used, or a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used. From the viewpoint of safety and environmental load, water alone or a mixture of water and an organic solvent miscible with water is preferred, and water alone is particularly preferred.

  The inkjet receiver of the present invention includes, for example, an aqueous dispersion containing the urethane resin (A) and an aqueous medium (E), polyvinyl alcohol (B), zirconium compound (C), and water-soluble polyvalent metal salt (D). , And if necessary, other components can be mixed.

  As such a production method, for example, an aqueous polyvinyl alcohol solution obtained by mixing the polyvinyl alcohol (B) and the aqueous medium (E), an aqueous dispersion of the urethane resin (A), a water-soluble polyvalent metal salt ( D) is mixed, and then the mixture and the zirconium compound (C) are mixed.

  In addition, as the production method, the polyvinyl alcohol (B) and the water-soluble polyvalent metal salt (D) are dispersed or dissolved in an appropriate aqueous medium (E) in advance, and the urethane resin (A ) Is dispersed using various stirrers and dispersers, and then the mixture and the zirconium compound (C) are mixed.

  Also, an aqueous dispersion of the urethane resin (A), polyvinyl alcohol (B), a water-soluble polyvalent metal salt (D), and other components added to an aqueous medium in any order and mixed, It can also be produced by a method of mixing the zirconium compound (C).

  The zirconium compound (C) may undergo a crosslinking reaction with the urethane resin (A) or polyvinyl alcohol (B). Therefore, it is preferable that the zirconium compound (C) is separately mixed and used immediately before the mixture of other components is used as the ink jet receiving agent.

  As an agitator that can be used when mixing the urethane resin (A) and an aqueous dispersion composed of an aqueous medium (E), polyvinyl alcohol (B), a water-soluble polyvalent metal salt (D), and other components, for example, A stirrer having a turbine blade, a propeller blade, a fiddler blade, a paddle blade, an anchor blade, a max blend blade, a ribbon blade, a disper blade, and the like can be used. As the disperser, for example, various homogenizers, bead mills, sand mills, line mills, sonorators, colloid mills, and the like can be used.

  Ratio of aqueous medium (E) and solid content [that is, urethane resin (A), polyvinyl alcohol (B), zirconium compound (C) and water-soluble polyvalent metal salt (D)] in the inkjet receiver of the present invention. Is not particularly limited, but needs to be determined in consideration of the viscosity and storage stability of the ink jet receiving agent. Generally, when a water-soluble resin is dissolved in an aqueous medium (E), its viscosity increases exponentially with respect to the concentration of the water-soluble resin. Moreover, storage stability tends to deteriorate as the concentration increases. Therefore, it is preferable to adjust the ratio of the aqueous medium to the solid content so that the viscosity of the ink jet receiving agent is 100,000 mPa · s or less. Moreover, it is also necessary to adjust the viscosity so as to be suitable for a coating apparatus or an impregnation processing apparatus used when coating or impregnating the ink-jet receiving agent of the present invention on various substrates. Specifically, the ratio is preferably in the range of 5 to 30% by mass.

  The ink jet receiving agent of the present invention may contain various additives as necessary within the range not impairing the effects of the present invention.

  As the additive, for example, a water-soluble resin other than the polyvinyl alcohol (B) may be used. For example, polyvinylpyrrolidone, polyvinyl acetal, polyalkylene oxide, starch, methylcellulose, hydroxycellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose. , Cellulose derivatives such as carboxymethylcellulose, polyethyleneimine, polyamide, various quaternary ammonium base-containing water-soluble resins, and modified products thereof, epichlorohydrin polyamide resin, amine epichlorohydrin resin, polyethyleneimine salt-containing resin, polyvinylamine salt-containing Resin, polyvinylamidine resin, polyallylamine salt-containing resin, polyaminesulfone salt-containing resin, polydiallyldimethylammonium chloride Ride, dicyandiamide - formalin polycondensates, cationic modified polyvinyl alcohol, cationic group-containing water-soluble acrylic resin, may be used cationically modified starch, neutral salt such as chitosan. Of these, the use of epichlorohydrin polyamide resin is more preferable because it has an effect of improving the color density of the printed image and improving the water resistance by strengthening the ink fixing force, and the mass ratio thereof is the urethane resin (A). 0.2 mass% to 50 mass% is preferable with respect to the total mass of the polyvinyl alcohol (B), the zirconium compound (C), and the water-soluble polyvalent metal salt (D), and 5 mass% to 20 mass%. % Is more preferable.

  The epihalohydrin polyamide resin is obtained by adding an epihalohydrin to a polyamide polyamine obtained by condensing a polyfunctional polyamine such as diethylenetriamine and a polybasic acid such as adipic acid. Specifically, it is preferable to use an epichlorohydrin polyamide obtained by reacting a polyamide polyamine and epichlorohydrin.

  In addition to the additives described above, the additive used in the inkjet receiver of the present invention includes, for example, various nonionic, cationic, anionic and amphoteric surfactants, pigment dispersants, silicones, fluorine And various leveling agents such as acetylene diol and colloidal silica, colloidal silica, colloidal alumina, inorganic pigments, anti-blocking agents such as resin beads, ultraviolet absorbers, antioxidants and antistatic agents.

  The amount of these additives used is not particularly limited as long as the effects of the present invention are not impaired, but is preferably in the range of 0.01 to 5% by mass with respect to the total amount of solids in the ink jet receiving agent. .

  In addition, the inkjet receiving agent of the present invention has different usage methods for applications in which it is desired to maintain gloss and transparency on the surface of the receiving layer and in applications in which it is desired to express concealment, but depending on the purpose and application, In addition, various porous pigments such as clay, alumina, and calcium carbonate may be included. As the porous pigment, it is particularly preferable to use silica or alumina which has good ink absorbability, is easily available industrially, and has good compatibility with the urethane resin (A) constituting the present invention. .

  In addition, the inkjet receiver of the present invention is a known resin that can be dispersed in an aqueous medium within a range not impairing the effects of the present invention, such as vinyl acetate, ethylene vinyl acetate, acrylic, epoxy, and polyester. , Polyamide-based, urethane-based, styrene-butadiene-based, acrylonitrile-butadiene-based, acrylic-butadiene-based synthetic rubber, and the like.

  Next, the ink jet recording medium of the present invention will be described.

  In the ink jet recording medium of the present invention, the ink jet receiving agent is coated or impregnated on various substrates, and then the aqueous medium (E) contained in the ink jet receiving agent is removed to form an ink receiving layer on the substrate. By doing so, a printed image having excellent water resistance and scratch resistance can be formed without impairing the ink absorbability.

  Examples of the substrate include paper, paperboard, resin-coated paper, various films, synthetic paper, fibers, nonwoven fabrics, spunbonds, and woven fabrics and nonwoven fabrics that are impregnated and / or coated with artificial leather and natural leather. Can be used.

  As a method for coating or impregnating the ink jet receiving agent on the various substrates, a known and usual method can be used, and is not particularly limited. For example, an air knife coater, a blade coater, a roll coater, a gravure coater, a comma A method using a coating machine such as a coater or a gate roll coater is simple.

  The ink jet receiving agent of the present invention hardly causes cracks when coated or impregnated on a substrate. Therefore, when coating or impregnating the inkjet receiving agent on the base material, there is no need for a process for preventing cracking of the film, for example, a drying process under low temperature conditions or a process of repeating coating several times. It is.

  The method for removing the aqueous medium (E) after coating the inkjet acceptor of the present invention on the substrate is not particularly limited, but for example, a method of drying using a dryer is common. It is. The drying temperature may be set to a temperature that can volatilize the aqueous medium (E) and does not adversely affect the substrate.

  The ink jet recording medium of the present invention obtained by the above production method is capable of accepting ink jets having a thickness in the range of 3 μm to 30 μm in order to maintain characteristics such as ink absorbability at a practical level and maintain good production efficiency. Those having a layer are preferable, and the range of 5 μm to 20 μm is particularly preferable in consideration of ink absorbability and manufacturing cost.

  The ink jet recording medium obtained by the present invention is excellent in the ink absorptivity of the pigment ink and the water resistance of the printed image, and therefore can be suitably used for the ink jet recording medium for the aqueous pigment ink. Further, it is particularly useful as an inkjet recording medium for a wide format printer.

  Hereinafter, the present invention will be described more specifically with reference to examples.

[Preparation Example 1] Preparation of Inkjet Receptor Composition (X-1) Hydran HW-970 [40% by weight aqueous dispersion of polycarbonate structure and sulfonic acid group-containing polyurethane manufactured by DIC Corporation] 8.3 parts by mass , Z-320 [Nippon Synthetic Chemical Co., Ltd., acetoacetylated polyvinyl alcohol] 10 mass% aqueous solution 77.8 parts by mass, calcium chloride 50 mass% aqueous solution 2.8 parts by mass, DK-6830 [Starlight] PMC Co., Ltd., 25% by mass aqueous solution of epichlorohydrin polyamide resin] 11.1 parts by mass were sufficiently mixed using a stirrer equipped with a propeller blade, and finally diluted with water to obtain a nonvolatile content of 15. A 0% by mass composition for ink jet receiving agent (X-1) was prepared.

[Preparation Example 2] Preparation of Composition for Inkjet Receiving Agent (X-2) Instead of Hydran HW-970, Hydran HW-930 [DIC Corporation Poester structure and 50% by mass dispersion of sulfonic acid group-containing polyurethane Body] 6.8 parts by mass, 10% by weight aqueous solution of Z-320 [manufactured by Nippon Synthetic Chemical Co., Ltd., acetoacetylated polyvinyl alcohol] 79.1 parts by weight and 50% by weight aqueous solution of calcium chloride 2.8% Part and DK-6830 [Seiko PMC Co., Ltd., 25% by mass aqueous solution of epichlorohydrin polyamide resin] 11.3 parts by mass are thoroughly mixed using a stirrer equipped with a propeller blade, and finally diluted with water. As a result, a composition for ink-jet receiving agent (X-2) having a nonvolatile content of 15.0% by mass was prepared.

[Comparative Preparation Example 1] Preparation of Inkjet Receptor Composition (X′-1) Instead of Hydran HW-970, APX-601 [40, a carboxyl group-containing polyurethane having a polycarbonate structure and a polyester structure manufactured by DIC Corporation] A composition for ink-jet receiving agent (X′-1) was prepared in the same manner as in Example 1 except that [mass% aqueous dispersion] was used.

Example 1 Preparation of Inkjet Receptor (I-1) and Inkjet Recording Medium (II-1) 100 parts by mass of the composition for inkjet acceptor (X-1) and Zircozol ZA-20 [First Rare Element Chemistry] Industrial Co., Ltd., 20 mass% aqueous solution of zirconium acetate] 4.5 parts by mass are sufficiently mixed using a stirrer equipped with a propeller blade, and diluted with water to obtain a non-volatile content of 15.0. A mass% inkjet acceptor (I-1) was prepared.

  The inkjet receiver (I-1) obtained above was applied to a transparent polyethylene terephthalate film (A-4100, manufactured by Toyobo Co., Ltd.) that had been subjected to easy adhesion treatment, using wire bar No. 40, The ink jet recording medium (II-1) having an ink receiving layer having a dry film thickness of 15 μm was produced by drying at 120 ° C. for 3 minutes using a hot air dryer.

[Example 2]
Example 1 except that the amount of Zircozole ZA-20 [Daiichi Rare Element Chemical Co., Ltd., 20% by mass aqueous solution of zirconium acetate] was changed from 4.5 parts by mass to 0.4 parts by mass. In the same manner, an inkjet receiver (I-2) and an inkjet recording medium (II-2) were obtained.

Example 3
Example 1 except that the amount of Zircozol ZA-20 [manufactured by Daiichi Rare Element Chemical Co., Ltd., 20 mass% aqueous solution of zirconium acetate] was changed from 4.5 parts by mass to 2.3 parts by mass. In the same manner, an inkjet receiver (I-3) and an inkjet recording medium (II-3) were obtained.

Example 4
Except that the amount used of Zircozol ZA-20 [Daiichi Rare Element Chemical Co., Ltd., 20 mass% aqueous solution of zirconium acetate] was changed from 4.5 parts by mass to 6.8 parts by mass, Example 1 and In the same manner, an inkjet receiver (I-4) and an inkjet recording medium (II-4) were obtained.

Example 5
Example 1 except that the amount of Zircozole ZA-20 [Daiichi Rare Element Chemical Co., Ltd., 20 mass% aqueous solution of zirconium acetate] was changed from 4.5 parts by mass to 9.0 parts by mass In the same manner, an inkjet receiver (I-5) and an inkjet recording medium (II-5) were obtained.

Example 6
Zircosol ZA-20 [Daiichi Rare Element Chemical Co., Ltd., 20 mass% aqueous solution of zirconium acetate] Instead of 4.5 parts by mass, Zircozole ZC-20 [Daiichi Rare Element Chemical Industries, Ltd., Oxygen 20 wt% aqueous solution of zirconium chloride] An ink jet receiving agent (I-6) and an ink jet recording medium (II-6) were obtained in the same manner as in Example 1 except that 4.5 parts by mass were used.

Example 7
Zircozole ZA-20 [Daiichi Rare Element Chemical Co., Ltd., 20 mass% aqueous solution of zirconium acetate] Instead of 4.5 parts by mass, Zircozole ZN [Daiichi Rare Element Chemical Industries, Ltd., zirconium nitrate 25 mass% aqueous solution] An ink jet receiving agent (I-7) and an ink jet recording medium (II-7) were obtained in the same manner as in Example 1 except that 3.6 parts by mass were used.

Example 8
Zircozole ZA-20 [produced by Daiichi Rare Element Chemical Industry Co., Ltd., 20 mass% zirconium acetate aqueous solution] 4.5 parts by mass of zirconium sulfate [produced by Daiichi Rare Element Chemical Industries, Ltd., zirconium sulfate 18 mass% aqueous solution] An ink jet receiving agent (I-8) and an ink jet recording medium (II-8) were obtained in the same manner as in Example 1 except that 5.0 parts by mass were used.

Example 9
Zircozol ZA-20 [Daiichi Rare Element Chemical Co., Ltd., 20 mass% aqueous solution of zirconium acetate] Instead of 4.5 parts by mass, Zircozol AC-7 [Daiichi Rare Element Chemical Industries, Ltd., carbonic acid 13 wt% aqueous solution of zirconium ammonium] An ink jet receiving agent (I-9) and an ink jet recording medium (II-9) were obtained in the same manner as in Example 1 except that 6.9 parts by mass were used.

Example 10
Inkjet was carried out in the same manner as in Example 1 except that 100 parts by mass of the composition for ink-jet receiving agent (X-2) was used instead of 100 parts by mass of the composition for ink-jet receiving agent (X-1). Receiving agent (I-10) and inkjet recording medium (II-10) were prepared.

[Comparative Example 1]
In the same manner as in Example 1, except that 100 parts by mass of the composition for ink-jet receiving agent (X′-1) is used instead of 100 parts by mass of the composition for ink-jet receiving agent (X-1). Inkjet receiving agent (I′-1) and inkjet recording medium (II′-1) were prepared.

[Comparative Example 2]
Except having changed the usage-amount of Zircozol ZA-20 [Daiichi Rare Element Chemical Co., Ltd. make, 20 mass% zirconium acetate aqueous solution] from 4.5 mass parts to 0 mass parts, it is the same as that of Example 1. By the method, an ink jet receiving agent (I′-2) and an ink jet recording medium (II′-2) were obtained.

[Comparative Example 3]
Example 1 except that the amount of Zircozole ZA-20 [manufactured by Daiichi Rare Element Chemical Co., Ltd., 20 mass% aqueous solution of zirconium acetate] was changed from 4.5 mass parts to 0.1 mass parts. In the same manner, an inkjet receiving agent (I′-3) and an inkjet recording medium (II′-3) were obtained.

[Comparative Example 4]
Except having changed the usage-amount of Zircozol ZA-20 [the 1st rare element chemical industry Co., Ltd. make, 20 mass% aqueous solution of zirconium acetate] from 4.5 mass parts to 11 mass parts, it is the same as that of Example 1. By the method, an inkjet receiver (I′-4) and an inkjet recording medium (II′-4) were obtained.

[Evaluation Method for Printability 1]
Using a wide format inkjet printer (PX-7000, manufactured by Seiko Epson Corporation), the following 9 colors of aqueous pigment inks were overlaid and printed in the order exemplified below on the inkjet recording media obtained in Examples and Comparative Examples. Each time printing was performed using each ink, the degree of ink absorption of the formed printed image was visually observed and evaluated.

[Method for evaluating printability 2]
Using a wide format ink jet printer (Nihon Hired Packard Co., Ltd., Designjet 5500 ps), the following 9 colors of aqueous pigment inks are printed in the order illustrated below on the ink jet recording media obtained in Examples and Comparative Examples. did. Each time printing was performed using each ink, the degree of ink absorption of the formed printed image was visually observed and evaluated.

[Description of 9 color inks]
・ C100% ink ・ Y100% ink ・ M100% ink ・ Bk100% ink ・ 200% total ink consisting of C100% and M100% ・ 200% total ink consisting of M100% and Y100% ・ Y100% and C100% A total of 200% ink consisting of: C100%, M100% and Y100% total 300% ink. C100%, M100%, Y100% and K100% total 400% ink

A: A print image formed after printing using the above “total 400% of ink” was free from color unevenness, bleeding, cracks, etc., and a uniform print image was formed.
○: The printed image formed after printing using the “total of 300% ink” had no color unevenness, bleeding, cracks, etc., but was subsequently superimposed on the printed image, Some blurring and color unevenness occurred in a printed image obtained by printing using the “400% ink in total”.
○ △: “200% total ink composed of C100% and M100%”, “200% total ink composed of M100% and Y100%”, and “200% total composed of Y100% and C100%” In the print image formed by printing using the “ink”, no color unevenness, blurring, cracks, etc. occurred, but the image was continuously superimposed on the print image, and the “300% total ink” The printed image obtained by printing using the ink developed blurring and color unevenness.
Δ: Color unevenness, blurring, cracks, etc. occur in the printed image formed after printing using the “C100% ink”, “Y100% ink”, “M100% ink” and “Bk100% ink”. Although it was not, bleeding and color unevenness occurred in the print image obtained by successively superimposing on the print image and printing using the “200% ink in total”.
X: Occurrence of bleeding, color unevenness, and cracks in the obtained printed image when printing was performed using any of the inks “C100% ink”, “Y100% ink”, “M100% ink”, and “Bk100% ink” It was observed.

[Evaluation method of water resistance]
(Evaluation of water resistance by color density)
For each of the ink jet recording media, an ink jet printer (manufactured by Seiko Epson Corporation, PX-7000) is used, and each color of the aqueous pigment ink of cyan (C), magenta (M), yellow (Y), and black (Bk) is used. A 100% solid image was printed separately to obtain a 100% solid image of each color.

  Next, the color density of each 100% solid image obtained above was measured using a color density measuring device (DensiEye700 manufactured by X-rite) to obtain the color density (color density before immersion) of each printed matter.

  Next, the printed matter was immersed in water at 25 ° C. and left for 6 hours. After immersion, the printed matter was left for 1 day under conditions of a temperature of 25 ° C. and a humidity of 65%, and was sufficiently dried.

  The color density of each printed product after drying was measured by the same method as described above to obtain the color density (color density after immersion) of each printed product.

  Based on the color density before immersion, the color density after immersion, and the following formula (1), the color density retention before and after immersion in water was calculated.

  Formula (1) Color density retention ratio (%) = [(Color density after immersion) / (Color density before immersion)] × 100

  The average value of color density retention of 100% solid images of each color obtained by printing using cyan, magenta, yellow and black aqueous pigment inks determined above was calculated and evaluated based on the following evaluation criteria. .

A: The average value of the color density retention rate is 81% or more and 100% or less B: The average value of the color density retention rate is 61% or more and less than 80% B: The average value of the color density retention rate is 41% or more and 60% Less than% Δ: The average value of the color density retention rate is less than 40%. X: The printed matter swelled and dissolved, and the image was not retained.

[Evaluation method of scratch resistance]
The surface of nine printed materials consisting of 100% to 400% solid images obtained by printing using each of the nine color inks was rubbed with a cotton swab containing enough water under a load of about 500 g. . The state of the printed image before and after the rubbing was visually evaluated under the following conditions.

A: No peeling or discoloration of ink was observed in all printed materials, and there was no change at all compared with that before rubbing.
○: The printed material consisting of a 100% solid image showed some peeling of the ink, discoloration, etc., but the other printed materials did not change at all compared to before the abrasion.
○ Δ: In the printed matter composed of 100% and 200% solid images, some ink peeling or discoloration was observed, but the other printed matter was not changed at all as compared with that before rubbing.
(Triangle | delta): The peeling of ink, discoloration, etc. were seen by the printed matter which consists of a 100% solid image, a 200% solid image, and a 300% solid image.
×: Ink peeling or discoloration was observed in all printed materials.

Abbreviations in Tables 1 to 3 will be described below.
Zircosol ZA-20: manufactured by Daiichi Rare Element Chemical Co., Ltd., 20% by mass aqueous solution of zirconium acetate Zircozole ZC-20: manufactured by Daiichi Rare Elemental Chemical Co., Ltd., 20% by mass aqueous solution of zirconium oxychloride Zircozole ZN: manufactured by Daiichi Rare Element Chemical Industry Co., Ltd., 25% by mass aqueous solution of zirconium nitrate • Zirconium sulfate: manufactured by Daiichi Rare Elemental Chemical Co., Ltd., 18% by mass aqueous solution of zirconium sulfate • Zircozol AC-7: No. 1 One rare element chemical industry, 13 mass% aqueous solution of ammonium zirconium carbonate and "content ratio of zirconium compound (mass%)" are the urethane resin (A), the polyvinyl alcohol (B), and the zirconium compound ( C represents the mass ratio of the zirconium compound (B) to the total amount of the water-soluble polyvalent metal salt (D).

Claims (10)

Urethane resin (A) having sulfonic acid group or sulfonate group, polyvinyl alcohol (B), zirconium compound (C), water-soluble polyvalent metal salt (D) other than zirconium compound (C), and aqueous medium (E), and the zirconium compound (C) is a total of the urethane resin (A), the polyvinyl alcohol (B), the zirconium compound (C), and the water-soluble polyvalent metal salt (D). An ink jet receiving agent which is contained in a range of 0.2% by mass to 15% by mass with respect to the mass , and wherein the water-soluble polyvalent metal salt (D) is a magnesium salt or a calcium salt . The ink jet receiving agent according to claim 1, which forms a swelling type ink receiving layer. The inkjet receiving agent according to claim 1, wherein the urethane resin (A) has a carbonate bond. The inkjet receiving agent according to claim 1, wherein the content of the zirconium compound (C) is 0.5% by mass to 30% by mass with respect to the total amount of the polyvinyl alcohol (B). The inkjet receiving agent according to claim 1, wherein the zirconium compound (C) is at least one selected from the group consisting of zirconium acetate, ammonium zirconium carbonate, zirconium oxychloride, zirconium nitrate, and zirconium sulfate. The inkjet receiving agent according to claim 1, wherein the polyvinyl alcohol (B) has a saponification degree in the range of 70 mol% to 99 mol%. The inkjet receiving agent according to claim 1 , wherein the magnesium salt is magnesium chloride or magnesium acetate, and the calcium salt is calcium chloride. The ink jet receiving agent according to claim 1, further comprising an epichlorohydrin polyamide resin. An ink receiving layer obtained by removing the aqueous medium (E) after coating or impregnating the inkjet receiving agent according to any one of claims 1 to 8 on the substrate. An ink jet recording medium formed on. A printed matter, wherein the ink receiving layer of the ink jet recording medium according to claim 9 is printed using an aqueous pigment ink.