JPH10282689A - Colored image forming method, image forming element and transfer element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to form high-resolution and high-grade color images to any paper sheet blanks by specifying the relations of the respective tacky adhesive farces between the stripping surface, tacky adhesive layer and colored pattern of a carrier element and the stripping surface and fixed base of a transfer element. SOLUTION: A photosensitive element is formed by laminating the carrier element 10 having the stripping layer, the tacky adhesive layer 11 and a first coloring agent- contg. photosensitive layer and the transfer element 16 is laminated thereon. The transfer element having the stripping layer adjoins the developed coloring agent-contg. layer 12' or layers 12', 13'. At this point, F1 is defined as the tacky adhesive force between the carrier base 10 and the tacky adhesive layer 11, F2 as the tacky adhesive force between the tacky adhesive layer 11 and the developed photosensitive layer 12' and F3 as the tacky adhesive force between first colored patterns consisting of at least one developed coloring agent-contg. photosensitive layer 12' and the transfer element 16 having the stripping surface. Further, the solid base is laminated by the tacky adhesive force F4 on the tacky adhesive layer 11 after removal of the carrier element 10. F2, F3 are set at the values larger than F1 and F2, F4 are respectively set at the values larger than F3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to color image formation. In particular, the present invention provides a method for forming a color image (coloring),
The present invention relates to an image forming method and a transfer element used for intermediate transfer to a transfer sheet having high dimensional stability and subsequent transfer of an image to an arbitrary support.

[0002]

2. Description of the Related Art Photosensitive elements which can be used in image copying methods are well known in the graphic arts industry. Such devices are typically exposed to actinic radiation through an imaged transparency, producing a negative or positive image depending on the transparency used.

[0003] Such photosensitive elements are designed to simulate images produced by printing by off-press color color printing.
Widely used for proofing. In imprint proofing, all of the color images are overlaid, for example, by multiple exposure, lamination, or transfer to a single support. Unlike overlay proofs, color images cannot be separated and cannot be viewed individually.

Various image copying methods, including photopolymerization and thermal transfer techniques, are described, for example, in US Pat. No. 3,060,023,
Known as disclosed in 3,060,024, 3,060,025, 3,481,736, 3,574,049, and 3,607,264. . In these methods, a photopolymerizable layer coated on a suitable support is imagewise exposed to photographic transparency.
Next, the surface of the exposed layer is pressed into contact with the image receiving surface of another element, and at least one element is heated at a temperature higher than the transfer temperature of the unexposed portion of the layer. The two elements are separated and the thermally transferable unexposed image areas of the composite are transferred to an image receiving element. If the element has not been previously colored, the tacky, unexposed image may be colored with the desired toner. All of these methods do not require the use of specially treated final receiver sheets, and are not applicable to obtaining color proofing images on paper sheet stock.

[0005] A pre-colored and rinsed system (Precol)
Ored wash-off systems are conventionally known. Examples of such systems include Van Beusekom US Pat. No. 3,671,236, Cederbu.
diazo which is developed in a mixture of water and 1-propanol as disclosed in U.S. Pat. No. 4,656,114 of U.S. Pat. No. 4,656,114 and U.S. Pat. No. 4,666,817 of Sachi. A pre-colored image forming system containing
U.S. Pat. No. 4,260,67 to Krech
No. 3,751,166 to Platzer, a system for developing in a base disclosed in US Pat.
No. 4,783,390 to Mino.
And a system for development in water as disclosed in US Pat. No. 5,075,722 to Adolphson et al. These systems provide improved resolution. However, in these systems where the image is transferred to a transfer element and then to a fixed receiver, problems arise when registering multicolor images. This is presumably because the transferred element expands or contracts dimensionally due to heat during the transfer of the image by heating and laminating, causing distortion of the transferred image. This distortion causes misalignment of the first transferred image with the subsequently transferred image in the process of producing the multicolor proof. Therefore, after transfer to the fixed receptor, the resolution of the multicolor image is reduced.

[0006]

Accordingly, there has been a need in the art for a method of producing a high resolution, high quality color image on virtually any paper sheet material.

[0007]

Means for Solving the Problems In order to solve the above-mentioned problems, a method for forming a colored image according to the present invention is a method for forming a colored image. (2) a carrier having a release layer and exhibiting resistance
A step of sequentially providing a photosensitive element comprising a first adhesive layer, and (3) a first photosensitive layer consisting essentially of a photosensitive composition developable with an aqueous developer and a water-permeable colorant-containing composition. And (B) the step (A) obtained in the step (A) for forming an imagewise exposed area and a non-imagewise exposed area in the first photosensitive layer containing the water-permeable colorant. Exposing the photosensitive element with actinic radiation,
(C) developing the exposed photosensitive element obtained by the step (B) by washing it with an aqueous liquid, to thereby obtain an imagewise exposed area or an imagewise unexposed area; By removing one of
A step of forming a first colored pattern, and (D) the photosensitive element which has been subjected to the step (C) and has been subjected to a heat treatment at a temperature of at least 60 ° C. prior to the step (D). Stacking a transfer element having a release layer adjacent to the first colored pattern, (E) exposing the adhesive layer by removing the carrier element having a release surface, and (F) A) laminating the device-fixed support obtained in the step (E), and making the adhesive layer adjacent to the fixed support by the lamination; and (G) the transfer device having a release surface. And the adhesive force between the release surface of the carrier element and the adhesive layer has a value of F1, between the adhesive layer and the first colored pattern. The adhesive strength has the value of F2, Adhesion between the release surface of said transfer element and the first colored pattern has a value of F3,
When the adhesive force between the adhesive layer and the fixed support has a value of F4, the values of F2 and F3 are greater than the value of F1, and each of the F2 and F4 has a value greater than F3. It is characterized by the following.

Preferably, the transfer element is heated at a temperature of preferably 60 to 150 ° C. prior to the step (D).

Preferably, the composition containing a water-permeable colorant contains an insoluble colorant.

Preferably, the water-permeable colorant-containing composition contains a pigment.

Preferably, the first photosensitive layer does not contain a water-permeable colorant-containing composition, and the water-permeable colorant-containing composition is added to the first photosensitive layer prior to the step (B). Applied.

Preferably, after the step (E), the steps (A) to (E) are performed at least once by using at least one different photosensitive element containing a different water-permeable colorant-containing composition. Reproduce. Alternatively, preferably after the step (E), at least one different water-permeable colorant-containing composition, a different photosensitive element containing no colorant,
And the steps (A) to (E) are reproduced at least once by using the element obtained from the step (E) as the transfer element of the step (D).

Preferably, the release surface on the carrier element has a release layer, or preferably the release surface on the carrier element has a buffer layer.

Preferably, the release surface on the transfer element comprises at least one buffer layer, preferably the release surface on the transfer element has a first buffer layer and a second buffer layer, The first buffer layer is adjacent to the first colored pattern, and further includes the first colored pattern and the first colored pattern.
Is larger than the adhesive force between the first buffer layer and the second buffer layer.

Preferably, the photosensitive composition contains a material selected from the group consisting of an N-alkylstyrylpyridinium derivative of polyvinyl alcohol, an N-alkylstyrylquinolinium derivative of polyvinyl alcohol, and a mixture of the derivatives.

[0016] Preferably, the adhesive layer comprises a material selected from the group consisting of vinyl chloride / vinyl acetate copolymer, ethylene / vinyl acetate copolymer, polyester, and mixtures thereof.

[0017] Preferably, the aqueous liquid is water.

Preferably, the composition containing a water-permeable colorant is provided as a layer on the first photosensitive layer.

Preferably, the composition containing a water-permeable colorant is absorbed by the first photosensitive layer.

Preferably, the composition containing a water-permeable colorant is printed on the first photosensitive layer containing no colorant by using an ink jet printer.

Preferably, the composition containing a water-permeable colorant exhibits photosensitivity.

Preferably, the composition containing a water-permeable colorant is non-photosensitive.

Preferably, the water-permeable colorant-containing composition is an ink containing an aqueous carrier medium and a colorant.

Preferably, the colorant is a pigment dispersion, or the colorant is a dye.

The image forming element according to the present invention is an element on which an image has been formed. The image forming element includes, in order, (1) a carrier element which is resistant to aqueous development and has a release surface, and (2) a first adhesive. A first photosensitive layer comprising a layer and a (3) water-permeable colorant-containing composition and a photosensitive composition, which is obtained by imagewise developing, washing and developing, and wherein the water-permeable colorant-containing composition is obtained. Is a first colored pattern present as a separate layer,
(4) a transfer element having a release surface heated to at least 60 ° C., wherein the adhesive force between the release surface of the carrier element and the adhesive layer has a value of F1, and 1
When the adhesive force between the first colored pattern and the release surface of the transfer element has a value of F3, the adhesive strength between the colored pattern of F2 and F3 is F2.
Is greater than the value of F1, and F2 is greater than F3.
It is characterized by having a value larger than.

[0026] Preferably, said transfer element is heated at a temperature of preferably 60 to 150 ° C.

Preferably, the composition containing a water-permeable colorant is applied to the first photosensitive layer using an ink jet printer, while the first photosensitive layer does not contain a composition containing a water-permeable colorant.

Preferably, the composition containing a water-permeable colorant is photosensitive.

Preferably, the composition containing a water-permeable colorant is non-photosensitive.

Preferably, the composition containing a water-permeable colorant is absorbed in the photosensitive layer.

Preferably, the composition containing a water-permeable colorant is an ink containing an aqueous carrier medium and a colorant.

Preferably, the colorant is a pigment dispersion.

Preferably, the transfer element is a dimensionally stable transfer element comprising a transfer support having a transfer surface layer, and is heated at a temperature of at least 60 ° C.

Preferably, the heating is performed at a temperature of 60 ° C. to 150 ° C.

[0035]

According to one embodiment of the present invention, a photosensitive element comprising a release surface, a first adhesive layer, and a first photosensitive layer containing a colorant is imagewise exposed to actinic radiation. To form a single color image on the fixed support. The first photosensitive layer is mainly composed of a photosensitive composition that can be developed with an aqueous liquid, and a colorant may be added to the photosensitive layer at the time of production, or the first photosensitive layer may be colored using a water-permeable colorant-containing composition. May be added to the photosensitive layer that is not used. The colorant-containing composition may be provided as a separate layer on the uncolored photosensitive layer, or may be incorporated into the uncolored photosensitive layer. Exposure forms areas imagewise exposed and unexposed to the colorant-containing first photosensitive layer. The exposed element is developed by washing with an aqueous liquid, thereby removing either the imagewise exposed area or the non-imagewise exposed area to form a first colored pattern. Thereafter, a transfer element having a release layer adjacent to the first colored pattern is laminated on the exposed and developed element. Next, the carrier element having the release layer is removed so that the adhesive layer is visible, and the element thus formed is laminated on a fixed support. Thereby, the adhesive layer is adjacent to the solid support. Further, the transfer support having a release surface is removed.

In another embodiment of the present invention, at least one photosensitive element is exposed and developed to provide a multicolored printed proof.
troof) is formed. This photosensitive element has a carrier element having a release surface, an adhesive layer, and a colorant-containing photosensitive layer, and forms a first color image into a color image formed in a state where printing registration is correct. Then, the carrier element having the release layer is removed, and the multicolor image formed on the fixed support is laminated. This multicolor imprint proof is laminated-in-in-
register) method. The colorant-containing photosensitive layer may be included in the photosensitive layer at the time of formation, or may be applied to the photosensitive layer to which no pigment is added. In the latter case, a water-permeable colorant-containing composition is used in a form in which another layer is formed on the photosensitive layer to which the pigment is not added, or in a form in which the layer is absorbed by the photosensitive layer to which the pigment is not added. Applied. The water-permeable colorant-containing composition may be photosensitive or non-photosensitive. The present invention provides a high resolution, high quality full color imprint proof on virtually any proof / paper sheet material or multiple fixed supports.

In practice, the method of the present invention requires at least three components. That is, (I) a colorant-containing photosensitive element in which a photosensitive layer and an adhesive layer are laminated on a carrier element having a release surface, (II) a transfer element in a dimensionally stable state, and (III) fixing. Support element. A dimensionally stable transfer element having a release surface has a transfer support and at least one buffer layer. Additional colorant-containing photosensitive elements are also used in forming multicolor images. In this case, the colorant contained in the colorant-containing photosensitive element is as shown in FIG.
As shown in (a) and FIG. 1 (b), it may be present in the photosensitive layer at the time of formation, or may be applied to the photosensitive layer to which no pigment is added. In the latter case, the light is absorbed in a form in which another layer is formed on the photosensitive layer to which no pigment is added, or in the photosensitive layer to which no pigment is added. See US Pat. No. 5,534,387 (issued Jul. 9, 1996) and US Pat. No. 5,534,859 for methods used in making useful photosensitive elements, stationary supports, monochromatic and multicolor imprint proofs. 5,56
No. 5,301 (issued on October 15, 1996), which is incorporated herein by reference.

Transfer element (Transfer Element)
nt) Transfer elements useful in the present invention are heat treated at a temperature of at least 60 ° C, preferably 60 ° C to 150 ° C, more preferably 65 to 120 ° C.

The function of the transfer element is to function as a temporary receptor (re
role). After the colored image is formed on the carrier support, the image is received and provided on a suitable support for the image, thereby preserving the image integrity until the image is transferred to the fixed support. The colored image on the transfer element is a read error image (wrongea) of the original image.
ding image).

FIG. 3 is a sectional view of the transfer element. The transfer element 16 has a structure in which an arbitrary temporary cover sheet (not shown), a transfer surface layer 18, and a transfer support 17 are sequentially stacked.

The transfer support 17 is made of a material having sufficient rigidity and dimensional stability to support an image so as not to cause a movement or a position error. Examples of suitable materials include polymeric membranes such as polyesters, generally polyethylene terephthalate or polyethylene naphthalate, polyamides, polycarbonates, fluoropolymers, polyacetals, polyolefins, and the like.
Also, the transfer support may be a thin metal film, paper substrate or synthetic paper. Polyethylene terephthalate (PET) is preferred. The transfer support is generally from about 20 to about 250
It has a thickness of μm (0.8 to 10 mil). The preferred thickness is about 75 to 200 μm (2 to 8 mi
l).

The transfer surface layer 18 is a buffer layer and has sufficient tackiness so that it can remain fixed to the support during all steps of the method. At the same time, the adhesiveness of the transfer surface layer is kept in a moderate balance with the adhesiveness of the carrier surface layer in order to perform a transfer step described later.

The transfer support and the transfer buffer layer have a release layer for separating the temporary cover sheet from any layers laminated subsequently to the transfer buffer layer. As already mentioned, the composition of the transfer buffer layer must be selected to produce a suitable viscosity in relation to the carrier buffer layer. Examples of suitable materials include: ethylene / vinyl acetate copolymers; ethylene / methacrylic acid copolymers and ionomers that generally have a high methacrylic acid content when used as a carrier buffer layer; Ethylene / methacrylic acid copolymers and ionomers having a high acrylic acid content; ethylene / methacrylate copolymers; generally higher ethylene / methacrylic acid / methacrylic acid / isobutylacrylic acid content than when used as a carrier buffer layer. Isobutylacrylic acid isomer and the like. Mixtures of these materials can also be used. A preferred material for the transfer buffer layer is an ethylene / vinyl acetate copolymer. Further, the transfer buffer layer can contain a surfactant, a plasticizer, a coating aid, and the like. Generally, colorants, antihalation dyes, optical brighteners and the like are not used in the transfer buffer layer. Because they are meaningless for the transfer buffer layer. The transfer buffer layer generally has a thickness of about 25 to 150 μm (1 to 6 mil),
Preferably 75 to 125 μm (3 to 5 mil)
It is.

The release surface on the transfer element may include first and second buffer layers, wherein the first buffer layer is adjacent to a first colored pattern and the first buffer layer is adjacent to the first colored pattern. The adhesive force between the colored pattern and the first buffer layer is larger than the adhesive force between the first buffer layer and the second buffer layer.

One or more anchor layers may need to be provided between the transfer indicator so that the transfer buffer layer has an adequate adhesion to the transfer indicator. Adhesive materials for joining different types of materials are known to those skilled in the art and are described, for example, in the Handbook of Adhesives.
es, 2nd Edition, IrvingSk
eist, Ed. (Van Nostrand R
einbold Co. , New York, 19
77)).

Conventional adhesives can be used for the anchor layer. Suitable materials include, for example, ethylene / vinyl acetate copolymer; vinyl chloride / vinyl acetate copolymer; vinyl chloride / vinylidene chloride copolymer; thermoplastic polyamide, and the like. The strict selection of the pressure-sensitive adhesive is made according to the composition of the transfer buffer layer and the transfer support. Antistatic agents, adhesives, surfactants, plasticizers, coating aids, and the like can be incorporated into the anchor layer. The transfer anchor layer generally has a thickness of 0.1 to 10 μm.
m, preferably 0.5 to 2 μm. When the number of anchor layers exceeds 1, the thickness of the entire plurality of anchor layers is controlled to fall within the above range.

The optional temporary cover sheet protects the layer underlying the cover sheet and is easily removed and is provided as needed.

The heat treatment of the transfer element may be performed by pre-lamination in-line heating in a box type oven or a sheet conveyor oven in the production process. The pre-lamination is marketed by Wilmington E. I. Dupont de Nemours & Company, Delaware, USA, preferably at a temperature of 100-120 ° C., a speed of 100-800 mm / min, and a standard set at a load of 150 lb. Water Proof Laminator
rproof (registered trademark)). Preferably,
The transfer sheet is heat-treated by an in-line heat treatment during the manufacturing process. It has a coating that passes through a laminator section prior to winding the film at a laminator temperature of at least about 79 ° C. Alternatively, the transfer sheet may be heated by leaving it in an oven at a temperature of at least 60 ° C., preferably at least 65 ° C., for about 5 minutes. Transfer the transfer sheet to about 71 ° C, preferably 10
It may be placed in a dryer at 4 ° C. to 116 ° C. for about 3 minutes.

The effect of the heat treatment was determined by a differential scanning calorimeter (D
SC). FIGS. 10-11 show DSC plots for untreated and treated transfer elements. The sample of FIG. 11 was heated using the pre-lamination technique described previously.

Method step : The present invention relates to a method of forming a monochromatic image on the fixed support 20 by exposing the colorant-containing photosensitive layer to light and developing it by washing to form a colored image on the carrier support 10 first. Formed. The colorant may be present in the photosensitive layer 12, or the colorant may be applied as a water-permeable colorant-containing composition on the photosensitive layer to form the separation layer 13. Alternatively, in the case of a pigment, it may be absorbed in the photosensitive layer. The transfer element 16 having the release surface is laminated on the photosensitive layer 12 or the separation layer 13 by treating at a temperature of at least 60 ° C, preferably 60 to 150 ° C, and more preferably 65 to 120 ° C. A transfer element having a release surface and heat-treated at a temperature of at least 60 ° C, preferably 60 to 150 ° C, more preferably 65 to 120 ° C is further laminated. After peeling the carrier element 10, the element is laminated on the fixed support 20.

Step A : The element shown in FIG. 1A is a photosensitive element in which a carrier element 10 having a release layer, an adhesive layer 11, and a first colorant-containing photosensitive layer 12 are sequentially laminated.
The device shown in FIG. 1B is obtained by applying at least one kind of water-permeable coloring agent-containing composition 13 on a photosensitive device. The photosensitive element is a carrier element 10 having a release surface.
And an adhesive layer 11 and a first photosensitive layer 12 containing no colorant (no pigment added) are sequentially laminated. Further, the colorant-containing composition is adjacent to the first photosensitive layer 12.
This colorant-containing composition is coated, sprayed, laminated,
Alternatively, it could be applied by printing. Preferably, composition 13 is printed by an ink jet printer. Use of the device shown in FIG. 1 (b) is beneficial. This is because it is not necessary to apply the colorant-containing composition to the entire surface of the first non-pigmented photosensitive layer, and two or more colorant-containing compositions can be applied to the non-pigmented photosensitive layer. is there. The region where the colorant-containing composition must be applied is approximately only the region where an image is formed in steps B and C (described below).

Step B : The device shown in FIG. 1A or 1B is exposed to actinic radiation in a conventional manner. Actinic radiation is absorbed by the photosensitive composition to activate the imaging reaction. As used herein, the term "actinic radiation" refers to any radiation that causes imaging, which is naturally or artificially generated, monochromatic or polychromatic, and also non-coherent or coherent. It can be. For efficient image formation, most of the actinic radiation should be absorbed by the photosensitive material. The absorption spectrum of the light-sensitive material can be determined by conventional spectrophotometry.

As a selectable conventional actinic radiation source, fluorescent X
Wire, mercury, mercury-xenon, metal addition, or arc
Lamps can be mentioned. A useful coherent radiation source may be, for example, a laser emitting in the absorption band of the photosensitive composition or in a wavelength band overlapping the band. Usually, the exposure is performed via a transparency having a halftone image, preferably a halftone color separation transparency. However, imagewise exposure of the photosensitive element may be performed using other means, such as a frequency modulated laser beam, a CRT (cathode ray tube), or the like.

In general, the device is exposed to actinic radiation via decomposition transparency. At this time, the photosensitive emulsion side of the transparency is brought into contact with the colorant-containing photosensitive layer if the water-permeable colorant-containing composition is present or absorbed in the photosensitive layer, or if one of the layers on the photosensitive layer If present as a layer, it is contacted with the water-permeable colorant composition. Exposure is conveniently performed in a standard vacuum-fired frame so that good contact between the transparency and the photosensitive layer overcoated with the water-permeable colorant-containing composition is maintained.

Step C : In the next step, if a water-permeable colorant-containing composition is present, the colorant-containing photosensitive layer is developed by washing with an aqueous solution. If the photosensitive layer is photoinsolubilized, the aqueous solution only removes unexposed areas of the photosensitive layer. If the photosensitive layer is photosoluble, the aqueous solution will only remove the unexposed areas of the photosensitive layer if a water-permeable colorant-containing composition is present. Photosoluble (photosolub)
The term ilizable means that the exposed area is wholly or partially soluble in an aqueous solution, or that the aqueous solution penetrates the exposed area and separates it from the underlying layer. I do. As a result of the development process,
A first colored pattern consisting of portions indicated by reference numerals 12 'or 12' and 13 'is formed.

The developing step is preferably carried out using ordinary tap water or the like. In turn, problems such as toxicity, waste disposal, and corrosion can be minimized.
Development can be performed by hand or using automated equipment. Although development can be performed at elevated temperatures, room temperature is often preferred.

Step D : The next step in this method is to laminate the transfer element 16 shown in FIG. 3 on the element formed as described above (FIGS. 4A and 4B). Prior to lamination, the telephoto element is heat treated to bring the temperature of the element to at least 60 ° C, preferably 60 to 150 ° C, more preferably 65 to 120 ° C.
At a higher temperature, the heat treatment time for the element is shorter than at a lower temperature. If there is a temporary cover sheet,
The temporary cover sheet is removed and the two elements are stacked, and the transfer element having the transfer surface layer 18 of FIG. 3 or the release layer shown in FIGS. Colorant-containing layer 12 '(FIG. 4 (a)) or layers 12' and 13 '(FIG. 4 (b)).

The resulting element is called an intermediate imaging element and has the structure shown in FIGS. 4 (a) and (b). The adhesion between the individual layers has the following values: F1 = adhesion between carrier support 10 and adhesive layer 11; F2 = adhesion between adhesive layer 11 and developed photosensitive layer 12 '; and F3 = at least one developed colorant Containing photosensitive layer 1
Adhesion between the first colored pattern consisting of 2 'and the transfer element 16 having the release surface.

Step E : The next step in this method is to remove the carrier element 10 having the release layer. Therefore, the image is transferred to the transfer element. This step is achieved by peeling and separating the transfer element and the carrier element. In order to obtain the desired result, the adhesion values F2 and F3 must each be separately greater than the adhesion value F1.

Step F : The next step in this method is to laminate the solid support 20 on the above element so that the fixed support 20 is adjacent to the adhesive layer 11 as shown in FIGS. 5 (a) and 5 (b). I do. The value of the adhesive force between the adhesive layer 11 and the fixed support 20 is F4.

Step G : The next step in this method is to remove the transfer element 16 having the release layer. Thereby, the image is transferred to the fixed support. This step is achieved by peeling the transfer element 16 from the fixed support 20. To obtain the desired result, the adhesion values F2 and F2
4 must individually be greater than the value of the adhesive force F3.

Multicolor Image Formation-Lamination Positioning (lami
Nate-in-register method When an image of a plurality of colors is formed by the lamination registration method , the method starts from the above steps A to E and forms a colored pattern on the transfer element. This is shown in FIGS. 4 (a) and (b) with the carrier element removed in step E while remaining intact. By repeating steps A to E, an additional layer including at least one photosensitive layer 12a 'containing a colorant formed by exposure and development of the element shown in FIG. 1A and an adhesive layer 11a under the carrier element 10a is added. Is transferred to a transfer element having a first color pattern having at least one colorant-containing photosensitive layer 12 'and an adhesive layer 11 overlaid thereon as shown in FIG.

By repeating steps A to E n times,
An element as shown in FIG. In the device shown in FIG. 7, the adhesive layer 11n is the outermost layer and has an underlying colored pattern consisting of the developed colorant-containing photosensitive layer 12n '. As shown in FIG. 8, the multicolor image on the transfer element 16 is transferred to the fixed support 20, and then the transfer element is removed. FIG. 9 shows the finally obtained multicolor proof.

The adhesion between the important individual layers has the following values: F8 = adhesion between carrier support 10a and adhesive layer 11a; F3 = at least one developed colorant-containing photosensitive layer 1
The adhesive force between the first colored pattern composed of 2a 'and the transfer element having the release layer, and F4 _n = the adhesive force between the fixed support 20 and the adhesive layer 11n.

The adhesive strength F3 and the adhesive strength between all the colored patterns and the adjacent adhesive layers are greater than the adhesive strength F8. The adhesive strength F4 and the adhesive strength between all the colored patterns and the adjacent adhesive layer are greater than the adhesive strength F3.

In the embodiment, a multicolor image is formed using an additional photosensitive element comprising a colorant-free, preferably unpigmented, photosensitive layer to which the water-permeable colorant-containing composition is applied. This method is described in US Pat. No. 5,534,387 from column 22, line 40 to column 23, line 19, with the following exception. Prior to lamination, the transfer element is heat-treated. The temperature of this heat treatment is at least 60 ° C.
Preferably it is 60 to 150 ° C, more preferably 65.
To 120 ° C.

The carrier element and transfer element of the present invention can be used repeatedly for forming several colored or multicolor images.

[0068] Example term dryer (Dryer) 900 p-toluenesulfonic acid Erubakusu (Elvax, registered trademark) 550 ethylene-vinyl acetate copolymer DuPont (DuPont) (Wilmington, Del.) LOE paper 100 lb Warren Rastro Gloss text (Warren Lustro Gloss Text) Lindenmeyr Munroe (Philadelphia, PA, USA) Mizukasil (registered trademark) SK-7 silica particles Mizusawa Industrial Chemical (Mizusawa Indu
stial Chemicals) (Japan) Ryron (registered trademark) KU-628 vinyl chloride / vinyl propionate / vinyl acetate / methyl methacrylate copolymer, Tosoh Corporation (Japan) SPP M-20 N-methyl- Polyvinyl alcohol acetalized with 4- (p-formylstil) pyridinium mesosulfate, Tokyo Gosei Kogyo Co., Ltd. (Ichikawa-shi, Chiba) Sunsperse (registered trademark) Blue B
HD-6015 Aqueous pigment dispersion, Sun Chemical, Dispersion Division (Amilia, Ohio, USA) Tispeel XA51-834A Melamine acrylic resin, Hitachi Chemical Polymer (Japan) Vylonal MD Heat sealable Polyester resin emulsion, Toyobo Co., Ltd. (Japan) Zonyl (registered trademark) FSO-100 Perfluoroalkyl Surfactant, DuPont
ont) (Wilmington, Delaware, USA) UGRA Test Strips Dot range 0.5% to 99.5%, Graphic Arts Technical Foundation
(Graphic Arts Techical Foundation) (Pittsburgh, PA, USA)

Positioning method Test method A1 size (63.5 × 96.52 cm) proof
It was manufactured using a test object having three alignment marks. Each mark is an X, one line is oriented in the direction of the laminating machine (MD) and the other line is oriented in a direction perpendicular to the MD (TD). FIG. 12 shows the arrangement of the alignment marks. Yellow, magenta, cyan,
And a single four-color proof consisting of a black image. The production method is based on a control (Cont
(roll) method 1, wherein the images of the four colors are aligned by the alignment marks before lamination. When transferring images in a completely aligned state, the four color images completely overlap at each mark. If not completely aligned, the entire bandwidth was measured. The width of the original mark was subtracted from the entire width, and the alignment error in each mark was obtained for MD and TD. FIG.
Indicates misalignment on a single mark after lamination of four colors (yellow, magenta, cyan, and black), and an alignment error in MD = X−11.
5 microns, where 115 represents the original width of the mark, X
Represents the entire width of the mark caused by the misalignment of the image. The largest alignment error among the 13 marks was taken as the overall alignment error. Since the error in the MD is more pronounced than the error in the TD, the maximum alignment error in the MD was measured for each of the samples.

Control 1 : photosensitive element: The photosensitive film element used in this embodiment is a commercially available film number from DuPont with stock numbers 831123, 83
1174, 831247, and 830976 WaterProof® tinted films.

Transfer element : The transfer element has the following structure. That is, a 100 μm (4 mil) transfer buffer layer made of Elvax (registered trademark) 550 is provided on a 100 μm (4 mil) PET support, and an approximately 25 μm (1 mil) PET cover sheet is further provided thereon.

Step 1 for forming colored image on fixed support : Four different colored photosensitive elements were exposed. Exposure involves contacting each colored photosensitive layer with the emulsion side of a negative resolution transparency corresponding to the colored photosensitive layer, through which transparencies 14 (for magenta), 20 (for yellow), and (For cyan and black) over a second. 6 before exposure
The device and transparency were evacuated for 0 seconds. About 137 from device and disassembly transparency
5 kW high-pressure mercury lamp (Olec L1261 lamp, Olek orix (O)
lectOlix) AL985 integrator and Olite AL53-100 power supply, Olec Inc, Irvine, CA, USA
Exposure of the element was performed by irradiation from.

After the exposure, the decomposition transparency was removed, and the device was developed and dried. During this development process,
Water proof (registered trademark) using 4 ° C water flow
Using a wash-off processor, the unexposed portions of the control photosensitive layer are further removed by rotating the brush. afterwards,
Hot air of about 110 ° C. was applied to the device with a dryer to dry the device.

Step 2 : The cover sheet of the transfer element was peeled off and removed. The element holding the black image is placed on the exposed layer of the transfer element with the image side down, and a water-proof laminator (DuPont)
Were laminated at 100 ° C., 150 lbs, and 400 mm / min. As a result, the black image was transferred to the transfer element as a wrong-reading black image.

Step 3 : Next, the yellow image was positioned with respect to the erroneously read black image on the transfer element, and transfer and lamination of the yellow image were performed as described in Step 2 above. As a result, an erroneous two-color image was formed on the transfer element.

Step 4 : By repeating the above step 3 for each of the developed magenta and cyan images, a four-color image with erroneous reading was obtained on the transfer element.

Step 5 : A four-color image having a reading error on the transfer element was transferred to a sheet material made of LOE paper. That is, a cyan image is placed on a paper sheet material, and the temperature is set to 100 ° C. and 450 lb.
The transfer was performed by laminating at s, 400 mm / min and peeling off the transfer element. As a result, a right-reading four-color proof was obtained on the LOE paper sheet material. The proof image results are shown in Table 1.

[0078]

[Table 1] UGRA UGRA UGRA Color density % dot resolution ^* 50% dot increase Yellow 1.39 0.5-99.5 6 13 Magenta 1.61 0.5-99.5 8 15 Cyan 1.48 0.5-99.5 8 18 Black 1.71 0.5-99.5 6 16 ^* Micrometer 126 μm A 13 point maximum registration error in the machine direction (MD) was obtained over a 7 proof average.

Example 1 Control 1 was repeated with the following exception. That is, prior to use in the method described above, 100 ° C., 40
The transfer element was heated by passing the transfer element through a laminator maintained at 0 lb / min and 150 lb load. The proof image results are shown in Table 2. A 13 point maximum registration error in the machine direction (MD) of 68 μm was obtained over a 7 proof average.

[0080]

[Table 2] UGRA UGRA UGRA Color density % dot resolution ^* 50% dot increase Yellow 1.42 0.5-99.5 6 12 Magenta 1.61 0.5-99.5 8 15 Cyan 1.48 0.5-99.5 6 17 Black 1.77 0.5-99.5 6 16 ^* Micrometer

Example 2 Control 1 was repeated with the following exception. That is, during the manufacturing process, the transfer element was heated by passing the transfer element through a laminator maintained at the temperature shown in Table 3 below. The proof image results were similar to those shown in Table 2. 13 points in machine direction (MD) (p
t. ) The maximum alignment error was determined and is shown in Table 3 below.

[0082]

Table 3 Laminator temperature in machine direction (MD) 13 pt. Maximum alignment error 79 ℃ 73μm 4 proof average 93 ℃ 63μm 4 proof average 107 ℃ 58μm 4 proof average

Example 3 Control 1 was repeated with the following exception. That is, prior to use, the transfer element was heated in an oven maintained at the temperature shown in Table 4 below. The proof image results were similar to those shown in Table 2. 1 in the machine direction (MD)
The three point (pt.) Maximum registration error was determined and is shown in Table 4 below.

[0084]

Table 4 Laminator temperature in machine direction (MD) 13 pt. Maximum alignment error 42 ° C 103μm 4 proof average 51 ° C 110μm 4 proof average 85 ° C 70μm 4 proof average 100 ° C 55μm 4 proof average 120 ° C 55μm 4 proof average

Example 4 Photosensitive element : The photosensitive film-like element used in this example is composed of (1) a photosensitive layer of about 1 μm containing no colorant,
(2) an adhesive layer of 1 μm, (3) a release layer of about 3 μm,
And (4) a structure comprising a 4 mil polyethylene terephthalate support. The photosensitive layer is composed of SSP M-20. The adhesive layer is Vylonal MD
-1400 and Vylonal MD-110
Consists of a 30:70 mixture with 0. The release layer was composed of Tispir XA51-824A (4.9 parts by weight), Ryuron (registered trademark) QU-628 (93.
2 parts by weight), Mizukasil (registered trademark) SK7 (1.5 parts by weight), and a dryer (Dry)
er) (0.4 parts by weight).

When the composition containing a water-permeable colorant is applied or
Inked photosensitive element : An inked photosensitive element was prepared as follows.

Transfer element : The transfer element has the following structure. That is, a 100 μm (4 mil) transfer buffer layer made of Elvax (registered trademark) 550 is laminated on a 100 μm (4 mil) PET support,
Further, a PET cover sheet of about 25 μm (1 mil) is laminated thereon. The transfer element was heat treated at a temperature of 93 ° C. as described in Example 2.

Method Steps : Step 1 : 1 g of Sunsperse,
(Registered trademark) Blue BHD-6015 and 49 g of water,
0.03 g of Zonyl® FSO-
100 is applied or inked on the photosensitive layer by coating using a wire wound rod.

Step 2 : The inked photosensitive element was placed in a vacuum printing frame. At this time, the ink layer was turned upward so that the ink layer faced the actinic radiation source. A negative decomposition transparency for blue was placed on the surface of the ink layer. At this time, the base side was turned up so that the emulsion side of transparency was in contact with the ink layer. Prior to exposure, the device and disassembly transparency were evacuated for approximately 90 seconds. Next, the device was exposed.
Exposure was performed by irradiation from a 5 KW high-pressure mercury lamp.
The mercury lamp is a 5 kW high-pressure mercury lamp (Olect L1261 lamp, Olek Olix AL985 integrator, commercially available from Olec, Inc., Irvine, Calif.)
And Olite AL53-100 power supply)
From the above element and decomposition transparency
Placed 7 cm above. After exposure, the resolution transparency is removed from the exposed photosensitive element.

Step 3 : The device was developed and dried using a Water Proof® wash-off processor utilizing a stream of water at 24 ° C., and the photosensitive layer and the unexposed portion of the inked portion were brushed. Rotate to remove. Thereafter, hot air at about 110 ° C. was applied to the element with a dryer to dry the element.

Step 4 : The cover sheet of the transfer element was removed by peeling. The image holding element is placed with the image facing down on the exposed transfer element at 100 ° C., 15 ° C. using a water-proof laminator (DuPont).
The layers were laminated at 0 lbs and 400 mm / min.

Next, the photosensitive element support and the release layer were removed by peeling, and the blue image was effectively transferred to the transfer element. As a result, an error in reading the blue image (wron)
g-reading) A blue image was formed on the transfer element.

Step 5 : Place the blue image on the transfer element downward on one sheet of LOE paper
C., 150 lbs, and 400 mm / min.
Next, the transfer element was removed by peeling to expose a stain-free blue proof on the LOE paper. The proof image results are shown in Table 5.

[0094]

TABLE 5 UGRA UGRA UGRA Color Density % Dot Resolution ^* 50% Dot Increase Blue 1.87 0.5-99.5 6 14 ^* Micrometer

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of a photosensitive element applied to the present invention, wherein (a) shows a case where a coloring agent is contained in a photosensitive layer;
(B) shows a case where a water-permeable colorant-containing composition is applied on a photosensitive layer containing no colorant.

FIG. 2 is a schematic sectional view of a carrier element applied to the present invention.

FIG. 3 is a schematic cross-sectional view for explaining an embodiment of a transfer element applied to the present invention.

4A and 4B are schematic cross-sectional views of a monochromatic intermediate image forming element, wherein FIG. 4A is manufactured using the photosensitive element of FIG. 1A, and FIG. 4B is a photosensitive element of FIG. The following shows what was manufactured using.

5A and 5B are schematic cross-sectional views showing an example of forming a monochromatic image on a fixed support prior to removal of a transfer element, and FIG.
1A shows a transfer element manufactured using the photosensitive element of FIG. 1A, and FIG. 1B shows a transfer element manufactured using the photosensitive element of FIG. 1B.

FIG. 6 is a schematic cross-sectional view of a two-color intermediate element manufactured by applying the lamination alignment method, which is manufactured using the element of FIG. 1A as a starting photosensitive element.

FIG. 7 is a schematic cross-sectional view of a multicolor intermediate element manufactured by applying the lamination alignment method, which is manufactured using the element of FIG. 1A as a starting photosensitive element.

FIG. 8 is a schematic cross-sectional view showing an example in which a multicolor image is formed on a fixed support prior to removal of a transfer element.
An element manufactured using the element (a) as a starting photosensitive element is shown.

FIG. 9 is a schematic cross-sectional view of a multicolor final device manufactured by applying the lamination alignment method, which is manufactured using the device of FIG. 1A as a starting photosensitive element.

FIG. 10 is a plot showing measurement results of a differential scanning calorimeter (DSC) for an unprocessed transfer element.

FIG. 11 is a plot diagram showing measurement results of a processed transfer element using a differential scanning calorimeter (DSC).

FIG. 12 is a schematic plan view showing the position of an alignment mark on a proof used to calculate an alignment error in producing a four-color proof.

FIG. 13 is a schematic plan view for explaining misalignment (misalignment) on a single mark after laminating four colors (yellow, magenta, cyan, and black).

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 Carrier support 11 Adhesive layer 12 Photosensitive layer 13 Separation layer 16 Transfer layer 17 Transfer support 18 Transfer surface layer 20 Fixed support

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Anti-Ho United States 08816 East Brunswick Hyde Park Drive, New Jersey 32 (72) Inventor Floyd A. Raymond United States 19810 Wilmington Brandywood Drive, Delaware 2143 (72) Inventor Bonnie Intan United States 08816 New Jersey East Brunswick P.O.Box 7231 (72) Inventor Thomas Peter Tufano United States 19707 Hockesin Shingham Drive, Delaware 334

Claims (32)

[Claims] 1. A method for forming a colored image, comprising: (A) (1) a carrier having a release layer, which is resistant to an aqueous developer, and (2) a first adhesive layer. And (3) providing a photosensitive element comprising a photosensitive composition developable with an aqueous developer and a first photosensitive layer consisting essentially of a water-permeable colorant-containing composition; In order to form an imagewise exposed area and an imagewise unexposed area in the first photosensitive layer containing a water-permeable colorant, the photosensitive element obtained in the step (A) is used. (C) developing the exposed photosensitive element obtained by the step (B) by washing with an aqueous liquid, and exposing the imagewise exposed area or Eliminate one of the imagewise unexposed areas By doing
A step of generating a first colored pattern; and (D) the photosensitive element that has been subjected to the step (C) and has been heat-treated at a temperature of at least 60 ° C. prior to the step (D). Stacking a transfer element having a release layer adjacent to the first colored pattern; (E) removing the carrier element having a release surface to expose the adhesive layer; and (F) A) laminating on the element fixing support obtained in the step (E), and making the adhesive layer adjacent to the fixing support by the lamination; and (G) the transfer element having a release surface. And the adhesive force between the release surface of the carrier element and the adhesive layer is F
1, the adhesive strength between the adhesive layer and the first colored pattern has a value of F2, and the adhesive strength between the first colored pattern and the release surface of the transfer element. The force has a value of F3, and the adhesive force between the adhesive layer and the fixed support is F3.
4, the value of F2 and F3 is greater than the value of F1,
Further, each of the F2 and F4 has a value larger than F3. 2. The method according to claim 1, wherein the transfer element is preferably set to 60 before the step (D).
A colored image forming method, wherein the colored image is subjected to a heat treatment at a temperature of from 150 to 150 ° C. 3. The method according to claim 1, wherein the water-permeable colorant-containing composition contains an insoluble colorant. 4. The method according to claim 1, wherein the water-permeable colorant-containing composition contains a pigment. 5. The method according to claim 1, wherein the first photosensitive layer does not contain a water-permeable colorant-containing composition, and the water-permeable colorant-containing composition is the same as the step (B). A colored image forming method, wherein the method is applied to the first photosensitive layer prior to the formation. 6. After the step (E), the steps (A) to (E) are reproduced at least once using at least one different photosensitive element containing a different water-permeable colorant-containing composition. A colored image forming method. 7. The method according to claim 1, wherein after the step (E), at least one different water-permeable colorant-containing composition, a different colorant-free photosensitive element, and the (D) A) using the element obtained from the step (E) as the transfer element to reproduce the steps (A) to (E) at least once. 8. The colored image forming method according to claim 1, wherein the release surface on the carrier element has a release layer. 9. The colored image forming method according to claim 1, wherein the release surface on the carrier element has a buffer layer. 10. The method according to claim 1, wherein the release surface on the transfer element comprises at least one buffer layer. 11. The method according to claim 10, wherein the release surface on the transfer element has a first buffer layer and a second buffer layer, and wherein the first buffer layer is Adhesive strength between the first colored pattern and the first buffer layer, which is adjacent to the first colored pattern, and between the first colored pattern and the first buffer layer. A method for forming a colored image. 12. The method according to claim 1, 6 or 7, wherein the photosensitive composition comprises N of polyvinyl alcohol.
-Alkylstyrylpyridinium derivatives, N-alkylstyrylquinolinium derivatives of polyvinyl alcohol,
And a material selected from the group consisting of a mixture of the derivatives. 13. The method according to claim 1, 6 or 7, wherein the adhesive layer comprises a vinyl chloride / vinyl acetate copolymer, an ethylene / vinyl acetate copolymer, a polyester, and a mixture thereof. A colored image forming method comprising a material selected from a group. 14. The method according to claim 1, wherein the aqueous liquid is water. 15. The method according to claim 5, wherein the composition containing a water-permeable colorant is provided as a layer on the first photosensitive layer. 16. The method according to claim 5, wherein the water-permeable colorant-containing composition is absorbed by the first photosensitive layer. 17. The method according to claim 1, 6 or 7, wherein the water-permeable colorant-containing composition is applied to the colorant-free first photosensitive layer using an inkjet printer. A colored image forming method characterized by being printed. 18. The method according to claim 1, wherein the water-permeable colorant-containing composition exhibits photosensitivity. 19. The method according to claim 1, wherein the water-permeable colorant-containing composition is non-photosensitive. 20. The method according to claim 17, wherein the water-permeable colorant-containing composition is an ink containing an aqueous carrier medium and a colorant. 21. The method according to claim 20, wherein the colorant is a pigment dispersion. 22. The method according to claim 20, wherein the colorant is a dye. 23. An element on which an image has been formed, in order: (1) a carrier element having a release surface that is resistant to aqueous development and (2) a first adhesive layer; The first photosensitive layer containing the water-soluble colorant-containing composition and the photosensitive composition is obtained by imagewise developing, washing, and developing, and the water-permeable colorant-containing composition is present as a separate layer. A first colored pattern, and (4) a transfer element having a release surface heated to at least 60 ° C., wherein the adhesive force between the release surface of the carrier element and the adhesive layer has a value of F1. The adhesive layer and the first
When the adhesive force between the first colored pattern and the peeling surface of the transfer element has a value of F3, the adhesive force between the colored pattern and the colored pattern of F2 has a value of F2. The value is greater than the value of F1,
The image forming device according to claim 1, wherein F2 has a larger value than F3. 24. The image forming device according to claim 23, wherein the transfer device is heated at a temperature of preferably 60 to 150 ° C. 25. The device of claim 23, wherein said water-permeable colorant-containing composition is applied to said first photosensitive layer using an ink jet printer, while said first photosensitive layer is water-permeable. An image forming device, comprising no composition containing a coloring agent. 26. The device according to claim 23, wherein the water-permeable coloring agent-containing composition is photosensitive. 27. The device according to claim 23, wherein the water-permeable colorant-containing composition is non-photosensitive. 28. The device according to claim 23, wherein the water-permeable colorant-containing composition is absorbed in the photosensitive layer. 29. The element according to claim 29, wherein the water-permeable colorant-containing composition is an ink containing an aqueous carrier medium and a colorant. 30. The image forming device according to claim 29, wherein the colorant is a pigment dispersion. 31. A dimensionally stable transfer element comprising a transfer support having a transfer surface layer, wherein the transfer element is heated at a temperature of at least 60 ° C. 32. The device according to claim 31, wherein
A transfer element heated at a temperature of 0 ° C. to 150 ° C.