JP2003080840A - Ink-jet recording sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink-jet recording sheet which is hardly discolored in long term storage when applied to full color printing. SOLUTION: The ink-jet recording sheet which forms a recorded image by using liquid ink contains at least one selected from compounds expressed by formula (1) [R1 is a directly bonded 1-12C saturated or unsaturated alkylene group, a phenylene group, or a substituent expressed by formula (2) (R2 and R3 are independently a 1-12C alkyl group; R4 and R5 are independently a hydrogen atom or a methyl group), formula (3) (I is 1 or 2; o and p are independently an integer of 1-11), and formula (4) (R6 -R9 are independently a hydrogen atom or a 1-4C alkyl group; m is 1 or 2)].

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 for forming a recording image using a liquid ink such as an aqueous ink or an oil ink, and particularly, it is printed in full color on the ink jet recording sheet. The present invention relates to an inkjet recording sheet which maintains the characteristics of high image printing density and excellent ink absorbency and which does not discolor during long-term storage, which is a drawback of conventional inkjet recording sheets.

[0002]

2. Description of the Related Art An ink jet recording system in which liquid ink is ejected from a fine nozzle onto a recording medium to form an image,
Printers for terminals, facsimiles, plotters, form printing, etc. because of low noise during recording, easy colorization, high-speed recording, and lower cost than other printing devices Widely used in. On the other hand, the rapid spread of printers, high definition and high speed,
Furthermore, with the advent of digital cameras, advanced characteristics have also been demanded on the recording medium side. In other words, there is a strong demand for the realization of a recording material having excellent ink absorbency, recording density, water resistance and storage stability, and having image quality and storage stability comparable to those of silver halide photography.

In order to meet such demands, many proposals have been made regarding a sheet having an ink receiving layer mainly composed of a pigment and an adhesive on a support. For example, a coating layer composed of amorphous silica and a polymer binder (JP-A-55-51583, JP-A-57-157786 and JP-A-62-158084), a coating layer having an ink adsorbing pigment such as zeolite ( JP-A-56-14417
No. 2), a coating layer composed of finely divided silicic acid and a water-soluble resin (JP-A-56-148583), and a coating layer containing a porous cationic alumina hydrate (JP-A-60-2).
No. 32990) is proposed on the support.

Further, from the viewpoint of improving the water resistance of printing, a cationic polymer (JP-A-56-84992, JP-A-6-84992, JP-A-6-84992) is used.
No. 0-49990, No. 61-125878), a basic latex (Japanese Patent Laid-Open No. 57-36692) and the like have been proposed in the ink receiving layer.

Further, from the viewpoint of improving the storability of printing, a method of adding at least one of metal oxides such as phosphotungstic acid, phosphomolybdic acid and chromic chloride, metal chlorides or tannic acid (special characteristics Kaisho 57-8798
7), a method of adding antioxidants such as hindered phenols (JP-A-57-74192), and a method of adding hindered amines (JP-A-61-1465).
91), a benzophenone-based, benzotriazole-based, phenylsalicylic acid-based, or other ultraviolet absorber (JP-A-57-74193 and 57-879).
88, 63-222885), a method for adding a thiourea compound (JP-A-61-163886), and a specific mercapto compound such as 2-mercaptobenzothiazole and 2-mercaptobenzimidazole. (JP-A-61-177279), a method of adding a dithiocarbamate, a thiuram salt, a thiocyanate or a thiocyanate (JP-A-7-3148).
No. 82) has been proposed.

However, full-color ink jet recorded images formed using these techniques are still insufficient for discoloration during long-term storage.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to significantly improve discoloration during long-term storage, which is a drawback of conventional ink jet recording sheets when printed in full color on ink jet recording sheets. And an inkjet recording sheet.

[0008]

The present invention includes the following aspects. [1] An inkjet recording sheet for forming a recorded image using a liquid ink, wherein the recording sheet contains at least one compound selected from the compounds represented by the general formula (1). Sheet.

[Chemical 8] [Wherein R ₁ is a direct bond, a C _{1 to} C ₁₂ saturated or unsaturated alkylene group, a phenylene group or the general formula (2) to
It represents a substituent represented by (4). ]

[Chemical 9] [In the formula, R ₂ and R ₃ each represent a C _{1 to} C ₁₈ alkyl group, and R ₄ and R ₅ each represent a hydrogen atom or a methyl group. ]

[Chemical 10] [In the formula, 1 is 1 or 2, o and p are 1 to 11 respectively.
Represents the integer. ]

[Chemical 11] [In formula, R < ₆ > -R < ₉ > is a hydrogen atom or C < ₁ > -C, respectively.
_{4 represents} an alkyl group, and m represents 1 or 2. ]

[2] at least one selected from the homopolymer of the diallylamine compound represented by the general formula (5) and the copolymer of the ethylenically unsaturated compound copolymerizable with the general formula (5). An ink jet recording sheet according to [1], characterized in that

[Chemical 12] [In the formula, R ₁₀ and R ₁₁ each represent a hydrogen atom or a methyl group, R ₁₂ represents a hydrogen atom or a C _{1 to} C ₄ alkyl group, and HX represents an acid. [3] The inkjet recording sheet according to [1], wherein R ₁ of the general formula (1) is the general formula (2). [4] The inkjet recording sheet according to [1], wherein R ₁ of the general formula (1) is the general formula (3). [5] The inkjet recording sheet according to [1], wherein the compound represented by the general formula (1) is 1,3-bis (hydrazinocarbonylethyl) -5-isopropylhydantoin. [6] The compound represented by the general formula (1) is 3,3′-
The ink jet recording sheet according to [1], which is thiodipropionic acid dihydrazide. [7] The inkjet recording sheet according to any one of [1] to [6], which further comprises at least one thioether compound. [8] The inkjet recording sheet according to [7], wherein the thioether compound is a compound represented by the general formula (6) or the general formula (7).

[Chemical 13]

[Chemical 14] [In the formula, R_Thirteen, R₁₄, R₁₅Are each C₁~ C_Four
Alkyl group of C₁~ C _FourHydroxyalkyl group
Is C₁~ C_FourThe dihydroxyalkyl group of r, u, v
Are 1 or 2 respectively, q is an integer of 1 to 3, and t is 1
Represents an integer of 6; ]

[9] The compound represented by the general formula (6) is
The inkjet recording sheet according to [8], which is 1,2-bis (2-hydroxyethylthio) ethane. [10] In an inkjet recording sheet having an ink receiving layer containing inorganic fine particles on a support, the inorganic fine particles have an average primary particle diameter of 30 nm or less, and B
The inkjet recording sheet according to any one of [1] to [9], which is silica having a specific surface area of 200 m ² / g or more measured by the ET method. [11] The inkjet recording sheet according to [1] to [10], wherein a cast gloss layer is provided on the inkjet recording sheet. [12] The ink jet recording sheet according to [1] to [10], which has a cast ink receiving layer. [13] The inkjet recording sheet according to [1] to [10], wherein the cyan dye used in the liquid ink is a phthalocyanine dye.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors, in an ink jet recording sheet for forming a recorded image using a liquid ink such as an aqueous ink, are selected from compounds represented by the general formula (1) in the recording sheet. By containing at least one kind, it is possible to obtain an ink jet recording sheet which greatly improves the discoloration during long-term storage, which is a drawback of the conventional ink jet recording sheet, when printed in full color on the ink jet recording sheet. The present invention has been completed and the present invention has been completed.

[Chemical 15] [In the formula, R ₁ is a direct bond, a C _{1 to} C ₁₂ saturated or unsaturated alkylene group, a phenylene group, or the general formula (2).
~ Represents a substituent represented by (4). R ₁ is preferably (CH ₂ ) n, a phenylene group or a substituent represented by any one of formulas (2) to (4), and n represents 0 or an integer of 1 to 10. ]

[Chemical 16] [In the formula, R ₂ and R ₃ each represent a C _{1 to} C ₁₈ alkyl group, and R ₄ and R ₅ each represent a hydrogen atom or a methyl group. ]

[Chemical 17] [In the formula, 1 is 1 or 2, o and p are 1 to 11 respectively.
Represents the integer. ]

[Chemical 18] [In formula, R < ₆ > -R < ₉ > is a hydrogen atom or C < ₁ > -C, respectively.
_{4 represents} an alkyl group, and m represents 1 or 2. ]

Specific examples of the compound represented by the general formula (1) include oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide,
Adipic acid dihydrazide, pimelic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, tetradecanedioic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide.
Phthalic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, 1,3-bis (hydrazinocarbonylethyl) hydantoin, 1,3-bis (hydrazinocarbonylethyl) -5-methylhydantoin,
1,3-bis (hydrazinocarbonylethyl) -5-ethylhydantoin, 1,3-bis (hydrazinocarbonylethyl) -5-n-propylhydantoin, 1,3-
Bis (hydrazinocarbonylethyl) -5-isopropylhydantoin, 1,3-bis (hydrazinocarbonylethyl) -5-n-butylhydantoin, 1,3-bis (hydrazinocarbonylethyl) -5-sec-butylhydantoin 1,3-bis (hydrazinocarbonylethyl) -5-n-amylhydantoin, 1,3-bis (hydrazinocarbonylethyl) -5-n-hexylhydantoin, 1,3-bis (hydrazinocarbonylethyl)
-5-n-octylhydantoin, 1,3-bis (hydrazinocarbonylethyl) -5-laurylhydantoin, 1,3-bis (hydrazinocarbonylethyl) -5
-Stearylhydantoin, 1,3-bis (hydrazinocarbonylethyl) -5,5-dimethylhydantoin,
1,3-bis (hydrazinocarbonylethyl) -5-ethyl-5-methylhydantoin, 1,3-bis (hydrazinocarbonylethyl) -5,5-diethylhydantoin, 1-hydrazinocarbonylethyl-3- ( 2-Methylhydrazinocarbonylethyl) hydantoin, 1-hydrazinocarbonylethyl-3- (2-methylhydrazinocarbonylethyl) -5-methylhydantoin, 1-
Hydrazinocarbonylethyl-3- (2-methylhydrazinocarbonylethyl) -5-isopropylhydantoin, 1-hydrazinocarbonylethyl-3- (2-methylhydrazinocarbonylethyl) -5,5-dimethylhydantoin, 1, 3-bis (2-methylhydrazinocarbonylethyl) hydantoin, 1,3-bis (2-methylhydrazinocarbonylethyl) -5-methylhydantoin, 1,3-bis (2-methylhydrazinocarbonylethyl) -5 -Isopropylhydantoin, 1,3-bis (2-methylhydrazinocarbonylethyl) -5,5
-Dimethylhydantoin,

2,2'-thiodiglycolic acid dihydrazide, 3,3'-thiodipropionic acid dihydrazide, 4,
4'-thiodibutanoic acid dihydrazide, 6,6'-thiodicaproic acid dihydrazide, 8,8'-thiodicaprylic acid dihydrazide, 10,10'-thiodicapric acid dihydrazide, 12,12'-thiodilauric acid dihydrazide,
2,2'-dithiodiglycolic acid dihydrazide, 3,3 '
-Dithiodipropionic acid dihydrazide, 4,4'-dithiodibutanoic acid dihydrazide, 6,6'-dithiodicaproic acid dihydrazide, 8,8'-dithiodicaprylic acid dihydrazide, 10,10'-dithiodicapric acid dihydrazide, 12, 12'-dithiodilauric acid dihydrazide,

3,3'-thiobis (2-aminopropionic acid hydrazide), 3,3'-thiobis (2-N-methylaminopropionic acid hydrazide), 3,3'-thiobis (2-N, N-dimethyl) Aminopropionic acid hydrazide), 3,3′-thiobis (2-N-ethylaminopropionic acid hydrazide), 3,3′-thiobis (2-N,
N-diethylaminopropionic acid hydrazide), 3,
3'-dithiobis (2-aminopropionic acid hydrazide), 3,3'-dithiobis (2-N-methylaminopropionic acid hydrazide), 3,3'-dithiobis (2-
N, N-dimethylaminopropionic acid hydrazide),
3,3′-dithiobis (2-N-ethylaminopropionic acid hydrazide), 3,3′-dithiobis (2-N, N
-Diethylaminopropionic acid hydrazide) and the like.

Among these compounds, the general formula (1)
The compound in which R ₁ is the general formula (2) is preferably used because it is excellent not only in preventing discoloration of images but also in preserving white paper.

[Chemical 19] [In the formula, R ₂ and R ₃ each represent a C _{1 to} C ₁₈ alkyl group, and R ₄ and R ₅ each represent a hydrogen atom or a methyl group. ]

Of these, 1,3-bis (hydrazinocarbonylethyl) -5-isopropylhydantoin is particularly preferably used because it has a particularly high effect of preventing discoloration of images.

Further, the compound in which R ₁ of the general formula (1) is the general formula (3) is particularly excellent in the effect of preventing discoloration of images, and is therefore preferably used.

[Chemical 20] [In the formula, 1 is 1 or 2, o and p are 1 to 11 respectively.
Represents the integer. ]

Of these, 3,3'-thiodipropionic acid dihydrazide is particularly preferably used because it is particularly excellent in the effect of preventing discoloration of images.

In the present invention, the general formula (5) is further added.
By containing at least one selected from the homopolymer of the diallylamine compound represented by and the copolymer of the general formula (5) and the ethylenically unsaturated compound copolymerizable with the general formula (5), a high synergistic effect for preventing discoloration can be obtained. Is recognized.

[Chemical 21] [In the formula, R ₁₀ and R ₁₁ each represent a hydrogen atom or a methyl group, R ₁₂ represents a hydrogen atom or a C _{1 to} C ₄ alkyl group, and HX represents an acid. ]

The acid represented by HX of the general formula (5) may be either an inorganic acid or an organic acid. As the inorganic acid, hydrochloric acid,
Sulfuric acid, nitric acid, phosphoric acid, pyrophosphoric acid, metaphosphoric acid, and the like, and organic acids include formic acid, acetic acid, propionic acid, methanesulfonic acid, p-toluenesulfonic acid, and the like. Among these acids, hydrochloric acid and sulfuric acid are particularly effective in preventing discoloration and are preferably used.

The homopolymer and copolymer of the diallylamine compound represented by the general formula (5) include, for example, polydiallylamine hydrochloride, polydiallylamine sulfate, polydiallylamine phosphate, polydiallylamine acetate and polydiallylamine. Of propionate,
Methanesulfonic acid salt of polydiallylamine, polydiallylmethylamine hydrochloride, polydiallylmethylamine sulfate, polydiallylethylamine hydrochloride, polydiallylethylamine sulfate, polydiallyl-n-propylamine hydrochloride, polydiallyl-n-butylamine hydrochloride , Poly (di-2-methylallylamine hydrochloride), poly (di-2
-Methylallylamine sulfate), diallylamine hydrochloride / acrylamide copolymer, diallylamine sulfate / acrylamide copolymer, diallylamine phosphate / acrylamide copolymer, diallylmethylamine hydrochloride /
Acrylamide copolymer, diallylmethylamine sulfate / acrylamide copolymer, diallylamine hydrochloride / sulfur dioxide copolymer, diallylamine sulfate / sulfur dioxide copolymer, diallylmethylamine hydrochloride / sulfur dioxide copolymer, etc. To be R ₁₀ and R ₁₁ are preferably hydrogen atoms. R _{12 is} also preferably a hydrogen atom. By using these, not only the water resistance is improved, but there is a synergistic effect in preventing discoloration.

In the present invention, a thioether compound,
In particular, the combined use of the compounds represented by the general formula (6) or the general formula (7) has a further synergistic effect for preventing discoloration of images.

[Chemical formula 22]

[Chemical formula 23] Wherein _each R _13, R _{14, R 15 is,} C 1 -C
₄ alkyl group, C ₁ -C ₄ hydroxyalkyl group or C ₁ -C ₄ dihydroxyalkyl group is replaced with r, u,
v represents 1 or 2, q represents an integer of 1 to 3, and t represents an integer of 1 to 6. ]

Specific examples of the compounds represented by the general formulas (6) and (7) include 2,2'-thiodiethanol, 2,2'-dithiodiethanol and 1,2-bis (2-hydroxyethyl). Thio) ethane, 1,2-bis (2-hydroxyethyldithio) ethane, 2,2′-bis (2-hydroxyethylthio) diethyl sulfide,
2,2'-bis (2-hydroxyethylthio) diethyl disulfide, bis (2-hydroxyethylthio) methane, bis (2-hydroxyethyldithio) methane, 1,
3-bis (2-hydroxyethylthio) propane, 1,
3-bis (2-hydroxyethyldithio) propane,
1,4-bis (2-hydroxyethylthio) butane,
1,4-bis (2-hydroxyethyldithio) butane,
1,6-bis (2-hydroxyethylthio) hexane,
1,6-bis (2-hydroxyethyldithio) hexane, ethylthioethanol, ethyldithioethanol,
n-propylthioethanol, isopropylthioethanol, isopropyldithioethanol, n-butylthioethanol, 1-ethylthio-1- (2-hydroxyethylthio) methane, 1-ethylthio-2- (2-hydroxyethylthio) ethane, 1-ethylthio-3- (2-
Hydroxyethylthio) propane, 1-ethylthio-4
-(2-hydroxyethylthio) butane, 1,1-bis (2,3-dihydroxypropylthio) methane, 1,2
-Bis (2,3-dihydroxypropylthio) ethane,
1,2-bis (2,3-dihydroxypropylthio) ethane, 1,3-bis (2,3-dihydroxypropyldithio) propane, 1,4-bis (2,3-dihydroxypropylthio) butane, 1, 6-bis (2,3-dihydroxypropylthio) hexane, 1-ethylthio-2-
(2,3-dihydroxypropylthio) ethane and the like can be mentioned.

Among these compounds, 1,2-bis (2-hydroxyethylthio) ethane is particularly preferably used because it has a particularly high discoloration preventing effect and a high safety.

The reason why the full-color ink jet recorded image is discolored during long-term storage is considered to be that the dye used is easily oxidized by a gas in the air, particularly a gas having a strong oxidizing power such as ozone. In particular, when a phthalocyanine dye is used as a dye for cyan ink, the discoloration is remarkable.

The reason why the compound represented by the general formula (1) found this time is particularly effective for preventing discoloration is not clear, but the compound represented by the general formula (1) itself is oxidized by ozone. Since it is easily oxidized by a strong gas, it is considered that the dye is oxidized before being oxidized, and as a result, the dye is prevented from being oxidized.

Further, since the compound produced by oxidizing the compound represented by the general formula (1) is colorless, it is also a great feature that it does not cause problems such as yellowing of the background.

The content of the compound represented by the general formula (1) in the ink jet recording sheet is 0.1.
To 4 g / ^{m 2} approximately, and preferably from 0.2 to 2 g / ^{m 2} approximately. Incidentally, if it is less than 0.1 g / m ² , the storage stability improving effect may be insufficient, and if it is more than 4 g / m ² , the image quality may be deteriorated.

When the homopolymer and copolymer of the compound represented by the general formula (5) are used in combination, the content thereof is generally 1 to 100 parts by mass, preferably 5 to 50 parts by mass, relative to 100 parts by mass of the pigment. Adjusted in range. If the blending amount is small, it is difficult to obtain the effect of improving the print water resistance and the print density, and if the blending amount is large, the print density is lowered or the image bleeding is likely to occur.

As a method for producing an ink jet recording sheet containing the compound represented by the general formula (1), for example, a method of coating or impregnating a base paper with a coating solution containing a specific compound by a size press or the like in a papermaking step, A coating machine for ink-receptive layer coating liquid obtained by mixing ink-absorbing pigments, adhesives, and specific compounds on substrates such as paper (acidic paper, neutral paper), synthetic paper, plastic film, and non-woven fabric. And a method of forming an ink receiving layer by coating and drying, and a method of applying a coating liquid containing a specific compound on the ink receiving layer made of a pigment, an adhesive, and a specific polymer.

Of these, the method of incorporating the above-mentioned specific compound in the ink receiving layer is preferable because it is more effective in preventing discoloration of the image.

When the compound represented by the general formula (1) is water-soluble, an aqueous solution is added to the coating liquid for the ink receiving layer or coated on the ink receiving layer for use. On the other hand, when the solubility in water is low, water is used as the dispersion medium and finely pulverized by a stirring / pulverizing machine such as a ball mill, attritor, sand mill or colloid mill before use.

As the support of the ink jet recording paper, paper (acidic paper, neutral paper), synthetic paper, plastic film, non-woven fabric or plastic film laminated with coated paper or high-quality paper via an adhesive, Alternatively, a paper laminated with plastic is used. Examples of such plastic film include films of polyester, polypropylene, nylon and the like.

Examples of pigments contained in the ink receiving layer include zeolite, light calcium carbonate, heavy calcium carbonate, magnesium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium oxide and zinc oxide.
Zinc sulfide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, silica, aluminum hydroxide, alumina, alumina hydrate, aluminosilicate, boehmite, pseudoboehmite, lithopone, urea-formalin. Examples thereof include resin fillers. These may be used alone or in combination of two or more.

Of these, silica, alumina, and alumina hydrate are preferable because they have excellent ink absorbency.

Furthermore, the average particle size of the primary particles is 30 nm.
It is preferable to use silica having a specific surface area of 200 m ² / g or more as measured by the BET method, since a high quality image can be obtained. The lower limit of the primary particles is not particularly limited, but 1
nm or more is preferable, and the upper limit of the specific surface area is not particularly limited, but 500 m ² / g or less is preferable.

The amount of pigment used in the ink receiving layer is
20 to 90% by weight based on the solid content of the ink receiving layer,
It is preferably about 30 to 80% by weight. If it exceeds 90% by weight, the coating strength of the ink receiving layer will decrease, and if it is less than 20% by weight, the ink absorbency will decrease, and the ink drying property after recording may be insufficient and the image quality may deteriorate. is there.

In the present invention, it is also possible to use as the cationic polymer, a polymer which dissociates when it is dissolved or emulsified in water and exhibits a cationic property. As such a cationic polymer, for example,
Polydiallyldimethylammonium chloride, diallyldimethylammonium chloride / acrylamide copolymer, diallyldimethylammonium chloride / sulfur dioxide copolymer, polyallylamine hydrochloride, N-vinylacrylamidine hydrochloride / acrylamide copolymer, dialkylamine / epichloro Hydrin addition polymer, polyamide polyamine epichlorohydrin polymer,
Dicyandiamide / formalin polycondensate, polyalkylenepolyamine / dicyandiamide polycondensate, polyethyleneimine hydrochloride, poly (meth) acryloyloxyalkyldialkylamine hydrochloride, (meth) acryloyloxyalkyldialkylamine hydrochloride / acrylamide copolymer, poly (Meth) acryloyloxyalkyltrialkylammonium chloride, (meth) acryloyloxyalkyltrialkylammonium chloride / acrylamide copolymer, poly (meth) acrylamidoalkyldialkylamine hydrochloride, (meth) acrylamidoalkyldialkylamine hydrochloride / acrylamide Polymer, poly (meth) acrylamidoalkyltrialkylammonium chloride, (meth) acrylamidoalkylt Alkyl ammonium chloride,
Examples thereof include acrylamide copolymers.

In the ink receiving layer, as an adhesive, for example, starch derivatives such as oxidized starch and etherified starch, cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, casein, gelatin, soybean protein,
Fully (partially) saponified polyvinyl alcohol, silicon-modified polyvinyl alcohol, acetoacetyl group-modified polyvinyl alcohol, styrene-maleic anhydride copolymer salt, styrene-butadiene latex, acrylic latex, polyester polyurethane latex, vinyl acetate A water-based adhesive such as latex or an organic solvent-soluble resin such as polymethylmethacrylate, polyurethane resin, unsaturated polyester resin, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral or alkyd resin may be used alone or in combination. These adhesives are generally used in an amount of 1 to 20 with respect to 100 parts by weight of the pigment.
It is used in an amount of about 0 parts by weight, preferably about 10 to 100 parts by weight.

Further, in the ink receiving layer, a pigment dispersant, a thickener, a crosslinking agent, a fluidity modifier, a defoaming agent, a foam suppressor,
A release agent, a foaming agent, a penetrating agent, a coloring dye, a coloring pigment, a fluorescent whitening agent, an antiseptic agent, an antibacterial agent, a water resistant agent and the like can be added as appropriate.

For the ink receiving layer, the coating liquid for the ink receiving layer is applied by a bar coater, a blade coater, an air knife coater,
It is formed by applying a coating method such as a gravure coater, a die coater, and a curtain coater on at least one surface of the support so that the coating amount after drying is about ² to 30 g / m ² . Incidentally, if the coating amount is less than 2 g / m ² , the recording image quality may be deteriorated, and if it is more than 30 g / m ² , the coating strength may be deteriorated.

After forming the ink receiving layer, it is also possible to impart surface smoothness through a roll nip under pressure with a super calender or gloss calender for the purpose of imparting high gloss.

A gloss layer may be further provided on the above-mentioned ink receiving layer. This glossy layer can have a resin as a main component. It may also be configured by containing a pigment and a resin. The gloss layer is preferably porous or liquid-permeable so as not to impair the gloss so that the ink can be quickly passed through or absorbed. In order to do so, it is advisable to add a pigment or select a drying condition such that the resin is not completely formed into a film within a range that does not reduce the gloss.

The pigment used in the gloss layer may be the same as that used in the ink receiving layer, but the gloss, transparency,
From the viewpoint of ink absorbability, colloidal silica, amorphous silica, aluminum oxide, aluminosilicate, zeolite, synthetic smectite and the like are preferable. These pigments are preferably contained in the gloss layer in an amount of 10 to 80% by weight. The larger the BET specific surface area of the pigment, the more excellent the ink absorbency, and therefore, it is preferably 150 m ² / g or more. There is no particular upper limit, but it is up to about 1000 m ² / g, 700 m ² / g
It is preferably not more than about this level. The average particle diameter of the pigment (in the case of aggregated particles, the diameter of aggregated particles) is preferably 0.01 to 5 μm,
It is more preferably 0.05 to 1 μm. More preferably, it is 0.05 to 0.8 μm. Particle size is 0.01μm
If it is less than 5 μm, the effect of improving ink absorbency may be poor, and if it exceeds 5 μm, gloss and print density may be reduced. As the pigment, the average particle size of the primary particles is 3 nm or more and 40 nm or less, and the average particle size of the secondary particles is 1
The use of silica fine particles having a particle size of 0 nm or more and 500 nm or less makes gloss and ink absorbability particularly excellent. When the gloss layer is formed with a pigment as a main component (10 to 80%), the ink absorbency is particularly preferable.

In this case, since the gloss layer is excellent in ink absorbency and transparency, when a cationic compound is blended in the gloss layer, the ink dye is efficiently fixed to the gloss layer, and in combination with the transparency of the gloss layer, the print density is increased. Very easy to become. As the resin for the gloss layer, a water-soluble resin (for example, polyvinyl alcohol such as polyvinyl alcohol, cation-modified polyvinyl alcohol, silyl-modified polyvinyl alcohol, casein, soybean protein, synthetic protein, starch, cellulose derivative such as carboxymethyl cellulose and methyl cellulose) , A styrene-butadiene copolymer, a conjugated diene polymer latex such as a methyl methacrylate-butadiene copolymer, a water-dispersible resin such as a vinyl copolymer latex such as a styrene-vinyl acetate copolymer, an aqueous acrylic resin, Various publicly known resins (adhesives) generally used in the coated paper field such as water-based polyurethane resin and water-based polyester resin are used alone or in combination.

When the gloss layer is formed mainly of a resin, a polymer or copolymer obtained by polymerizing a monomer having an ethylenically unsaturated bond (hereinafter referred to as an ethylenic monomer) (hereinafter collectively referred to as a polymer) Is referred to as “)” as a main component. Further, substituted derivatives of these polymers may be used. In addition, the above-mentioned ethylenic monomer is polymerized in the presence of colloidal silica, and Si
-R (R: polymer component) form a complex or a functional group capable of reacting with colloidal silica such as SiOH group is introduced into the above polymer, and the complex is reacted with colloidal silica. It is also possible to use it in a modified form. When this composite is used, it tends to have excellent gloss and ink absorbency.

Further, in the embodiment in which the gloss layer is obtained by a casting method using a heated mirror surface drum, the resin such as the above-mentioned polymer preferably has a glass transition point of 40 ° C. or higher,
More preferably, it is in the range of 50 to 100 ° C. If the glass transition point is low, film formation will proceed excessively during drying, and the porosity of the surface will decrease, which may result in a decrease in the ink absorption rate. Also, the drying temperature is important, and if the drying temperature is too high, the film formation proceeds too much, and the surface porosity decreases, resulting in a decrease in the ink absorption rate. Conversely, if the drying temperature is too low, the gloss is poor. And the productivity will decrease. A cast method can also be used for the gloss layer. In this mode, the mold releasability from the cast drum tends to be excellent. Although the composite particles are not particularly limited, for example, the average particle size is about 20 to 200 nm.

In the wet method, while the glossy layer coated on the base paper is in a wet state, the glossy developing layer is pressed against the heated mirror-finished drum surface to give a strong glossy finish. In the gelation method, while the glossy layer coated on the base paper is in a wet state, this glossy layer is brought into contact with the gelling agent bath, and the gelled glossy layer is pressed against the heating drum surface to give a strong glossy finish. Is to do. In the rewetting method, the glossy layer in a wet state is once dried, then again brought into contact with the wetting liquid, and then pressed against the surface of the heating drum to give a strong gloss finish.

The coating amount of the gloss layer is 0.2 to about the dry solid content.
30 g / m ^2, preferably from from 1 to 20 g / m ^2.
If the amount is less than 0.2 g / m ² , the gloss may not be sufficient, and if the amount exceeds 30 g / m ² , the ink drying property may be poor or the recording density may be lowered.

Further, a protective layer may be provided on the back surface of the support,
It is of course possible to provide an intermediate layer between the support and the recording layer, and various known techniques in the field of inkjet recording sheet manufacturing can be added.

The liquid ink for forming a recorded image is a recording liquid composed of a colorant, a liquid medium, and other additives. Examples of the colorant include various water-soluble dyes such as direct dyes, acid dyes, and reactive dyes. The liquid medium of the water-based ink may be water alone or a combination of water and a water-soluble organic solvent. Further, oil-based ink may be used. Examples of the water-soluble organic solvent include monohydric alcohols such as ethyl alcohol and isopropyl alcohol, polyhydric alcohols such as ethylene glycol, diethylene glycol, polyethylene glycol and glycerin, triethylene glycol monomethyl ether, triethylin, triethylene glycol monomethyl ether and triethylene. Examples thereof include lower alkyl ethers of polyhydric alcohols such as glycol monoethyl ether. Furthermore, as an additive,
For example, a pH adjusting agent, a sequestering agent, an antifungal agent, a viscosity adjusting agent, a surface tension adjusting agent, a surfactant, and a rust preventive agent can be mentioned.

[0052]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In addition, "part" and "%" in an example show a weight part and weight%, respectively, unless there is particular notice. Example 1

(Preparation of coating liquid A for ink receiving layer) Synthetic amorphous silica (trade name: Fineseal X60, manufactured by Tokuyama Corporation, average particle diameter 5.9 μm, specific surface area 290 m ² / g)
100 parts, silicon modified polyvinyl alcohol (trade name:
R-1130, a 10% aqueous solution of Kuraray Co., Ltd. 250
Part, diallylamine hydrochloride / acrylamide copolymer (trade name: Sumirez Resin 1001, Sumitomo Chemical Co., Ltd.
Of 40% aqueous solution, 10 parts of 1,3-bis (hydrazinocarbonylethyl) -5-methylhydantoin, a small amount of a defoaming agent, a dispersant, and water for an ink receiving layer having a solid content of 15%. A coating liquid A was obtained.

(Preparation of Inkjet Recording Sheet) 6
After providing the ink-receiving layer by coating and drying a wire bar such that the 12 g / m ² coating liquid A for ink-receiving layer in solid content quality paper of 5 g / m ^2, the ink jet Super calendering A recording sheet was created.

Examples 2 to 11 Inkjet ink jets were prepared in the same manner as in Example 1 except that the following compounds were used instead of 1,3-bis (hydrazinocarbonylethyl) -5-methylhydantoin. A recording sheet was created. Example 2: 1,3-bis (hydrazinocarbonylethyl) -5-ethylhydantoin Example 3: 1,3-bis (hydrazinocarbonylethyl) -5-isopropylhydantoin Example 4: 1,3-bis ( Hydrazinocarbonylethyl) -5-sec-butylhydantoin Example 5: 1,3-bis (hydrazinocarbonylethyl) -5,5-dimethylhydantoin Example 6: adipic acid dihydrazide Example 7: succinic acid dihydrazide Example 8: Malonic acid dihydrazide Example 9: 3,3'-thiodipropionic acid dihydrazide Example 10: 3,3'-Dithiodipropionic acid dihydrazide Example 11: 2,2'-thiodiglycolic acid dihydrazide

Example 12 (Preparation of dispersion of sebacic acid dihydrazide) 100 parts of sebacic acid dihydrazide, 5 parts of sulfo group-modified polyvinyl alcohol (trade name: Gocelan L-3266, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), a small amount of interface A composition containing an activator, an antifoaming agent and water and having a solid content concentration of 20% was pulverized with a sand grinder until the average particle size became 0.5 μm to obtain a dispersion liquid.

(Preparation of coating liquid B for ink receiving layer) 100 parts of synthetic amorphous silica (trade name: Fineseal X60, manufactured by Tokuyama Corporation), silicon-modified polyvinyl alcohol (trade name: R-1130, stock company) ) Kuraray's) 10% aqueous solution 2
50 parts, diallylamine hydrochloride / acrylamide copolymer (trade name: Sumirez Resin 1001, Sumitomo Chemical
Co., Ltd.) to obtain 75 parts of 40% aqueous solution, 50 parts of 20% dispersion of sebacic acid dihydrazide, and a small amount of antifoaming agent, dispersant, and water. It was

(Preparation of Inkjet Recording Sheet) 6
After providing the ink-receiving layer by coating and drying a wire bar such that the 12 g / m ² coating liquid B for ink-receiving layer in solid content quality paper of 5 g / m ^2, the ink jet Super calendering A recording sheet was created.

Examples 13 to 15 Ink jet recording sheets were prepared in the same manner as in Example 12 except that the following compounds were used instead of sebacic acid dihydrazide. Example 13: Dodecanedioic acid dihydrazide Example 14: Isophthalic acid dihydrazide Example 15: 3,3'-thiobis (2-aminopropionic acid hydrazide)

Examples 16 to 18 The same procedure as in Example 1 was repeated except that the following compounds were used in place of 10 parts of 1,3-bis (hydrazinocarbonylethyl) -5-methylhydantoin. To prepare an ink jet recording sheet. Example 16: 1,3-bis (hydrazinocarbonylethyl) -5-isopropylhydantoin 10 parts and 1,
2-bis (2-hydroxyethylthio) ethane 10 parts Example 17: 1,3-bis (hydrazinocarbonylethyl) -5-isopropylhydantoin 10 parts and 1,
4-bis (2-hydroxyethylthio) butane 10 parts Example 18: Succinic acid dihydrazide 10 parts and 1,2
10 parts of -bis (2-hydroxyethylthio) ethane

Examples 19 to 21 In Example 3, a diallylamine hydrochloride / acrylamide copolymer (trade name: Sumirez Resin 1001,
An inkjet recording sheet was prepared in the same manner as in Example 3 except that the following compounds were used instead of Sumitomo Chemical Co., Ltd.). Example 19: diallylamine hydrochloride / sulfur dioxide copolymer (trade name: PAS-92, Nitto Boseki Co., Ltd.) Example 20: polydiallylmethylamine hydrochloride (trade name: PAS-M-1, Nitto Boseki) Example 21: Polydiallyldimethylammonium chloride / acrylamide copolymer (trade name: PAS-J-8)
1. Nitto Boseki Co., Ltd.) Example 22

(Preparation of coating liquid C for ink receiving layer) 100 parts of synthetic amorphous silica (trade name: Fineseal X60, manufactured by Tokuyama), 10 parts of silicon-modified polyvinyl alcohol (trade name: R-1130, manufactured by Kuraray) % Aqueous solution 250
Part, diallylamine hydrochloride / acrylamide copolymer (trade name: Sumirez Resin 1001, Sumitomo Chemical Co., Ltd.
A coating liquid C for an ink receiving layer having a solid content concentration of 15%, which is composed of 75 parts of a 40% aqueous solution of Mfg. Co., Ltd.), a small amount of an antifoaming agent, a dispersant and water, was obtained.

(Preparation of Inkjet Recording Sheet) 6
After providing the ink-receiving layer was applied and dried using a wire bar such that the 12 g / m ² on a high-quality paper of 5 g / m ² coating liquid C for the ink receiving layer in solid content, further 1,3-bis (Hydra A 5% aqueous solution of dinocarbonylethyl) -5-isopropylhydantoin was applied and dried with a wire bar so that the solid content was 1.0 g / m ^2, and a super calender treatment was carried out to prepare an inkjet recording sheet.

Example 23 (Preparation of coating liquid D for gloss-developing layer) A composite of styrene-2-ethylhexyl acrylate copolymer and colloidal silica having a glass transition point of 75 ° C. (the copolymer and the colloidal silica are in a weight ratio. 40:60) 100 parts, 5 parts of alkyl vinyl ether / maleic acid derivative copolymer as a thickening / dispersing agent, and 3 parts of lecithin as a releasing agent.
A coating liquid D for 0% gloss development layer was obtained.

(Preparation of Inkjet Recording Sheet) 6
After coating the ink-receiving layer coating liquid of Example 3 with a wire bar on a wood free paper of 5 g / m ² to a solid content of 12 g / m ² and providing an ink-receiving layer, the gloss-developing layer was formed. Immediately after the coating liquid D was applied, it was pressed against a mirror surface drum having a surface temperature of 85 ° C., dried and released from the mold to prepare a gloss type inkjet recording sheet having a gloss layer. The coating amount of the glossy layer at this time was 8 g / m ² in terms of solid content.

Example 24 Example 23 was repeated except that 3,3-bis (hydrazinocarbonylethyl) -5-isopropylhydantoin was replaced with 3,3'-thiodipropionic acid dihydrazide. Similarly, an inkjet recording sheet was prepared.

Example 25 (Preparation of coating liquid E for gloss developing layer) A composite of a styrene-2-ethylhexyl acrylate copolymer and colloidal silica having a glass transition point of 75 ° C. (the copolymer and the colloidal silica are in a weight ratio. 40:60) 100 parts, 1,3-bis (hydrazinocarbonylethyl) -5-isopropylhydantoin 10 parts, alkyl vinyl ether / maleic acid derivative copolymer 5 parts as a thickening / dispersing agent, lecithin 3 as a releasing agent. To obtain a gloss developing layer coating liquid E having a solid content concentration of 30%.

(Preparation of Inkjet Recording Sheet) 6
The coating liquid A for the ink receiving layer of Example 3 was coated on a 5 g / m @ 2 high-quality paper with a wire bar so that the solid content was 12 g / m @ 2, and dried to provide an ink receiving layer. Immediately after applying the liquid E, it was pressed against a mirror surface drum having a surface temperature of 85 ° C., dried and released from the mold to prepare a gloss type inkjet recording sheet. The coating amount of the glossy layer at this time was 8 g / m @ 2 in terms of solid content.

Example 26 (Preparation of coating liquid F for ink receiving layer) 100 parts of synthetic amorphous silica (trade name: Fineseal X60, manufactured by Tokuyama),
Silicon modified polyvinyl alcohol (trade name: R-113
0, Kuraray's 10% aqueous solution 250 parts, diallylamine hydrochloride / acrylamide copolymer (trade name: Sumirez Resin 1001, Sumitomo Chemical Co., Ltd.'s 40% aqueous solution 75 parts, 1,2-bis (2 -Hydroxyethylthio) ethane (10 parts) and a small amount of a defoaming agent, a dispersant, and water to obtain a coating liquid F for an ink-receiving layer having a solid content concentration of 15%.

(Preparation of Inkjet Recording Sheet) 6
Coating solution F for ink receiving layer was coated on a 5 g / m2 high-quality paper with a wire bar so as to have a solid content of 12 g / m2, dried to provide an ink receiving layer, and then coating solution E for gloss developing layer was coated. Immediately after the working, it was pressed against a mirror surface drum having a surface temperature of 85 ° C., dried and released from the mold to prepare a gloss type ink jet recording sheet. The coating amount of the glossy layer at this time was 8 g / m @ 2 in terms of solid content.

Example 27 (Preparation of coating liquid G for ink receiving layer) Vapor phase method silica (trade name: Aerosil 300, average particle size of primary particles 0.00)
7 μm, specific surface area by BET method 300 m ² / g, 100 parts by Nippon Aerosil Industrial Co., Ltd., polyvinyl alcohol (trade name: PVA-235, manufactured by Kuraray Co., Ltd.) 1
200 parts of 0% aqueous solution, diallylamine hydrochloride / sulfur dioxide copolymer (trade name: PAS-92, manufactured by Nitto Boseki Co., Ltd.)
20% aqueous solution of 50%, 1,3-bis (hydrazinocarbonylethyl) -5-isopropylhydantoin 10 parts, and a small amount of a defoaming agent, a dispersant, and water, and a coating liquid for an ink-receiving layer having a solid content concentration of 10%. Got G.

(Preparation of Inkjet Recording Sheet)
Minate coated paper (commercial coated paper (trade name: OK coated
Paper, 127.9 g / m ^Two, Oji Paper Co., Ltd. coated surface
Polyethylene 15 μm laminated on top)
20 g / m in solid content of coating liquid G for ink receiving layer^TwoSo that
Coated with a wire bar and dried to provide an ink receiving layer
After that, super calender process and inkjet recording
I made a sheet for.

Example 28 Example 27 was repeated except that 3,3'-thiodipropionic acid dihydrazide was used in place of 1,3-bis (hydrazinocarbonylethyl) -5-isopropylhydantoin. Similarly, an inkjet recording sheet was prepared.

Comparative Example 1 An ink jet recording sheet was prepared in the same manner as in Example 1 except that 1,3-bis (hydrazinocarbonylethyl) -5-methylhydantoin was not used.

Comparative Example 2 An ink jet recording sheet was prepared in the same manner as in Example 1 except that acetylhydrazide was used instead of 1,3-bis (hydrazinocarbonylethyl) -5-methylhydantoin. It was created.

Comparative Example 3 An ink jet recording sheet was prepared in the same manner as in Example 23 except that 1,3-bis (hydrazinocarbonylethyl) -5-isopropylhydantoin was not used.

Comparative Example 4 An ink jet recording sheet was prepared in the same manner as in Example 27 except that 1,3-bis (hydrazinocarbonylethyl) -5-isopropylhydantoin was not used.

With respect to the ink jet recording sheets obtained in the examples and comparative examples, solid printing of mixed black and cyan inks by cyan, magenta and yellow mixed colors and an image of ISO-400 (" High-definition color digital standard image data ISO / JIS-SCI
D ”, p13, image name: portrait, published by Japan Planning Association), the following evaluations were performed, and the results are shown in Table 1. A phthalocyanine dye is used as a cyan dye in PM-800C.

[Printing Density] The density of the solid printing portion of the mixed black and cyan inks obtained by mixing cyan, magenta, and yellow colors is measured by a Macbeth densitometer (type: RD-914,
It was measured using a Macbeth).

[Ozone Resistance] Ozone resistance having a high correlation with long-term storage stability was evaluated. Solid-color printing of mixed black and cyan inks with cyan, magenta, and yellow mixed colors, and ISO-400 images, ozone concentration 10p
It was left in a pm container for 12 hours. In the case of solid printing, the Macbeth density after the test was measured, and the image residual rate was calculated by the following formula. On the other hand, in the case of an image, the degree of discoloration was visually observed and evaluated. Image residual rate (%) = [(density after processing) / (density before processing)] × 100 (evaluation standard) ◎: No discoloration is observed ○: Discoloration is slightly observed, but good ×: Discoloration There is a problem in practical use because of fading

[Blank paper heat-resistant storage stability] The ink jet recording sheet was allowed to stand for 1 week at 80 ° C and 50%, and L ^* , a ^* , and b ^* of the white paper before and after the test were measured by a color difference meter (type: CR
-321, manufactured by Minolta Co., Ltd., and ΔE ^* _ab was calculated from the following formula. ΔE ^* _ab = [(ΔL ^* ) ² + (Δa ^* ) ² + (Δ
b ^* ) ² ] ^1/2 (where ΔL ^* , Δa ^* and Δb ^* are L before and after the test.
^It means the difference between the coordinates of ^* , a ^* , and b ^* . )

[0082]

[Table 1]

[0083]

As is apparent from Table 1, the ink jet recording sheet of the present invention is a recording sheet which exhibits very little discoloration of images even when exposed to ozone gas and has excellent long-term storage stability. .

Claims (13)

[Claims] 1. An inkjet recording sheet for forming a recorded image using a liquid ink, wherein the recording sheet contains at least one compound selected from the compounds represented by formula (1). Recording sheet. [Chemical 1] [Wherein R ₁ is a direct bond, a C _{1 to} C ₁₂ saturated or unsaturated alkylene group, a phenylene group or the general formula (2) to
It represents a substituent represented by (4). ] [Chemical 2] [In the formula, R ₂ and R ₃ each represent a C _{1 to} C ₁₈ alkyl group, and R ₄ and R ₅ each represent a hydrogen atom or a methyl group. ] [Chemical 3] [In the formula, 1 is 1 or 2, o and p are 1 to 11 respectively.
Represents the integer. ] [Chemical 4] [In formula, R < ₆ > -R < ₉ > is a hydrogen atom or C < ₁ > -C, respectively.
_{4 represents} an alkyl group, and m represents 1 or 2. ] 2. A homopolymer of a diallylamine compound represented by the general formula (5) and at least one selected from a copolymer of the ethylenically unsaturated compound copolymerizable with the general formula (5). The inkjet recording sheet according to claim 1, wherein the sheet is an inkjet recording sheet. [Chemical 5] [In the formula, R ₁₀ and R ₁₁ each represent a hydrogen atom or a methyl group, R ₁₂ represents a hydrogen atom or a C _{1 to} C ₄ alkyl group, and HX represents an acid. ] 3. The ink jet recording sheet according to claim ₁ , wherein R ₁ of the general formula (1) is the general formula (2). 4. The ink jet recording sheet according to claim ₁ , wherein R ₁ of the general formula (1) is the general formula (3). 5. A compound represented by the general formula (1) is 1,
The ink jet recording sheet according to claim 1, which is 3-bis (hydrazinocarbonylethyl) -5-isopropylhydantoin. 6. A compound represented by the general formula (1) is 3,
3. A 3'-thiodipropionic acid dihydrazide.
The inkjet recording sheet described above. 7. The ink jet recording sheet according to claim 1, further comprising at least one thioether compound. 8. The ink jet recording sheet according to claim 7, wherein the thioether compound is a compound represented by the general formula (6) or the general formula (7). [Chemical 6] [Chemical 7] _{Wherein, R 13, R 14, R} 15 each _C 1 -C ₄
A C ₁ -C ₄ hydroxyalkyl group or a C ₁ -C ₄ dihydroxyalkyl group of r, u, v
Are 1 or 2 respectively, q is an integer of 1 to 3, and t is 1
Represents an integer of 6; ] 9. A compound represented by the general formula (6) is 1,2
The inkjet recording sheet according to claim 8, which is -bis (2-hydroxyethylthio) ethane. 10. An ink jet recording sheet having an ink receiving layer containing inorganic fine particles on a support,
10. The ink jet recording sheet according to claim 1, wherein the inorganic fine particles are silica having an average particle diameter of primary particles of 30 nm or less and a specific surface area according to the BET method of 200 m ² / g or more. 11. The ink jet recording sheet according to claim 1, wherein a cast gloss layer is provided on the ink jet recording sheet. 12. The ink jet recording sheet according to claim 1, which has a cast-treated ink receiving layer. 13. The ink jet recording sheet according to claim 1, wherein the cyan dye used in the liquid ink is a phthalocyanine dye.