JPH0930108A - Receiving material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance the storage stability of a dye receiving layer forming soln. and the fixing properties of an image, especially, the water resistance thereof. SOLUTION: A dye receiving layer containing at least an interlaminar compd. and a nonionic surfactant is formed on a support and a resin is pref. contained in the dye receiving layer other than the interlaminar compd. and the nonionic surfactant.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording material on which an image formed by ink is applied. For more information,
The present invention relates to a recording material in which an intercalation compound and a nonionic surfactant are contained in a dye receiving layer of the recording material.

[0002]

2. Description of the Related Art In recent years, along with the widespread use of personal computers and the like, it has been required to display images displayed on the personal computers on photographic paper in the same manner as silver halide photographs. As means for printing on photographic paper, electric fields, heat,
An ink jet recording system or the like is used in which a solution-like ink is ejected from a nozzle onto a photographic printing paper by using pressure or the like as a driving source, and an image is formed by the ink for printing.

When printing on photographic printing paper by the ink jet recording system as described above, photographic printing paper having a dye receiving layer formed on a support is generally used as the printing paper. In the inkjet recording method, a water-soluble direct dye or acid dye is mainly used as the ink. In the dye receiving layer of the photographic paper, a water-soluble polymer having an excellent affinity for the dye, an organic or inorganic filler, and other auxiliary substances are blended to control dye penetration and image bleeding. .

By the way, the dye used in the above-mentioned ink jet recording system, after being transferred to the dye receiving layer as typified by the dyeing theory of direct dye, van der Waals with the dye receiving layer component. It is held in the receptor layer by interaction such as force and hydrogen bond.

Therefore, when a solvent or resin having a higher affinity for the dye of the image formed by the ink containing the dye as described above comes into contact with the dye, or the interaction between the dye and the dye receiving layer is canceled. When the heat energy is supplied, the dye elution and migration are induced, and the image is blurred.

Therefore, for example, as shown in Japanese Patent Publication No. 62-798, a reactive dye is used as a dye for aqueous ink,
A method of forming a covalent bond with an active group in a dye-receiving layer, or a method of forming an ionic bond between a dye anion and an organic polymer cation in the dye-receiving layer as shown in US Pat. No. 4,693,302, JP-B-63-11158. As shown in (1), means based on a chemical bond such as a method of forming an ionic bond between the dye anion and the inorganic low molecular cation in the dye receiving layer has been proposed.

[0007]

However, in the method described above, the reactivity of the ink or dye receiving layer becomes very high, and the ink or the dye receiving layer is formed on the support of the recording material in order to form the ink or dye receiving layer. It becomes difficult to secure the storability of the dye-receiving layer forming solution to be applied, and the solution cannot be stored for a long time
There is an inconvenience such as a factor that increases the cost.

Further, since the reaction between the dye and the dye receiving layer is not completed in a short time, the adsorption speed of the dye to the dye receiving layer is slow,
It takes a long time for an image to be stably formed, or a heat treatment is required to stably form an image, which requires time or labor for printing, resulting in a decrease in productivity.

Further, it is difficult to adjust the dye and the usable hue is limited.

Further, even if the water resistance of the image can be improved by these means, the solvent resistance and the light resistance are not sufficient, and it is difficult to make the image fixability sufficient.

From the above, it is said that it is difficult to put an image formed by the conventional ink jet recording technique into practical use in a field requiring a high degree of image durability such as a certification photograph or a photograph for outdoor exhibition. However, even in such a field, improvement of the fixability of an image represented by water resistance is desired so that an image formed by an inkjet recording method can be put to practical use.

Therefore, the present invention has been proposed in view of the conventional circumstances, and provides a recording material which can reduce the cost, time and labor at the time of printing, and can improve the fixing property of images, especially the water resistance. The purpose is to do.

[0013]

Means for Solving the Problems As a result of intensive studies by the present inventors in order to achieve the above-mentioned object, as a result, a water-soluble dye was used as a dye, and in particular, a direct dye and an acid dye were used in the dye receiving layer. When an exchangeable anion is image-transferred directly to a dye or acid dye using an intercalation compound excellent in water adsorption or swelling in water, it should be converted into a dye image and firmly fixed. Found out. on the other hand,
When a basic dye is used among water-soluble dyes, and when an exchangeable cation is used in the dye-receiving layer with an intercalation compound excellent in water adsorption or swelling in water, the basic dye is image-wise transferred. It was also found that they were converted into dye images and firmly fixed.

Further, as a result of intensive studies by the present inventors, the dye-receptive layer forming solution contains a nonionic surfactant together with an intercalation compound to enhance the storage stability thereof, whereby the dye-receptive layer is formed. By forming a non-ionic surfactant together with the above-described intercalation compound in the dye-receiving layer, the ink containing the water-soluble dye enhances the absorption speed of the ink when attached to the dye-receiving layer. Found that is possible.

Further, as a result of intensive studies by the present inventors, the dye receiving layer exhibits high transparency by containing a resin in addition to the intercalation compound and the nonionic surfactant in the dye receiving layer. It was also found that it is possible to let. Furthermore, they have found that the nonionic surfactant also has the effect of improving the dispersibility of the intercalation compound in the resin.

That is, the present invention is characterized in that a dye receiving layer containing at least an intercalation compound and a nonionic surfactant is formed on a support.

The content of the nonionic surfactant in the dye receiving layer is 5 to 30 parts with respect to the content of the intercalation compound.
If it is less than 5 parts, it is difficult to sufficiently secure the storage stability of the dye receiving layer forming solution,
When it is more than 30 parts, the drying property of the dye-receiving layer forming solution at the time of forming the dye-receiving layer becomes low, which is not preferable.

Further, in the recording material of the present invention, in addition to the intercalation compound and the nonionic surfactant in the dye receiving layer,
It is preferable that a resin is contained.

The content of the resin in the dye receiving layer is preferably 10 parts to 90 parts with respect to the content of the intercalation compound, and when it is less than 10 parts, the dye receiving layer forming solution is applied to the support. It is not preferable that the coating film cannot be formed into a highly flexible film, and if it is more than 90 parts, the fixing property of the image to the dye receiving layer may be impaired.

The above-mentioned intercalation compound is preferably a layered inorganic polymer material having exchangeable cations between the layers, and is a montmorillonite group mineral which is a layered silicate having a 3-octahedral smectite structure. Those having are preferred.

[0021]

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At this time, depending on the combination of X and Y and the number of substitutions, montmorillonite, magnesian montmorillonite, iron montmorillonite, iron magnesian montmorillonite, beidellite, aluminian beidellite,
Many kinds of nontronite, aluminian nontronite, saponite, aluminian saponite, hectorite, sauconite, etc. exist as natural products.

Further, as the intercalation compound, a layered inorganic polymer material having exchangeable anions between the layers is also preferable, and a hydrotalcite group mineral which is a layered salt composed of an AlO ₆ octahedral sheet of 0: 1 type clay mineral. Among them, those having the structure shown in Chemical formula 6 are preferable.

[0024]

[Chemical 6]

As the nonionic surfactant, polyoxyethylene alkylphenyl ethers having the structure shown in the chemical formula 7 below, polyoxyethylene alkyl ethers having the structure shown in the chemical formula 8 below, Polyoxyethylene fatty acid esters having the structures shown in the following chemical formulas 9 to 11 are preferable, and it is preferable to use at least one of them.

[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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Furthermore, it is preferable that the resin is at least one of acetalization products of vinyl alcohol, cellulose resins, and polyvinylpyrrolidone resins.

That is, in the recording material of the present invention,
Since the dye receiving layer containing at least the intercalation compound and the nonionic surfactant is formed on the support, the ink absorption rate when the ink containing the dye adheres to the dye receiving layer is nonionic. While being enhanced by the agent, the dye contained in the ink is firmly fixed in the dye receiving layer by the intercalation compound. Further, since it contains a nonionic surfactant, the storage stability of the dye-receiving layer-forming solution becomes good.

Furthermore, when a resin is contained in the dye receiving layer, the dye receiving layer exhibits a high degree of transparency. In addition,
At this time, since the nonionic surfactant is contained in the dye receiving layer, the dispersibility of the intercalation compound in the resin also becomes good.

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION Specific embodiments of the present invention will be described below. That is, the recording material of the present invention is a recording material in which a dye receiving layer is formed on a support,
The dye receiving layer contains at least an intercalation compound and a nonionic surfactant.

Examples of the support include those generally used as a support for photographic paper. Papers such as plain paper and synthetic paper, plastic films such as polyethylene terephthalate, and papers. Examples thereof include those coated with plastics.

An intercalation compound or an exchangeable anion, in which a water-soluble dye is used as a dye, particularly a direct dye or an acid dye is used, and the exchangeable anion is excellent in water adsorption or swelling in water in the dye receiving layer When a dye or acid dye is directly imagewise transferred by using an intercalation compound in which a part of the above is replaced with an organic anion, it is converted into a dye image and firmly fixed. On the other hand, among the water-soluble dyes, a basic dye is used, and in the dye receiving layer, an exchangeable cation is an intercalation compound excellent in water adsorption or swelling in water or a part of the exchangeable cation is a quaternary ammonium ion Even when a basic dye is imagewise transferred by using an intercalation compound substituted with phosphonium ion or the like, it is converted into a dye image and firmly fixed.

Therefore, in the recording material of the present invention, the dye contained in the ink is firmly fixed in the dye receiving layer by the intercalation compound, an image is formed by the dye, and the fixing property becomes good.

Further, in the recording material of the present invention, the absorption speed of the ink containing the dye when it adheres to the dye receiving layer is increased by the nonionic surfactant, and the time required for printing is shortened. Therefore, it is not necessary to perform a special process at the time of printing, and the productivity is improved.

As the above-mentioned intercalation compound, a layered inorganic polymer material having exchangeable cations between layers as described above is preferable, and a montmorillonite group mineral which is a layered silicate having a 3-octahedral smectite structure, especially Those having a structure represented by are preferred.

[0040]

[Chemical 12]

At this time, depending on the combination of X and Y and the number of substitutions, montmorillonite, magnesian montmorillonite, iron montmorillonite, iron magnesian montmorillonite, beidellite, aluminian beidellite,
Many kinds of nontronite, aluminian nontronite, saponite, aluminian saponite, hectorite, sauconite, etc. exist as natural products.

Further, as the above-mentioned intercalation compound, a layered inorganic polymer material having an exchangeable anion between layers as described above is also preferable, and a hydrolyzed salt which is a layered salt composed of an AlO ₆ octahedral sheet of 0: 1 type clay mineral. Talcite group minerals, especially those having the structure shown in Chemical formula 13, are preferable.

[0043]

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By the way, as the above-mentioned intercalation compound, the following compounds may be mentioned. Examples of the intercalation compound having an exchangeable cation between the layers include a natural product of the above montmorillonite group minerals and a synthetic product in which the OH group in the above Chemical formula 12 is substituted with fluorine. Other examples include mica group minerals such as sodium silicic mica, sodium teniolite, and lithium teniolite. However, kaolinite, talc, pyrophyllite, etc., which have a layered structure but do not have exchangeable cations between layers, are not suitable. Although zeolite has an alkali metal ion or an alkaline earth metal ion as an exchangeable cation, its performance is remarkably inferior because its structure is reticulated and its pore size is small.

The intercalation compound used in the present invention is an inorganic ion such as water or alcohol which is easily solvated in a high dielectric constant medium such as alkali metal such as Li ⁺ , Na ⁺ , K ⁺ or Mg ^2+. Alternatively, even if it has H ⁺ , it may be used as an acceptor of a basic dye (which becomes so-called clay acid). On the other hand, alkaline earth metal ions such as Ca ²⁺ and Ba ²⁺ are not preferable because they give an interlayer that is difficult to solvate.

Further, in the present invention, in consideration of the dispersibility in the resin described later, a part of these exchangeable inorganic ions may be substituted with an organic cation for use. Suitable as the organic cations are quaternary ammonium ions and phosphonium ions such as alkylphosphonium ions and arylphosphonium ions.

However, for example, in the case of a quaternary ammonium ion, at least three of the four alkyl groups each have 4 or more carbon atoms, preferably 8 or more carbon atoms. When the number of long-chain alkyls is small, the effect as a pillar is small and it becomes difficult to secure the interlayer as the fixing reaction seat (exchangeable inorganic ion). For example, when n-octyltrimethylammonium ion is used, even if it occupies most of the fixing seat, the layer spacing does not increase to about 4 angstroms or more, and it provides a hydrophobic surface, which is completely unsuitable for the present invention.

In addition to the above-mentioned synthetic intercalation compound, there is amorphous synthetic silica as a synthetic silicate showing a strong affinity with a basic dye, but its fixing performance in a high dielectric constant medium such as water, that is, its ion exchange ability. Remarkably inferior and impractical. Also,
As an inorganic polymer having a layered structure like synthetic clay minerals and having exchangeable cations, there are acid salts such as zirconium phosphate and layered hydrous titanium oxide. Although there are heteropolyacids, hexacyanoiron salts, etc. that have similar ion exchange capacities although they are not morphologically layered, their transparency, gloss, and
It is unsuitable for inclusion in the receiving layer of a recording material that requires whiteness.

On the other hand, examples of the intercalation compound having an exchangeable anion between the layers include the above-mentioned natural minerals of the hydrotalcite group minerals and synthetic products having slightly different compositions. Unlike the natural product, this synthetic product is pure white with no impurities, and the crystal itself is optically transparent. Further, inorganic ions such as NO ₃ ⁻ , SO ₄ ^{2 −} , ClO ₄ ⁻ , Fe (CN) ₆ ⁴ which are easily solvated in a high dielectric constant medium such as water or alcohol at the ion exchange sites of the hydrotalcite group minerals.
^- , Those having a hydrophilic organic anion such as a heteropolyphosphate ion or a lower carboxylate ion, and these may be contained in the dye receiving layer. On the other hand, a substance having an ion that provides an interlayer that is difficult to hydrate, such as a higher carboxylate ion, is not preferable because it deprives the fixing seat of the hydrophilic dye.

Further, as the above-mentioned intercalation compound, a compound in which a part of these exchangeable ions is substituted with an organic anion in consideration of dispersibility in a resin described later can be mentioned. Suitable organic anions include carboxylate anions, sulfonate anions, sulfate ester anions,
It is a phosphoric acid ester anion, and preferably has an alkyl group or an alkenyl group having 5 to 20 carbon atoms.
When the carbon number is small, the effect as a pillar is small, and it becomes difficult to secure the interlayer as a fixing reaction seat (exchangeable inorganic ion).

In addition to the above hydrotalcites, there are inorganic polymers having exchangeable anions, such as hydrous oxides such as titanium, zirconium, lanthanum and bismuth, and hydroxyphosphates. It is unsuitable for inclusion in the dye receiving layer of a recording material that requires transparency, gloss and whiteness due to its inherent coloring.

Particularly preferred among these are synthetic silicates which are pure white and free of contaminants such as natural products, and whose crystals themselves are optically transparent.

As the nonionic surfactant, polyoxyethylene alkyl phenyl ethers having a structure shown in the chemical formula 14 below, polyoxyethylene alkyl ethers having a structure shown in the chemical formula 15 below, Polyoxyethylene fatty acid esters having the structures shown in Chemical formulas 16 to 18 below are preferable, and it is preferable to use at least one of these.

[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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As the nonionic surfactant, in addition to the above-mentioned ones, polyoxyethylene polyoxypropylene block polymers having the structure shown in Chemical formula 19 and those shown in Chemical formulas 20 and 21 are also used. Sorbitan fatty acid esters, polyoxyethylene alkylamine ethers having the structure shown in Chemical formula 2, Chemical formula 2
Fatty acid diethanolamides having a structure as shown in 3 and sucrose fatty acid esters having a structure as shown in Chemical formula 24 can be used.

[0060]

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[0061]

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[0062]

[Chemical 21]

[0063]

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[0064]

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[0065]

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In the recording material of the present invention, it is preferable that the dye receiving layer contains a resin in addition to the intercalation compound and the nonionic surfactant.

Examples of the above-mentioned resin include acetalization products of vinyl alcohol such as polyvinyl butyral, ethyl cellulose, cellulose acetate butyrate and the like, and cellulosic resin of hydroxypropyl cellulose having a function of improving water absorption, polyvinylpyrrolidone or polyvinylpyrrolidone-vinyl acetate. It is preferably at least one kind of polyvinylpyrrolidone-based resin having a function of improving water absorption, such as a copolymer.

As the above-mentioned resin, in addition to the above-mentioned resins, general thermoplastic resins can be applied, but in the present invention, those having an action of enhancing the dispersibility of the intercalation compound are preferable. Specific examples thereof include resins having an OH group in the molecule. On the other hand, those containing a substituent that causes aggregation or inhibits the fixing action of an image, for example, an ion that is relatively easily ion-exchanged as compared with an ionic dye, are not preferable.

Examples of such resin include polyamide resin, starch-polyacrylamide,
Examples thereof include acrylic resins such as polyacrylic acid.

To produce the above-mentioned recording material of the present invention,
A dye-receptive layer-forming solution may be prepared and coated on a support. The solution for forming the dye-receptive layer is prepared by adding an intercalation compound, a nonionic surfactant, and a resin to the solvent,
This is mixed and adjusted, but the storage stability becomes good by containing the nonionic surfactant as described above,
It is possible to reduce the cost for printing.

A plasticizer for controlling the glass transition point of the resin may be added to the dye-receptive layer-forming solution as long as it does not impair the fixability of the image. For other purposes, for example, water repellent property. An auxiliary additive for control, an ultraviolet absorber for improving light resistance, or a fluorescent whitening agent for improving quality may be added.

At this time, the content of the nonionic surfactant in the dye receiving layer is 5 parts to 3 parts with respect to the content of the intercalation compound.
It is preferable to adjust the dye-receiving layer-forming solution to be 0 part, and it is difficult to ensure sufficient storage stability of the dye-receiving layer-forming solution when it is less than 5 parts, and when it is more than 30 parts. The drying property of the dye-receptive layer-forming solution at the time of forming a layer will be low.

When a resin is contained in the dye receiving layer, the dye receiving layer forming solution is added so that the content of the resin in the dye receiving layer is 10 parts to 90 parts with respect to the content of the intercalation compound. It is preferable to adjust it. If it is less than 10 parts, a film having high flexibility cannot be formed when the dye-receptive layer-forming solution is applied on a support. It is not preferable because it may impair the fixability to the dye receiving layer. At this time, the nonionic surfactant also has the effect of increasing the dispersibility of the intercalation compound in the resin.

In the recording material of the present invention, the dye can be firmly fixed in the dye receiving layer by the intercalation compound and the ink absorbing speed is increased, so that the ink jet recording method, the sublimation recording method, etc. It can be applied as a recording paper of a printer to which the general recording method of.

By the way, as a dye for forming an image,
Examples of the water-soluble dye include water-soluble cationic dyes (water-soluble basic dyes) and water-soluble anionic dyes (water-soluble direct dyes and water-soluble acidic dyes).

As the above water-soluble cationic dyestuff, an azo dye having an amine salt or a quaternary ammonium group, a triphenylmethane dye, an azine dye, an oxazine dye, a thiazine dye and the like can be used.

Specifically, as a yellow type, C.I. I.
Basic Yellow 1, 2, 11, 11, 13, 1
4, 19, 21, 25, 28, 32, 3
3, the same 34, the same 35 or the same 36, as a magenta system,
C. I. Basic Red 1, the same 2, the same 9, the same 12, the same 13, the same 14, the same 15, the same 17, the same 18, the same 22, the same 2
3, 24, 27, 29, 32, 38, 3
9, 40, C.I. I. Basic Violet 7, 1
0, ibid 15, ibid 21, ibid 25, ibid 26, ibid 27 or ibid 2
8, as a cyan system, C.I. I. Basic Blue 1, 3, 5, 7, 7, 9, 19, 21, 22, 22
4, 25, 26, 28, 29, 40, 4
1, the same 44, the same 45, the same 47, the same 54, the same 58, the same 5
9, 60, 64, 65, 66, 67, 68
Or 75, as a black type, C.I. I. Basic Black 2 or 8 and the like.

Particularly preferred dyes are C.I. I. Basic yellow 21, the same 36, the same 67, the same 73, and those shown in Chemical formula 25, Chemical formula 26, Chemical formula 27, Chemical formula 28, Chemical formula 29, Chemical formula 30, Chemical formula 31, 32.

[0079]

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[0080]

[Chemical formula 26]

However, in the chemical formulas 25 and 26, R ¹ , R ² ,
R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R
¹¹ and R ¹² are independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group, a cycloalkyl group, an alkoxy group,
An aryl group, an aryloxy group, an aralkyl group, an aralkoxy group, an alkenyl group, an alkenoxy group, an alkoxycarbonyl group, an acyloxy group or an acyl group, which may be substituted, and R ¹ , R ² and R ³
And R ⁴ , R ⁷ and R ⁸ , R ⁹ and R ¹⁰ , R ¹⁰ and R ¹¹ , and R
¹¹ and R ¹² may be linked to each other to form a ring, and Z ⁻ is a counterion.

[0082]

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However, in Chemical formula 27, R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are independently a hydrogen atom, a halogen atom, a cyano group,
Alkyl group, cycloalkyl group, alkoxy group, aryl group, aryloxy group, aralkyl group, aralkoxy group, alkenyl group, alkenoxy group, alkoxycarbonyl group, acyloxy group or acyl group, which may be substituted, And Z ^- is a counterion.

[0084]

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However, in the chemical formula 28, R ¹⁷ , R ¹⁸ , R ¹⁹ , and R
²⁰ and R ²¹ are independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group, a cycloalkyl group, an alkoxy group,
An aryl group, an aryloxy group, an aralkyl group, an aralkoxy group, an alkenyl group, an alkenoxy group, an alkoxycarbonyl group, an acyloxy group or an acyl group, which may be substituted, and R ²⁰ and R ²¹ are mutually May be linked, and Z ⁻ is a counterion.

[0086]

[Chemical 29]

However, in the formula 29, R ²² , R ²³ , R ²⁴ , R
²⁵ and R ²⁶ are independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group, a cycloalkyl group, an alkoxy group,
An aryl group, an aryloxy group, an aralkyl group, an aralkoxy group, an alkenyl group, an alkenoxy group, an alkoxycarbonyl group, an acyloxy group or an acyl group, which may be substituted, and R ²⁵ and R ²⁶ are mutually different. May be linked, and Z ⁻ is a counterion.

[0088]

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Wherein R ²⁷ is a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle, and R ²⁸ and R ²⁹ are independently a hydrogen atom, a halogen atom, a cyano group, Alkyl group, cycloalkyl group, alkoxy group, aryl group, aryloxy group, aralkyl group, aralkoxy group, alkenyl group, alkenoxy group,
An alkoxycarbonyl group, an acyloxy group, an acyl group or an acylamino group, which may be substituted, R ³⁰ is a substituted or unsubstituted alkyl group, R ^30
31 and R ³² are independently a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aralkyl group, or R ³¹ and R ³² may be linked to each other,
And Z ^- is a counterion.

[0090]

[Chemical 31]

However, in the formula 31, R ³³ , R ³⁴ , R ³⁵ and R ³⁶ are independently a hydrogen atom, a halogen atom, a cyano group,
Alkyl group, cycloalkyl group, alkoxy group, aryl group, aryloxy group, aralkyl group, aralkoxy group, alkenyl group, alkenoxy group, alkoxycarbonyl group, acyloxy group or acyl group, which may be substituted, R ³⁵ and R ³⁶ may also be linked together and Z ⁻ is a counterion.

[0092]

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However, in the chemical formula 32, R ³⁷ , R ³⁸ , R ³⁹ and R ⁴⁰ are independently a hydrogen atom, a halogen atom, a cyano group,
Alkyl group, cycloalkyl group, alkoxy group, aryl group, aryloxy group, aralkyl group, aralkoxy group, alkenyl group, alkenoxy group, alkoxycarbonyl group, acyloxy group or acyl group, which may be substituted, R ³⁹ and R ⁴⁰ may also be linked together and Z ⁻ is a counterion.

These water-soluble cationic dyes usually have an inorganic anion as a counter ion, and most of them exist as a salt of a strong acid. Therefore, since the aqueous solution generally shows acidity, it is preferable to neutralize with a basic salt in order to prevent corrosion of the metal member that comes into contact with the ink composition containing such a water-soluble cationic dye. For example, it is preferable that the inorganic anion as a counter ion is treated with a soda salt of an organic anion such as a carboxylate ion or the like to substitute the organic anion. In this case, in order not to reduce the affinity of the interlayer compound for the water-soluble cationic dye, it is preferable that the affinity with the interlayer compound is not reduced by salt formation with an organic anion.

On the other hand, the water-soluble anionic dye has a monoazo group, a diazo group, an anthraquinone skeleton, a triphenylmethane skeleton, etc. as a chromophore, and further has 1 to 3 sulfonic acid groups or carboxyl groups in the molecule. Those having an anionic water-soluble group can be used.

Specifically, as a yellow direct dye,
C. I. Direct Yellow 1, 8, 11, and 1
2, 24, 26, 27, 28, 33, 3
9, 44, 50, 58, 85, 86, 8
7, 88, 89, 98, 100, 110, and magenta direct dyes such as C.I. I. Direct red
1, 1, 2, 4, 9, 9, 11, 13, 17, 17, 2
0, 23, 24, 28, 31, 33, 3
7, 39, 44, 46, 62, 63, 7
5, 79, 80, 81, 83, 84, 8
9, 95, 99, 113, 197, 201,
218, 220, 224, 225, 226,
227, 228, 229, 230, 321
As a cyan direct dye, C.I. I. Direct Blue 1, 2, 6, 8, 15, 15, 22, 25, 4
1, 71, 76, 77, 78, 80, 8
6, 90, 98, 106, 108, 120,
158, 160, 163, 165, 168,
192, 193, 194, 195, 196,
199, 200, 201, 202, 203,
207, 225, 226, 236, 237,
246, 248, 249, and black direct dyes such as C.I. I. Direct Black 17, 19, 22, 22, 32, 51, 56, 62, 7
1, 74, 75, 77, 94, 105, 1
06, 107, 108, 112, 113, 1
17, 118, 132, 133, and 146 are preferably exemplified.

As a yellow acid dye, C.I.
I. Acid Yellow 1, 3, 7, 11, 11
7, 19, 23, 25, 29, 36, 3
8, 40, 42, 44, 49, 59, 6
1, 70, 72, 75, 76, 78, 7
9, 98, 99, 110, 111, 112,
114, 116, 118, 119, 127,
128, 131, 135, 141, 142,
161, 162, 163, 164, 165,
As magenta acid dyes, C.I. I. Acid Red 1, 6, 8, 9, 13, 14, 18, 18, 2
6, 27, 32, 35, 37, 42, 5
1, 52, 57, 75, 77, 80, 8
2, 83, 85, 87, 88, 89, 9
2, 94, 97, 106, 111, 114,
115, 117, 118, 119, 129,
130, 131, 133, 134, 138,
143, 145, 154, 155, 158,
168, 180, 183, 184, 186,
194, 198, 199, 209, 211,
215, 216, 217, 219, 249,
252, 254, 256, 257, 262,
265, 266, 274, 276, 282,
283, 303, 317, 318, 320,
Nos. 321, 322, and C.I.
I. Acid Blue 1, 7, 7, 9, 15, 22,
23, 25, 27, 29, 40, 41, 43, 45, 54, 59, 60, 62, 7
2, 74, 78, 80, 82, 83, 9
0, 92, 93, 100, 102, 103,
104, 112, 113, 117, 120,
126, 127, 129, 130, 131,
138, 140, 142, 143, 151,
154, 158, 161, 166, 167,
168, 170, 171, 175, 182,
183, 184, 187, 192, 199,
Same 203, Same 204, Same 205, Same 229, Same 234,
236, C.I. I. Acid Black 1, 2, 7, 24, 26, 2
9, same 31, same 44, same 48, same 50, same 51, same 5
2, 58, 60, 62, 63, 64, 6
7, 72, 76, 77, 94, 107, 1
08, 109, 110, 112, 115, 1
18, 119, 121, 122, 131, 1
32, 139, 140, 155, 156, 1
57, 158, 159, and 191 can be preferably exemplified.

[0098]

EXAMPLES Preferred examples to which the present invention is applied will be described below based on experimental results.

Experimental Example 1 In this Experimental Example, the storage stability of a dye-receiving layer forming solution for forming a dye-receiving layer of a recording material to which the present invention was applied was investigated.

[Preparation of Sample] <Dye Receptor Layer Forming Solution Implementation Sample 1> First, synthetic hydrotalcite (trade name: DHT-4A manufactured by Kyowa Chemical Industry Co., Ltd.) 1 was added to 80 g of ethanol as an intercalation compound.
Polyvinyl butyral resin, which is an acetalization product of 6 g and vinyl alcohol as a resin (trade name: S-REC B
2 g of L-S Sekisui Chemical Co., Ltd. was added, and a polyoxyethylene nonylphenyl ether-based nonionic surfactant (trade name: polyoxyethylene alkylphenyl ether) as a nonionic surfactant. 0.8 g of Neugen EA120 Daiichi Kogyo Seiyaku Co., Ltd. was added and dispersed by a roll mill for 2 weeks to obtain a suspension solution.
Subsequently, in the above suspension solution, a polyvinylpyrrolidone-vinyl acetate copolymer, which is a polyvinylpyrrolidone-based resin as a resin in 10 g of ethanol (trade name: rubiscol VA
A solution in which 2 g of 64E BASF Co., Ltd.) was dissolved was added and uniformly stirred to obtain a dye receiving layer forming solution execution sample 1.

<Dye Receptor Layer Forming Solution Implementation Sample 2> Next, in 80 g of ethanol, 16 g of synthetic hydrotalcite (trade name: DHT-4C manufactured by Kyowa Chemical Industry Co., Ltd.) as an intercalation compound and a cellulosic resin as a resin were used. A certain ethyl cellulose resin (manufactured by Shin-Etsu Chemical Co., Ltd.) 2
g, and as a nonionic surfactant, a polyoxyethylene oleic acid ester-based nonionic surfactant which is a polyoxyethylene fatty acid ester (trade name:
Neugen ES129 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 4.8
g was added and dispersed by a roll mill for 2 weeks to obtain a suspension solution. Subsequently, a solution in which 4 g of a hydroxypropyl cellulose (manufactured by Nippon Soda Co., Ltd.), which is a cellulosic resin, was dissolved in 20 g of ethanol as a resin was added to the above suspension solution, and the mixture was stirred uniformly to form a dye receiving layer forming solution. It was set as the execution sample 2.

<Dye Receptor Layer Forming Solution Implementation Sample 3> Furthermore, in 80 g of isopropyl alcohol, 10 g of synthetic smectite (trade name: manufactured by SWN Corp Chemical) as an intercalation compound and polyvinylpyrrolidone-vinyl acetate copolymer which is a polyvinylpyrrolidone resin as a resin. Polymer (trade name: Rubiscol VA64 BASF Ltd.) 1
0 g was added, and a nonionic surfactant having a structure as shown in the following chemical formula 33 which is a polyoxyethylene fatty acid ester as a nonionic surfactant (trade name: manufactured by Lionon DT-600 Lion Co., Ltd.) ) 0.5 g was added and dispersed by a roll mill for 2 weeks to obtain a suspension solution, which was designated as Dye Receptor Layer Forming Solution Implementation Sample 3.

[0103]

[Chemical 33]

<Dye Receptor Layer Forming Solution Implementation Sample 4> Furthermore, synthetic smectite (trade name: manufactured by SWN Corp Chemical) as an intercalation compound in 80 g of ethanol 1
8 g and 2 g of a hydroxypropyl cellulose resin (manufactured by Nippon Soda Co., Ltd.), which is a cellulosic resin, are added, and a polyoxyethylene alkyl ether-based nonionic surfactant (trade name: as a nonionic surfactant). Rheox LC-70 Lion Co., Ltd. 5.
4 g was added and dispersed by a roll mill for 2 weeks to obtain a suspension solution, which was designated as Dye Receptor Layer Forming Solution Implementation Sample 4.

<Comparative Samples 1 to Dye Receptor Layer Forming Solution>
4> For comparison, a dye-receiving layer-forming solution containing the above-mentioned dye-receiving layer-forming solution-executed samples 1 to 4 except for the nonionic surfactant was prepared, and these were prepared. Solution comparison samples 1 to 4 were used.

[Storage Stability Test] Next, storage stability tests of the above-mentioned dye receiving layer forming solution execution samples 1 to 4 and dye receiving layer forming solution comparative samples 1 to 4 were conducted. That is,
These were sealed and stored in a cool dark place at a temperature of 5 ° C. for 1 month, and the change in the dispersed state was visually confirmed. And, if the precipitation of intercalation compounds etc. is not confirmed on the bottom of the container, ○, if the precipitation of intercalation compounds etc. is confirmed on the bottom of the container, △,
The case where a precipitate was confirmed at the bottom of the container and a transparent part (supernatant solution) was present at the top was evaluated as x. The results are shown in Table 1.

[0107]

[Table 1]

From the results shown in Table 1, in the dye-receiving layer-forming solution execution samples 1 to 3 containing the nonionic surfactant, the dye-receiving layer forming solution comparative sample 1 containing no nonionic surfactant was used. It was confirmed that the storage stability was greatly improved as compared with Nos. 3 to 3, and that the nonionic surfactant also improved the dispersibility of the intercalation compound in the dye-receiving layer forming solution with respect to the resin.

Experimental Example 2 In this Experimental Example, recording paper was formed as the recording material of the present invention, and the ink absorbency of the recording paper and the water resistance of the image formed on this recording paper were investigated.

[Preparation of Sample] First, the thickness is 125 μm.
Of polyethylene terephthalate film prepared above, and a sample 1 for carrying out the solution for forming a dye-receptive layer thereon is dried to a thickness of 10 μm.
Recording paper was manufactured by applying a bar coater so as to have a thickness of m to form a dye-receptive layer.
And

Similarly, recording papers were manufactured using the dye receiving layer forming solution execution samples 2, 3 and 4, and the recording paper execution samples 2, 3 and 4 were prepared.

For comparison, recording papers were prepared as described above using the dye receiving layer forming solution comparative samples 1 to 4 to obtain recording paper comparative samples 1 to 4.

Further, a dye receiving layer forming solution prepared by removing the intercalation compound from each of the dye receiving layer forming solution comparative samples 1 to 4 was prepared, and these were used to prepare recording paper as described above. Recording paper comparison sample 5
To 8.

[Ink Absorption and Image Water Resistance Test] Next, when an image is formed on the recording paper working samples 1 to 4 and recording paper comparative samples 1 to 8 by an inkjet printer, the ink penetrates into the dye receiving layer. The time required for the image formation and the durability of the formed image were investigated.

That is, an ink sample 1 which is a dedicated ink for a printer (model name: DESKJET1200C) manufactured by Hured Packard Co., and an ink sample 2 having the following composition are used as inks for the above printer, and Recording paper execution samples 1 and 2 and recording paper comparison samples 1, 2, 5 and 6 were subjected to full color printing to form images.

(Ink Formulation) Dye 2 parts Glycerin 2 parts Diethylene glycol 6 parts Water 30 parts (However, as dyes, yellow CI Direct Yellow 87, magenta CI Direct Red 227, cyan C.I. I. Direct Blue 199 is used to prepare ink of each color.) Instead of the ink samples 1 and 2, the dye of the ink sample 1 is a yellow C.I. I. Basic yellow 2, magenta C.I. I. Basic Red 46, Cyan C.I. I. Ink sample 3 having a composition changed to Basic Blue 3 was prepared and used as ink for the printer, and full-color printing was performed on the recording paper execution samples 3 and 4 and the recording paper comparison samples 3, 4, 7 and 8 by the printer. Performed to form an image.

Then, the time required for the ink to permeate the receiving layer when forming an image was investigated, and within 10 seconds, ◯
The evaluation was made with 10 seconds to 30 seconds as Δ, and 30 seconds or more as x. However, this test is for recording paper sample 1
4 and recording paper comparison samples 1 to 4 only. The results are also shown in Table 1.

Further, each recording paper on which an image was formed was immersed in water for 24 hours so that the image forming surface was in contact with water, and the presence or absence of dye elution was investigated.
The case where the image bleeding did not occur was evaluated as ◯, the case where the dye did not elute into the water but the case where the image bleeding occurred was evaluated as Δ, and the case where the dye leaching into the water occurred was evaluated as x. . The results are also shown in Table 1.

From the results shown in Table 1, in the recording paper working samples 1 to 4 in which the dye receiving layer was formed by the dye receiving layer forming solution containing the nonionic surfactant, the nonionic surfactant was contained. Recording Paper Comparative Samples 1 to 4 in which the dye receiving layer is formed by the dye receiving layer forming solution
It was confirmed that the time required for the ink to permeate was significantly shortened, and it was confirmed that the nonionic surfactant improves the ink absorbability of the dye receiving layer.

Further, from the results of Table 1, in the recording paper working samples 1 to 4 and the recording paper comparison samples 1 to 4 in which the dye receiving layer was formed by the dye receiving layer forming solution containing the interlayer compound, the interlayer compound The water resistance of the image formed on the recording paper comparative samples 5 to 8 in which the dye receiving layer is formed by the dye receiving layer forming solution containing no dye is significantly improved. It was confirmed that the dye was firmly fixed therein, the fixing property of the image was improved, and the water resistance was also improved.

[0121]

As is clear from the above description, in the recording material of the present invention, since the dye receiving layer containing at least the intercalation compound and the nonionic surfactant is formed on the support, the dye When the ink containing the ink adheres to the dye receiving layer, the absorption rate of the ink is increased by the nonionic surfactant, the productivity is improved, and the dye contained in the ink is added to the dye receiving layer by the intercalation compound. It is firmly fixed, an image is formed by the dye, and its fixing property becomes good. Further, since it contains a nonionic surfactant, the storage stability of the dye-receptive layer-forming solution becomes good, and if this is used, the cost during printing is reduced and the productivity becomes good.

Further, when a resin is contained in the dye receiving layer, the dye receiving layer exhibits a high degree of transparency. In addition,
At this time, since the nonionic surfactant is contained in the dye receiving layer, the dispersibility of the intercalation compound in the resin also becomes good.

Claims (19)

[Claims] 1. A recording material having a dye-receptive layer formed on a support, wherein the dye-receptive layer contains at least an intercalation compound and a nonionic surfactant. 2. The recording material according to claim 1, wherein the content of the nonionic surfactant in the dye receiving layer is 5 to 30 parts with respect to the content of the intercalation compound. 3. The recording material according to claim 1, wherein the intercalation compound is a layered inorganic polymer material having an exchangeable cation between the layers. 4. The recording material according to claim 3, wherein the layered inorganic polymer material is a montmorillonite group mineral. 5. The recording material according to claim 4, wherein the montmorillonite group mineral has a structure represented by the following chemical formula 1. Embedded image 6. The recording material according to claim 1, wherein the intercalation compound is a layered inorganic polymer material having exchangeable anions between the layers. 7. The recording material according to claim 6, wherein the layered inorganic polymer material is a hydrotalcite group mineral. 8. The recording material according to claim 7, wherein the hydrotalcite group mineral has a structure represented by the following chemical formula 2. Embedded image 9. The nonionic surfactant is at least one selected from polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl ethers, and polyoxyethylene fatty acid esters. Recording material. 10. The recording material according to claim 1, wherein the dye receiving layer contains a resin. 11. The recording material according to claim 10, wherein the content of the resin in the dye receiving layer is 10 to 90 parts with respect to the content of the intercalation compound. 12. The recording material according to claim 10, wherein the resin is at least one of an acetalized product of vinyl alcohol, a cellulose resin, and a polyvinylpyrrolidone resin. 13. The recording material according to claim 10, wherein the intercalation compound is a layered inorganic polymer material having an exchangeable cation between the layers. 14. The recording material according to claim 13, wherein the layered inorganic polymer material is a montmorillonite group mineral. 15. The recording material according to claim 14, wherein the montmorillonite group mineral has a structure represented by the following chemical formula 3. Embedded image 16. The recording material according to claim 10, wherein the intercalation compound is a layered inorganic polymer material having exchangeable anions between the layers. 17. The recording material according to claim 16, wherein the layered inorganic polymer material is a hydrotalcite group mineral. 18. The hydrotalcite group mineral is represented by the following chemical formula 4.
18. The recording material according to claim 17, which has a structure shown in FIG. Embedded image 19. The nonionic surfactant is at least one selected from polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl ethers, and polyoxyethylene fatty acid esters. Recording material.