JP2000181170A - Color image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To widen the color reproduction region of a hard copy, to improve hues and to obtain the color reproduction approximate to the color reproduction of CRT images or liquid crystal images by commonly using substractive mixture of colors and additive mixture of colors in color correction. SOLUTION: The color correction is executed by using the additive mixture of colors in conjunction with the substractive mixture of colors. Fluorescent material is preferably used as the additive mixture of colors. A compound having absorption in a visible region and fluorescent material having light emission in the visible region are mixed. The fluorescent material is mixed at a ratio at which the absorption intensity (abs. value) after mixing of the compound having the absorption in the visible region and fluorescent having the light emission in the visible region does not be below minus 0.3. The compound having the absorption in the visible region is color material. The fluorescent material is preferably the fluorescent material having the light emission in the undesirable absorption wavelength region of the compound having the absorption in the visible region. The phosphor to be added may be one kind or the combination use of >=2 kinds is equally well.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a reflection and transmission color image forming method.

[0002]

2. Description of the Related Art Reflection and transmission color images refer to all characters and images consisting of object colors other than the light source color.
Printed matter using intaglio, planographic printing, etc., output by a printer (including ink jet printer, laser printer, sublimation printer, transfer printer, electrostatic printer and all other known printers), photosensitive material,
Copy, all other reflective and transparent originals (hereinafter referred to as
These are called hard copies. ). The quality of a hard copy is determined by the gradation, resolution, color gamut, sharpness, and the like.

[0003] The color of a hard copy depends on the color of an image carrier such as paper or an OHP sheet, the color of a dye, and the ink or toner composition. Conventionally, in order to expand the color reproduction range or improve the hue, the search for dyes with higher color purity, that is, improvements based on the chemical structure have been made, and efforts have been made to reduce side absorption, but lightfastness, Considering cost and other conditions, the improvement was limited.

[0004] In addition, the aggregation state of the dye and the light transmittance of the activator and the polymer constituting the ink or the toner have been devised, but the side absorption of the dye has not been eliminated. Further, fluorescent substances have been used for improving color images. For example, it is known to use a fluorescent whitening agent. However, a fluorescent dye used as a fluorescent whitening agent is itself a visible light. It is a colorless compound having no absorption in the wavelength range, and the emission wavelength range is limited to blue. Therefore, it is only an improvement and adjustment of a white background against yellowing or the like, and does not exert an effect of cutting off the side absorption of the dye.

Also, US Pat. No. 4,774,181 discloses a method using a coupler that emits a fluorescent substance (fluorescent dye-emitting coupler). The fluorescent dye releasing coupler is uniformly incorporated in the photosensitive material, and becomes a fluorescent dye after a process such as development. Furthermore, the fluorescent dye releasing coupler has poor storage stability and is not practical. As an example of using a fluorescent substance for a hard copy, there is an example of using a fluorescent substance for the purpose of preventing forgery. However, the phosphor used here does not emit color in the visible light range under normal light such as natural light or fluorescent light. Ink that emits fluorescence under normal light is also known, but these are intended to make images look flashy or visually impact, increase color purity, or expand the color reproduction range It is not used for any purpose.

[0006] As digitization advances in the future, it is desired that the hue and color reproduction range of a hard copy approach those of a CRT. The approach for that purpose is being developed in terms of digital signal processing as color management, but is still limited to the above method from the viewpoint of materials. The concept of using both subtractive color mixing and additive color mixing has been applied to displays. In these methods, a color filter is applied to the color of the phosphor to absorb extraneous color and increase the color purity. That is, the image formed by additive color mixture is color corrected by subtractive color mixture. However, conversely, the idea of increasing the color purity by using additive color mixing in the case of subtractive color mixing is only the use of a fluorescent whitening agent for the purpose of improving the white background, if it were to be mentioned. There was no idea to increase the color purity for the purpose of correction. Accordingly, the present inventors have conducted various studies to expand the color reproduction range of an image and improve hue, and as a result, by performing color correction using a fluorescent substance, the color reproduction range can be expanded or the hue can be increased. We found that it could be improved.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to broaden the color reproduction range of a hard copy composed of only subtractive color mixture, improve the hue, and obtain color reproduction close to a CRT image or a liquid crystal image. Another object of the present invention is to provide a color image forming method capable of obtaining a hard copy.

[0008]

The above object is achieved by the following method. (1) A color image forming method characterized by performing color correction by using additive color mixture in addition to subtractive color mixture. (2) The color image forming method as described in (1) above, wherein a fluorescent substance is used as additive color mixture. (3) The color image forming method as described in (1) or (2) above, wherein a compound having absorption in the visible region and a fluorescent substance having emission in the visible region are mixed. (4) Absorption intensity (a) of the fluorescent substance after mixing a compound having absorption in the visible region and a fluorescent substance having emission in the visible region.
bs. (3) is mixed in an amount not less than −0.3. (5) The color image forming method as described in (3) or (4) above, wherein the compound having absorption in the visible region is a coloring material. (6) The color image forming method according to any one of (3) to (5) above, wherein the fluorescent substance is a fluorescent substance which emits light in an undesired absorption wavelength region of the compound having absorption in the visible region. . (7) The area of the figure formed by the absorption waveform in the undesired absorption wavelength region of the color image is set to the same undesired absorption wavelength region of the compound having absorption in the visible region where the fluorescent substance having emission in the visible region is not mixed. The color image forming method according to any one of the above (3) to (5), wherein the area of the figure formed by the absorption waveform is 98% or less. (8) The height of the absorption peak in the undesired absorption wavelength region of the color image is determined by the height of the absorption peak in the same undesired absorption wavelength region of the compound having absorption in the visible region where the fluorescent substance having emission in the visible region is not mixed. The color image forming method according to any one of the above (3) to (5), wherein the color image is 98% or less. (9) The full width at half maximum of the main absorption peak of the color image is 99.sup.th of the half width of the main absorption peak of the compound having absorption in the visible region where the fluorescent substance having light emission in the visible region is not mixed
The color image forming method according to any one of the above (3) to (5), wherein the content is 5% or less.

(10) The fluorescent substance has an excitation light wavelength of 350 nm or more.
(3) characterized in that it is a 420 nm fluorescent substance.
The color image forming method according to any one of (1) to (9). (11) The fluorescent substance has an emission peak wavelength of 400 nm to 500 nm.
(2) to (1), wherein
0) The color image forming method according to any one of the above. (12) The fluorescent substance has an emission peak wavelength of 500 nm to 600 nm.
(2) to (1), wherein
0) The color image forming method according to any one of the above. (13) The fluorescent substance has an emission peak wavelength of 600 nm to 700 nm.
(2) to (1), wherein
0) The color image forming method according to any one of the above. (14) The above (2) to (13), wherein the fluorescent substance is a fluorescent substance having a Stokes shift width of 10 nm or more.
The color image forming method according to any one of the above. (15) The fluorescent substance has a Stokes shift width of 10 nm to 10
The color image forming method according to the above (11), which is a fluorescent substance of 0 nm. (16) The fluorescent substance has a Stokes shift width of 100 nm to 2
(12) characterized in that it is a 00 nm fluorescent substance.
3. The color image forming method described in 1. above. (17) The fluorescent substance has a Stokes shift width of 200 nm to 3
(13) characterized in that it is a 00 nm fluorescent substance
3. The color image forming method described in 1. above. (18) The color material is a yellow color material, and the area of a figure formed by an absorption waveform in a region having a wavelength of 500 nm or more in a color image has a wavelength of the yellow color material in which a fluorescent substance having light emission in a visible region is not mixed. The color image forming method according to any one of the above (5) to (10), wherein the area of the figure formed by the absorption waveform in the region of 500 nm or more is 98% or less.

(19) The color material is a magenta color material, and the area of a figure formed by an absorption waveform other than a wavelength of 500 nm to 600 nm of a color image is a magenta color which does not mix a fluorescent substance having light emission in a visible region. Material wavelength 500nm ～ 6
(5) to (1), wherein the area is not more than 98% of the area of the figure formed by the absorption waveform in the region other than 00 nm.
0) The color image forming method according to any one of the above. (20) The color material is a cyan color material, and the area of a figure formed by an absorption waveform having a wavelength of 600 nm or less in a color image is 600 nm or less of a cyan color material that does not mix a fluorescent substance that emits light in the visible region. The color image forming method according to any one of the above (5) to (10), wherein the area is not more than 98% of the area of the figure formed by the absorption waveform in the region. (21) The color image forming method according to any one of (2) to (20), wherein the fluorescent substance is an inorganic fluorescent substance. (22) The color image forming method according to any one of (2) to (21), wherein the fluorescent substance is a fluorescent substance having a composition containing an oxygen atom. (23) A color image forming method for forming an image on an image carrier by a plurality of pixels, wherein the pixels are formed of a mixture of a fluorescent substance and a coloring material. (24) A color image forming method comprising: preparing an image forming material which is a mixture of a fluorescent substance and a coloring material; and adding the prepared image forming material to an image carrier in an image-wise manner. (25) The color image forming method according to (24), wherein the imagewise addition of the image forming material to the image carrier is performed by transferring the image forming material to the image carrier. (26) Imagewise addition of the image forming material to the image bearing member is performed for each of yellow, cyan, magenta, and black by (a) an OPC charging step, (b) an OPC exposure step, and (c) an image. A process of adsorbing the forming material to the OPC,
(D) using at least one step of transferring the image forming material from the OPC to the intermediate transfer member, and then transferring the image of the image forming material formed on the intermediate transfer member to the image carrier. Fixing the color image. (27) The color image forming method as described in (24) above, wherein the imagewise addition of the image forming material to the image carrier is performed by spraying the image forming material onto the image carrier. (28) Imagewise addition of the image forming material to the image carrier is performed by: (e) discharging the image forming material from the nozzle of the recording head for each of yellow, cyan, magenta, and black; A step of adsorbing the released image forming material to an image carrier, at least one of the steps is performed.

Hereinafter, the present invention will be described in detail. In the present invention, color correction refers to changing at least one of the absorbance, absorption waveform, half width, absorption peak, color purity, lightness, and saturation of a dye. That is, it includes changing the hue of the dye, reducing the side absorption, changing the color reproduction range, and the like. It also includes improving or lowering the color purity and enlarging or reducing the color gamut. Color purity refers to the ratio of absorption in the absorption wavelength region other than the absorption peak, and the smaller the ratio of absorption in the absorption wavelength region other than the absorption peak, the higher the color purity.

In the present invention, the color gamut refers to the entire area in which a color image can be colored, and for example, the entire color gamut represented on the CIE (International Commission on Illumination) chromaticity diagram (JIS Z-8721). Area or JIS Z-8722
It refers to the entire area represented by the L ^* a ^* b ^* space measured according to the method defined in (Method of Measuring Object Color). The expansion of the color gamut in the present invention means that the color gamut is expanded by using additive color mixing using a fluorescent substance or the like as compared with a case where no additive color mixing is used. For example, CI
This means that on the E-chromaticity diagram, the area of the entire colorable region represented or the volume of the L ^* a ^* b ^* space is increased.

The term "change in hue" in the present invention refers to a change in dominant wavelength or color purity obtained by measuring a reflection or transmission spectrum of a hard copy. Normal hard copy consists of subtractive color mixture of yellow, magenta and cyan dyes,
Since the original absorption of the dye is directly reflected in the formed image, if the dye has side absorption, it is impossible to produce a color with higher purity. However, the additive absorption can be canceled by, for example, adding a fluorescent substance that emits light to the secondary absorption portion of the dye to cancel the secondary absorption.

FIG. 1 shows an absorption curve after a coloring material and a fluorescent substance are added to the coloring material. In the color image forming method of the present invention, it is possible to mix a compound having absorption in the visible region to perform subtractive color mixing and a luminescent substance having light emission in the visible region to perform additive color mixing in an arbitrary amount or ratio,
Since the appearance of fluorescent light has an effect different from that of color correction, the fluorescent substance has an absorption intensity (ab) shown in FIG. 1 at an arbitrary point in the absorption waveform after the fluorescent substance is added to the coloring material.
s. It is preferred to mix in such an amount or ratio that the value or value does not fall below the line of -0.3. More preferably, the absorption intensity (abs. Value) does not fall below -0.1, and more preferably does not fall below 0.

The preferred amount or ratio varies depending on the combination of the compound and the fluorescent substance used, but may be any amount or ratio that satisfies the above in each case. Further, one kind of phosphor may be added, or two or more kinds may be used in combination. For example, desired light emission can be obtained by using a wavelength-convertable combination.
The fluorescent substance may be added to a coloring material such as ink or toner,
It may be uniformly applied to the support. In the case of coating on a support, it is preferable to use a mixture of two or more kinds of phosphors whose emission peaks differ by 30 nm or more.

Usually, the hard copy is 400 nm to 500 nm.
Yellow with main absorption at nm, 500 nm-600
Magenta with main absorption at nm, 600 nm to 700
Color reproduction is performed by subtractive color mixing using a cyan dye having a main absorption at nm. When color reproduction is performed with yellow, magenta, and cyan, the main absorption wavelength region is a wavelength region of 400 nm to 500 nm for yellow, a wavelength region of 500 nm to 600 nm for magenta, and a cyan region. Refers to a wavelength region of 600 nm to 700 nm, and the undesired absorption wavelength region refers to a magenta and cyan region for yellow, a yellow and cyan region for magenta, and a yellow and magenta region for cyan. Good, for example 500nm for yellow
As described above, the absorption wavelength range is 500 nm or less and 600 nm or more for magenta, and 600 nm or less for cyan.

FIG. 2 shows the area of the figure formed by the absorption waveform in the undesired absorption wavelength region and the absorption in the same undesired absorption wavelength region of the compound having absorption in the visible region without mixing the fluorescent substance emitting light in the visible region. FIG. 3 is an explanatory diagram illustrating the area of a figure formed by a waveform. The area of a figure formed by an absorption waveform in an undesired absorption wavelength region is defined as an absorption curve and an absorption intensity after mixing a fluorescent material with a coloring material (a compound having absorption in the visible region) in the undesired absorption wavelength region. abs. value) is an area (indicated by a vertical line in FIG. 2) surrounded by a line of 0.0, which is the same as a compound having absorption in the visible region where a fluorescent substance having light emission in the visible region is not mixed. Is the area of the figure formed by the absorption waveform in the undesired absorption wavelength region, the absorption curve and the absorption intensity (abs. Value) of the coloring material in the undesired absorption wavelength region.
The area of the area surrounded by the line of 0.0 (shown by a horizontal line in FIG. 2). The area of the figure formed by the absorption waveform in the undesired absorption wavelength region is formed by the absorption waveform in the same undesired absorption wavelength region of the compound having absorption in the visible region where the fluorescent substance having emission in the visible region is not mixed. Preferably, the area is 98% or less of the area of the figure. More preferably, it is 95% or less, and more preferably 9% or less.
3% or less. For example, when the compound having absorption in the visible region is cyan, the absorption curve and the absorption intensity (abs. Value) in the absorption wavelength region of 600 nm or less after the combined use of the fluorescent substance with cyan are surrounded by a line of 0.0. Area of the cyan area without fluorescent material
Absorption curve and absorption intensity (ab
s. (Value) means not more than 98% of the area of the area enclosed by the line of 0.0.

FIG. 3 shows the height of the absorption peak in the undesired absorption wavelength region and the height of the absorption peak in the same undesired absorption wavelength region of the compound having absorption in the visible region without mixing the fluorescent substance emitting light in the visible region. FIG. In FIG. 3, A shows the height of the absorption peak in the undesired absorption wavelength region of the absorption curve after mixing the fluorescent substance with the coloring material, and B shows the absorption peak in the undesired absorption wavelength region of the absorption curve of only the coloring material. Indicates the height of In the present invention, the height A of the absorption peak in the undesired absorption wavelength region after applying the fluorescent substance to the coloring material is 98% or less of the height B of the absorption peak in the undesired absorption wavelength region of only the coloring material. Is preferred. More preferably, it is 95% or less, and more preferably, it is 93% or less.

For example, when the compound having an absorption in the visible region is cyan, the height of the absorption peak in the absorption wavelength region of 600 nm or less is determined by comparing the height of the absorption peak in the absorption wavelength region of 600 nm or less of cyan itself without using a fluorescent substance. It means that it is 98% or less of the height of the peak.

FIG. 4 is an explanatory diagram for explaining the half width of the main absorption peak. In the figure, C indicates the half width of the absorption curve after mixing the fluorescent material with the coloring material, and D indicates the half width of the absorption curve of only the coloring material. In the present invention, it is assumed that the half width of the main absorption peak is 99.5% or less of the half width of the main absorption peak of a compound having absorption in the visible region where a fluorescent substance emitting light in the visible region is not mixed with C in FIG. To 99.5% or less of D. In the present invention, it is further preferable that the half width of the main absorption peak after mixing the fluorescent substance with the coloring material has a half width of the main absorption peak of 99% or less of the half width of the main absorption peak of only the coloring material. And more preferably 98% or less.

When performing an operation satisfying the above requirements,
Although the desired absorption may decrease, there is no problem if the amount of the phosphor added is the amount described later. Further corrections may be made by adding other dyes to compensate for the desired reduction in absorption.

In the present invention, the excitation wavelength range of the phosphor is preferably in the ultraviolet region which does not affect the image, but may be in the visible region as long as the image formation is not adversely affected. Preferably from 300 nm to 450 nm, more preferably from 350 nm to 4 nm
20 nm. The effect of color correction may be obtained when irradiating black light together with incandescent light, fluorescent light, and daylight, but the effect of color correction can be obtained without using a special light source. , And 350 nm to 420 nm, preferably under visible light (incandescent light, fluorescent light, daylight).

In the present invention, as the phosphor used in the color image forming method, any known organic phosphor or inorganic phosphor which emits light in an undesired absorption region can be used arbitrarily. it can.

As the organic phosphor, any substance currently known can be used. For example, brilliantsulfoflav
ine FF, basic yellow HG, eosine, rhodamine 6G, rho
damine B or a phosphor having a pyrene ring, for example, sodium pyrene trisulfonate or sodium pyrene tetrasulfonate, their hydroxy-substituted, amino-substituted,
Acetamide-substituted product, C.I. I. Basic Red 1,
C. I. Basic Red 2, C.I. I. Basic Red 9, C.I. I. Basic Red 12, C.I. I. Basic Red 13, C.I. I. Basic Red 14, C.I.
I. Basic Red 17, C.I. I. Acid Red 5
1, C.I. I. Acid Red 52, C.I. I. Acid Red 92, C.I. I. Acid Red, C.I. I. Basic Violet 1, C.I. I. Basic Violet 3, C.I. I. Basic Violet 7, C.I. I. Basic violet 10, C.I. I. Basic Violet 14 and the like, but are not limited thereto.

The composition of the inorganic phosphor used in the present invention is as follows:
For example, JP-A-50-6410 and 61-652.
No. 26, No. 64-22987, No. 64-60
671 and JP-A-1-168911. Although the composition of the inorganic phosphor used in the present invention is not particularly limited, it is a crystal matrix of Y ₂ O ₂ S, Zn ₂ SiO _4, Ca ₅ (PO
₄ ) Metal oxides such as ₃ Cl and sulfides such as ZnS, SrS, and CaS are added to Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb,
Dy, Ho, Er, Tm, Yb and other rare earth metal ions and Ag, Al,
A combination of metal ions such as Mn and Sb as an activator or co-activator is preferred.

Preferred examples of the crystal base are listed below.
ZnS, Y_TwoO_TwoS, Y_ThreeAl_FiveO₁₂, Y_TwoSiO_Three, Zn_TwoSiO_Four, Y_TwoO_Three, BaMgA
l_TenO₁₇, BaAl₁₂O₁₉, (Ba, Sr, Mg) O ・ aAl_TwoO_Three, (Y, Gd) B
O_Three, YO_Three, (Zn, Cd) S, SrGa_TwoS_Four, SrS, GaS, SnO _Two, Ca
_Ten(PO_Four)₆(F, Cl)_Two, (Ba, Sr) (Mg, Mn) Al_TenO₁₇, (Sr, Ca,
 (Ba, Mg)_Ten(PO_Four)₆Cl_Two, (La, Ce) PO_Four, CeMgAl₁₁O₁₉, GdMg
B_FiveO_Ten, Sr_TwoP_TwoO₇, Sr_FourAl₁₄O_{twenty five}

The above-mentioned crystal base and activator or co-activator may be partially replaced with homologous elements. The elemental composition of the inorganic phosphor is not particularly limited as long as it absorbs light in the ultraviolet to blue region and emits visible light.

In the following, inorganic phosphors preferably used in the present invention are shown, but the present invention is not limited to these compounds. [Blue-emitting inorganic fluorescent _{compound] (BL-1) Sr 2} P 2 O 7: Sn 4+ (BL-2) Sr 4 Al 14 O 25: Eu 2+ (BL-3) BaMgAl 10 O 17: Eu 2+ (BL-4) SrGa ₂ S ₄ : Ce ³⁺ (BL-5) CaGa ₂ S ₄ : Ce ³⁺ (BL-6) (Ba, Sr) (Mg, Mn) Al ₁₀ O ₁₇ : Eu ²⁺ ( BL-7) (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu ²⁺ (BL-8) ZnS: Ag (BL-9) CaWO ₄ (BL-10) Y ₂ SiO ₅ : ce (BL-11) ZnS: Ag, Ga, Cl (BL-12) Ca 2 B 5 O 9 Cl: Eu 2+ (BL-13) BaMgAl 14 O 23: Eu 2+

[Green-emitting inorganic fluorescent compound] (GF-1) (Ba, Mg) Al ₁₆ O ₂₇ : Eu ²⁺ , Mn ²⁺ (GF-2) Sr ₄ Al ₁₄ O ₂₅ : Eu ²⁺ (GF- 3) (Sr, Ba) Al ₂ Si ₂ O ₈ : Eu ²⁺ (GF-4) (Ba, Mg) ₂ SiO ₄ : Eu ²⁺ (GF-5) Y ₂ SiO ₅ : Ce ³⁺ , Tb ^{3 +} (GF-6) Sr ₂ P ₂ O ₇ -Sr ₂ B ₂ O ₅ : Eu ²⁺ (GF-7) (Ba, Ca, Mg) ₅ (PO ₄ ) ₃ Cl: Eu ²⁺ (GF-8 ) Sr ₂ Si ₃ O ₈ -2 SrCl ₂ : Eu ²⁺ (GF-9) Zr ₂ SiO ₄ , MgAl ₁₁ O ₁₉ : Ce ³⁺ , Tb ³⁺ (GF-10) Ba ₂ SiO ₄ : Eu ²⁺ ( GF-11) ZnS: Cu, Al (GF-12) (Zn, Cd) S: Cu, Al (GF-13) ZnS: Cu, Au, Al (GF-14) Zn 2 SiO 4: Mn (GF- 15) ZnS: Ag, Cu ( GF-16) (Zn, Cd) S: Cu (GF-17) ZnS: Cu (GF-18) Gd 2 O 2 S: Tb (GF-19) La 2 O 2 S : Tb (GF-20) Y ₂ SiO ₅ : Ce, Tb (GF-21) Zn ₂ GeO ₄ : Mn (GF-22) CeMgAl ₁₁ O ₁₉ : Tb (GF-23) SrGa ₂ S ₄ : Eu ²⁺ (GF- 4) ZnS: Cu, Co ( GF-25) MgO · nB 2 O 3: Ce, Tb (GF-26) LaOBr: Tb, Tm (GF-27) La 2 O 2 S: Tb

[Inorganic fluorescent compound emitting red light] (RL-1) Y ₂ O ₂ S: Eu ³⁺ (RL-2) (Ba, Mg) ₂ SiO ₄ : Eu ³⁺ (RL-3) (Ba, Mg ) Al ₁₆ O ₂₇ : Eu ³⁺ (RL-4) (Ba, Ca, Mg) ₅ (PO ₄ ) ₃ Cl: Eu ³⁺ (RL-5) YVO ₄ : Eu ³⁺ (RL-6) CaS: Eu ³⁺ (RL-7) Y ₂ O ₃ : Eu (RL-8) 3.5MgO, 0.5MgF ₂ GeO ₂ : Mn (RL-9) (Y, Cd) BO ₃ : Eu

Further, in the present invention, a phosphor used for a three-wavelength phosphor, calcium halophosphate, and the like can also be used. In the color image forming method of the present invention, among the inorganic phosphors, it is preferable to use an inorganic oxide phosphor or an inorganic halide phosphor, and it is particularly preferable to use an inorganic oxide phosphor.

Further, among the inorganic phosphors, an inorganic phosphor exhibiting a Stokes-type shift with good luminous efficiency is desirable. The Stokes shift value may be 10 nm or more,
Preferably, it is at least 20 nm, more preferably at least 30 nm. For example, if the unwanted absorption region is at a wavelength of 400 nm to 500 nm, the Stokes shift value is 10
If the undesired absorption range is from 500 nm to 600 nm, the Stokes shift value is 10 nm.
0 nm to 200 nm, unwanted absorption region at wavelength 600
When the wavelength is from nm to 700 nm, the Stokes shift value is preferably 200 nm and 300 nm.

The emission wavelength of the phosphor used is, for example, 500 nm to 600 nm or 600 nm for yellow.
From 700 nm to 400 nm for magenta
nm or 600 to 700 nm, 4 for cyan
It is preferably from 00 nm to 500 nm or from 500 nm to 600 nm. The emission waveform may be broad or sharp, and it is preferable to cover the entire sub-absorption region.However, if color correction can be performed, sub-absorption may remain.For example, only a portion where human visibility is strong can be specifically emitted. No problem.

It is preferable that the inorganic phosphor used has a small load on the environment and the human body. The inorganic phosphor can be manufactured by any conventionally known method. From the viewpoint of light emission intensity, those which do not undergo a mechanical crushing step at the time of production, that is, those synthesized by a build-up method are preferable, and in particular, Sol-G
Those manufactured by a liquid phase method such as the el method are preferred.

The production method by the Sol-Gel method generally means that an element (metal) used for a base material, an activator or a coactivator is, for example, Si (OCH ₃ ) ₄ or Eu ³⁺ (CH ₃ C
Double alkoxides (eg, Al (OBu) ₃ ] ₂ 2-alkoxides prepared by adding a simple metal to a metal alkoxide or metal complex such as OCH ＝ C (O ⁻ ) CH ₃ ) ₃ or a solution thereof in an organic solvent.
Mg made by adding metallic magnesium to butanol solution
[Al (OBu) ₃ ] ₂ etc.), a metal halide, a metal salt of an organic acid, a required amount of a metal as a simple substance, and a thermal or chemical polycondensation. Firing, reduction treatment, or the like may be performed. In particular, So
In the case of manufacturing by the l-Gel method, a precursor solution of a phosphor or a solution containing primary particles is patterned on a transparent substrate by a printing method, an inkjet method, or the like, and then subjected to a crystallization treatment such as a baking or reduction treatment or a brightness enhancement treatment. You may. The inorganic phosphor may be surface-modified or improved in dispersibility by a surface-modifying agent, a surfactant, a matting agent such as fine-particle silica gel, aerosil, and alumina, if necessary. The higher the luminous efficiency, water resistance, light resistance, and weather resistance of these phosphors, the better, but they may be low as long as they have an effect. In this case, surface treatment or the like can be used.

In the formation of a color image of the present invention, a dye which has been conventionally used for forming an image by subtractive color mixing can be used for forming an image by subtractive color mixing. Examples of these dyes include the following, but are not limited thereto.

Benzoazo type, spiropyran type, fulgide type, diallylethene type, dipidropyrene type, benzothiospiropyran type, spirooxazine type, spirocoumarinopyran, spiroindoline, spirothiazine, oxazolyl, thiazolylethene, dialkyl used as photochromic dyes Ethene, dioxypyrimidine, naphthacene derivative, porphyrin, polymethine, polydiacetylene, thiophenoxysulfonium tetraborate, thioindigo, succinate dialkyl ester, hexaphenylimidazolyl.

Carbon black, benzidine yellow, diphenylmethane dyes, quinacridone, rhodamine, phthalocyanine blue, oil blue, alkali blue, phthalocyanine green, indophenol dyes, phthalocyanine dyes, azo dyes used for toners Anthraquinone dyes, nigrosine dyes, aniline blue, calcoil blue, chrome yellow, ultramarine blue, Dupont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, malachite green oxalate, rose bengal.

Triphenylmethane-phthalide-based, fluoran-based,
Phenothiazines, indolyl phthalides, leuco auramines, spiropyrans, rhodamine lactams,
Triphenylmethane, thiofluorane, xanthene, methine, aminophenylpentadiene, benzopyran. More specifically, CVL, BLMB, OD
B, Red 2, S-205, ATP, DEBW, PSD-: P, V, O, R, HR, G, 150, 17
0, TH-: 106, 107

Azo, anthraquinone, azomethine, methine, indoaniline, and spiro systems used for thermal transfer.

For example, CI Disperse Yellow 54, CI
Disperse Red60, CI Disper
seBlue14.

Yellows used for melt transfer: chrome yellow (yellow), zinc chromade (zinc yellow), lemon yellow (barium chromate), cadmium yellow, naphthol yellow S, Hansa yellow 5G, Hansa yellow 3G, Hansa Yellow G, Hansa Yellow GR, Hansa Yellow A, Hansa Yellow RN, Hansa Yellow R, Benzin Yellow, Benzin Yellow G, Benzin Yellow GR,
Permanent yellow NGG, quinoline yellow lake, auramine. Magenta: Permanent Red 4R, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Carmine FB, Risor Red, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Rhodamine. Cyan: Victoria Blue Lake, Metal-Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Victoria Blue.

Yellow, which is used as a water-soluble dye for inkjet, CI: Direct Yellow; 12,
27, 33, 39, 50, 58, 85, 86, 88, 1
00, 110 CI Acid Yellow; 7, 17, 23, 2
9, 42, 99 Magenta: CI Direct Red; 1, 11, 3
7, 62, 75, 83, 99, 220, 227 CI Acid Red; 35, 87, 92, 94, 1
15, 131, 154, 186, 254, 265 Cyan: CI Direct Blue;
8, 15, 22, 25, 71, 76, 78, 86, 9
0,98,108,120,192-196,199,
200-203,207,236,237 CI Acid Blue; 1,7,9,23,43,
78, 82, 127, 234, 236 Black: CI Direct Black;
17, 19, 22, 32, 38, 51, 56, 62, 7
1,74,75,77,105,108,112,15
4,168 CI Acid Black; 1,2,7,24,3
1,52,94 CI Food Black; 1,2

Solvent Yellow: used as an oil-soluble dye for inkjet, Solvent Yellow: 19, 21,
61,80 Orange: Solent Orange; 1,37,4
0 Red system: Solvent Red; 8, 81, 82, 8
4,100 Pink: Diaresin Pink M, Sumip
last Pink R • FF Purple: Solvent Violet; 8,21 Blue: Solvent Blue; 2, 11, 25
36 Green type: Solvent Green; 3 Brown type: Solvent Brown 3, Diare
sin Brown A Black: Solvent Black; 3, 5, 7, 2
2. Quinophthalone-based, naphthoquinone-based, anthraquinone-based, perylene-based,
Azo type.

Cyanine-based, azurenium-based, naphthalocyanine-based, naphthoquinone-based, indoaniline-based, benzenethiol-based, diamine-based, diaminonaphthoquinone-based, naphthalenedicarboxylic acid diamide, benzenethiol metal complex, diamine used for optical disks Metal complex system, indoaniline metal complex system, tetrakisaminophenylbenzene, bithienylidenebisbenzoquinone, benzothiopyrylium, squarylium, benzenediolate ethylphosphonium metal complex, phthalide compound, pentaphenylpentadiene, condensate, fluorene derivative, Pentadiene.

Chlorine, quinizarin, carbazole, dimethyl-S-tetrazine, tetraporphyrin derivative, tetraphenylporphine used for PHB (photochemical hole burning).

Further, Ni, Cu, Co, Zn, C, which have recently attracted attention due to their good color development and high light resistance, have been developed.
Dyes that form complexes with metals such as r, Pt, Pd and Fe, and dyes that are precursors of metal complex dyes, for example, Japanese Patent Application Nos. 9-261904 and 8-092478.
Dyes described in the specification.

For example, JP-A-3-214103 and JP-A-3-220 used as photographic dyes
No. 502, JP-A-2-278204, JP-A-2-228604, JP-A-2-156203, JP-A-2-127603, JP-A-7-159
610, a dye formed by a coupling reaction between the dye precursor and a developing agent.

Further, pigments used in color pencils, crayons, poster colors, watercolor paints, oil paints, felt pens, etc. can also be used as the pigments of the present invention.

The present invention is particularly effective when used for low-saturation dyes and pigments. Dyes, binders, activators, polymers, and the like used as compounds having absorption in the visible region are preferably those whose absorption wavelength does not overlap with the excitation wavelength of the fluorescent substance. May have absorption in the excitation wavelength region of the phosphor. When processing into ink or toner, the specific gravity, particle size, charging characteristics, etc. may be similar to the original color material or may be different. The position of the fluorescent substance on the hard copy may be added near the surface to enhance the effect, or may be deep.

The color image forming method of the present invention can be applied to any transmission type or reflection type hard copy. The transmissive hard copy referred to here is one in which the support is light transmissive and the transmitted light is used for appreciation. The reflective hard copy refers to a copy in which the support is light-reflective and the reflected light is used for appreciation. These may be part or whole, or may be combined. The image carrier in the invention is a general term for a support itself or a medium holding a colorant on the support and coated with a layer for forming an image. An antistatic layer or various functional layers may be laminated on the back surface or the front surface.

Examples of a support for forming a color image include baryta paper, paper laminated with an α-olefin polymer or the like, a paper support, a paper support from which a resin layer can be easily peeled,
Synthetic paper, cellulose acetate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate,
A film made of semi-synthetic or synthetic polymer such as polyamide, polyethylene sulfone, ARTON, polylactic acid,
Rigid bodies such as glass, metal, tile, and porcelain, cloth, and leather can be used.

The pixel in the present invention indicates a unit when an image forming material forms an image. The term "image-like" in the present invention means that the image forming material is not uniform on the image carrier according to the density and color tone of the image to be formed. In the color image forming method of the present invention, a method such as a transfer type or a spray type can be used. Examples of the transfer type include printing using letterpress, intaglio, and lithographic printing, a transfer printer, more specifically (1) charging the OPC, (2) exposing the OPC, and (3) adsorbing the image forming material to the OPC. Let
(4) transferring the image forming material from the OPC to the intermediate transfer member; (5) performing steps 1, 2, 3, and 4 for each color of yellow, cyan, magenta, and black; and (6) on the intermediate transfer member. The method includes part or all of the process of transferring and fixing the image forming material to the image carrier, and the order may be changed depending on the type. Specifically, a laser printer, electrophotography, or the like can be used. The spray type includes (1) discharging the image forming material from the nozzle of the recording head, (2) adsorbing the discharged image forming material to the image carrier, (3) 1,2
Is performed for each of the colors yellow, cyan, magenta, and black. Specifically, an inkjet method, a toner jet method, or the like can be used.

[0054]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention.

Example 1 An image sample was prepared as follows. << How to make an image sample >> Output device Color laser printer KL-2010
(Konica) Driver Genuine driver Output medium Konica plain paper copy paper (neutral paper) Output image ISO / JIS-SCID sample S7 ~
S10

The used toners are as follows. Toner 1-1 (comparison) Pure phthalocyanine based cyan toner toner Toner 1-2 (comparative) Pure phthalocyanine based cyan toner has an emission peak of 3
50 nm phosphor mixed (5% phosphor mixture) Toner 1-3 (invention) Pure phthalocyanine copper cyan toner has an emission peak of 5
Mix phosphor of 02nm (mixing ratio of phosphor 5%)

The color reproducibility of the obtained image sample was visually evaluated. In addition, the color reproduction gamut volumes of the obtained image samples in the L ^* a ^* b ^* space were determined. Below, L ^* a ^* b ^*
This section describes how to measure and calculate the color gamut volume in space. << Measurement and calculation method of color gamut volume in L ^* a ^* b ^* space >> Stimulus value direct reading method Type of measurement method Sa (double beam) Type of color matching function X ₁₀ Y ₁₀ Z ₁₀ color system (10 degrees) Field of view) Standard light type D ₅₀ (Fluorescent lamp) Geometric conditions of illumination and light reception 0-45 3 stimulus value calculation method W10 Measuring instrument X-Rite 938 Effective wavelength 400-700 nm

[0058] Using the obtained color reproduction range volume in the L ^* a ^* b ^* space, in the L ^* a ^* b ^* space of the image obtained using the toners 1-1 and 1-2 of the comparative From the color reproduction area volume, the increase value of the color reproduction area volume in the L ^* a ^* b ^* space of the image obtained using the toner 1-3 of the present invention was determined. Table 1 also shows the obtained results.

[0059]

[Table 1]

From the results shown in Table 1, it can be seen that when a phosphor emitting light in the visible light region is added to the coloring material, the color reproduction range is increased and the effect of the present invention is remarkably exhibited.

Example 2 An image was formed in the same manner as in Example 1 except that the following toner was used. Toner 1-3 (Invention) Toner 1-3 described in Example 1 Toner 1-4 to 1-6 (Invention) Pure phthalocyanine-based pure cyan toner has an emission peak of 5
Mix phosphors of 02 nm (mixing ratio of phosphors shown in Table 2)

The minimum value of the absorption intensity (abs. Value) of the obtained image was determined by the following measuring method.

<< Measurement of Minimum Value of Absorption Intensity (abs. Value) >> Type of Measurement Method Type of Single Beam Color Matching Function X ₁₀ Y ₁₀ Z ₁₀ Color System (10-degree View) Standard Type of Light D ₅₀ ( Fluorescent light) Geometric conditions of illumination and light reception 0-45 3 stimulus value calculation method W10 Measuring instrument MCPD-1000 (manufactured by Otsuka Electronics) Effective wavelength 400 to 700 nm

In the same manner as in Example 1, a comparative toner
L of the image obtained using -1-1 ^*a^*b^*Color in space
Obtained by using toners 1-3 to 6 of the present invention from the reproduction region volume
L of the image obtained^*a^*b^*Increase value of color gamut volume in space
I asked. Table 2 also shows the obtained results.

[0065]

[Table 2]

From the results in Table 2, the minimum value of the absorption intensity is-
If it is less than 0.3, the fluorescence is enhanced and the intended color correction is not sufficiently achieved, but if the minimum value of the absorption intensity is more than -0.3, the intended color correction of the present invention is remarkably exhibited. You can see that it is.

Example 3 An image was formed in the same manner as in Example 1 except that the following toner was used. Toner 1-3 (Invention) Toner 1-3 described in Example 1 Toner 1-7 to 1-8 (Invention) Phosphor having an emission peak shown in Table 3 mixed with copper phthalocyanine-based pure cyan toner ( Phosphor mixture ratio 5%)

Smell of toners 1-3, 1-7 and 1-8
And the phosphor when the absorption peak height of the coloring material is 100
Calculate the absorption peak height when mixing coloring material and fluorescent substance by
Was. << Measurement of absorption peak height >> Type of measurement method Single beam Type of color matching function X_TenY_TenZ_TenColor system (10 degree field of view) Standard light type D₅₀(Fluorescent light) Geometric condition of illumination and light reception 0-45 3 stimulus value calculation method W10 Measuring instrument MCPD-1000 (manufactured by Otsuka Electronics) Effective wavelength 400 to 700 nm Further, in the same manner as in Example 1, comparative toner 1 Use -1
L of the image obtained ^*a^*b^*Is the color gamut volume in space?
Images obtained using the toners 1-3 to 1-6 of the present invention.
L of the image^*a^*b^*Find the increase in the color gamut volume in space
Was. Table 3 also shows the obtained results.

[0069]

[Table 3]

According to the results shown in Table 3, when the absorption peak height of the coloring material is set to 100 and the absorption peak height when the phosphor and the coloring material are mixed is 98% or less, bright and vivid colors and images can be obtained. It turns out that it can be obtained.

Example 4 An image was formed in the same manner as in Example 1 except that the following toner was used. Toner 1-1 (Comparative) Toner 1-1 described in Example 1 Toner 1-3 (Invention) Toner 1-3 described in Example 2 Toner 1-9 (Comparative) Light emission from copper phthalocyanine-based pure cyan toner A phosphor having a peak wavelength of 500 nm was mixed (phosphor mixture ratio: 5%). The excitation peak wavelengths of the phosphors used in the toners 1-6 and 9 are shown in Table 4.

The color reproduction of the obtained image sample was visually evaluated.
Valued. Further, in the same manner as in Example 1, the comparative toner 1
L of the image obtained using -1 ^*a^*b^*Color reproduction in space
Obtained using the toners 1-6 and 9 of the present invention in terms of area volume.
L of the image^*a^*b^*Increase the value of the color gamut volume in space
I asked. Table 4 also shows the obtained results.

[0073]

[Table 4]

From the results shown in Table 4, when a fluorescent substance having an excitation peak wavelength in the wavelength region of 350 to 420 nm is used,
It can be recognized that the fluorescent light can be emitted under natural light such as sunlight or under a fluorescent lamp, so that the color reproduction range can be further expanded.

Example 5 An image was formed in the same manner as in Example 1 except that the following toner was used. Toners 2-1 to 2-3 (Invention) Phosphors having an excitation peak wavelength of 405 nm and an emission peak wavelength of 502 nm are mixed with a copper phthalocyanine-based pure cyan toner at a mixing ratio shown in Table 5.

In the toners 2-1 to 2-3, when the undesired absorption peak height of the coloring material is set to 100, the absorption peak height when the phosphor coloring material is mixed and the half width of the original absorption peak of the coloring material are set as follows. The half-value width of the absorption peak at the time of mixing the phosphor coloring material with 100 was determined as follows.

<< Measurement of FWHM of Absorption Peak >> Type of Measurement Method Type of Single Beam Color Matching Function X ₁₀ Y ₁₀ Z ₁₀ Color System (10 ° Field of View) Standard Light Type D ₅₀ (Fluorescent Lamp) Illumination and Geometric condition of light reception 0-45 3-stimulus value calculation method W10 Measuring instrument MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.) Effective wavelength 400-700 nm

<< Measurement of Absorption Peak Height >> Type of Measurement Method Single Beam Type of Color Matching Function X_TenY_TenZ_TenColor system (10 degree field of view) Standard light type D₅₀(Fluorescent light) Geometric condition of illumination and light reception 0-45 3 stimulus value calculation method W10 Measuring instrument MCPD-1000 (manufactured by Otsuka Electronics) Effective wavelength 400 to 700 nm Further, in the same manner as in Example 1, comparative toner 1 Use -1
L of the image obtained ^*a^*b^*Is the color gamut volume in space?
Of the images obtained using the toners 1-3 to 6 of the present invention.
L^*a^*b^*The increase value of the color gamut volume in space was determined. Profit
The results are shown in Tables 5 and 6.

[0079]

[Table 5]

[0080]

[Table 6]

From the results shown in Tables 5 and 6, the mixing ratio of the phosphor was controlled so that the undesired absorption peak height of the coloring material was 100%.
The height of the absorption peak of the phosphor and the colorant mixture when
It can be seen that the color reproduction range can be expanded by setting it to 8 or less. Further, the half width of the original absorption peak of the coloring material is set to 100.
It can be seen that the color reproduction range can be expanded by setting the half width of the phosphor and color material mixture to 98 or less.

Example 6 An image was formed in the same manner as in Example 1 except that the following toner was used. Toner 3-1 (comparative) Benzidine genuine yellow toner Toner 3-2 (comparative) Benzidine genuine yellow toner has an emission peak of 350
(3) (in the present invention) Benzidine-based genuine yellow toner has an emission peak of 540
nm phosphor mixed (fluorescent mixing ratio 5%)

Toner 3-4 (comparative) The copper phthalocyanine-based genuine cyan toner has an emission peak of 3
50 nm phosphor mixed (phosphor mixing ratio 5%) Toner 3-5 (invention) Pure phthalocyanine-based pure cyan toner has an emission peak of 4
50 nm phosphor mixed (phosphor mixing ratio 5%) Toner 3-6 (invention) Copper phthalocyanine pure cyan toner has an emission peak of 5
40nm phosphor mixed (mixing ratio of phosphor 5%)

Toner 3-7 (comparative) A quinacridone genuine magenta toner having an emission peak of 35
0 nm phosphor mixed (phosphor mixture ratio 5%) Toner 3-8 (invention) A quinacridone genuine magenta toner having an emission peak of 45
0 nm phosphor mixed (phosphor mixture ratio 5%) Toner 3-9 (invention) A quinacridone genuine magenta toner has an emission peak of 61
Mix phosphors of 0 nm (mixing ratio of phosphors 5%)

The color reproduction of the obtained image sample was visually evaluated. Further, the volume of the color gamut in the L ^* a ^* b ^* space of the obtained image sample was determined in the same manner as in Example 1.

Using the obtained color gamut volume in the L ^* a ^* b ^* space, for the image samples obtained from the yellow toners 3-1 to 3-3, the comparative toners 3-1 and 3--3 were used. 2 of the image obtained by using the toner 3-3 of the present invention from the color gamut volume in the L ^* a ^* b ^* space of the image obtained by using
The increase in the color gamut volume in the ^* a ^* b ^* space was determined. Table 7 shows the obtained results.

For the image samples obtained from the cyan toners 3-4 to 3-6, the color reproduction area volume in the L ^* a ^* b ^* space of the image obtained using the comparative toner 3-4 was obtained. Of the images obtained using the toners 3-5 and 3-6 of the present invention from L.A. in the L ^* a ^* b ^* space. Table 8 shows the obtained results.

For the image samples obtained from the magenta toners 3-7 to 3-9, the color reproduction area volume in the L ^* a ^* b ^* space of the image obtained using the comparative toner 3-7 was obtained. The increase in the color gamut volume in the L ^* a ^* b ^* space of the image obtained using the toners 3-8 and 3-9 of the present invention was obtained. Table 9 shows the obtained results.

[0089]

[Table 7]

From the results shown in Table 7, when the coloring material is yellow, the addition of a fluorescent substance having an emission peak at 500 to 600 nm increases the volume increase of the color reproduction region, and the effect of the present invention is large and bright. It can be seen that bright colors and images can be obtained.

[0091]

[Table 8]

From the results shown in Table 8, when the coloring material is cyan, mixing a fluorescent substance having an emission peak at 400 to 500 nm and 500 to 600 nm increases the color reproduction area volume increase, and the effect of the present invention. It is clear that bright and vivid colors and images can be obtained.

[0093]

[Table 9]

From the results shown in Table 9, when the coloring material is magenta, the addition of a fluorescent substance having an emission peak at 400 to 500 nm and 600 to 700 nm increases the volume increase of the color reproduction region, and the effect of the present invention. It is clear that bright and vivid colors and images can be obtained.

Example 7 An image was formed in the same manner as in Example 1 except that the following toner was used. Yellow toner Toner 4-1 (comparison) Benzidine genuine yellow toner has an emission peak of 450
nm, absorption peak is 445 nm, Stokes shift width is 5 nm
(A phosphor mixing ratio of 1%) Toner 4-2 (the present invention) A benzidine-based genuine yellow toner has an emission peak of 450
nm, absorption peak 400 nm, Stokes shift width 50
Fluorescent substance of nm (mixing ratio of fluorescent substance: 3%) Toner 4-3 (invention) Benzidine genuine yellow toner has an emission peak of 450
nm, absorption peak 250 nm, Stokes shift width 15
Mix phosphors of 0 nm (mixing ratio of phosphors 5%)

Cyan toner Toner 4-4 (comparative) The copper phthalocyanine-based genuine cyan toner has an emission peak of 5
Phosphor having 40 nm, absorption peak of 535 nm and Stokes shift width of 5 nm is mixed (phosphor mixture ratio: 1%). Toner 4-5 (present invention) Copper phthalocyanine-based pure cyan toner has an emission peak of 5
A phosphor having a wavelength of 40 nm, an absorption peak of 400 nm, and a Stokes shift width of 140 nm is mixed (phosphor mixture ratio: 3%). Toner 4-6 (invention) A copper phthalocyanine-based pure cyan toner has an emission peak of 5
A phosphor having a wavelength of 40 nm, an absorption peak of 290 nm and a Stokes shift width of 250 nm is mixed (phosphor mixture ratio 5%).

Magenta Toner 4-7 (Comparison) Luminescent peak of quinacridone genuine magenta toner is 61
0 nm, absorption peak is 605 nm, Stokes shift width is 5
Fluorescent substance of nm (mixing ratio of fluorescent substance: 1%) Toner 4-8 (invention) A quinacridone genuine magenta toner has an emission peak of 61
0 nm, absorption peak 400 nm, Stokes shift width 2
10 nm phosphor mixed (phosphor mixture ratio 3%) Toner 4-9 (comparative) Emission peak of quinacridone genuine magenta toner is 61
0 nm, absorption peak 260 nm, Stokes shift width 3
A 50 nm phosphor was mixed (phosphor mixing ratio: 5%). The color reproduction of the obtained image sample was visually evaluated. Tables 10 to 12 show the obtained results.

[0098]

[Table 10]

From the results shown in Table 10, when the fluorescent material having an emission peak wavelength of 400 to 500 nm is mixed with the yellow coloring material, the effect of the present invention is great by setting the Stokes shift width to 10 to 100 nm. It can be seen that bright colors and images can be obtained.

[0100]

[Table 11]

From the results shown in Table 11, when a fluorescent material having an emission peak wavelength of 500 to 600 nm is mixed with a cyan coloring material, the effect of the present invention is large by setting the Stokes shift width to 100 to 200 nm. It can be seen that bright colors and images can be obtained.

[0102]

[Table 12]

From the results shown in Table 12, when the fluorescent material having an emission peak wavelength of 600 to 700 nm is mixed with the magenta coloring material, the effect of the present invention is large by setting the Stokes shift width to 200 to 300 nm. It can be seen that bright colors and images can be obtained.

Example 8 An image was formed in the same manner as in Example 1 except that the following toner was used. Yellow toner Toner 5-1 (the present invention) Benzidine genuine yellow toner (absorption peak 435)
and a phosphor having an emission peak of 405 nm and an emission peak of 540 nm at a mixing ratio of phosphor of 1%. Toner 5-2 (invention) Pure benzidine yellow toner (absorption peak 435)
In addition, a phosphor having an excitation peak of 405 nm and an emission peak of 540 nm is mixed at a mixing ratio of the phosphor of 3%. Toner 5-3 (invention) Pure benzidine yellow toner (absorption peak 435)
405 nm excitation peak and 540 nm emission peak at a mixing ratio of 5%

Magenta Toner Toner 5-4 (Invention) Pure quinacridone magenta toner (absorption peak 57
0 nm), a phosphor having an excitation peak of 405 nm and an emission peak of 610 nm mixed at a phosphor mixing ratio of 1.5%. Toner 5-5 (Invention) Pure quinacridone-based magenta toner (absorption peak 57)
A phosphor having an excitation peak of 405 nm and an emission peak of 610 nm at 0 nm) is mixed at a phosphor mixing ratio of 3.5%. Toner 5-6 (Invention) Quinacridone-based genuine magenta toner (absorption peak 57)
0 nm), a phosphor having an excitation peak of 405 nm and an emission peak of 610 nm is mixed at a phosphor mixing ratio of 5.5%.

Cyan Toner Toner 5-7 (Invention) Pure copper phthalocyanine cyan toner (absorption peak 6
60 nm) with an excitation peak of 405 nm and an emission peak of 502 nm
5-8 (invention) Copper phthalocyanine genuine cyan toner (absorption peak 6)
60 nm) with an excitation peak of 405 nm and an emission peak of 502 nm
3-9% of phosphor mixed with toner 3-9 (invention) Copper phthalocyanine-based pure cyan toner (absorption peak 6)
60 nm) with an excitation peak of 405 nm and an emission peak of 502 nm
Phosphor mixed at a phosphor mixing ratio of 5%

The areas of the absorption peaks of the mixture of the coloring material and the phosphor in the toners 5-1 to 5-9 were determined. In Tables 13 to 15, the area of the absorption peak of the mixture of the coloring material and the phosphor is shown as a relative value with the area of the original absorption peak of the coloring material being 100.

The L of the obtained image sample is^*a^*b^*space
Was determined in the same manner as in Example 1. Get
L^*a^*b^*Using the color gamut volume in space, yellow
-Image samples obtained from toners 5-1 to 5-3
Is the L of the image obtained using the genuine toner. ^*a^*b^*space
5-1 to 5-3 of the present invention from the color reproduction area volume of
L of the image obtained using^*a^*b^*Color gamut in space
The increase of the product was determined. Table 13 shows the obtained results.

The image samples obtained from the magenta toners 5-4 to 5-6 were obtained from the volume of the color reproduction area in the L ^* a ^* b ^* space of the image obtained using the genuine toner. L ^{* of} an image obtained using the toners 5-4 to 5-6 of FIG ^.
The increase value of the color gamut volume in the a ^* b ^* space was determined. Table 14 shows the obtained results.

The image samples obtained from the cyan toners 5-7 to 5-9 were obtained from the color reproduction area volume in the L ^* a ^* b ^* space of the image obtained using the genuine toner. L ^* a ^{* of} images obtained using toners 5-7 to 5-9 of
The increase value of the color gamut volume in the b ^* space was determined. Table 15 also shows the obtained results.

[0111]

[Table 13]

From the results shown in Table 13, when the coloring material used is a yellow coloring material, the absorption in the wavelength region of 500 nm or more is 9%.
It is understood that when the content is 8% or less, the effect of the present invention is large, and bright and vivid color development and an image can be obtained.

[0113]

[Table 14]

From the results shown in Table 14, when the color material to be used is a magenta color material, 400 to 500 nm, 600 to 700 nm
It can be seen that when the absorption in the wavelength region of nm is 98% or less, the effect of the present invention is great, and bright and vivid color development and images can be obtained.

[0115]

[Table 15]

From the results shown in Table 15, when the coloring material used is a cyan coloring material, the absorption in the wavelength region of 600 nm or less is reduced by 98%.
%, The effect of the present invention is large, and bright and vivid color development and images can be obtained.

Example 9 An image sample was prepared as follows. << How to make an image sample >> Output equipment Color inkjet printer BJ F6
00 (Canon) genuine driver Output medium Konica Photo Jet Paper Photol
ike QP glossy paper / thick output image ISO / JIS-SCID sample S7 ~
S10

The used inks are as follows. Ink 6-1 (comparison) Genuine ink (BC-31) Ink 6-2 (comparison) Phosphor having an emission peak of 350 nm is mixed with genuine ink (BC-31) (mixing ratio of phosphor: 3%) Ink 6 3 (Invention) Phosphor having an emission peak of 502 nm was mixed with the genuine ink (BC-31) (mixing ratio of phosphor: 5%)

The color reproduction of the obtained image sample was visually evaluated. In addition, the color reproduction gamut volumes of the obtained image samples in the L ^* a ^* b ^* space were determined. The method of measuring and calculating the color gamut volume in the L ^* a ^* b ^* space will be described below.

<< Measurement and Calculation Method of Color Reproduction Area Volume in L ^* a ^* b ^* Space >> Direct Stimulus Value Reading Method Type of Measurement Method Sa (Double Beam) Type of Color Matching Function X ₁₀ Y ₁₀ Z ₁₀ Color System (10-degree field of view) Standard light type D ₅₀ (Fluorescent lamp) Geometric condition of illumination and light reception 0-45 3 Stimulus value calculation method W10 Measuring instrument X-Rite 938 Effective wavelength 400-700 nm

[0121] Using the obtained color reproduction range volume in the L ^* a ^* b ^* space, the color of the yellow color of L ^* a ^* b ^* space of the image obtained using the ink 6-1 comparison From the reproduction area volume, the increase value of the color reproduction area volume in the L ^* a ^* b ^* space of the yellow color of the image obtained using the ink 6-3 of the present invention was determined.
Table 16 also shows the obtained results.

[0122]

[Table 16]

From the results shown in Table 16, it can be seen that when a phosphor emitting light in the visible light region is added to the coloring material, the color reproduction range is increased, and the effect of the present invention is remarkably exhibited.

[0124]

According to the color image forming method of the present invention,
The color reproduction range is wide, the hue is improved, and color reproduction close to a CRT image or a liquid crystal image can be obtained.

[Brief description of the drawings]

FIG. 1 shows an absorption curve after adding a fluorescent material to a coloring material and the coloring material, wherein the fluorescent material is a mixture of a compound having absorption in the visible region and a fluorescent material having emission in the visible region. It is explanatory drawing explaining the requirement that the absorption intensity (abs. Value) after that does not fall below minus 0.3.

FIG. 2 shows the area of a figure formed by an absorption waveform in an undesired absorption wavelength region and the same undesired absorption wavelength region of a compound having absorption in the visible region without mixing a fluorescent substance having emission in the visible region. FIG. 9 is an explanatory diagram illustrating an area of a figure formed by an absorption waveform.

FIG. 3 shows the height of the absorption peak in the undesired absorption wavelength region and the height of the absorption peak in the same undesired absorption wavelength region of a compound having absorption in the visible region without mixing a fluorescent substance having emission in the visible region. FIG.

FIG. 4 is an explanatory diagram illustrating a half-value width of a main absorption peak.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B41M 5/38 B41M 5/18 103 G03G 9/09 5/26 A H04N 1/23 101 101Z 1/29 G03G 9/08 361 // B41J 2/21 B41J 3/04 101A (72) Inventor Yusuke Kawahara 1 Sakuracho, Hino-shi, Tokyo Inside Konica Corporation (72) Inventor Hiroshi Kita 1 Sakuracho, Hino-shi, Tokyo Konica Inside the Company (72) Inventor Daisuke Ishibashi 1 Konica Sakuracho, Hino-shi, Tokyo Inside the Company (72) Inventor Masayuki Ushiku 1 Konica Sakuracho, Hino-shi Tokyo

Claims (28)

[Claims] 2. A color image forming method comprising: performing color correction by using additive color mixing with subtractive color mixing. 2. The color image forming method according to claim 1, wherein a fluorescent substance is used as the additive color mixture. 3. The color image forming method according to claim 1, wherein a compound having absorption in a visible region and a fluorescent substance having emission in a visible region are mixed. 4. The fluorescent substance is mixed in such an amount that the absorption intensity (abs. Value) of the compound having absorption in the visible region and the fluorescent substance having emission in the visible region after mixing is not less than −0.3. The color image forming method according to claim 3, wherein: 5. The color image forming method according to claim 3, wherein the compound having absorption in the visible region is a coloring material. 6. The color image forming method according to claim 3, wherein the fluorescent substance is a fluorescent substance which emits light in an undesired absorption wavelength region of the compound having absorption in the visible region. 7. The area of a figure formed by an absorption waveform in an undesired absorption wavelength region of a color image is determined by the same undesired absorption wavelength of a compound having an absorption in a visible region which is not mixed with a fluorescent substance having an emission in a visible region. 6. The color image forming method according to claim 3, wherein the area of the figure formed by the absorption waveform of the region is 98% or less. 8. The absorption peak in the same undesired absorption wavelength region of a compound having absorption in the visible region where a fluorescent substance having emission in the visible region is not mixed with the height of the absorption peak in the undesired absorption wavelength region of the color image. 98% of the height of
6. The color image forming method according to claim 3, wherein: 9. The half width of a main absorption peak of a color image is 99.5% or less of the half width of a main absorption peak of a compound having absorption in a visible region where a fluorescent substance having emission in a visible region is not mixed. The method according to claim 3, wherein
The color image forming method according to any one of the above. 10. The fluorescent substance has an excitation light wavelength of 350 nm to 42 nm.
The color image forming method according to any one of claims 3 to 9, which is a fluorescent substance having a wavelength of 0 nm. 11. The fluorescent substance has an emission peak wavelength of 400 nm or more.
A fluorescent substance having a wavelength of 500 nm.
10. The color image forming method according to any one of the above items 10. 12. The fluorescent substance having an emission peak wavelength of 500 nm or more.
3. A fluorescent material having a wavelength of 600 nm.
10. The color image forming method according to any one of the above items 10. 13. A fluorescent substance having an emission peak wavelength of 600 nm or more.
3. A fluorescent material having a wavelength of 700 nm.
10. The color image forming method according to any one of the above items 10. 14. A fluorescent substance having a Stokes shift width of 10
2. A fluorescent substance having a wavelength of not less than nm.
3. The method for forming a color image according to any one of 3. 15. A fluorescent substance having a Stokes shift width of 10
The color image forming method according to claim 11, wherein the color image is a fluorescent substance having a wavelength of from 100 nm to 100 nm. 16. The fluorescent substance having a Stokes shift width of 10
13. The color image forming method according to claim 12, wherein the fluorescent material has a wavelength of 0 nm to 200 nm. 17. The fluorescent substance has a Stokes shift width of 20.
14. The color image forming method according to claim 13, which is a fluorescent substance having a wavelength of 0 nm to 300 nm. 18. A yellow color material in which the color material is a yellow color material, and the area of a figure formed by an absorption waveform in a region having a wavelength of 500 nm or more of a color image does not contain a fluorescent substance emitting light in a visible region. The color image forming method according to any one of claims 5 to 10, wherein the area is not more than 98% of the area of the figure formed by the absorption waveform in the region having a wavelength of 500 nm or more. 19. A magenta color material in which the color material is a magenta color material and the area of a figure formed by an absorption waveform other than a wavelength of 500 nm to 600 nm of a color image is not mixed with a fluorescent substance which emits light in a visible region. Wavelength of 500nm ~ 600nm
98% of the area of the figure formed by the absorption waveform in the region other than
The color image forming method according to claim 5, wherein: 20. The color material is a cyan color material, and the area of a figure formed by an absorption waveform having a wavelength of 600 nm or less in a color image has an area of a wavelength of the cyan color material in which a fluorescent substance having light emission in a visible region is not mixed. 11. The color image forming method according to claim 5, wherein the area of the figure formed by the absorption waveform in the region of 600 nm or less is 98% or less. 21. The color image forming method according to claim 2, wherein the fluorescent substance is an inorganic fluorescent substance. 22. The color image forming method according to claim 2, wherein the fluorescent substance is a fluorescent substance having a composition containing an oxygen atom. 23. A color image forming method for forming an image on an image carrier using a plurality of pixels, wherein the pixels are formed of a mixture of a fluorescent substance and a coloring material. 24. A color image forming method comprising: preparing an image forming material which is a mixture of a fluorescent substance and a coloring material; and adding the formed image forming material to an image carrier imagewise. 25. The color image forming method according to claim 24, wherein the imagewise addition of the image forming material to the image carrier is performed by transferring the image forming material to the image carrier. 26. An image-wise addition of a material for image formation to an image carrier, for each color of yellow, cyan, magenta and black, (a) an OPC charging step, (b) an OPC exposure step, and (c) And (d) transferring the image-forming material from the OPC to the intermediate transfer member by using at least one of the following steps: (d) adsorbing the image-forming material onto the OPC; A color image forming method, wherein an image of a forming material is transferred to an image carrier and fixed. 27. The color image forming method according to claim 24, wherein the imagewise addition of the image forming material to the image carrier is performed by spraying the image forming material onto the image carrier. 28. An imagewise addition of an image forming material to an image carrier, for each of yellow, cyan, magenta, and black, (e) discharging the image forming material from a nozzle of a recording head; f) a step of adsorbing the released image forming material to the image carrier, at least one of which is performed.