JPH11129613A - Print - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a print, which has an excellent whiteness and brightness in white ground, a little deterioration of the white ground with time and a favorable color image keepability, by a method wherein a layer including solid fine particles having a fluorescent whitening effect is equipped in the print having color images on a reflective support. SOLUTION: An HDPE is laminated onto both the sides of a pulp paper. A melted PE containing 15 wt.% of an anatase-type titanium oxide is laminated on the side, on which an emulsion layer is applied, of the pulp paper. An ink jet recording sheet is obtained by applying a first layer consisting of 4.0 g/m<2> of gelatine treated with lime, 1.5 g/m<2> of PVP(K-90) and 0.1 g/m<2> of the following dispersion and a second layer consisting of 4.0 g/m<2> of the gelatine treated with lime, 1.5 g/m<2> of the PVP(K-90), 0.01 g/m<2> of an activator SF-1 and 0.01 g/m<2> of an activator SF-2 on a gelatine undercoating layer provided on this reflective support. The dispersion consists of 300 g of solid fine particles having a fluorescent whitening effect, 750 ml of a 5% aqueous solution of gelatine treated with lime, 30 ml of a 10% aqueous solution of a polyoxyethylene-nonyl phenyl ether.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a print, and more particularly, to a print having excellent whiteness and lightness of a white background, little deterioration of the white background over time, and good storage stability of a dye image. About.

[0002]

2. Description of the Related Art As a printing material, a printing material which forms an image by wet processing silver halide photographic printing paper has hitherto been mainly used. A printing material such as a photothermographic material which forms an image by thermal development, a printing material comprising an image receiving sheet on which a sublimable dye in a coloring material layer of a thermal transfer sheet is transferred by heating, and ink droplets are formed by an inkjet recording method. A wide variety of printing materials are used, such as a printing material made of a recording material ejected and recorded at high speed.

In prints formed from these print materials, a print material having high image quality, improved whiteness, and high image storability has been desired, and the tendency has been increasing in recent years.

In terms of whiteness, the visual whiteness is
Although it depends on personal preference, it is generally known that bluish white looks more white than achromatic whiteness, and it is important to improve such bluish whiteness. Applying optical brighteners is a well-known technique. Generally, a fluorescent whitening agent has an effect of making an object appear whiter by absorbing ultraviolet light and emitting slightly bluish fluorescent light.

As such a fluorescent whitening method, there is known a method in which a fluorescent whitening agent is added to a support of a printing material or to a hydrophilic colloid layer or a polymer layer forming the printing material.

As a method of adding a fluorescent whitening agent to the support of these print materials, JP-A-53-117 discloses a method.
U.S. Pat. Nos. 3,449,257 and 3,50
There is known a method of adding the compound to a paper support or a polyethylene laminate layer used for a silver halide photographic light-sensitive material, as described in JP-A Nos. 1,298, 3,558,316 and the like.

However, according to the conventional method of adding a fluorescent whitening agent to a support of a printing material, sufficient whiteness is obtained because the fluorescent whitening agent is decomposed by heat during the production of the support. I couldn't.

In addition, in the method of adding to a hydrophilic colloid layer or a polymer layer forming a printing material, a water-soluble optical brightener is directly added, or British Patent No. 1,072,915.
As described in the specification, a method is known in which an oil-soluble fluorescent whitening agent is dissolved in an organic solvent, and emulsified and dispersed.

However, when such a method is used, a good white background is obtained immediately after a print image is formed. However, when a print material is stored for a long period of time, not only is the degree of deterioration of the white background large, but also the dye image It also has an adverse effect on image storability.

[0010]

Accordingly, an object of the present invention is to provide a print having excellent whiteness and lightness on a white background, little deterioration of the white background over time, and good storage stability of a dye image. About.

[0011]

The above object of the present invention is attained by the following constitutions. (1) A print having a dye image on a reflective support, wherein the print has a layer containing solid fine particles having a fluorescent whitening effect. (2) A print having a dye image on a reflective support, wherein the print has a layer containing solid fine particles of a substantially water-insoluble organic salt represented by the following general formula [I]. And print.

Formula [I] An ^n- n [B ⁺ ] wherein A represents a fluorescent brightener component having an anionic group, and B represents an organic cation having a total carbon number of 15 or more. , N represents an integer of 1 to 9. (3) A print having a dye image on a reflective support, the print having a layer containing solid fine particles of a substantially water-insoluble organic salt represented by the following general formula [II]: The print to feature.

Formula [II] C ^n- n [D ⁺ ] [wherein C represents a fluorescent brightener component having a sulfonic acid group, and D represents an organic cation having a total carbon number of 15 or more. , N represents an integer of 1 to 9. Hereinafter, details of the present invention will be described.

The compound having a fluorescent whitening effect used in the present invention is a compound having a fluorescent whitening effect substantially insoluble in water, and a compound which is substantially insoluble in water and has a fluorescent whitening effect at room temperature. Any type of compound can be used. Here, “substantially insoluble in water” means that the solubility in 100 g of pure water at 25 ° C. is 1.0 g or less.

As the compound having a substantially water-insoluble fluorescent whitening effect, a general water-insoluble fluorescent whitening agent can be used, but the substantially water-insoluble fluorescent whitening agent represented by the general formula [I] can be used. Is preferable, and a substantially water-insoluble organic salt represented by the general formula [II] is more preferable.

[0016] In the general formula ^{[I] A n- n [B} +] formula [I], A may for example, represent a fluorescent whitening agent component having an anionic group such as a carboxyl group, B
Represents an organic cation having a total carbon number of 15 or more, such as ammonium and pyridinium, and n represents 1
Represents an integer of from 9 to 9.

As the fluorescent whitening agent component having an anionic group, a substituted stilbene fluorescent whitening agent, a substituted coumarin fluorescent whitening agent and a substituted thiophene fluorescent whitening agent having an anionic group are preferable.

General formula [II] C ^n- n [D ⁺ ] In the general formula [II], C represents a fluorescent whitening agent component having a sulfonic acid group, and D represents a total of 15 or more carbon atoms. For example, it represents an organic cation such as ammonium and pyridinium, and n represents an integer of 1 to 9.

The above-mentioned fluorescent whitening agent having a sulfonic acid group is preferably a substituted stilbene fluorescent whitening agent, a substituted coumarin fluorescent whitening agent or a substituted thiophene fluorescent whitening agent having a sulfonic acid group.

The optical brightener components represented by A in the general formula [I] and C in the general formula [II] of the present invention include:
For example, "Fluorescent Whitening Agent" edited by Chemical Industry Association, UK Patent No. 9
It can be easily synthesized with reference to 20,988, German Patent 1,065,838, US Pat. No. 2,610,152, and the like.

The compound represented by the general formula [I] of the present invention,
The compound represented by the general formula [II] is, for example, a compound represented by the general formula [I] of the present invention, which is an optical brightener component corresponding to A in the general formula [I] and C in the general formula [II]. Can be easily synthesized by mixing with an organic cation such as ammonium, pyridinium or the like having a total carbon number of 15 or more, corresponding to B in the formula (I) and D in the general formula [II]. As the organic cation, an ammonium ion having a total carbon number of 15 or more is preferable.

As the ammonium ion having a total carbon number of 15 or more corresponding to B in the general formula [I] and D in the general formula [II] of the present invention, the following general formula [III]
The ammonium cation represented by is preferred.

[0023]

Embedded image In the general formula [III], R ₁ , R ₂ , R ₃ and R ₄ each represent an alkyl group or a phenyl group. Where R ₁ , R ₂ ,
The total number of carbon atoms of R ₃ and R ₄ is 15 or more.

The total number of carbon atoms of R ₁ , R ₂ , R ₃ and R ₄ is 2
It is preferably 0 or more.

The pyridinium cation having a total carbon number of 15 or more corresponding to B in the general formula [I] and D in the general formula [II] of the present invention includes the following general formula [IV]
The pyridinium cation represented by is preferred.

[0026]

Embedded image In the general formula [IV], R ₅ represents an alkyl group having 10 or more carbon atoms or a phenyl group.

The total number of carbon atoms of R ₅ is preferably 15 or more.

Next, specific examples of the compound having a fluorescent whitening effect substantially insoluble in water used in the present invention will be described.
The present invention is not limited to these.

[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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The compound having a fluorescent whitening effect of the present invention is
It is added to the layer constituting the print of the present invention as solid fine particles.

The solid fine particles of the compound having a fluorescent whitening effect of the present invention can be added as a solid fine particle dispersion when a layer constituting a printing material is coated on a support.

The method for dispersing solid fine particles of a compound having a fluorescent whitening effect according to the present invention includes dispersing the compound in water or an aqueous solution of hydrophilic colloid such as gelatin using a high-speed stirring type disperser;
A method of grinding and dispersing in water or an aqueous solution of hydrophilic colloid such as gelatin with a ball mill or a sand mill. A dispersion method, a dispersion method using an ultrasonic disperser, and the like can be given.

In dispersing the compound having a fluorescent whitening effect of the present invention to obtain solid fine particles, a surfactant can be used for the purpose of increasing dispersibility and improving dispersion stability. Preferred surfactants are anionic surfactants,
Nonionic surfactants and betaine-type amphoteric surfactants are exemplified.

The average particle size of the solid fine particle dispersion of the compound having a fluorescent whitening effect of the present invention is 0.05 to 5 μm, preferably 0.1 to 2 μm, more preferably 0.2 to 2 μm. 1 μm.

The compound having a fluorescent whitening effect of the present invention is
It may be added to any of the layers constituting the printing material, but is preferably added to a layer closer to the support than the dye image forming layer.

The amount of the compound having a fluorescent whitening effect of the present invention is 10 to 2000 mg in the print material of the present invention.
/ M ² may be added, but 50 to 100
It is preferable to add 0 mg / m ² .

Preferred embodiments of the print of the present invention are silver halide photographic prints, ink jet prints, and thermal transfer recording prints.

Examples of silver halide photographic prints include prints from color paper, color reversal paper, silver halide print materials for forming positive images, display print materials, and color proof print materials. These silver halide photographic print materials can be produced by a conventional method.

Examples of the ink-jet print material for forming an ink-jet print include an ink-jet print material provided with an alumina hydrated layer and an ink-jet print material provided with a gelatin layer. Can be manufactured. The ink is fixed on the print material by an ink jet method to form a print image.

As the thermal transfer recording material for forming the thermal transfer recording print, a thermal transfer recording material based on a sublimation transfer recording method using a sublimation dye is preferable.

[0045]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 High-density polyethylene was laminated on both sides of a pulp paper having a basis weight of 180 g / m ² to form a reflective support. However,
On the side on which the emulsion layer is applied, a molten polyethylene containing anatase-type titanium oxide having a surface treatment dispersed therein at a content of 15% by weight is laminated. After the reflective support was subjected to corona discharge treatment, a gelatin undercoat layer was provided, and an ink receiving layer shown below was further provided and dried to obtain an ink jet recording sheet sample 101.

<Ink receiving layer> First layer: lime-treated gelatin 4.0 g / m ² PVP K-90 (BASF) 1.5 g / m ² Second layer: lime-treated gelatin 4.0 g / m ² PVP K- 90 (BASF) 1.5 g / m ² activator SF-1 0.01 g / m ² activator SF-2 0.01 g / m ²

[0048]

Embedded image

Next, except that the following water-soluble fluorescent whitening agent W-1 was added to the first layer of the sample 101 at a concentration of 0.2 g / m ² , the sample 102 was prepared in the same manner as the sample 101. Created.

[0050]

Embedded image Subsequently, Exemplified Compound F of the present invention was added to the first layer of Sample 101.
Sample 101 was prepared in the same manner as Example 101 except that 0.1 g / m ^{2 was} added as a dispersion liquid obtained by dispersing -11 in the following solid fine particle dispersion method.
A sample 103 was prepared in the same manner as described above.

[Method for Dispersing Solid Fine Particles of Exemplified Compound F-11] 300 g of Exemplified Compound F-11 of the present invention was weighed, added to 750 ml of a 5% aqueous solution of lime-treated gelatin, and then polyoxyethylene (10 mol added). Nonyl phenyl ether (nonionic surfactant) 10% solution 30
Then, after the temperature was adjusted to 40 ° C., the mixture was dispersed for 90 minutes at 6000 rpm using a high-speed stirring type disperser,
Then, it was finished to 1000 ml to obtain a solid fine particle dispersion of F-11.

The average particle size of the obtained dispersion was 0.5 μm.

In Sample 103, Sample 1 was prepared in the same manner as in Sample 103 except that the exemplified compound of the present invention was changed from F-11 to the exemplified compounds of the present invention shown in Table 3.
04 to 110 were created.

In dispersing the exemplified compounds of the present invention shown in Table 3 by the method for dispersing solid fine particles, the average particle diameter of the solid fine particles was adjusted to the value shown in Table 3.

The following evaluations were performed on the obtained samples 101 to 110. <Evaluation of immediate white background> The reflection density of the white background of each sample was measured with a color analyzer (type 607, manufactured by Hitachi, Ltd.).

At this time, the reflection density (D ₄₄₀ ) and lightness (L *) at a wavelength of 440 nm were measured and used as a measure of the white background.

It is preferable that the value of the reflection density (D ₄₄₀ ) is small and the value of the lightness (L ^* ) is large.

Table 3 shows the obtained results. <Evaluation of White Background> Each sample was stored at 85 ° C. and 40% for 7 days, and then the reflection density (D ₄₄₀ ) and lightness (L ^* ) were obtained in the same manner as in the evaluation of the immediate white background.

Those with a small difference between the evaluation of the white background over time and the evaluation of the immediate white background are excellent in the white background over time.

Table 3 shows the obtained results. <Evaluation of discoloration property> Each sample was printed with the following magenta ink using an inkjet printer (DesignJet 650C, manufactured by Hewlett-Packard Co.) to form a magenta image. [Magenta Ink] Xylene Red B (CI45100) 6 parts Diethylene glycol 47 parts Water 47 parts The color tone of the obtained magenta image was measured using a color analyzer 60.
The measurement was carried out using a 7-inch type (manufactured by Merit Manufacturing).

Further, the color tone of the magenta color-developed sample after being exposed to sunlight for 7 days using an underglass outdoor exposure table was measured.

CIE1976L * a before and after solar irradiation
The color difference in the * b * color system was used as a measure of discoloration.

The smaller the discoloration value, the better the image storability.

Table 3 shows the obtained results.

[0065]

[Table 3]

As shown in Table 3, it can be seen that the print material of the present invention has an excellent white background, has little deterioration of the white background over time, and has good dye image preservability.

Example 2 100 parts by weight of barium sulfate, 8 parts by weight of gelatin, and 0.1 part of chromium sulfate (hardener) were added to the paper support described in Example 1 provided with a gelatin undercoat layer by corona discharge treatment. The coating solution containing 24 parts by weight was coated with an air knife coater at 20 g / m2.
^By applying and drying in ² , an ink receiving layer was formed, and an ink jet recording sheet 201 was obtained.

Next, in the same manner as in Sample 201, except that the water-soluble fluorescent whitening agent W-1 used in Example 1 was added to the ink receiving layer of Sample 201 so as to be 0.3 g / m ^2. Sample 202 was prepared.

Subsequently, Except Compound 0.1 of the present invention was dispersed in the ink receiving layer of Sample 201 by the following method of dispersing solid fine particles in the following manner except that 0.1 g / m ^{2 was} added. A sample 203 was prepared in the same manner as described above.

[Method for Dispersing Solid Fine Particles of Exemplified Compound F-10] 300 g of Exemplified Compound F-10 of the present invention was weighed and added to 750 ml of a 5% aqueous solution of gelatin. After adding 30 ml of a 10% solution of ether (nonionic surfactant) and adjusting the temperature to 40 ° C., the mixture was treated with a high-speed stirring type dispersing machine.
Dispersed at 000 rpm for 90 minutes, then
By finishing to 1000 ml, a solid fine particle dispersion of F-10 was obtained.

The average particle size of the obtained dispersion was 0.4 μm.

The obtained samples 201 to 203 were evaluated in the same manner as in Example 1. Table 4 shows the obtained results.

[0073]

[Table 4]

As shown in Table 4, it can be seen that the print material of the present invention has an excellent white background, has little deterioration of the white background over time, and has good dye image preservability.

Example 3 100 g of alumina sol having a solid content of 18% by weight synthesized by hydrolysis and peptization of aluminum alkoxide, 32 g of a 6.2% by weight aqueous solution of polyvinyl alcohol, and the present invention prepared by the following solid fine particle dispersion method Exemplified Compound F
A coating liquid was prepared by mixing 15 ml of the solid fine particle dispersion of -10.

[Method for Dispersing Solid Fine Particles of Exemplified Compound F-10] 200 g of Exemplified Compound F-10 of the present invention was weighed, added to 750 ml of pure water, and then polyoxyethylene (10 mol addition) nonylphenyl ether ( After adding 30 ml of a 10% solution of a nonionic surfactant) and adjusting the temperature to 40 ° C., the mixture was dispersed at 8000 rpm for 60 minutes using a high-speed stirring type disperser, and then finished to 1000 ml to obtain F-10. Was obtained.

The average particle size of the obtained dispersion was 0.4 μm.

This coating solution was dried on a polyethylene terephthalate film (thickness: 100 μm) in an amount of 20
g / m ² was applied using a bar coater to form an alumina hydrate layer.

The coated surface of this sheet was immersed in a 3% by weight ethanol solution of stearic acid, and the solution was uniformly applied. After drying, this was heat-treated at 140 ° C. to obtain a recording sheet.

When the obtained sample was evaluated in the same manner as in Example 1, it was found that the sample had an excellent white background, had little deterioration of the white background over time, and had good image storability. Had.

Example 4 Vinyl chloride-vinyl acetate copolymer resin (trade name: VYH)
D; manufactured by Union Carbide Co.) was dissolved in 30 parts by weight of methyl ethyl ketone, and 0.05 parts by weight of nickel dibutyldithiocarbamate was added to the solution as a light stabilizer. -10 to 0.
Of a release agent (trade name: KF39)
(3, Shin-Etsu Chemical Co., Ltd.) in an amount of 0.5 part by weight to prepare a coating solution for the image receiving layer.

The exemplified compound F-10 of the present invention was added as a solid fine particle dispersion prepared by the following solid fine particle dispersion method. [Method of Dispersing Solid Fine Particles of Exemplified Compound F-10] 100 g of Exemplified Compound F-10 of the present invention was weighed, added to 500 ml of methyl ethyl ketone, and then dispersed in a ball mill for 5 hours to obtain a dispersion of solid fine particles of F-10. I got

This image-receiving layer coating solution was applied to a 150 μm-thick propylene synthetic paper with a wire bar, and then dried.
An image receiving body for thermal transfer recording having an image receiving layer having a dry film thickness of 5 μm was prepared.

The whiteness of the surface of the image receiving layer was good, and the whiteness did not change even after long-term storage.

[0085]

The print material of the present invention has an excellent white background, has little deterioration of the white background over time, and has good image storability.

Claims (3)

[Claims] 1. A print having a dye image on a reflective support, wherein the print has a layer containing solid fine particles having a fluorescent whitening effect. 2. A print having a dye image on a reflective support, wherein the print has a layer containing solid fine particles of a substantially water-insoluble organic salt represented by the following general formula [I]. Print characterized by. General formula [I] An ^- n [B ⁺ ] [wherein A represents a fluorescent brightener component having an anionic group, B represents an organic cation having a total carbon number of 15 or more, and n represents Represents an integer of 1 to 9. ] 3. A print having a dye image on a reflective support, said print having a layer containing solid fine particles of a substantially water-insoluble organic salt represented by the following general formula [II]: Print characterized by. General formula [II] C ^n- n [D ⁺ ] [wherein C represents a fluorescent whitening agent component having a sulfonic acid group, D represents an organic cation having a total carbon number of 15 or more, and n represents Represents an integer of 1 to 9. ]