JP2001171159A - Thermal imaging process providing color versatility - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method and a product for forming a laser induction image providing color versatility. SOLUTION: There is disclosed the method for forming a laser thermal image and an imaged laserable assemblage. The method comprise the steps of: (1) forming a first coating solution of a first colorant and a second coating solution of a second colorant; (2) providing a first base element; (3) forming a first imageable element; (4) forming a first laserable assemblage; (5) forming a first imaged receiver element; (6) providing a second base element; (7) forming a second imageable element; (8) forming a second laserable assemblage; (9) forming a second imaged receiver element; and (10) producing an imaged receiver element having revealed image.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to an improved method for performing laser induced thermal transfer imaging. More particularly, it relates to an improved method of providing color versatility that operates effectively at high speeds, increases image density, and increases the durability of images present on a receiver element during thermal imaging.

[0002]

BACKGROUND OF THE INVENTION Laser induced thermal transfer is well known in applications such as color proofing and lithographic printing. Such laser induction methods include, for example, dye sublimation, dye transfer, melt transfer, and abrasive transfer. These methods are described in GB 2,083,726 (Baldock), US Pat. No. 4,942,141 (DeBoer), US Pat. No. 5,019,549 (Kellogg), US Pat. No. 4,948. No. 5,776,938 (Evans), US Pat.
Oley et al.), U.S. Patent No. 5,171,650 (El
lis et al.) and U.S. Pat. No. 4,643,917 (K
Oshizuka et al.).

[0003] Laser guidance uses a laserable assembly with (a) a thermally imageable layer, ie, an imageable element containing the material to be transferred, and (b) a receiver element, which are in contact with each other. The laserable assembly is exposed by a laser, usually an infrared laser,
The material is transferred from the imageable element to the receiver element. The (image-wise) exposure is done only once in a small selected area of the laserable assembly so that the transfer of material from the imageable layer to the receiver element is stacked on one pixel at a time. High-resolution and high-speed transfer is realized by computer control. The laserable assemblage that undergoes laser exposure as described above is hereinafter referred to as an imaging laserable assembly.

[0004] With respect to creating images for proofing applications and creating images in photomask formation, the thermal imageable layer, ie, the exposed areas that are transferred as they are exposed, contain a colorant. Laser guidance is fast and transfers material with high resolution. However, in many cases, the available methods do not provide the color flexibility required for proofing applications.

[0005] US Patent 5,681,681 describes one way to achieve this color flexibility. Instead of using a “colored” foil, the toner image is used to form a laser exposed abrasive discontinuous topcoat film. An electrostatic mechanism is provided to use the toner image. Electrostatic color development is disadvantageous in that it is susceptible to humidity and the topcoat film can be non-uniform. This non-uniformity limits the resolution that can be achieved in the final image.

There remains a need for a method of providing color versatility that operates effectively at high speeds, increases image density, and increases the durability of images present on a receiver element during thermal imaging. .

[0007] Thermal imageable coatings use solvent-based systems in production-scale equipment that can safely contain volatile solvents. In the thermal imageable coating, a volatile solvent is used for the polyester substrate for easy application. A problem encountered when applying solvent-based paints using coaters that are not equipped to contain volatile solvents is that sparks and electrostatic discharge can cause volatile solvents to ignite under operating conditions That is.

[0008]

A solution to such a problem is to use a water-based formulation instead of a solvent-based formulation for coaters that are not equipped to contain volatile solvents. That is.

[0009]

SUMMARY OF THE INVENTION A method and product for laser induced thermal imaging with color flexibility is disclosed herein.

The present invention provides (1) forming a first coating solution of a first coloring agent and a second coating solution of a second coloring agent; and (2) forming a first coating solution having a first coating surface. Providing a first base element; and (3) applying a quantity of the first coating solution to the application surface to form a first thermal imageable layer thereon. Forming said first thermal imageable layer having a first thermal sensitivity; and (4) said first imageable element;
Forming a first laserable assembly including a receiver element having an image receiving layer in contact with the first imageable element; and (5) a first image-wise assemblage for the first laserable assembly. Performing an exposure to transfer the exposed areas of the first thermal imageable layer to a receiver element to form a first imaging receiver element; and (6) a second imaging receiver element.
Providing a second base element having an application surface of (a), and (7) applying an amount of the second coating solution to the application surface to form a second thermal imageable layer thereon. Forming a second imageable element, wherein the second thermal imageable layer has a second thermal sensitivity; and (8) the second thermal imageable element has a second thermal sensitivity.
Forming a second laserable assemblage, the first imageable element of which includes a first imageable receiver element adjacent to the second imageable element, and a first image of the second imageable element; For the two laserable assemblies, exposing the exposed area of the second thermal imageable layer by imagewise exposing the laser radiation with substantially the same laser fluence as the first imagewise exposure. Transferring to the first imaging receptor element to form a second imaging receptor; and (10) separating at least the second imageable element from the second imaging receptor. Generating an imaging receptor having an exposed image.

[0011] In one embodiment, the present invention relates to the second aspect.
Applying the imaging receptor of claim 1 to a permanent substrate.

Typically, the choice of base colors is at most fifty base colors, and at most each of the fifty base colors is a colorant,
Typically, it contains an aqueous colorant. The base color is typically about 1
A coating solution having a viscosity between centipoise and about 10 centipoise is formed. In one embodiment of the present invention, the coating solution further comprises a component selected from a near infrared absorbing agent, a foaming component and a combination thereof.

Typically, the thermal imageable layer has a thickness between about 1 micron and about 1.5 microns, and the laser is at most 80 inches long and 152.4 cm wide. (60 inches).

[0014]

DETAILED DESCRIPTION OF THE INVENTION A method and product for laser induced thermal transfer imaging with improved color flexibility is described.

By mixing predetermined amounts according to the prescription, the target colors of the first and second thermal imageable layers (collectively "thermal imageable layers") can be obtained, usually Achieve the target color strictly according to the prescription. Formulations that form a collection of base colors encompass a range of colors using various pigment systems. By mixing a predetermined amount of a plurality of solutions selected from the basic assembly of the formulation, a plurality of colors according to a pre-specified formula can be obtained. The aqueous color solution is then applied to a first or second base element (collectively "base elements") each having an application surface for forming a thermal imageable layer. The imageable element with the thermal imageable layer obtained in this way allows the user to create different colors and even adapt to the Pantone® color guide.

The first laserable assembly formed is:
(A) a first thermal imageable layer, ie, a first imageable element containing the material to be transferred;
And (b) a receptor element in which (a) and (b) are in contact. The first laserable assemblage is imagewise exposed by a laser, typically an infrared laser, to transfer the material imagewise from the first imageable element to the receiver element (eg, simultaneously into one pixel). ) Transfer. Once the material has been exposed and transferred image-wise, the resulting laserable assembly will be referred to as a first imaging laserable assembly. In many cases, the first imaging laser-emissive assembly following imaging is divided into two parts: an exposed thermal imageable layer and an imaging receiver element. The exposed thermal imageable layer and / or imaging receiver element can be representative of an imaging product made according to the present invention.

Before describing the improved method of the present invention in further detail, some exemplary laserable assemblies will be described. The method of the present invention is fast and provides images with higher durability in laser imaging as well as higher endurance and higher optical density than the comparable method (prior art). Preferably, it is carried out using any of the laserable assemblies described above.

Imageable Element As shown in FIG. 1, an exemplary imageable element useful for thermal imaging by the method of the present invention comprises a thermal imageable layer (14) and an optional extruded or subbing layer (12). And a base element with a heating layer (13). As mentioned earlier, each of these layers has a distinct function and a different function. Optionally, a support (11) for the imaging element may be present. In one embodiment, the heating layer (13) can be directly on the support (11).

A thermal imageable layer formed by applying a coating solution to a base element having a thermal imageable layer application surface;
Comprises (i) a polymer binder different from the polymer of the extruded layer and (ii) a colorant.

The polymer (binder) for the thermally imageable layer is a polymeric substance having a decomposition temperature above 300 ° C., preferably above 350 ° C. The binder has a film-forming property and can be applied by a solution or a dispersion. Binders having a melting point of less than about 250 ° C. or a plasticized glass transition temperature of less than about 70 ° C. are preferred. However, while heat fusible binders such as waxes are useful as co-binders in lowering the melting point of the upper layer, such binders are not durable and should be avoided as a single binder.

The binder (polymer) is autoxidized, decomposed or degraded at the temperature achieved during laser exposure so that exposed areas of the thermal imageable layer containing the colorant and binder are transferred without damage and remain durable. Preferably do not occur. Examples of suitable binders include styrene /
Copolymers of styrene and (meth) acrylate esters such as methyl methacrylate, styrene / ethylene /
Copolymers of styrene and olefin monomers such as butylene, copolymers of styrene and acrylonitrile, fluoropolymers, copolymers of (meth) acrylate esters with ethylene and carbon monoxide, polycarbonates with relatively high decomposition temperatures, homopolymers of (meth) acrylate and Copolymers, polysulfones, polyurethanes and polyesters are mentioned. The monomers directed to the polymer can be substituted or unsubstituted. It is also possible to use mixtures of polymers.

Preferred polymers for the thermal imageable layer include homopolymers and copolymers of acrylates, homopolymers and copolymers of methacrylates, block copolymers of (meth) acrylates, and other comonomers such as styrene ( Meta)
Acrylate copolymers include, but are not limited to.

The binder (polymer) is generally about 15 to 50% by weight, preferably 30 to 40% by weight, based on the total weight of the thermal imageable layer.

[0024] The thermal imageable layer also contains a colorant. Colorants include formulations of at least two colors depending on the choice of the base color. The colorant can be a pigment or a dye, preferably a non-sublimable dye. The pigments are preferably used for stability and color density, as well as for high decomposition temperatures. Examples of suitable inorganic pigments include carbon black and graphite. Examples of suitable organic pigments include Rubin F6B (CI No. Pigment 18).
4), Chromophtal (registered trademark) Yellow 3G (C.I.
I. No. Pigment Yellow 93), Hosta Palm (registered trademark) Yellow 3G (CI No. Pigment Yellow 154), Monastral (registered trademark) Violet R (CI No. Pigment Violet 1)
9), 2,9-dimethylquinacridone (CI No.
Pigment Red 122), India First (registered trademark) Brilliant Scarlet R6300 (CIN)
o. Pigment Red 123), Kind Magenta RV
6803, Monastral (registered trademark) Blue G (C.I.
I. No. Pigment Blue 15), Monastral (registered trademark) Blue BT383D (CI No. Pigment Blue 15), Monastral (registered trademark) Blue GB
T284D (CI No. Pigment Blue 15) and Monastral (registered trademark) Green GT751D
(CI No. Pigment Green 7). It is also possible to use combinations of pigments and / or dyes. For color filter array applications, small particle size (ie, about 100 nanometers) highly transparent (ie, the pigment has a light transmission of at least about 80%).
Are preferred.

The choice of colorant concentration according to principles well known to those skilled in the art will achieve the desired optical density in the final image. The amount of colorant will depend on the thickness of the effective coating and the absorbency of the colorant. Optical densities higher than 1.3 at the wavelength of maximum absorption are generally required. Higher optical densities are preferred. By applying the present invention, it is possible to achieve optical densities in the range of 2-3 or higher.

In order to achieve maximum color strength, transparency and gloss, dispersions are usually used when transferring pigments. The dispersion is generally an organic polymer compound used to separate the fine powder of the pigment and prevent coagulation and aggregation. Various dispersions are commercially available. The dispersion will be selected according to the properties of the pigment surface and other components of the formulation, as practiced by those skilled in the art. However, one class of dispersion suitable for carrying out the invention is the class of AB dispersion. Part A of the dispersion adsorbs on the surface of the pigment. Part B of the dispersion penetrates the solvent in which the pigment is dispersed. Part B establishes a barrier between the pigment powders to resist the suction of the powders, thereby preventing agglomeration. Part B must have good affinity for the solvent used. For the selected AB dispersion, 199
U.S. Pat. No. 5,085,69 issued to Assignee et al.
No. 8 is widely described. Conventional pigment dispersion techniques such as ball milling and sand milling can be used.

[0027] The colorant may be present in an amount of about 25 to 95%, preferably about 35 to 65% by weight, based on the total weight of the thermal imageable layer formulation. The above description was directed to color proofing,
The elements and methods of the present invention apply equally to other types of materials in different fields. In general, the scope of the present invention is intended to include any application in which a solid material is applied to a receiver in a pattern.

Although the thermal imageable layer can be applied to the base element by a solution in a suitable solvent, it is preferred that the layer be applied by a dispersion. Any suitable solvent can be used as a paint solvent utilizing conventional coating or printing techniques, such as gravure printing, as long as the properties of the assembly are not adversely affected. The preferred solvent is water. Dupont (Wi
The coating of the thermally imageable layer can also be accomplished using a Waterproof® color versatility coater sold by LM (Mington, DE). Thereby, it is possible to carry out the coating of the thermal imageable layer in a short time prior to the exposure step. This allows you to mix various basic colors,
It allows the creation of a wide variety of colors that match the Pantone® color guide currently used as one of the standards in the proofing industry.

[0029] The first thermal imageable layer has a first thermal sensitivity. The second thermal imageable layer has a second thermal sensitivity. Their thermal sensitivity of the thermal imageable layer is the first
The same laser fluence can be used for both the imagewise exposure step and the second imagewise exposure step. This feature of the invention is:
This can be achieved by matching the colors of the coating solutions so that each coating solution is heat absorbing, or by adding a heat absorber to one or both coating solutions.

[0030] long as they do not interfere with the basic function of the additive layer may have other materials present in the thermally imageable layer as an additive. Examples of such additives are known to be used in the formation of coating accelerators, plasticizers, glidants, slip agents, antihalation agents, antistatic agents, surfactants and coatings. Other substances may be mentioned. However, it may adversely affect the final product after transfer,
It is preferred to minimize the amount of additive material in this layer. Additives may add undesirable color in color proofing applications or reduce durability and print life in lithographic printing applications. Base element having application surface In the method of the present invention, the first base element and the second base element are provided.
Base element exists. The first base element has a first application surface. The second base element has a second application surface. The imageable element is
It is formed by applying a certain amount of a coating solution to an application surface.

One preferred base element is an optional extrusion or subbing layer (1) on the support (11).
2) and a heating layer (13). The surface of the heating layer is the application surface on which the thermal imageable layer is applied.

[0032] Support Support is preferably a thick (400 gauge (about 101.6 microns)) of coextruded polyethylene terephthalate film. Alternatively, the support may be polyester, especially polyethylene terephthalate which has been plasma treated to receive the heating layer. When the support is subjected to a plasma treatment, it is common to not provide an undercoat or extrusion layer on the support. An optional carrier layer can be provided on the support. These carrier layers can contain fillers to provide a rough surface on the back of the support. Or, the support itself,
A filler such as silica may be included to provide a rough surface on the back of the support.

Extrusion or Subbing Layer The elastic extrusion or subbing layer of the base element (12) shown in FIG. 1 provides the force to transfer the thermal imageable layer to the receiver element in the exposed areas.
This layer decomposes upon heating, extruding the exposed areas of the thermal imageable layer onto the receiver element,
Or gas molecules that provide the necessary pressure to release. This is because the decomposition temperature is relatively low (less than about 350 ° C,
Preferably less than about 325 ° C, more preferably about 280 ° C
(Less than) polymers. For polymers having multiple decomposition temperatures, the first decomposition temperature must be less than 350 ° C. further,
For the extruded layer to have a reasonably high degree of elasticity and conformability, its tensile modulus must be 2.5 gigapascal (GPa).
Or less, preferably less than 1.5 GPa,
More preferably, it is less than 1 gigapascal (GPa).
The polymer chosen must also be dimensionally stable. If the laser-emitting layer is imaged via the elastic extrusion layer, the elastic extrusion layer shall be able to transmit laser radiation and shall not be adversely affected by this radiation.

Examples of suitable polymers include: (a) a polycarbonate having a low decomposition temperature (Td) such as polypropylene carbonate; (b) a substituted styrene polymer having a low decomposition temperature such as poly (alpha-methylstyrene); (C) polyacrylates and polymethacrylates such as methyl methacrylate and polybutyl methacrylate; (d) cellulose materials having a low decomposition temperature (Td) such as cellulose acetate butyrate and nitrocellulose; and polyvinyl chloride and poly (chloro chloride). (E) other polymers such as vinyl) polyacetals, polyvinylidene chloride, low Td polyurethanes, polyesters, polyorthoesters, acrylonitrile and substituted acrylonitrile polymers, maleic resins, and copolymers of the above compounds. It is. Mixtures of polymers can also be used. Additional examples of low decomposition temperature polymers are disclosed in US Pat. No. 5,156,938 (Fole).
y etc.). These include polymers that undergo acid catalyzed degradation. For these polymers, it is often desirable to include one or more hydrogen donors with the polymer.

Preferred polymers for the extruded layer include polyacrylate and polymethacrylate esters, low Td polycarbonate, nitrocellulose, poly (vinyl chloride) (PVC) and chlorinated poly (vinyl chloride) (CPVC). . Most preferred are poly (vinyl chloride) and chlorinated poly (vinyl chloride).

Other materials can be used in the extruded layer as additives as long as they do not interfere with the basic function of the extruded layer. Such additives include coating accelerators, glidants, slip agents, antihalation agents, plasticizers, antistatic agents, surfactants, and other materials known to be used in forming film. Is mentioned.

Alternatively, the undercoat layer (12) is provided at a predetermined position of the extruded layer, and at least one undercoat layer (1) is provided.
2) It is possible to obtain an imageable element comprising, in sequence, at least one heating layer (13) and at least one thermal imageable layer (14). Some suitable subbing layers include polyurethane, polyvinyl chloride, cellulosic materials, acrylate or methacrylate homopolymers and copolymers, and mixtures thereof. Other custom made degradable polymers can also be utilized in the subbing layer. An acrylic subbing layer is preferably used as a subbing layer for polyester, specifically polyethylene terephthalate. The thickness of the undercoat layer is 100 to 1000
A (angstrom) is preferred.

Thermal amplification additive Optionally and preferably, the thermal amplification additive is present in the extruded layer, subbing layer or thermal imageable layer. Thermal amplification additives are present in any of these layers. Typically, when a thermal amplification additive is used in a thermal imageable layer, a sufficient amount of thermal sensitivity is provided to the thermal imageable layer to adjust the thermal sensitivity so that an image-wise exposure step is performed at the same laser fluence. An amplification additive is added.

The function of the thermal amplification additive is to amplify the effect of the heat generated in the heating layer, thereby improving sensitivity. The additive must be stable at room temperature. The additive can be (1) a compound that decomposes to produce gaseous by-products upon heating, (2) a dye that absorbs incident laser radiation, or (3) a compound that undergoes heat-induced monomolecular rearrangement that generates heat. It is also possible to use combinations of these types of additives.

Examples of the heat amplification additive which decomposes when heated include diazoalkyl, diazonium salt and azide (-
N3) compounds that decompose to produce nitrogen, such as compounds, ammonium salts, oxides and carbonates that decompose to produce oxygen,
Peroxides and the like. It is also possible to use mixtures of additives. Preferred thermal amplification additives of this type are diazo compounds such as 4-diazo-N, N'diethylaniline fluoroborate (DAFB).

When the absorbing dye is incorporated into the extruded or subbing layer, its function is to absorb incident radiation and convert it to heat, resulting in higher heating efficiency. Preferably, the dye absorbs in the infrared region. Further, for image forming applications, it is preferable that the absorption of the dye in the visible region is very low. Examples of suitable NIR (near infrared absorption) dyes that can be used alone or in combination include poly (substituted) phthalocyanine compounds and metal-containing phthalocyanine compounds, cyanine dyes, squarylium dyes, chalcogenopyrioacrylidene dyes Croconium dyes, metal thiolate dyes, bis (chalcogenopyrrolo) polymethine dyes, oxyindolizine dyes, bis (aminoallyl) polymethine dyes, merocyanine dyes and quinoid dyes.

Here, US Pat. No. 4,778,128
No. 4,942,141, No. 4,948,778
No. 4,950,639, No. 5,019,549
Nos. 4,948,776, 4,948,777 and 4,952,552 may also be suitable. For example, the weight percentage of the heat amplification additive to the total solids weight formulation of the extruded or subbing layer can range from 0 to 20%. When present in the thermal imageable layer, the weight percentage of the thermal amplification additive is generally at a level of 0.95 to 11.5%. The percentage is 25% of the total weight percentage in the thermal imageable layer.
%. These percentages are not limiting and those skilled in the art can vary them depending on the particular composition of the extruded or thermally imageable layer.

[0043] The thermal imageable layer has a thickness in the range of about 0.1 to 5 micrometers, preferably in the range of about 0.1 to 1.5 micrometers. Thicknesses greater than about 5 micrometers are generally not preferred because extra energy is required for efficient transfer to the receiver.

It is possible to have more than two thermal imageable layers. That is, it is the third thermal imageable layer. The third thermal imageable layer can have the same or a different composition as the first and second thermal imageable layers, as long as they do not interfere with the functions described above. The thickness of the composite thermal imageable layer shall be in the range described above.

Heating Layer A heating layer (13) as shown in FIG. 1 is laminated on the elastic extrusion layer or the undercoat layer. The function of the heating layer is to absorb the laser radiation and convert the radiation into heat. Suitable materials for the layer are inorganic or organic, which essentially absorb the laser radiation or may comprise additional laser radiation absorbing compounds.

Examples of suitable inorganics include IIIB, I
Transition metal elements or metal elements of groups VB, VB, VIB, VIII, IIB, IIIA and VA, their alloys, and alloys of elements IA and IIA of the Periodic Table of the Elements (CAS version) and their alloys. Tungsten (W) is an example of a suitable and available Group VIB metal. Carbon (a Group IVA non-metallic element) can also be used. Preferred metals include Al, Cr,
Examples include Sb, Ti, Bi, Zr, Ni, In, Zn, and alloys thereof. Carbon is a preferred non-metal. More preferred metals and non-metals include Al, N
i, Cr, Zr and C. Most preferred metals are Al, Ni, Cr and Zr. Useful inorganic substance is TiO _2.

The thickness of the heating layer is from about 20 angstroms to 0.1 micrometers, preferably from about 40 to 1
00 angstroms.

Although it is preferred to have a single heating layer, it is also possible to have multiple heating layers, provided that they function as described above, different layers having the same or different compositions. be able to. The total thickness of all heating layers must be in the above range, ie, 20 Angstroms to 0.1 micrometers.

The heating layer can be deposited using any of the well-known techniques for providing thin metal layers, such as sputtering, chemical vapor deposition, and electron beam.

Additional Layers The imageable element can also have additional layers (not shown). For example, an antihalation layer can be used on the side of the elastic extruded layer opposite the thermally imageable layer. Materials that can be used as antihalation agents are known in such art. Other anchoring or subbing layers may be present on either side of the elastic extrusion layer, and are well known in such arts.

In some embodiments of the present invention, a pigment such as carbon black is present in a single layer called the top layer. Such pigments function as heat absorbers and colorants, so the top layer has the dual function of a heating layer and a thermally imageable layer. The preferred colorant / heat absorber is carbon black.

Other Embodiments of the Imageable Element Other imageable elements may include alternative thermal imageable layers or layers on the support. Additional layers may be present depending on the particular method used for image-wise exposure and transfer of the formed image. Some suitable imageable elements are disclosed in U.S. Patent No. 5,773,188, U.S. Patent No. 5,622,795.
No. 5,593,808; U.S. Pat.
No. 334,573, U.S. Pat. No. 5,156,938,
U.S. Patent No. 5,256,506, U.S. Patent No. 5,42
No. 7,847, U.S. Pat. No. 5,171,650 and U.S. Pat. No. 5,681,681.

FIG. 9 is a graph showing an image forming area and a decomposition area. The transfer efficiency is high in the image forming area, and the transfer efficiency is low in the decomposition area. This emphasizes the value of the method of the present invention. The ability to match the thermal sensitivity of the coating solution facilitates imaging with the coating solution having different decomposition and imaging areas.

[0054] shown in receptor elements Figure 2 receptor element (20) is a non-degradable polymer (polymeric binder) and a transfer destination of the exposed areas of the thermally imageable layer comprising colorant Rezaburu assemblage Is the second part. In most cases, the exposed areas of the thermal imageable layer will not be removed from the imageable element in the absence of the receiver element. That is, exposing the laser radiation to only the imageable elements does not remove or transfer material. The exposed areas of the thermal imageable layer are removed from the imageable element only when it is exposed to laser radiation and the imageable element is in contact with or adjacent to the receiver element. In a preferred embodiment, the imageable element is in contact with the receiver element.

[0055] The receiver element (20) can be light-insensitive or light-sensitive. Preferably, the non-photosensitive receiver element includes a receiver support (21) and an image receiving layer (22). The receiver support (21) comprises a dimensionally stable sheet material. If the support is transparent, the assemblage can be imaged via the receptor support. Examples of transparent films for receiver support include, for example, polyethylene terephthalate, polyethersulfone, polyimide, poly (vinyl alcohol coacetal) polyethylene, or cellulose esters such as cellulose acetate. Examples of opaque support materials include, for example, polyethylene terephthalate filled with white pigments such as titanium dioxide, ivory paper or synthetic paper such as Tyvek® spun bonded polyolefin. For proofing applications, paper supports are common and preferred, while for medical hard copy and color filter array applications, support for polyesters such as poly (ethylene terephthalate) is common and preferred. A roughened support can also be used for the receiver element.

The image receiving layer (22) may be made of, for example, polycarbonate, polyurethane, polyester, polyvinyl chloride, styrene / acrylonitrile copolymer, poly (caprolactone), vinyl acetal copolymer of ethylene and / or vinyl chloride, homopolymer of (meth) acrylate (Butyl methacrylate) and copolymers, polycaprolactone, and mixtures thereof. The image receiving layer is preferably a crystalline polymer layer. The crystalline image-receiving layer polymer preferably has a melting point in the range of 50 to 64 ° C, more preferably 56 to 64 ° C, most preferably 58 to 62 ° C.
5-40% of Kapa® 650 (melting range 58-60 ° C.) and Tone® P-300 (melting range 58-62 ° C.), both of which are polycaprolactones
Formulations prepared from are useful in the present invention. 100%
It is preferred to use the Tone® P-300 of the US Pat. Useful receptor elements are also disclosed in U.S. Pat. No. 5,534,387 issued Jul. 9, 1996. One preferred example is the Waterproof® transfer sheet sold by DuPont. Preferably, the surface layer has an ethylene / vinyl acetate copolymer containing more ethylene than vinyl acetate.

The image receiving layer can be present in any amount that is effective for the intended purpose. In general, good results have been obtained at a coverage of from 10 to 150 mg / dm ² , preferably from 40 to 60 mg / m ² .

[0058] In addition to the image receiving layer, the receiver element can optionally include one or more other layers (not shown) between the receiving support and the image receiving layer. An additional layer between the image receiving layer and the support is a release layer. The receiver support alone or the combination of the receiver support and the release layer may be referred to as a first temporary carrier. The release layer is
A desired adhesion balance can be provided to the receiver support such that the image receiving layer adheres to the receiver support when exposed and separated from the imageable element, but the image receiving layer may be, for example, a lamination. Promotes the separation of the image-receiving layer from the receiver support upon transition to a permanent substrate. Examples of materials suitable for use as release layers include polyamides, silicones, polymers and copolymers of vinyl chloride, polymers and copolymers of vinyl acetate, and plasticized polyvinyl alcohol. Release surface is 1 to 5
It is possible to have a thickness in the range of 0 microns. A buffer layer may be present in the receiver element, typically a deformable layer between the release layer and the receiver support. A buffer layer may be present to enhance contact between the receiver element and the imageable element.
Examples of materials suitable for use as a buffer layer include copolymers of styrene and olefin monomers such as styrene / ethylene / butylene / styrene, styrene / butylene / styrene block copolymers, and as binders in flexographic printing plate applications. Other useful elastomers are listed.

Since the laser imaging step is usually followed by one or more transfer steps for transferring the exposed areas of the thermal imageable layer to a permanent substrate, the receiver element is an intermediate element in the method of the present invention. It is.

Image Fixing Element Optionally, the image fixing element (30) shown in FIG. 3 is used, which includes a support (31) having a release surface, also referred to as a second temporary carrier, and a thermoplastic polymer layer (34). be able to.

A support having a release surface or a second temporary key
The support (31) or second temporary carrier having a carrier release surface can include a support (32) and a surface layer (33) that can be a release layer. If the material used as support has a release surface, such as for example polyethylene or fluoropolymer, no additional layers are required. The surface or release layer (33) must have sufficient adhesion to maintain adhesion to the support (32) throughout the processing steps of the present invention. Almost any material with a reasonable stiffness and dimensional stability is useful as a support. Some examples of useful supports include polyesters, including polyethylene terephthalate and polyethylene naphthalate, polyamides, polycarbonates, fluoropolymers, polyacetals,
Polymer films such as polyolefins are included.
The support may be a thin metal sheet or a natural or synthetic paper substrate. The support can be transparent, translucent or opaque. The support may be colored and additives such as fillers incorporated therein to facilitate movement of the image-fixing element through the lamination device during lamination to the color image-containing receiver element. Is also good.

The support may be coated with an antistatic agent on one or both sides. This can be useful to reduce static when removing support from the thermoplastic polymer layer through the method of the present invention. Generally, it is preferred to provide an antistatic layer on the back of the support, i.e., on the support surface remote from the thermoplastic polymer layer. Materials that can be used as antistatic agents are well known in such arts. The support may optionally have a matte embossing to facilitate transport and handling of the image fixing element.

The support is typically from about 20μ to about 25
It has a thickness of 0μ. Preferred thickness is about 55 to 200
μ.

The release surface of the support is provided by a surface layer (33). The release layer is generally a very thin layer that facilitates layer separation. Materials useful as release layers are well known in the art and include, for example, silicones, melamine acrylics, vinyl chloride polymers and copolymers, vinyl acetate polymers and copolymers, plasticized polyvinyl alcohol, ethylene and propylene. Polymers and copolymers. When a separate release layer is applied over the support, that layer generally has a thickness in the range of 0.5 to 10 micrometers.

The release layer (33) comprises an antistatic agent, a coloring agent,
It may also contain antihalation agents, brighteners, surfactants, plasticizers, coating accelerators, matting agents and the like.

Thermoplastic Polymer Layer The thermoplastic polymers useful in this layer are preferably amorphous, that is, essentially non-crystalline, have a high softening point, a medium to high level of molecular weight, and have a low molecular weight component. For example, it has excellent affinity with polycaprolactone. In addition, crack-free flexibility and throughput for affixing to many different substrates are advantageous. The polymer is preferably dissolved in a solvent, has excellent solvent and light stability, and is a good film-forming product.

There are many useful thermoplastic polymer materials. Preferred for use in the present invention is a Tg (glass transition temperature) of about 27 to 150 ° C, preferably 40 to 7 ° C.
0 ° C., more preferably 45 to 55 ° C., and has a relatively high softening point (for example, Tg of 47 ° C. and melt flow of 14 ° C.
Elongation at break specified in ASTM D822A is small, for example, 3 and the weight average molecular weight (Mw)
Is a moderate, for example, about 67,000 thermoplastic polymer. For example, a polyester polymer having a Tg of about 47 ° C. is preferable because a good affinity is secured between the image-receiving polymer such as crystalline polycaprolactone and the polyester polymer of the image-fixing layer. However, other suitable polymers have proven to provide acceptable results. Some suitable materials include methacrylate / acrylates, polyvinyl acetate, polyvinyl butyral, polyvinyl formal, styrene-isoprene-styrene and styrene-ethylene-butylene-styrene polymers and the like.

The thermoplastic polymer is from about 60 to 90% by weight, preferably from about 70 to 85% by weight, based on the total weight of the thermoplastic polymer layer formulation.

The thermoplastic polymer layer and the image receiving layer
It is interrelated in that the colored image is captured between the lamination to the substrate, e.g. paper, and the colored image during cooling so as not to shift significantly. This significantly reduces, and even negligibly reduces, midtone dot shift, band-like boundary cracking and banding compared to similar methods that do not use such thermoplastic polymer layers, i.e., image-fixing elements. , Or substantially removed.

The use of thermoplastics in the methods and products of the present invention allows lamination rates from 200 mm / min to about 600-800 mm without disadvantages.
Per minute (3-4 times) to ensure a lamination range that allows image transfer to many different types of permanent substrates.

The thermoplastic polymer layer also provides a vehicle and mechanism for introducing chemical bleaching to reduce the effect on the final color associated with the NIR dye in transferring a color image to a permanent substrate.

Additives The thermoplastic polymer layer may contain additives as long as the function of this layer is not hindered. For example, additives such as plasticizers, other modifying polymers, coating accelerators, surfactants and the like can be used. Some useful plasticizers include polyethylene glycol, polypropylene glycol, phthalate esters, dibutyl phthalate, and glycerin derivatives such as triacetin. The plasticizer is preferably present in an amount of about 1 to 20%, most preferably 5 to 15%, based on the total weight of the thermoplastic polymer layer formulation.

As mentioned above, the thermoplastic polymer layer may be present in the thermally imageable element or the NI which may be present in the imageable element and / or the receiver element.
It preferably also contains a dye bleach to bleach thermal amplification additives such as R dyes. Some useful bleaches include amines, azo compounds, carbonyl compounds, organometallic compounds and carbanions. Useful oxides include peroxides, diacyl peroxides, peroxides, hydroperoxides, persulfates, and halides. Particularly preferred dye bleaches having NIR dyes of the polymethine type are hydrogen peroxide, organic peroxides, hexaallylbimidazole, halogenated organic compounds, persulfates, perborates, perphosphates, hypochlorites. It is a substance selected from the group consisting of acid salts and azo compounds.

The dye bleach is present in an amount of about 1 to 20%, preferably 5 to 15%, based on the total weight of the thermoplastic polymer layer formulation.

Permanent Substrate One advantage of the method of the present invention is that a permanent substrate, also known as a permanent support or final receiver, for receiving a colored image can be selected from almost any desired sheet material. For most proofing applications, a paper support is used, preferably the same paper on which the image is ultimately printed. Almost any paper raw material can be used. Other materials that can be used as permanent substrates include:
Cloth, wood, glass, pottery, most polymer films,
Synthetic paper, a thin metal plate or a metal foil may, for example, be mentioned. Almost any material that adheres to the thermoplastic polymer layer (34) can be used as the permanent substrate.

Processing Steps Colorant Formulation and Coating Method The target color of the coating solution for the thermal imaging enriched layer can be obtained by mixing predetermined amounts according to a strict formula. Formulations that form a basic color assemblage encompass a range of colors using various pigment / dispersion systems. A plurality of colors, according to a pre-specified formula or calculated by a suitable toning algorithm, are formed by mixing a predetermined amount of a plurality of solutions selected from at most 50 basic assemblies of these formulations. . Preferably, the coating solution further comprises an infrared absorber. Typically, the coating solution is about 1 centipoise and about 10 centipoise.
It has a viscosity between centipoise.

The thermal imageable layer can be applied to the base element by a solution or dispersion of a suitable solvent, but it is preferred that the layer be applied by a dispersion. Any suitable solvent can be used as a paint solvent while utilizing conventional coating or printing techniques, such as gravure, as long as the properties of the assembly are not adversely affected. The solvent is preferably water. Preferably, the coating is accomplished using a Waterproof® color versatility coater sold by DuPont, Wilmington, DE.

The imageable element obtained in this way allows the end user to create a wide range of colors and match it with the Pantone® color guide currently used as a standard in the proofing industry. enable. The imageable element made in this way can be imaged using a commercially available infrared laser device that allows the creation of digital proofing prints.

Exposure The next step in the method of the present invention is to imagewise expose the laser radiation to the laserable assembly, for example, as shown in FIG. The exposure step is preferably about 6
00 mJ / cm ² or less, most preferably about 250 to 4
It is performed with a laser fluence of 40 mJ / cm ² . As mentioned above, the laserable assembly includes an imageable element and a receiver element.

The assemblage is usually such that after removal of the lidding sheet, if present, the imageable element is such that the coating of the colored or top layer actually makes contact with the image-receiving layer on the receiver element. Is placed in contact with the receptor element. This is shown in FIG. Reduced pressure and / or increased pressure can be used to maintain contact between the two elements. Or,
Spacer particles can also be used in the thermal imageable or image receiving layer to slightly separate the imageable element and the receiver element. As a variant, the contact between the imageable element and the receiver element can be maintained by fusing around the layer. In other variations, the imageable element and the receiver element can be taped and fastened to the imaging device with tape, or a pin / clamp device can be used. As another variation, the imageable element can be affixed to a receiver element to provide a laserable assembly. The laserable assemblage can be conveniently mounted on the drum to facilitate laser imaging.

Various types of lasers can be used to expose the laserable assembly. The laser preferably emits in the infrared, near-infrared, or ultraviolet regions. Particularly advantageous are diode lasers emitting in the 750 to 870 nm region, which offer substantial advantages in terms of small size, low cost, stability, reliability, durability and ease of modulation. 780 to 850n
Most preferred is a diode laser emitting in the region of m.
Such lasers can be obtained, for example, from Spectrodiode Laboratories (San Jose, CA).

Exposure can be effected through an elastic extrusion layer or subbing layer of the imageable element, or through a receiver element, provided that they are substantially transparent to laser radiation. In most cases, the elastic extrusion layer or subbing layer of the imageable element is a film that is transparent to infrared radiation, and the exposure is conveniently effected via the elastic extrusion layer or subbing layer. However, if the receiver element is substantially transparent to infrared radiation, the treatment of the present invention can also be accomplished by exposing the receiver element to infrared laser radiation image-wise.

The laserable assemblage is imagewise exposed so that the exposed areas are transferred to the receiver element in a pattern. The pattern itself can be in the form of, for example, a computer-generated dot or linework, a shape obtained by scanning artwork to be copied, a digitized image taken from the original artwork, or a laser exposure. Can be any combination of these forms that can be synthesized electronically on a computer before The laser light and laserable assemblage are such that each small area, or "pixel", of the assemblage is individually processed by the laser.
Take a constant movement with respect to each other. This is commonly accomplished by mounting the laserable assembly on a rotating drum. It is also possible to use a flat-bed recorder.

Separation The next step in the method of the invention is to separate the imageable element from the receiver element. Usually this is done by peeling off the two elements. The peel force required for this is generally very small, which is achieved by separating the support of the imageable element from the receiver element. This can be done using any conventional separation technique, and may be manual or automatic without operator intervention.

As shown in FIG. 5A, by separation,
A laser-produced color image, also known as an image, comprising a transferred exposed area of the thermal imageable layer, preferably a digital halftone dot color image, also referred to as a halftone dot image or a digitally formed color image, is provided in the receiver Exposed above the image receiving layer of the element. Preferably, the image formed by the exposing and separating steps is a laser-generated halftone dot color image formed on the crystalline polymer layer, wherein the crystalline polymer layer is located on the first temporary carrier .

Transfer of Image to Permanent Substrate The color image on the receptor element is then brought into contact with, preferably pasted on, the permanent substrate by contacting the color image on the image receiving layer shown in FIG. Transfer to permanent substrate. Preferably, lamination is accomplished using a Waterproof® Laminator manufactured by DuPont. However, this contact can be accomplished using other conventional means to obtain the laminate shown in FIG. 5 (B).

In another embodiment, the receptor support (2
1) removing (preferably peeling) (also known as first temporary carrier) to obtain the assembly shown in FIG. 5 (C). In a preferred embodiment, the assemblage shown in FIGS. 5 (B) and 5 (C) comprises a laser-produced halftone dot color formed between an image receiving layer, preferably a crystalline polymer layer, and a permanent substrate. Represents a printed proofing print containing a thermal image.

Alternative Method Lamination of the Image Fixing Element In an alternative embodiment, the image fixing element is brought into contact with the receiver element, preferably with the image in contact with the thermoplastic polymer layer of the image fixing element. The application places a color image within the thermoplastic polymer layer and the image receiving layer of the anchoring element. This is most clearly shown in FIG. Preferably, the lamination is accomplished using a DuPont Waterproof® Laminator. However, other conventional means can also be used to achieve contact between the image bearing receiving element and the thermoplastic polymer layer of the stationary element. A fixed element support (31), also known as a second temporary carrier with a release surface
It is important that the adhesion between the layer and the thermoplastic polymer layer (34) be less than the adhesion between any other layers in the laminate. The novel assembly or laminate shown in FIG. 6A is very useful, for example, as a modified proofing system.

Transfer of Image to Permanent Substrate Next, the support (32) (or second temporary carrier) having the release surface (33) is removed, preferably by peeling, as shown in FIG. 6 (B). Expose the thermoplastic film. The image on the receiver element is then transferred to the permanent substrate by contacting and preferably affixing the permanent substrate to the exposed thermoplastic polymer layer of the laminate shown in FIG. 6 (A). Again, lamination is preferably accomplished using a Waterproof® Laminator manufactured by DuPont. However, this contact can be accomplished using other conventional means to obtain the laminate shown in FIG.

Another embodiment is a receptor support (21)
(Also known as first temporary carrier), preferably by peeling, to obtain the assembly or laminate shown in FIG. In a preferred embodiment, the assemblage shown in FIGS. 7 and 8 has a laser-generated intermediate tone formed over the crystalline polymer layer such that the image is contained between the crystalline polymer layer and the thermoplastic polymer layer. FIG. 5 represents a printed proofing print comprising a dot color thermal image and a thermoplastic polymer layer having one surface affixed to the crystalline polymer layer and the other surface affixed to a permanent substrate.

Formation of Multicolor Images In proofing applications, the receiver element can be an intermediate element on which the multicolor image is laminated. An imageable element having a thermal imageable layer containing a first colorant is prepared and exposed and separated as described above. The first receiving element is preferably a laser-produced halftone dot color thermal image.
Having an image formed using the coloring agent of Thereafter, a second imageable element having a thermal imageable layer different from that of the first thermal imageable element forms a laserable assemblage with a status element having an image of the first colorant, as described above. Is separated by exposure. To laminate digitally formed multicolor images of color proofing onto a receiver element,
(A) forming a laserable assemblage with a thermal imageable element having a colorant different from the previously used colorant and a previously imaged receiver element; and (b) performing an exposure. , (C) performing the separation step as necessary.

In one embodiment of the present invention, in forming these multicolor images, at least 2
There are three primary colors, and their color formulations have substantially similar thermal sensitivities. Techniques for achieving such similarity in thermal sensitivity use NIR dyes. Both color formulations are typically 100 to 6
It has a thermal sensitivity of 00 mJ / cm ² , more typically 350 mJ / cm ² or less, and more typically in the range of 200 to 350 mJ / cm ² .

Next, the permanent substrate is brought into contact with, preferably affixed to, the composite image on the image receiving element such that the final image contacts the permanent substrate.

In an alternative method, the fixed element is then contacted with the composite image on the image receiving element such that the final image contacts the thermoplastic polymer layer.
Next, the processing is completed as described above.

[0095] Example These examples give a wide variety of colors image shows a method and products claims and described herein. Unless otherwise specified, all temperatures throughout the specification are in ° C. (Celsius) and all percentages are by weight.

The L * a * b color is composed of composite wavelength information that is converted by the human eye into a ternary system of primary colors in order to simplify processing. Hue, its basic colors (pink, orange and red), saturation (clearness or turbidity) and brightness (lightness or darkness).
These attributes provide three coordinates that can be used to map colors in a three-dimensional color space. In the color space,
Lightness is the center of the vertical axis, saturation is the horizontal axis, and hue is the angle between the axis of saturation and the axis of lightness. This three-dimensional form is a convenient way to compare the relationship between any two colors by their distance in the color space. In 1931, the International Commission on Illumination (CIE) established a standard for a series of color spaces representing the visible spectrum. In the data shown here, reference is made to a color scale called CIEL * a * b. It is a highly balanced system of color space based on the theory that colors cannot be red and green at the same time, and cannot be blue and yellow at the same time. As a result, a single value can be used to indicate red / green and yellow / blue attributes. In the following examples, colors are represented by CIEL * a and * b, where L * defines lightness, a * indicates a red / green value, and b * indicates a yellow / blue value. One of the more versatile measuring devices used to measure color is a colorimeter. The measuring device measures the light and decomposes the light into RGB components. Then, L * a *
The color values are determined using the b color space. In each example, the color coordinates of the colored coating are matched to the corresponding colors in the Pantone® Color Formula Guide. X Light Color Head (Grand Billet (M
ichigan)).
The most widely used light source for proofing applications for color verification is D50. The measured colors can then be matched to a standard color matching system, such as a Pantone® matching system.

The following procedure is used to prepare a solution of the colored or thermally imageable layer and change the color by combining the two colors from the basic assembly, green and white, or green and black as defined below. Prove that it is possible.

E is the difference in L *, a *, b * between the Pantone® color and the measured color, typically less than about 6, more typically less than about 4 .

In the following procedure, individual pantone colors are checked very strictly, ie within an aE of less than 6, by adding other colors selected from the basic collection of colors. Prove that you can.

Procedure 1 : The following components were mixed and stirred.

[0101]

[Table 1]

In the above table, GJD3007, YJD
3174 and RJD3022 are green, yellow and red dispersions from Sun Chemicals, respectively, and Polymer 1 and Polymer 2 are MMA / BA / M
AA and GMA ratios of 87/0/3/10 respectively
And a terpolymer of 7/80/3/10. PE
G300 is a polyethylene glycol having a molecular weight of 300, and Zonyl FSA (DuPont) is a fluorine-based surfactant. Grs in this and all following tables
Represents gram.

After stirring for 30 minutes, the control solution was applied to LOE paper using a # 6 Meyer bar to an apparent thickness of about 1 micron. After the coated paper was dried in a 60 ° C. oven for 1 minute, the color coordinates were measured using an X-light color head. The results are shown in Table 2 below.

[0104]

[Table 2]

It has been found that with certain pigments sufficient absorption can be obtained without the need for NIR. Examples of such pigments include green and black.

Procedure 2 : Procedure 2 demonstrates that additional colors can be generated by adding a second color from a basic collection of colors. To prepare samples 1 to 5a, a white solution was added to the control sample formulations listed above. The white solution consisted of 27.7 grams of WND-DC06 white dispersion from Sun Chemicals and 72.2 grams of water. This corresponds to a 15% solids white solution. The formulations obtained by mixing the control solution and the white solution are listed below. The application and measurement procedures performed are the same as those described for the control.

[0107]

[Table 3]

Step 3 : Step 3 also proves that additional colors can be generated by adding other colors from the basic collection of colors. To prepare samples 6 and 7, the black solution was added to the control sample formulations listed above. The black solution consisted of 31.38 grams of LHD-9303 black dispersion from Sun Chemicals and 68.61 grams of water. this is,
This corresponds to a 15% solids black solution. The formulations obtained by mixing the control solution and the white solution are listed below. The application and measurement procedures performed were the same as those described for the control. Table 4 shows the results.

[0109]

[Table 4]

Procedure 3a : This procedure demonstrates that additional colors can be imaged under moderate exposure conditions by adding a second color from the color assemblage and an infrared dye. To prepare samples 1a to 5a shown in Table 5, a white solution was added to a control sample (C1 in Procedure 1). The white solution was WND-DC06 white dispersion 27.7 from Sun Chemicals.
And 72.2 grams of water. This corresponds to a 15% solids white solution. The formulations obtained by mixing the control solution and the white solution are as shown in Table 5. The application and measurement procedures performed were the same as described for procedure 1.

[0111]

[Table 5]

Procedure 4 : A basic red dispersion was prepared by mixing and stirring the components shown in Table 6.
Step 1 was repeated.

[0113]

[Table 6]

In the above table, Fraser Red is an ink jet dispersion (DuPont) and Castle Magenta is an ink jet dispersion (DuPont). Polymer 1
Is MMA / BA / MAA with a ratio of 87/0/3/10
And a terpolymer of GMA. SDA4927,
It is an infrared dye that absorbs at 850 nm as the laser wavelength. PEG 300 is ethylene glycol having a molecular weight of 300, and Zonyl (registered trademark) FSA (DuPont) is a fluorine-based surfactant.

After stirring for 30 minutes, a control solution was applied to LOE paper using a # 6 Meyer bar to an apparent thickness of about 1 micron. After the coated paper was dried in an oven at 60 ° C. for 1 minute, the color coordinates were measured using an X-light color head. The results are shown in Table 7 below.

[0116]

[Table 7]

Step 5 : Step 5 demonstrates that additional colors can be generated by adding other colors from the basic collection of colors. Samples 8 to 13 (S
To prepare S13) from 8 a white solution was added to the control sample formulation according to procedure 4. The white solution consisted of 27.7 grams of WND-DC06 white dispersion from Sun Chemicals and 72.2 grams of water. This corresponds to a 15% solids white solution. The formulations obtained by mixing the control solution and the white solution are listed below. The application and measurement procedures performed were the same as those described in Procedure 4. Table 8 shows the results.

[0118]

[Table 8]

Step 6 : Step 6 also demonstrates that additional colors can be generated by adding other colors from the basic collection of colors. Samples 14 to 18
To prepare (S14 to S18), a black solution was added to the control sample formulation from Procedure 4. The black solution consisted of 31.38 grams of LHD-9303 black dispersion from Sun Chemicals and 68.61 grams of water. This corresponds to a 15% solids black solution. The formulations obtained by mixing the control solution and the white solution are listed below. The application and measurement procedures performed were the same as those described for the control. Table 9 shows the results.

[0120]

[Table 9]

Procedure 6a : Samples 8 to 11 according to Table 8
(S8 to S11) and samples 3 and 4 in Table 3
NIR (near infrared absorption) dye was added to (S3 and S4) to increase the thermal sensitivity of the sample to a thermal sensitivity substantially similar to that of the sample containing the black solution.

[0122]

[Table 10]

In the following examples, the films had the following structures. The substrate is 4 mil (10.16
Micron), with a thin undercoat applied to the back through extrusion. A thin metal layer of Cr is laminated to the extruded layer by sputtering, and a micron colored coating of the formulation listed in each specific example is applied over the metal layer provided by sputtering. .

Example 1 The following structure, namely the assisted Mylar®
A base element having a substrate, an extruded layer and a heated layer was prepared. The base, i.e., 4 mil (10.16 micron) Mylar® 200D,
A micron PVC (polyvinyl chloride) (Aldrich, molecular weight: 78,000) projecting layer was applied by 54 inch (about 137.2 cm) wide reverse gravure at a line speed of M. The thickness of the film is 15 mg / dm ²
Was about 1 micron (10 ^-4 cm), which corresponds to the coating amount. 10% by weight of diphenylphthalate was added to the formulation to prevent cracking of the protruding layer when handling the film. 11. the solids content in the PVC solution
Adjusted to 5% to give a viscosity of about 300 centipoise. The solvent contained 80% methyl ethyl ketone (MEK) and 20% cyclohexanone (Cy). The latter was used to promote dilution and slow down film drying. 1
The solution was filtered in-line using a 0 micron filter. After the application of the projecting layer is completed, the film is removed from a vacuum deposit company (Louisville, KY).
And send it to 40% (80 °)
A heating layer of Cr was laminated by sputtering. The thickness of the metal was monitored in-line using a quartz crystal plate and after lamination was monitored by measuring the reflectance and transmittance of the film.

Next, the three-layer imageable element was placed on a piece of paper fixed on a Waterproof (registered trademark) carrying plate, and the solution of the colored coating film was prepared using the solution shown in Table 11. Application was performed.

[0126]

[Table 11]

In the above table, Fraser Red is a red ink jet dispersion (DuPont) and Castle Magenta is an ink jet magenta dispersion (DuPont). ADS-830 is an NIR with absorption at 850 nm
(Gold infrared absorption) dye, PEG300 is polyethylene glycol having a molecular weight of 300, and Zonyl (registered trademark) FSA (DuPont) is a fluorine-based surfactant.

The paper sheet serves to prevent color stains. The paper secured to the carrier was discarded after the application was completed. The imageable element, including the substrate, the undercoat layer and the metal layer, was cut to the desired size and placed on paper with the metal layer away from the surface of the carrier. 6
The numbered Meyer rod was inserted into the corresponding coater hole with the tip of the imageable element immediately below the Meyer rod. The solution was applied to the base element prepared as described above using a syringe. 9 ml of the solution was weighed and drawn into a 10 ml plastic syringe, and a 2 micron filter was attached to the mouth of the syringe to filter the solution during liquid transfer. The solution is then evenly spread over a 23 inch (about 58.4 cm) Meyer bar and the carrier is mechanically transported from the nip area to the drying area using drive rollers mounted on the side frame of the apparatus. To apply the coating solution. Using a dial gauge in the apparatus, the drying time and temperature of the dryer were set to 60 ° C. for 4 minutes. After drying is completed, pull out the imageable element and
4 inches (approximately 59.1 cm) x 31 1/4 inches (approximately 79.4 cm).

The receiver element (P300) used in this example consisted of 4 mil (10.16 microns) Mylar® 400D coated with a 2 micron layer of polycaprolactone.

Next, the imageable element and
The receptor element was analyzed using the Creo 3244 Spectrum Train.
4 of Ndosetta (Cleo, Vancouver, BC)
An image was formed by loading into an up cassette. Civec
(Registered trademark) sheet
Separate the receiver and receptor elements for automatic loading
Was. Place the receiver element on the imaging drum and
Fixed by the sky. When the attachment is complete,
Imageable element slightly larger than the element
The thermal imageable layer is the receptor for polycaprolactone
On the receptor, making direct contact with the surface
Was. Emit at 830 nm and 1 microsecond pulse width
20 watt infrared diode laser light valve open
And a series of 240 5 x 2 micron rows emitted by
Exposed to this laserable assembly using a row of spots
Was done. Change drum speed, 200-350mJ
/ Cm ^TwoSensitivity in the range of The results are shown in Table 12.
You.

[0131]

[Table 12]

The image on the receiver element was pasted on paper using a Waterproof® laminator. The temperature of the upper roller and the lower roller was set to 115 ° C. and 120 ° C., respectively, and the transfer speed was set to 600 m.
m / min. After lamination was completed and the image was cooled for 2 minutes, the receiver element backing was removed.
L *, a * and b * of the transferred image at 250 mJ / cm ² were 53, 64.63 and 38.19, respectively.
Met. Color match and .E were 711 and 5.0, respectively. This indicates that lamination does not substantially affect the color coordinates of the transferred image.

Example 2 Example 1 was repeated except that the coating layer had the following formulation:

[0134]

[Table 13]

In the above table, GJD3007, YJD
3147 and RJD3022 are green, yellow and red dispersions from Sun Chemicals,
G300 is a polyethylene glycol having a molecular weight of 300, and Zonyl (registered trademark) FSA (DuPont) is a fluorine-based surfactant.

The following table shows the color coordinates of the image digitally transferred from the green imageable element to the receiver element as a function of the laser fluence used for the transfer.

[0137]

[Table 14]

Example 3 This example shows a color obtained by mixing two basic colors, in this case magenta and Pantone Red 185. The basic colors are obtained from the following formula.

[0139]

[Table 15]

[0140]

[Table 16]

After stirring for 30 minutes, a control solution was applied to LOE paper using a # 6 Meyer bar to an apparent thickness of about 1 micron. After the coated paper was dried in an oven at 60 ° C. for 1 minute, the color coordinates were measured using an X-light color head. Table 17 shows the results of Pantone (registered trademark) color and ΔE.

[0142]

[Table 17]

Example 4 This example illustrates the use of special colors for proofing applications. The six-color imageable element had the structure shown in Example 1 where the colored coatings were primary colors, namely cyan, yellow, magenta and black. Two special color imageable elements having the compositions listed in Tables 1 and 5 were applied according to the procedure described above. Six imageable elements and one receiver element were loaded into a Creo 3244 Spectrum Trendsetter 4-up cassette to form an image. The imageable element and the receiver element were separated using a Tibex® sheet and auto-loaded. The receiver element was mounted on an imaging drum and fixed by vacuum. Upon completion of the mounting, an imageable element slightly larger than the receiver element was mounted on the receiver with the black thermal imageable layer in direct contact with the surface of the receiver and held by vacuum. The laserable assemblage was exposed using a series of 2405 x 2 micron parallel spots emitted by opening a light valve of a 20 watt infrared diode laser light emitting at 830 nm and 1 microsecond pulse width. . The image obtained on the exposed imageable element corresponded to a color-separated negative RIP image. Assemblies were loaded, digitally exposed and unloaded in the order black, cyan, magenta, yellow, green, red imageable elements. The corresponding drum speed, sensitivity, and laser power for each different color are listed below.

Table 18 shows the results.

[0145]

[Table 18]

[Brief description of the drawings]

FIG. 1 shows the invention comprising a support (11), a base element having an application surface including an elastic projecting or undercoat layer (12) and a heating layer (13), and a thermal imageable layer (14). FIG. 4 illustrates a useful imageable element.

FIG. 2. Receptor support (21) and image receiving layer (22)
(20) A receptor element useful in the present invention, comprising:
FIG.

FIG. 3 shows an image-fixing element (30) useful in the present invention with a support having a release surface (31) and a thermoplastic polymer layer (34).

FIG. 4 shows a thermal imageable layer (14) comprising an image receiving layer (2)
FIG. 4 is a view showing a laminate formed by contacting the imageable element (10) and the receiver element (20) so as to be adjacent to 2).

FIG. 5 (A) shows the image (14a) obtained by exposing the laminate of FIG. 4 and then separating the imageable element and the receiver element from the image receiving layer (2).
2) shows a receiving element (20) having on it,
(B) shows a color image (14a) of the permanent substrate (40).
Is brought into contact with the permanent substrate (40), and FIG.
FIG. 2C shows a laminate formed by contacting the laminate shown in FIG. 1C, where (C) is the final element formed when the support (21) is separated from the image receiving layer (22), for example, a printed proofing print. FIG.

FIG. 6A shows an image receiving layer (2) having an image (14a) thereon such that the image (14a) fits between the thermoplastic polymer layer (34) and the image receiving layer (22).
Figure showing an image fixing element (30) in contact with 2);
FIG. 6B is a view showing the laminate of FIG. 6A from which the fixed support having the peeling surface (31) is removed.

FIG. 7 shows a laminate shown in FIG.
0) shows a laminate obtained, for example, by attaching a thermoplastic polymer layer (34) to paper so that it is adjacent to the paper.

FIG. 8 shows the final element formed when the support (21) is separated from the image receiving layer (22), for example a printed proofing print.

FIG. 9 is a diagram illustrating an image forming area related to thermal sensitivity and transfer efficiency.

[Description of sign]

 REFERENCE SIGNS LIST 10 imageable element 11 support 12 undercoat layer 13 heating layer 14 thermal imageable layer 20 receptor element 21 receptor support 22 image receiving layer 30 image fixing element 31 support having release surface 32 support 33 surface layer 34 thermoplastic polymer layer 40 permanent substrate

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) B41M 5/26 Z (72) Inventor Michael F. Moore United States 19808 Wilmington Hogan Drive, Delaware 4818

Claims (21)

[Claims] (1) forming a first coating solution of a first coloring agent and a second coating solution of a second coloring agent; and (2) forming a first coating solution having a first application surface. Providing a base element; and (3) forming a first imageable element by applying an amount of the first coating solution to the application surface to form a first thermal imageable layer thereon. And wherein the first thermal imageable layer comprises a first thermal imageable layer.
(4) forming a first laserable assembly including the first imageable element and a receiver element having an image receiving layer in contact with the first imageable element. (5) transferring an exposed area of the first thermal imageable layer to a receiver element by performing a first image-wise exposure to the first laserable assembly; (6) providing a second base element having a second application surface; and (7) applying an amount of the second coating solution to the application surface. Forming a second imageable element by forming a second thermal imageable layer thereon, wherein the second thermal imageable element comprises: The bubble layer is the second
And (8) a second imageable element, and a second image of which the first image includes the first imaging receptor element adjacent to the second imageable element.
Forming a laserable assemblage of (9) by image-wise exposing the second laserable assembly to laser radiation with substantially the same laser fluence as the first image-wise exposure. Transferring the exposed areas of the second thermal imageable layer to the first imaging receptor element to form a second imaging receptor; (10) at least the second imager Separating the flexible element from the second imaging receptor to produce an imaging receptor having an exposed image. 2. The method of claim 1, further comprising applying the second imaging receptor to a permanent substrate.
The method described in. 3. The exposed image and the image receiving layer such that the receiver element further comprises a support, wherein the support is removed such that the exposed image is contained between the image receiving layer and the permanent substrate. 3. The method according to claim 2, wherein the step of transferring is performed on the permanent substrate. 4. The method of claim 3, wherein said permanent substrate is paper. 5. The method of claim 1, wherein the imagewise exposure step is repeated to form a multi-image including four colors. 6. Contacting the second imageable element with an image-fixing element comprising: (a) a support having a release surface; and (b) a thermoplastic polymer layer, the image being adjacent to the thermoplastic polymer. Thereby placing the image between the thermoplastic polymer layer and the image receiving layer; exposing the thermoplastic polymer layer by removing the support; and permanently removing the exposed thermoplastic polymer layer. Contacting with a substrate. 7. The exposure step is performed at 600 mJ / cm ^2.
2. The method according to claim 1, wherein the method is performed with the following laser fluence. 8. The method of claim 1, wherein the first base element and the second base element include: (a) an extruded or subbed layer; and (b) a heating layer. 9. The method of claim 1, wherein the first base element and the second base element include: (a) a heating layer; and (b) a base element support. 10. The method of claim 1, wherein said first imageable element and said second imageable element further comprise a polymer binder. 11. The method according to claim 1, wherein the polymer binder has a temperature of about 350 ° C.
11. The method of claim 10, wherein the polymer is a low decomposition temperature polymer having a decomposition temperature greater than. 12. The method of claim 1, wherein said first colorant and said second colorant comprise a dispersed pigment. 13. The method of claim 1, wherein said first colorant and said second colorant comprise a dye. 14. The method of claim 1, wherein the first and / or second thermal imageable layers are near infrared absorbing dyes. 15. The NIR dye is a poly (substituted) phthalocyanine compound, a metal-containing phthalocyanine compound, a cyanine dye, a squarylium dye, a chalcogenopylioacridene dye, a croconium dye, a metal thiolate dye, a bis (chalcogenopyrrolo) polymethine dye. 15. The method of claim 14, wherein the method is selected from the group consisting of: an oxyindolizine dye, a bis (aminoallyl) polymethine dye, a merocyanine dye, a quinoid dye, and mixtures thereof. 16. The method of claim 1, wherein said image receiving layer of said receiver element comprises a crystalline polymer. 17. The method of claim 16, wherein said crystalline polymer is polycaprolactone. 18. The thermoplastic polymer essentially comprises polyester, methacrylate, acrylate, polyvinyl acetate, polyvinyl butyral, polyvinyl formal,
The method of claim 6, wherein the method is selected from the group consisting of styrene-isoprene-styrene and styrene-ethylene-butylene-styrene polymers. 19. The method according to claim 18, wherein said thermoplastic polymer is polyester. 20. The method of claim 6, wherein said thermoplastic polymer comprises a NIR dye bleach. 21. The NIR dye bleaching agent is a group consisting of amines, azo compounds, carbonyl compounds, organometallic compounds, carbanions, peroxides, diacyl peroxides, peroxy acids, hydroperoxides, persulfates and halogen compounds. 21. The method of claim 20, wherein the method is selected from: