JP2003089266A - Ink jet recording sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink jet recording sheet which significantly inhibits the discoloration of the ink in the long-term preservation of the sheet as a defect of a conventional ink jet recording sheet, when the sheet is printed in full color, especially the discoloration due to the color fading of a phthalocyanine dye when it is used as a dye for a cyan ink. SOLUTION: In the ink jet recording sheet for forming a recording image is formed using a liquid ink, at least one kind selected from copolymers of a diallyl amine compound, and an ethylene unsaturated compound having a sulfide group or a thiocarbonyl group, is added to the ink jet recording sheet.

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 recorded image using a liquid ink such as a water-based ink or an oil-based ink.
An ink jet that does not discolor during long-term storage, which is a drawback of conventional ink jet recording sheets, while maintaining the characteristics that the image printed in full color on the ink jet recording sheet has high print density and excellent ink absorbency. It relates to a recording sheet.

[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 which is excellent in absorption, recording density, water resistance, and storage stability and which has image quality and storage stability comparable to those of silver salt 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, the full-color ink jet recorded image formed by using these techniques is not yet affected by discoloration during long-term storage, especially when a phthalocyanine dye is used as a dye for cyan ink, discoloration due to its fading. It was insufficient.

[0007]

DISCLOSURE OF THE INVENTION The object of the present invention is, when printed in full color on an ink jet recording sheet, discoloration during long-term storage, which is a drawback of conventional ink jet recording sheets, especially for cyan ink. The present invention relates to an ink jet recording sheet in which discoloration caused by fading is remarkably reduced when a phthalocyanine dye is used as the dye.

[0008]

[1] In an ink jet recording sheet for forming a recorded image using a liquid ink, a diallylamine compound represented by the general formula (1) and a sulfide group or a thiol group are contained in the recording sheet. An ink jet recording sheet comprising at least one selected from a copolymer with an ethylenically unsaturated compound having a carbonyl group.

[Chemical 5] [In the formula, R₁, R_TwoAre hydrogen atom or methyl group respectively
To R_Three, R_FourAre hydrogen atom and C respectively₁~ C_FourThe al
Kill group, C₁~ C_FourHydroxyalkyl group, C ₁~ C
₆Represents an alkoxyalkyl group or a benzyl group. Well
X^-Represents an acid residue. ]

[2] In the general formula (1), R ₁ , R
The inkjet recording sheet according to [1], wherein both ₂ are hydrogen atoms. [3] The inkjet recording sheet according to [1] or [2], wherein in the general formula (1), R ₃ is a hydrogen atom. [4] The ethylenically unsaturated compound having a sulfide group or a thiocarbonyl group is a compound represented by the general formula (2), (3) or (4), [1] to [3]. Inkjet recording sheet.

[Chemical 6]

[Chemical 7]

[Chemical 8] [In the formula, R ₅ and R ₆ are each a C _{1 to} C ₁₈ alkyl group, a C _{2 to} C ₁₈ alkenyl group, a phenyl group, or a benzyl group; R ₇ , R ₈ , and R ₉ are each a hydrogen atom, and C
Alkyl group of ₁ -C _18, alkenyl group of C 2 _{-C 18,} a phenyl group or a benzyl group. ]

[5] The ink jet recording sheet according to [4], wherein the compound represented by the general formula (2) is diallyl sulfide. [6] The compound represented by the general formula (4) is 1-allyl-2.
-The inkjet recording sheet according to [4], which is thiourea. [7] The inkjet recording sheet according to any one of [1] to [4], which further contains acrylamide as a copolymer component. [8] The inkjet recording sheet according to any one of [1] to [7], wherein a cast gloss layer is provided on the inkjet recording sheet. [9] The ink jet recording sheet according to any one of [1] to [7], which has a cast ink receiving layer. [10] The inkjet recording sheet according to any one of [1] to [9], wherein the cyan dye used in the liquid ink is a phthalocyanine dye.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the ink jet recording sheet for forming a recorded image using a liquid ink, the present inventors have added a diallylamine compound represented by the general formula (1) to a sulfide group or a thiol group in the recording sheet. By containing at least one selected from a copolymer with an ethylenically unsaturated compound having a carbonyl group, long-term storage which was a drawback of conventional inkjet recording sheets when printed in full color on inkjet recording sheets The inventors have found that when a phthalocyanine-based dye is used as a dye for cyan ink, especially when a phthalocyanine-based dye is used as the dye for cyan ink, an inkjet recording sheet in which the discoloration due to the fading is significantly reduced can be obtained, and the present invention has been completed.

[0012]

[Chemical 9]

[Wherein R₁, R_TwoAre hydrogen atoms
Or methyl group, R_Three, R_FourAre hydrogen atom and C respectively₁
~ C_FourAlkyl group of C₁~ C_FourHydroxyalkyl
Base, C ₁~ C₆Alkoxyalkyl group or benzyl
Represents a group. Also, X⁻Represents an acid residue. ]

Specific examples of the compound represented by the general formula (1) include diallylamine hydrochloride, diallylamine sulfate, diallylamine nitrate, diallylamine phosphate, diallylamine pyrophosphate, diallylamine metaphosphate and diallylamine acetate. , Diallylamine propionate, diallylamine methanesulfonate, N-methyldiallylamine hydrochloride, N-methyldiallylamine sulfate, N-ethyldiallylamine hydrochloride,
N-ethyldiallylamine sulfate, N-n-propyldiallylamine hydrochloride, Nn-propyldiallylamine sulfate, N- (hydroxyethyl) diallylamine hydrochloride, N- (hydroxyethyl) diallylamine sulfate,
N- (ethoxyethyl) diallylamine hydrochloride, N-
(Ethoxyethyl) diallylamine sulfate, N-benzyldiallylamine hydrochloride, N-benzyldiallylamine sulfate, N, N-dimethyldiallylammonium chloride, N, N-dimethyldiallylammonium sulfonate, N, N-dimethyldiallylammonium phosphate, N , N-dimethyldiallylammonium acetate, N-methyl-N-hydroxyethyldiallylammonium chloride, N-methyl-N-hydroxyethyldiallylammonium sulfonate, N-methyl-N-
Benzyl diallyl ammonium chloride, N-methyl-N-benzyl diallyl ammonium sulfonate,
N, N-diethyldiallylammonium chloride,
N, N-diethyldiallylammonium sulfonate,
N, N-di (2-methylallyl) amine hydrochloride, N, N
-Di (2-methylallyl) amine sulfate, N, N-dimethyl-N, N-di (2-methylallyl) ammonium chloride, N, N-dimethyl-N, N-di (2-methylallyl) ammonium sulfonate, N , N-dimethyl-N-benzyl-N- (2-methylallyl) ammonium chloride, N, N-dimethyl-N-benzyl-N-
(2-methylallyl) ammonium sulfonate etc. are mentioned.

Among these compounds, the general formula (1)
In the above, a compound in which both R ₁ and R ₂ are hydrogen atoms is excellent in image quality and is preferably used.

Among these compounds, the general formula (1)
In the above, a compound in which at least one of R ₃ and R ₄ is a hydrogen atom is particularly preferably used because it has a particularly high effect of preventing discoloration of images.

In the present invention, the ethylenically unsaturated compound having a sulfide group or a thiocarbonyl group which forms a copolymer with the diallylamine compound represented by the general formula (1) is represented by the general formulas (2) and (3). Alternatively, the compound represented by (4) is preferable. General formula (2),
Specific examples of the compound represented by (3) or (4) include allyl methyl sulfide, allyl ethyl sulfide, allyl-n-propyl sulfide, allyl-n-butyl sulfide, diallyl sulfide, allyl-n-octyl sulfide, Allylbenzyl sulfide, allyl phenyl sulfide, methyl vinyl sulfide, ethyl vinyl sulfide, isopropyl vinyl sulfide, n
-Butyl vinyl sulfide, n-octyl vinyl sulfide, n-dodecyl vinyl sulfide, n-octadecyl vinyl sulfide, benzyl vinyl sulfide, phenyl vinyl sulfide, 1-allyl-2-thiourea,
1-allyl-3-methyl-2-thiourea, 1-allyl-3-ethyl-2-thiourea, 1-allyl-3-n-
Butyl-2-thiourea, 1,3-diallyl-2-thiourea, 1-allyl-3-benzyl-2-thiourea,
1-allyl-3-phenyl-2-thiourea, 1-allyl-3,3-dimethyl-2-thiourea, 1,3-diallyl-2-thiourea and the like can be mentioned.

Among these compounds, diallyl sulfide and 1-allyl-2-thiourea are particularly preferable because they have a particularly high effect of preventing discoloration of images.

In the copolymer of the present invention, by further containing acrylamide as a copolymer component, the water resistance is improved, and not only the image but also the long-term storability of the blank paper is excellent, which is particularly preferable.

The proportion of the ethylenically unsaturated compound having a sulfide group or a thiocarbonyl group in the cationic polymer of the present invention is preferably 5 to 50 mol%. If it is less than 5 mol%, the effect of preventing discoloration of the image is small, and if it exceeds 50 mol%, the image quality is greatly deteriorated.

A full-color ink jet recorded image is discolored during long-term storage, and particularly when a phthalocyanine dye is used as a dye for cyan ink, the discoloration due to its fading is a significant factor because the cyan dye having a phthalocyanine skeleton is a gas in the air. Especially, it is considered that it is easily and selectively oxidized by a gas having a strong oxidizing power such as ozone.

The reason why the compound found this time was particularly effective in preventing discoloration is not clear, but since this compound has a cation group, it exists in the vicinity of the dye and more effectively suppresses the oxidation of the cyan dye. It is considered that

The content of the above compound is generally 100% for pigments.
1 to 100 parts by weight, preferably 5 to 50 parts by weight
Adjusted in the range of parts by weight. If the content is small, not only the effect of improving the storage stability is low, but also the effect of improving the print water resistance and the print density is difficult to obtain, and if the content is too large, the print density is lowered, and image bleeding is likely to occur.

As a method for producing an ink jet recording sheet containing the above compound, for example, a method of coating or impregnating a base paper with a coating liquid containing a specific compound by a size press or the like in a papermaking process, an ink absorbing pigment, an adhesive, The ink receiving layer coating liquid obtained by mixing a specific compound is applied to a support such as paper (acidic paper or neutral paper), synthetic paper, plastic film, or non-woven fabric using a coating machine and dried to form an ink. Examples thereof include a method of forming a receiving layer, a method of applying a coating liquid containing a specific compound on the ink receiving layer including a pigment and an adhesive.

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

As a support for 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, zinc oxide,
Zinc sulfide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, amorphous silica, aluminum hydroxide, alumina,
Alumina hydrate, aluminosilicate, lithopone, urea-formalin resin filler and the like can be mentioned. These may be used alone or in combination of two or more. Among these, amorphous silica, alumina, and alumina hydrate are preferably used because they have excellent ink absorbency.

The amount of pigment used in the ink receiving layer is as follows.
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 a conventionally known cationic polymer in combination. Examples of such a cationic polymer include polydiallylamine hydrochloride, polydiallylamine sulfate, diallylamine hydrochloride / acrylamide copolymer, diallylamine sulfate / acrylamide copolymer, polydiallyldimethylammonium chloride, diallyldimethylammonium chloride. Acrylamide copolymer, diallyldimethylammonium chloride / sulfur dioxide copolymer, polyallylamine hydrochloride, N-vinylacrylamidine hydrochloride / acrylamide copolymer, dialkylamine / epichlorohydrin addition polymer, polyamide polyamine epichlorohydride Phosphorus polymer, dicyandiamide / formalin polycondensate, polyalkylenepolyamine / dicyandiamide polycondensate, polyethyleneimine hydrochloride, poly (meth) a Liloyloxyalkyldialkylamine hydrochloride, (meth) acryloyloxyalkyldialkylamine hydrochloride / acrylamide copolymer, poly (meth) acryloyloxyalkyltrialkylammonium chloride, (meth) acryloyloxyalkyltrialkylammonium chloride / acrylamide Polymer, poly (meth) acrylamidealkyldialkylamine hydrochloride, (meth) acrylamidealkyldialkylamine hydrochloride / acrylamide copolymer, poly (meth) acrylamidealkyltrialkylammonium chloride, (meth) acrylamidealkyltrialkylammonium 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,
Thickener, cross-linking agent, fluidity modifier, defoaming agent, foam suppressor, release agent, foaming agent, penetrant, coloring dye, coloring pigment, fluorescent whitening agent, preservative, anti-bacterial agent, water resistance. Agents 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 for the purpose of imparting high gloss, for example, by passing between roll nips under pressure with a super calender or gloss calender.

A gloss layer can 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, is excellent in ink absorbability, more preferably 150m ² / g. The average particle diameter of the pigment is preferably 0.01 to 5 μm, and 0.05 to
It is more preferably 1 μm. If the particle size is less than 0.01 μm, the effect of improving ink absorbency is poor, and the particle size is 5 μm.
If it exceeds the range, gloss and print density may be reduced. The average particle size of primary particles as a pigment is 3 nm or more 40
nm or less, the average particle size of secondary particles is 10 nm or more and 50
When silica fine particles having a size of 0 nm or less are used, the gloss,
The ink absorbency is 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 mainly formed 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, a cast method can be used.
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 embodiment in which the gloss layer is obtained by a casting method using a heated mirror drum, the polymer preferably has a glass transition point of 40 ° C. or higher, more preferably 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.

As a method of casting treatment, there are a wet method, a gelling method and a rewet method. In the wet method, while the gloss-developing layer coated on the base paper is in a wet state, the gloss-developing layer is pressed against the heated specular drum surface to perform a strong gloss finish. The gelling method is that while the gloss-developing layer coated on the base paper is in a wet state, the gloss-developing layer is brought into contact with the gelling agent bath, and the gelled gloss-developing layer is pressed against the heating drum surface. It is a high gloss finish. In the rewetting method, the gloss developing 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.

In the glossy layer coating composition, whiteness, viscosity,
Various additives such as pigments, defoaming agents, colorants, antistatic agents, preservatives and dispersants, thickeners, etc., which are used in general printing coated paper and inkjet paper, are used to control the fluidity. The agent is added appropriately. Further, it is possible to add a cationic compound such as the above-mentioned cationic resin to impart ink dye fixing property to the glossy layer. The coating amount of the gloss layer is 0.2 to 30 g / m ² on a dry solid basis, preferably 1 to 20.
It is 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.

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 ink receiving layer, and various known techniques in the field of inkjet recording sheet manufacturing can be added.

A liquid ink such as an aqueous 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. 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, and polyhydric alcohols such as triethylene glycol monomethyl ether and triethylene glycol monoethyl ether. Examples include lower alkyl ethers of alcohols. Further, as an additive, for example, a pH adjusting agent,
Metal sequestering agents, antifungal agents, viscosity modifiers, surface tension modifiers,
Examples include surfactants and rust preventives.

[0044]

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 for ink receiving layer) Synthetic amorphous silica (trade name: Fineseal X60, manufactured by Tokuyama Corporation) 100
Part, silicon-modified polyvinyl alcohol (trade name: R-1
130, 250 parts of a 10% aqueous solution of Kuraray Co., Ltd., a copolymer of diallylamine hydrochloride / diallyl sulfide / acrylamide (molar ratio 2: 1: 4, average molecular weight 5).
A coating solution for an ink-receiving layer having a solid content concentration of 15% consisting of 150 parts of a 20% aqueous solution of 10,000), a small amount of a defoaming agent, a dispersant, and water 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 of the ink-receiving layer coating solution on a solids to fine paper of 5 g / m ^2, and super calendering the inkjet recording I made a sheet for.

Examples 2 to 18 In Example 1, a copolymer of diallylamine hydrochloride / diallyl sulfide / acrylamide (molar ratio 2:
An ink jet recording sheet was prepared in the same manner as in Example 1 except that the following compounds were used instead of 1: 4, average molecular weight 50,000).

Example 2: Copolymer of diallylamine hydrochloride / diallyl sulfide / acrylamide (molar ratio
2: 1: 2, average molecular weight 30,000)

Example 3: Copolymer of diallylamine sulfate / diallyl sulfide / acrylamide (molar ratio
2: 1: 4, average molecular weight 30,000)

Example 4 Copolymer of diallylamine sulfate / diallyl sulfide / acrylamide (molar ratio
2: 1: 2, average molecular weight 20,000)

Example 5: Copolymer of diallylamine hydrochloride / 1-allyl-2-thiourea / acrylamide (molar ratio 2: 1: 4, average molecular weight 60,000)

Example 6 Copolymer of diallylamine hydrochloride / 1-allyl-2-thiourea / acrylamide (molar ratio 2: 1: 2, average molecular weight 50,000)

Example 7: Copolymer of diallylamine sulfate / 1-allyl-2-thiourea / acrylamide (molar ratio 2: 1: 4, average molecular weight 50,000)

Example 8: Copolymer of diallylamine sulfate / 1-allyl-2-thiourea / acrylamide (molar ratio 2: 1: 2, average molecular weight 30,000)

Example 9: Copolymer of N-methyldiallylamine sulfate / diallyl sulfide / acrylamide (molar ratio 2: 1: 4, average molecular weight 30,000)

Example 10: Copolymer of N-methyldiallylamine sulfate / 1-allyl-2-thiourea-acrylamide (molar ratio 2: 1: 4, average molecular weight 50,000)

Example 11: Phosphate of diallylamine
Copolymer of 1-allyl-2-thiourea-acrylamide (molar ratio 2: 1: 4, average molecular weight 30,000)

Example 12: Copolymer of diallylamine hydrochloride / ethyl vinyl sulfide / acrylamide (molar ratio 2: 1: 4, average molecular weight 30,000)

Example 13: Copolymer of dimethyldiallylammonium chloride / diallyl sulfide / acrylamide (molar ratio 2: 1: 2, average molecular weight 50,000)

Example 14: Copolymer of dimethyldiallylammonium sulfonate / 1-allyl-2-thiourea / acrylamide (molar ratio 2: 1: 2, average molecular weight 30,000)

Example 15: N-methyl-N-benzyldiallylammonium chloride diallyl sulfide
Acrylamide copolymer (molar ratio 2: 1: 2, average molecular weight 30,000)

Example 16: Copolymer of N-methyl-N-benzyldiallylammonium chloride 1-allyl-2-thiourea acrylamide (molar ratio 2:
1: 2, average molecular weight 50,000)

Example 17: Copolymer of dimethyldiallylammonium chloride / diallyl sulfide (molar ratio 4: 1, average molecular weight 50,000)

Example 18: Copolymer of dimethyldiallylammonium sulfate / 1-allyl-2-thiourea (molar ratio 4: 1, average molecular weight 30,000)

Example 19 (Preparation of coating liquid 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 colloidal silica are in a weight ratio of 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 solution 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 applying the coating liquid, 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 20 In Example 19, a copolymer of diallylamine sulfate / diallyl sulfide / acrylamide (molar ratio) was used.
Instead of 2: 1: 4, average molecular weight 30,000), a copolymer of diallylamine sulfate / 1-allyl-2-thiourea / acrylamide (molar ratio 2: 1: 4, average molecular weight 5)
An ink jet recording sheet was prepared in the same manner as in Example 19 except that 10,000) was used.

Comparative Example 1 In Example 1, a copolymer of diallylamine hydrochloride / diallyl sulfide / acrylamide (molar ratio 2:
An ink jet recording sheet was prepared in the same manner as in Example 1 except that a homopolymer of diallylamine hydrochloride (average molecular weight 50,000) was used instead of 1: 4, average molecular weight 50,000).

Comparative Example 2 In Example 1, a copolymer of diallylamine hydrochloride / diallyl sulfide / acrylamide (molar ratio 2:
An ink jet recording sheet was prepared in the same manner as in Example 1 except that a homopolymer of dimethyldiallylammonium chloride (average molecular weight 60,000) was used instead of 1: 4, average molecular weight 50,000).

With respect to the ink jet recording sheets obtained in Examples and Comparative Examples, solid printing of mixed black and cyan inks by mixing of cyan, magenta and yellow inks and an image of ISO-400 were used by using Epson inkjet printer PM-800C. 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 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 Criteria) ◎: No discoloration is observed ○: Discoloration is slightly observed, but practically no problem ×: Discoloration and discoloration are remarkable, and there is a problem in practical use

[Water resistance] One drop of water was dropped on the printed portion and allowed to stand for 1 minute. Then, water was wiped off and the state was observed and evaluated. (Evaluation Criteria) ◎: Almost no ink was removed ○: Ink was slightly removed but there was no problem in practical use ×: Ink was removed and there was a problem in practical use

[0074]

[Table 1]

[0075]

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. .

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) B41J 2/01 C08F 226/04 C08F 226/04 228/02 228/02 C08J 5/18 CER C08J 5/18 CER C08L 39:00 // C08L 39:00 41:00 41:00 B41J 3/04 101Y F term (reference) 2C056 EA13 FC06 2H086 BA01 BA02 BA13 BA15 BA35 BA37 BA56 4D075 AE03 CA35 CA38 CA48 CB04 DA04 DB18 DB36 DB48 DB53 DC27 EA07 EA10 EB13 EB19 EB38 4F071 AA35X AA37X AA39X AA76 AB26 AH16 AH19 BA03 BB02 BC01 4J100 AM15R AN03Q AN14P AP01Q BA31Q BA54Q CA04 CA05 DA36 JA13 JA57

Claims (10)

[Claims] 1. A recorded image is formed using liquid ink.
In the inkjet recording sheet, in the recording sheet
A diallylamine compound represented by the general formula (1)
And ethyl having a sulfide group or a thiocarbonyl group
Less selected from copolymers with lenically unsaturated compounds
Ink jet, characterized by containing both
Recording sheet. [Chemical 1] [In the formula, R₁, R_TwoAre hydrogen atom or methyl group respectively
To R_Three, R_FourAre hydrogen atom and C respectively₁~ C_FourThe al
Kill group, C₁~ C_FourHydroxyalkyl group, C ₁~ C
₆Represents an alkoxyalkyl group or a benzyl group. Well
X^-Represents an acid residue. ] 2. The ink jet recording sheet according to claim ₁ , wherein in the general formula (1), R ₁ and R ₂ are both hydrogen atoms. 3. The ink jet recording sheet according to claim 1, wherein in the general formula (1), R ₃ is a hydrogen atom. 4. An ethylenically unsaturated compound having a sulfide group or a thiocarbonyl group is represented by the general formula (2) or (3).
The ink jet recording sheet according to any one of claims 1 to 3, which is a compound represented by (4). [Chemical 2] [Chemical 3] [Chemical 4] [In the formula, R ₅ and R ₆ are each a C _{1 to} C ₁₈ alkyl group, a C _{2 to} C ₁₈ alkenyl group, a phenyl group, or a benzyl group; R ₇ , R ₈ , and R ₉ are each a hydrogen atom, and C
Alkyl group of ₁ -C _18, alkenyl group of C 2 _{-C 18,} a phenyl group or a benzyl group. ] 5. The ink jet recording sheet according to claim 4, wherein the compound represented by the general formula (2) is diallyl sulfide. 6. The ink jet recording sheet according to claim 4, wherein the compound represented by the general formula (4) is 1-allyl-2-thiourea. 7. The inkjet recording sheet according to claim 1, further comprising acrylamide as a copolymer component. 8. The ink jet recording sheet according to claim 1, wherein a cast gloss layer is provided on the ink jet recording sheet. 9. The inkjet recording sheet according to claim 1, which has a cast-treated ink-receiving layer.
Ink jet recording sheet according to the item. 10. The ink jet recording sheet according to claim 1, wherein the cyan dye used in the liquid ink is a phthalocyanine dye.