JPH1052972A - Photographic paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a fixability comparable to a silver salt photographic image by adding an interlaminar compound which fixedly holds a dye by intercalation reaction in a dye accepting layer to be formed on a support member of a photographic paper and providing an intermediate layer formed out of a resin having water absorbing property and adhesive property arranged between the support member and the dye accepting layer. SOLUTION: A photographic paper is formed by providing a support member 1, an intermediate layer 2, and a dye accepting layer 3 arranged in the described order. In the dye accepting layer 3, a water-soluble cationic dye or a water-soluble anionic dye is fixedly held between hydrophilic layers of an interlaminar compound having cation exchange function or anion exchange function due to intercalation reaction. The intermediate layer 2 is formed out of a resin having water absorbing property and adhesive property and made to accept components other than a dye in an ink component which permeates and diffuses from the dye accepting layer 3 at printing. Thus, an absorbing capacity of a water base solvent is increased, ink permeating speed is made faster, and deterioration of resolution due to leakage of ink and defective color reproducibility in picture element level are avoided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printing paper which can form a dye image having excellent fixability by using an ink composition containing a water-soluble dye, and is particularly suitable for ink jet recording.

[0002]

2. Description of the Related Art As a method for fixing image information produced by a personal computer or the like on a photographic paper, a method of forming a dye image on a photographic paper by using an ink composition by an ink jet recording system is considered to be promising.

In such an ink jet recording system, a solution ink is ejected from a nozzle by using an electric field, heat, pressure or the like as a driving source to transfer a dye to a dye receiving layer of photographic paper.

Here, water-soluble direct dyes and acid dyes are mainly used as dyes used in inks.
The dye-receiving layer of photographic paper uses water-soluble polymers with high affinity for dyes, organic or inorganic fillers, and other auxiliary substances, which are used to control dye penetration and image bleeding. It is blended in.

By the way, the dye used in this method is as follows:
As represented by the dyeing theory of direct dyes, after the dye is transferred to the dye receiving layer, the dye is held in the dye receiving layer by interaction with the components of the dye receiving layer such as van der Waals force and hydrogen bonding. However, if another object such as a solvent or a resin having a higher affinity for the dye comes into contact after image formation, the dye may flow out or migrate from the dye-receiving layer to the other object. There is a problem in that the image is blurred and does not show perfect fixability as in a so-called silver halide photographic image.

[0006] In order to use the image formed by the conventional ink jet recording method in a field where high image durability is required, for example, for use in a photograph for certification or a printed matter for outdoor exhibition, the fixing property of the dye image is required. There is a strong demand for improvements. Further, there is a strong demand that ink jet recording can be performed not only on paper products using cellulose, but also on a support such as a non-absorbable plastic film such as an OHP sheet.

[0007] In Japanese Patent Application Laid-Open No. 7-68925,
As means for solving such a problem, it has been proposed to fix and hold the dye on the dye receiving layer by an intercalation reaction based on an ion exchange action. This dye receiving layer contains an interlayer compound having ion exchange ability,
The dye is firmly held by an intercalation reaction based on ion exchange.

[0008]

However, in the photographic paper described above, when the amount of ink discharged is larger than that of the conventional printing paper (40 picoliters or more per dot),
If the swelling capacity of the dye receiving layer with respect to the solvent composition of the ink is insufficient, the drying speed of the image becomes extremely poor due to a decrease in the penetration rate of the dye, or the dots constituting the image are expanded more than necessary. However, there is a problem in that the resolution and the color reproducibility are significantly deteriorated due to a problem in the superposition.

Further, when a non-water-absorbing plastic film or the like is used for the support, 100
If you apply more than microliters of ink,
There have been problems in that the solvent of the water-soluble ink exceeding the permeation capacity causes bleeding of the image and that the ink is transferred due to contact between the image and the hand.

An object of the present invention is to solve the above-described problems. When an image is formed on a photographic paper by an ink jet recording method, a silver halide photographic image is obtained while exhibiting practical ink drying properties. It is an object of the present invention to provide a photographic paper which has a fixing property comparable to that of photographic paper and is capable of obtaining a high-quality image excellent in resolution and color reproducibility.

[0011]

Means for Solving the Problems The inventors of the present invention have made intensive studies on achieving the above-mentioned object, and as a result, have found that an intermediate layer having excellent water absorption and adhesiveness is provided between the dye-receiving layer and the support. Has been found to solve the above-mentioned problem.

The photographic paper according to the present invention has been completed on the basis of such findings. In a photographic paper comprising a support and a dye-receiving layer formed thereon, the dye-receiving layer comprises a dye-receiving layer. An intermediate layer made of a resin having water absorbency and adhesiveness is provided between the support and the dye receiving layer, containing an intercalation compound for fixing and retaining by an intercalation reaction based on ion exchange action. It is characterized by.

The intermediate layer is preferably made of a water-soluble boron polymer compound having a BO bond in the main chain, or a mixture of the water-soluble boron polymer compound and another general-purpose water-absorbing resin.

In a printing paper having an intermediate layer provided between the dye receiving layer and the support, the intermediate layer receives components other than the dye in the ink component that penetrates and diffuses from the dye receiving layer during printing. By doing so, the absorption capacity of the aqueous solvent can be increased. In addition, since not only the apparent drying speed is increased but also the ink permeation speed is increased, it is possible to eliminate degradation in resolution and defective color reproduction at the pixel level due to ink leakage on the landing surface. .

In particular, B- having a semipolar bond in the main chain
Boron polymer compounds containing O bonds are excellent in adhesiveness to celluloses constituting films or pulp having a polar portion such as polyester used as a support due to its polarity, and are used in aqueous inks. Also excellent in swelling properties for polar organic solvents.

As described above, since the photographic paper according to the present invention has the intermediate layer having excellent water absorbency and adhesiveness, the intermediate layer is other than the dye which permeates and diffuses from the dye receiving layer during printing. It accepts ink components and increases the drying speed and penetration speed of the ink. Therefore, in the photographic paper according to the present invention, it is possible to provide a high-quality image excellent in resolution and color reproducibility.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS As shown in FIG. 1, a photographic paper according to the present invention has a support 1, an intermediate layer 2, and a dye receiving layer 3 formed in this order. In the dye receiving layer 3, a water-soluble cationic dye or a water-soluble anion dye is fixed and held between hydrophilic layers of an interlayer compound having a cation exchange ability or an anion exchange ability by an intercalation reaction based on an ion exchange action.

The intermediate layer 2 which is in contact with both the support 1 and the dye receiving layer 3 is made of a resin having a water absorbing property and an adhesive property, and ink components permeating and diffusing from the dye receiving layer 3 at the time of printing. It accepts components other than the dye in it. As a result, the photographic paper provided with the intermediate layer 2 can increase the absorption capacity of the aqueous solvent and not only increase the apparent drying speed, but also increase the ink penetration speed. Degradation of resolution and defective color reproduction at the pixel level due to leakage can be eliminated.

As described above, since the photographic paper to which the present invention is applied is provided with the intermediate layer 2 having excellent water absorbency and adhesiveness, the photographic paper has a fixing property comparable to a silver salt type photographic image, and has an ink drying property. It is possible to obtain a high-quality image having excellent resolution and color reproducibility.

The intermediate layer 2 is made of a resin having water absorbency and adhesiveness.
Boron polymer compounds containing O bonds are preferred, for example,
A boron polymer compound represented by Formula 1 is preferable.

[0021]

Embedded image

Such a boron polymer compound is excellent in adhesiveness to a film having a polar portion such as polyester used as the support 1 or cellulose constituting pulp due to its polarity. On the other hand, this boron polymer compound is also excellent in swelling properties for polar organic solvents used in aqueous inks.

As described above, for the intermediate layer 2, it is preferable to use a boron polymer compound having excellent water absorption and adhesiveness. For the intermediate layer 2, a boron polymer compound may be used alone,
You may use together with other general-purpose water-absorbing resins. The content of the boron polymer compound in the intermediate layer 2 is preferably 20% by weight or more. When the content of the boron polymer compound is less than 20 parts by weight, the effect of addition is reduced.

The thickness of the intermediate layer 2 is 0.5-30 μm.
m is preferable. The thickness of the intermediate layer 2 is 0.5 μm
If it is less than the above, the water absorption capacity is small, and the above-mentioned effects are reduced. When the thickness exceeds 30 μm, the above-mentioned effect is no longer different, and the rigidity is rather increased, the film forming property is deteriorated, and the economic efficiency is deteriorated.

As long as the intermediate layer 2 does not dissolve to the dye receiving layer 3 side when forming the dye receiving layer 3 and inhibits the fixing property,
A plasticizer may be added to control the glass transition temperature (Tg), and for other purposes, for example, an auxiliary additive for controlling water absorption, an ultraviolet absorber for improving light resistance,
Alternatively, various additives such as a fluorescent whitening agent may be contained for quality improvement.

In the present invention, as the interlayer compound used in the composition for forming the dye receiving layer 3, a layered inorganic polymer having an exchangeable cation or an exchangeable anion can be used.

Examples of the layered inorganic polymer having exchangeable cations include natural or synthetic layered silicates and calcined products thereof. Typically, the following formula having a 3-octahedral smectite structure is used. The montmorillonite group represented by (1) can be used.

(X, Y) _2-3 Z ₄ O ₁₀ (OH) ₂ .mH ₂ O. (W _1/3 ) (1) (where, in the formula (1), X represents Al, Fe (III), Mn
(III) or Co (III), wherein Y is Mg,
Fe (II), Ni, Zn or Li, wherein Z is S
i is Al or Al, W is K, Na, or Ca, H ₂ O is interlayer water, and m represents an integer. )

The layered inorganic polymer having exchangeable anions is a kind of 0: 1 type clay mineral, and a preferred example is a layered hydrotalcite group mineral composed of AlO ₆ octahedral sheet. A typical example of such hydrotalcite group minerals is hydrotalcite represented by the formula (2).

Mg ₆ Al ₂ (OH) ₁₆ .CO ₃ .4H ₂ O (2) The above-mentioned interlayer compound is dispersed and held in the binder resin. As such a binder resin, a general thermoplastic resin can be used, but a hydrophilic resin that easily disperses an interlayer compound and that is permeable to water or alcohol, which is a solvent of a water-soluble ink composition, is used. It is preferable to use, for example, polyvinyl butyral resin, hydroxypropyl cellulose resin, vinyl pyrrolidone-vinyl acetate copolymer resin, polyvinyl alcohol resin, polyvinyl acetal resin and the like.

The content of such an interlayer compound or binder resin is appropriately selected in consideration of the fixing effect and flexibility of the dye receiving layer 3.

The support 1 used in the present invention
Can be arbitrarily selected from paper, synthetic paper, plastic paper, metal plate, metal foil, plastic film on which aluminum or the like is deposited.

The ink composition used in the present invention contains at least water and a water-soluble dye which can be fixed and held by an intercalation reaction based on an ion exchange action in an interlayer compound in the dye receiving layer 3. . Here, when the interlayer compound in the dye receiving layer 3 is a layered inorganic polymer having exchangeable cations, a water-soluble cationic dye (water-soluble basic dye) can be used. When the compound is a layered inorganic polymer having exchangeable anions, an exchangeable water-soluble anionic dye (a water-soluble direct dye or a water-soluble acid dye) can be used.

Examples of the water-soluble cationic dye include an azo dye having an amine salt or a quaternary ammonium group, a triphenylmethane dye, an azone dye, an oxazine dye, and a thiazine dye. .

The water-soluble anionic dye has a monoazo group, a diazo group, an anthraquinone skeleton, a triphenylmethane skeleton, or the like as a chromophore, and further contains 1 to 3 in the molecule.
And those having an anionic water-soluble group such as a single sulfonic acid group or a carboxyl group.

When the above-described image is actually formed, an ordinary ink jet recording apparatus equipped with a bubble driving jet nozzle, a piezo element driving jet nozzle, or the like is used to selectively form the ink composition according to an image signal. May be discharged onto the dye receiving layer 3.

[0037]

EXAMPLE An image was formed on a photographic paper to which the present invention was applied, and the drying property, fixing property and resolution of the ink were examined.

Example 1 First, an aqueous boron resin (trade name: MCB300, manufactured by Boron International Co., Ltd.) was applied on one side of a neutral paper having a thickness of 100 μm using a wire bar to a dry coating amount of 3 g / m 2. ² so as to film coating, to form an intermediate layer 2.

Next, as an interlayer compound, synthetic hydrotalcite (trade name: KW2200, Kyowa Chemical Industry Co., Ltd.)
10) adsorbed 50% of the exchange capacity of malic acid on
0 g was prepared. Then, the powder was added to 1 kg of an aqueous ethanol solution containing 5% by weight of polyvinyl butyral (trade name: BL-1, manufactured by Sekisui Chemical Co., Ltd.), and dispersed by a roll mill for one week to obtain a suspension. The suspension was applied onto the intermediate layer 2 of neutral paper using a doctor blade and impregnated with the suspension, and dried with hot air at 110 ° C. for 1 minute to form the dye receiving layer 3. 1) was obtained.

On the other hand, the ink solution represented by the composition (1) and a diluent obtained by removing the dye from the composition of the ink solution are quantitatively mixed, and ink droplets having a predetermined density are printed based on the given density data. We prepared a carrier jet inkjet printer made by Sony to attach it on paper. And
The photographic paper was mounted on the paper feeding tray, and full-color printing of a two-liquid mixing system was performed. In addition, from the diameter of the mixed ejection droplet, the appropriate amount of liquid at a portion having a large amount of liquid was estimated to be 60 picoliters.

(Composition 1) 2 parts by weight of dye Yellow: C.I. I. Acid Yellow 23 Magenta: C.I. I. Acid magenta 52 cyan: C.I. I. Acid cyan 9 black: C.I. I. Direct Black 154 Isopropyl alcohol 2 parts by weight Diethylene glycol 3 parts by weight Water 30 parts by weight Nonionic surfactant 0.05 parts by weight (trade name: Neugen EA120, Daiichi Kogyo Seiyaku Co., Ltd.)
Made)

Examples 2 to 5 First, an aqueous boron resin (trade name: MCB300, trade name: MCB300) was placed on one side of a white polyester film having a thickness of 110 μm.
The weight ratio of Boron International Co., Ltd.) to a polyester emulsion (trade name: Vironal MD-1200, manufactured by Toyobo Co., Ltd.) is 4: 1, 2: 3, 1: 4, 1: 5.
Each of the mixtures was coated with a wire bar so that the coating thickness when dry was 15 μm (the coating thickness when wet was 50 μm) to form an intermediate layer 2.

Next, as an interlayer compound, synthetic hydrotalcite (trade name: KW2200, Kyowa Chemical Industry Co., Ltd.)
10) adsorbed 40% of the exchange capacity of malic acid on
0 g was prepared. The powder was added to 1 kg of an ethanol aqueous solution containing 10% by weight of hydroxypropylcellulose (trade name: HPC-M, manufactured by Nippon Soda), and dispersed by a roll mill for 60 hours to obtain a suspension.

This suspension is applied onto the intermediate layer 2 of the polyester film using a doctor blade, impregnated with the suspension, and dried with hot air at 110 ° C. for 1 minute to form a dye receiving layer 3. Examples 2 to 5 were obtained.

Then, a full-color printing of a two-liquid mixing system was performed using the same carrier jet ink jet printer manufactured by Sony as in Example 1.

Examples 6 to 9 On one side of a 110 μm thick white polyester film,
When a weight ratio of an aqueous boron resin (trade name: MCB300, manufactured by Boron International Co., Ltd.) and a polyester-based emulsion (trade name: Vironal MD-1200, manufactured by Toyobo Co., Ltd.) is 4: 1 by using a wire bar and dried. The intermediate layer 2 was formed by applying and forming films so that the application thicknesses became 0.5, 1.0, 5.0, and 30 μm, respectively. Except for this, photographic papers (Examples 6 to 9) were obtained in the same manner as in Example 2, and full-color printing using a two-liquid mixing system was performed using a carrier jet type inkjet printer manufactured by Sony.

Comparative Example 1 A photographic paper (Comparative Example 1) was produced in the same manner as in Example 1 except that the intermediate layer 2 was omitted, and the carrier paper type inkjet printer manufactured by Sony was used. Full-color printing of a two-liquid mixing system was performed.

Comparative Example 2 A photographic paper (Comparative Example 2) was prepared in the same manner as in Example 2 except that the intermediate layer 2 was omitted, and the carrier paper type inkjet printer manufactured by Sony was used. Full-color printing of a two-liquid mixing system was performed.

Evaluation of Image In Examples 1 to 9, the ink has good drying properties (permeability) and has a perfect circular dot shape from the low density portion to the high density portion. An image with no resolution and good resolution could be obtained. On the other hand, in Comparative Example 2 in which the intermediate layer 2 was not provided and the printing was performed directly on the polyester film, dot aggregation due to ink overflow was observed in the entire density region, and the ink which was not absorbed by the dye receiving layer 3 when touched with a finger was observed. Adhered to the finger.

Next, in order to examine the fixability of the image, neutral paper was superimposed on the image immediately after printing obtained in Example 1 and Comparative Example 1, and a pressure of 20 g / cm ² was applied thereto and pressed for 10 seconds. did. As a result, in Example 1, almost no image transfer was observed, whereas in Comparative Example 1, image transfer up to a reflection density of 0.4 occurred.

Next, Examples 2 to 9 and Comparative Example 2
Was left for 5 minutes after the image was output, and an adhesive tape was stuck on the recorded image. As a result, in Examples 2 to 9, the recorded image remained on the support 1, whereas in Comparative Example 2, the recorded image was separated from the support 1 and transferred to the adhesive tape. Was.

Next, Examples 1 to 9 and Comparative Example 1,
The image obtained in Comparative Example 2 was immersed in water for 1 minute. As a result, in the images obtained in Examples 1 to 9, no ink elution was observed, whereas in Comparative Examples 1 and 2, remarkable ink elution was observed.

Table 1 summarizes the above results together with the experimental conditions.
Shown in The image evaluations in Table 1 are comprehensive evaluations of the respective experimental results. ◎ indicates that a very good recorded image was obtained, ○ indicates that a good recorded image was obtained, and Δ indicates Indicates that the mark was slightly inferior to the mark, and x indicates that a blurred recorded image was obtained. When the support is made of neutral paper, the amount of ink contained in the neutral paper is large, and therefore the thickness of the intermediate layer is indicated by the amount of coating (unit: g / m ² ).

[0054]

[Table 1]

As can be seen from Table 1, the photographic papers of Examples 1 to 9 provided with the intermediate layer 2 have not only practical drying properties but also excellent fixing properties and resolution and high quality. A recorded image can be formed. However, as can be seen from the results of Examples 2 to 5, the content of the aqueous boron resin in the intermediate layer 2 is preferably 20% by weight or more, and more preferably 40% by weight or more.

Further, as can be seen from the results of Examples 6 to 9, the thickness of the intermediate layer 2 was 0.5 μm in dry thickness.
m or more, more preferably 5 μm or more. 30μ
If it exceeds m, no further difference is recognized in the improvement effect of the intermediate layer 2, and the rigidity of the photographic paper itself is increased, which is not preferable.

The printing paper (Comparative Example 1) was subjected to full-color printing using a commercially available ink jet printer (trade name: 1200C, manufactured by Hulett Packard) with an ink solution having the composition (2). In this case, since there is not much problem with the quality of the image, it can be seen that the improvement effect by the provision of the intermediate layer 2 appears more remarkably when the support 1 is a non-pulp material such as a polyester film.

As can be seen from the above examples, in the photographic paper to which the present invention is applied, by providing the intermediate layer 2 made of an aqueous boron resin between the dye receiving layer 3 and the support 1, the fixing property, A high-quality recorded image having excellent drying properties and resolution can be obtained.

[0059]

As is clear from the above description, the printing paper according to the present invention has an intermediate layer provided between the support and the dye receiving layer. It accepts components other than dyes in the ink components that penetrate and diffuse from the receiving layer, and increases the drying speed and penetration speed of the ink. Therefore, in the photographic paper according to the present invention, it shows practical ink drying properties even in an ink jet format, and has fixing properties comparable to silver halide photographic images,
A high-quality image excellent in resolution and color reproducibility can be formed.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating a configuration of a photographic paper to which the present invention is applied.

[Explanation of symbols]

 1 support, 2 intermediate layers, 3 dye receiving layer

Claims (4)

[Claims] 1. A printing paper comprising a support and a dye-receiving layer formed thereon, wherein the dye-receiving layer contains an intercalation compound for fixing and holding the dye by an intercalation reaction based on ion exchange. A printing paper characterized in that an intermediate layer made of a resin having water absorbency and adhesiveness is provided between the support and the dye receiving layer. 2. An intermediate layer comprising a water-soluble boron polymer compound having a BO bond in the main chain or a mixture of the water-soluble boron polymer compound and another general-purpose water-absorbing resin. The photographic paper according to claim 1, wherein 3. The printing according to claim 2, wherein the water-soluble boron polymer compound having a BO bond in the main chain is contained in the intermediate layer at a ratio of 20% by weight or more. paper. 4. The photographic paper according to claim 1, wherein the thickness of the intermediate layer is 0.5 to 30 μm.