JP2003185826A - Method for forming color filter, color filter forming material used therefor, and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a material and a method for forming a color filter with no gap and no difference in level between respective pixels of blue (B), green (G) and red (R) colors and a black matrix and further with an excellent edge shape, and to provide the color filter. <P>SOLUTION: The method for forming the color filter comprises a step for superposing a wet developing transfer sheet with a black (K) photosensitive resin layer on a picture receiving sheet, a step for transferring the photosensitive resin layer thereon, a step for subsequently applying radiation thereto from a front and/or rear surface sides of the picture receiving sheet via a mask, and a step for forming the black matrix by wet-developing the same. The method comprises a step for superposing three kinds of laser thermal transfer sheets with an R, G or B picture forming layer on the picture receiving sheet, a step for making laser light irradiate the superposed sheets in a shape of a picture from the thermal transfer sheets side, and a step for forming a picture composed of R, G and B in spacing of the black matrix or in the spacing of the black matrix and on a peripheral part of the black matrix of the picture receiving sheet. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for forming a color filter, a color filter forming material used therefor, and a color filter. The present invention particularly relates to high resolution color filter formation using a laser thermal transfer sheet and a wet development transfer sheet.

[0002]

2. Description of the Related Art A color filter used for a liquid crystal display or the like is produced using a photosensitive transfer material. The principle of making a color filter is based on multicolor image formation of a photosensitive transfer material. An image forming method using this photosensitive transfer material will be described. The photosensitive resin layer is attached to the substrate under pressure and heating, then the temporary support is peeled off, exposed through a predetermined mask or the like (in some cases, the thermoplastic resin layer, the intermediate layer), and then developed. . The development is carried out by a known method by immersing in a solvent or an aqueous developing solution, particularly an aqueous alkali solution, or applying a spray of the developing solution from a spray, and further, rubbing with a brush or treating while irradiating ultrasonic waves. . A multicolor image can be formed by using a photosensitive transfer material having photosensitive resin layers colored in different colors and repeating this step a plurality of times.
In addition, with the progress of OA in recent years, copying machines and printers using various recording methods such as an electrophotographic method, an inkjet method, and a thermal transfer recording method are used according to their respective applications. Of these, the thermal transfer recording method has advantages such as easy operation and maintenance, downsizing of the apparatus, and cost reduction, and therefore, it can be applied to a color filter forming material. It is being done. In the thermal transfer recording system, for example, a recording system for directly producing a color proof from a digital signal has been developed with the spread of an electronic system in a pre-printing process (prepress field) recently. Such an electronic system is
In particular, the purpose is to produce a high-quality color proof, and generally, a halftone dot image of 150 lines / inch or more is reproduced. In order to record a high-quality proof from a digital signal, a laser beam that can be modulated by the digital signal and that can narrow down the recording light is used as a recording head. Therefore, it is necessary to develop a recording material that exhibits high recording sensitivity to laser light and high resolution capable of reproducing high-definition halftone dots.

As a recording material used in a transfer image forming method using a laser beam, a photothermal conversion layer which absorbs a laser beam to generate heat, and a wax and a binder whose pigments are heat-meltable are used as a recording material. A heat-melt transfer sheet having an image-forming layer dispersed in the above-mentioned components in this order (Japanese Patent Laid-Open No. Hei 5-
58045) is known. In the image forming method using these recording materials, the image forming layer corresponding to the region is melted by the heat generated in the laser light irradiation region of the photothermal conversion layer, and transferred onto the image receiving sheet laminated on the transfer sheet. A transfer image is formed on the image receiving layer.

Further, in JP-A-6-219052, a photothermal conversion layer containing a photothermal conversion substance, a very thin layer (0.03 to 0.3 μm) of a heat releasing layer, and a coloring material are provided on a support. A thermal transfer sheet in which an image forming layer containing the same is provided in this order is disclosed. In this thermal transfer sheet, the binding force between the image forming layer and the photothermal conversion layer, which are bound by the interposition of the thermal release layer, is reduced by being irradiated with laser light, and the thermal transfer sheet is laminated on the thermal transfer sheet. A high-definition image is formed on the image receiving sheet. The image forming method using the thermal transfer sheet utilizes so-called "ablation". Specifically, in a region irradiated with laser light, the thermal peeling layer partially decomposes and vaporizes, so that region The phenomenon in which the bonding force between the image forming layer and the photothermal conversion layer is weakened and the image forming layer in that region is transferred to the image receiving sheet laminated thereon is used.

In these image forming methods, it is possible to use a printing main paper provided with an image receiving layer (adhesive layer) as an image receiving sheet material, and to transfer a multicolor image onto the image receiving sheet one after another with different colors. An image forming method utilizing ablation has an advantage that a high-definition image can be easily obtained, and color proof (DDCP: direct digital color proof), Alternatively, it is useful for producing a high-definition mask image.

The laser thermal transfer multicolor image forming material used in the DDCP technique is useful as a color filter forming material. The color filter has a structure in which R, G, and B stripe-shaped images or dot-shaped images are arranged on a transparent image-receiving sheet, and each boundary is divided by a black matrix in some cases. For example, the positional accuracy of the colored patterns (eg R, G and B and black (K)) is very important, especially the black matrix must be positioned without gaps between other colored patterns. However, the K color is a stripe of several μm to 20 μm and must be formed in the gap between the pixels of BGR, but the recording (writing) width of the pixel and the black matrix by laser thermal transfer is 0.5 to 20 μm, and especially It is not easy to produce K color with the laser thermal transfer method with high positional accuracy.
There is a problem that the positions of the GR pixels and the black matrix do not match, a gap or a step is likely to occur, and the edge shape is not good.

[0007]

SUMMARY OF THE INVENTION According to the present invention, there is no gap or step between a BGR pixel and a black matrix.
Moreover, it is an object of the present invention to provide a material and method for forming a color filter having a good edge shape, and a color filter.

[0008]

[Means for Solving the Problems] Means for solving the above problems are as follows. (1) After the wet development transfer sheet having a black (K) photosensitive resin layer is superposed on the image receiving sheet to transfer the photosensitive resin layer, the surface of the image receiving sheet and / or the back surface of the sheet is transferred through a mask. And then wet development to form a black matrix, and then three types of laser thermal transfer sheets having image forming layers of red (R), green (G) or blue (B) are superposed on the image receiving sheet. An image of R, G and B is formed by imagewise irradiating a laser beam from the thermal transfer sheet side between the black matrices on the image receiving sheet or between the black matrices and at the peripheral edge of the black matrix. Method of forming color filter. (2) A step of heat-treating an image-receiving sheet carrying an image composed of R, G and B and the black matrix prepared by the method described in (1), and then a step of polishing the surface of the image-receiving sheet. The method for forming a color filter according to (1) above. (3) Three types of laser thermal transfer sheets having at least a photothermal conversion layer and a red (R), green (G) or blue (B) image forming layer on a support, and at least black (K) on the support. A color filter forming material for use in the method for forming a color filter according to the above (1) or (2), which comprises a wet development transfer sheet having a photosensitive resin layer. (4) A color filter manufactured by the method for forming a color filter according to (1) or (2) above.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The method for forming a color filter of the present invention comprises the steps of superimposing a wet development transfer sheet having a black (K) photosensitive resin layer on an image-receiving sheet and transferring the photosensitive resin layer, A step of irradiating radiation from the front surface and / or the back surface of the image receiving sheet through a mask and then performing wet development to form a black matrix (referred to as a wet development processing step), and red (R), green (G) or blue (B). ) The three types of laser thermal transfer sheets each having an image forming layer are superposed on the image receiving sheet and imagewise irradiated with a laser beam from the side of the thermal transfer sheet so that the black matrix on the image receiving sheet or between the black matrix and the circumference of the black matrix. The process includes a step of forming an image composed of R, G, and B at an end portion (referred to as a laser processing step), but preferably, Preferably includes a heat treatment step and the polishing step later. The present invention is characterized in that a wet development processing step of forming a black matrix on an image receiving sheet using a wet development transfer sheet is performed prior to a laser processing step using a laser thermal transfer sheet. As a result, the positional accuracy of the black matrix can be ensured and the shape of the edge portion can be made a right angle.

The color filter forming material of the present invention comprises a wet development transfer sheet having at least a black (K) photosensitive resin layer on a support, which is used in a wet development process, and a support which is used in a laser process. And a laser heat transfer sheet of three types having at least a light-heat conversion layer and a red (R), green (G) or blue (B) image forming layer. A K color, that is, a black matrix is formed by using a wet development transfer sheet, and R, G and B are formed between the black matrices or between the black matrices and the peripheral edge portion of the black matrix by using the above three types of laser thermal transfer sheets. Image is formed. Here, the image composed of R, G and B means the pixel of the red filter (R) and the pixel of the green filter (G) between the black matrix of the color filter or between the black matrix and at the peripheral edge of the black matrix.
And the pixel (B) of the blue filter is located, and a group of those pixels is present. When pixels also exist at the peripheral edge portion of the black matrix, it is referred to as pixel (R1, G1, B1), and the peripheral edge of the black matrix is indicated. The case where there are almost no pixels in the area and the ideal arrangement is described as pixel (R, G, B).

As the pixel (R, G, B) of the color filter, for example, an arrangement of pixels as shown in FIG. 3 can be mentioned, but the present invention is not limited to this and is arbitrary. The sizes of the pixel (R), the pixel (G), and the pixel (B) are, for example,
In the figure, a is 100 to 300 μm, b is about 300 μm,
The line width of the black matrix of c is about several μm to 20 μm, but it can be appropriately changed. Pixel (R1,
As G1, B1), when the pixel is present at the peripheral edge of the black matrix, that is, the overlapping width d of the pixel on the black matrix is preferably about 0 to 10 μm (only one pixel is shown in FIG. 3). , The other pixels are the same). Pixels existing in this width d are preferably finally removed by polishing. A known polishing tape or the like is used for the polishing treatment. The polishing tape is composed of a polishing layer and the like formed on the polymer support and an abrasive and a binder formed on the polymer support, and by adjusting the particle size of the abrasive particles, a tape having a surface with a desired roughness can be obtained. By using it, the flatness of the pixels (R, G, B) and the black matrix can be adjusted. As described above, the color filter must be formed on the image receiving sheet without any space between the pixels (R, G, B) and the black matrix. Conventionally, the black matrix has to be formed in a gap in which pixels (R, G, B) are formed or vice versa, but the recording width by laser thermal transfer for forming pixels (R, G, B) is 0. 5-20 μm
Therefore, it is not easy to fabricate the black matrix by the laser thermal transfer method, and there is a problem that a gap or a step is generated between the pixel (R, G, B) and the black matrix, and the edge shape of the black matrix is sufficient. However, in the present invention as described above, these problems have been solved by adopting the above configuration.

Next, the wet development transfer sheet will be described. The wet development transfer sheet used in the present invention has a black (K) photosensitive resin layer on at least a support.
The photosensitive resin layer is a mixture of carbon black, a black pigment, and a combination of a plurality of coloring pigments, or a black dye dispersed in the photosensitive resin. A photosensitive resin in which carbon black, a black pigment or a pigment mixture is dispersed is superior in that it provides a light-shielding layer having excellent heat resistance and light resistance. The photosensitive resin includes those that can be developed with an alkaline aqueous solution and those that can be developed with an organic solvent, but those that can be developed with an alkaline aqueous solution are preferable in terms of safety and cost of the developing solution. The photosensitive resin may be a negative type in which a radiation receiving part is cured or a positive type in which a non-radiation receiving part is cured. To use the former, it is necessary to perform radiation treatment through a mask in which only the portion corresponding to the black matrix has been removed. To use the latter, it is necessary to perform radiation treatment through a mask opposite to the former.

Examples of the positive photosensitive resin include novolac resins. For example, the alkali-soluble novolac resin system described in JP-A-7-43899 can be used. Further, a positive photosensitive resin layer described in JP-A-6-148888, that is, an alkali-soluble resin described in the publication, a 1,2-naphthoquinonediazidesulfonic acid ester as a photosensitizer, and a thermosetting agent described in the publication. A photosensitive resin layer containing a mixture can be used. In addition, JP-A-5-26
The composition described in Japanese Patent No. 2850 can also be used.

The negative type photosensitive resin will be described in detail below, but the method of the present invention is similarly applied to the positive type resin. Examples of the negative photosensitive resin include a photosensitive resin composed of a negative diazo resin and a binder, a photopolymerizable composition, a photosensitive resin composition composed of an azide compound and a binder, and a cinnamic acid photosensitive resin composition. To be Among them, particularly preferred is a photosensitive resin containing a photopolymerization initiator, a photopolymerizable monomer and a binder as basic constituent elements. For the photosensitive resin layer, "polymerizable compound B", "polymerization initiator C", "surfactant", "adhesion aid" described in JP-A-11-133600, and other compositions can be used. For example, a negative type photosensitive resin which can be developed in an aqueous alkaline solution includes a carboxylic acid group-containing binder (such as an alkali-soluble thermoplastic resin described below) as a main component, a polyfunctional acrylic monomer, and a photopolymerization initiator. Is included.
A preferable photosensitive resin contains carbon, titanium carbon, and iron oxide as a pigment, alone or as a mixture, as described in JP-A-1-152449, and as a polyfunctional acrylic monomer, ethylene glycol di (meth) acrylate. , Triethylene glycol di (meth)
Acrylate, 1,3-butanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,4-hexanediol di (meth) (Meth) acrylates such as acrylate, pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate are used, and unsaturated organic acid compounds such as acrylic acid and methacrylic acid are used as a carboxylic acid group-containing binder, and methyl acrylate, It contains a copolymer of unsaturated organic acid ester compounds such as ethyl acrylate and benzyl methacrylate, and as a photopolymerization initiator, a halomethyloxadiazole compound or halomethyl-s-
A composition containing a triazine-based compound. The preferred content of each component is, in terms of mass% in the total solid content, 10% to 50% for pigments, 10% to 50% for polyfunctional acrylate monomers, and 20% for carboxylic acid group-containing binders. 60%, and the photopolymerization initiator is 1% to 20%. However, the photosensitive resin that can be used for the photosensitive resin layer of the wet development transfer sheet is not limited to these, and may be appropriately selected from the light and / or heat reactive compositions and known materials used for the laser thermal transfer sheet described below. You can choose.

The photosensitive resin layer may be provided alone on the support, or may be provided on another layer, for example, on the support provided with a thermoplastic resin, an oxygen barrier layer or the like. When the image forming layer is transferred onto the pixels (R, G, B) provided on the sheet, it is preferably transferred together with at least the oxygen barrier layer. The thermoplastic resin layer may be alkali-soluble.
The alkali-soluble thermoplastic resin used in the construction of the alkali-soluble thermoplastic resin layer is a resin soluble in an alkaline aqueous solution that enables alkali development after transfer. further,
This thermoplastic resin layer has a transfer defect caused by unevenness of the pixel (R, G, B) when the photosensitive resin layer is transferred to the pixel (R, G, B) provided on the image receiving sheet. Since it plays a role as a cushioning material for preventing the above, it is preferable that it has a property that it can be deformed according to the irregularities on the substrate when it is brought into close contact with the image receiving sheet by heating.

Therefore, it is preferable that the resin constituting the alkali-soluble thermoplastic resin layer has a substantial softening point of 80 ° C. or lower. Examples of the alkali-soluble thermoplastic resin having a softening point of 80 ° C. or lower include saponified products of ethylene and an acrylic ester copolymer, saponified products of styrene and a (meth) acrylic ester copolymer, vinyltoluene and (meth). ) A saponified product with an acrylic ester copolymer,
It is preferably at least one selected from poly (meth) acrylic acid esters, saponified products such as (meth) acrylic acid ester copolymers of butyl (meth) acrylate and vinyl acetate, and the like. "Plastic Performance Handbook" (edited by Japan Plastics Industry Federation, All Japan Plastics Molding Federation, published by Industrial Research Board, 1968, 10)
Among the organic polymers having a softening point of about 80 ° C. or lower described in (issued on May 25), those soluble in an alkaline aqueous solution can also be used.

Further, even if an organic polymer substance having a softening point of 80 ° C. or higher is added, various plasticizers which are compatible with the organic polymer substance are added to the organic polymer substance to substantially soften it. The point can be lowered to 80 ° C. or lower for use. Examples of the plasticizer include polypropylene glycol, polyethylene glycol, dioctyl phthalate,
Examples thereof include diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate and biphenyl diphenyl phosphate.

Further, when these organic polymer substances are used, various polymers, supercooling substances, and adhesion are adhered within a range in which the substantial softening point does not exceed 80 ° C. for the purpose of adjusting the adhesive force with the support described later. Improvers or surfactants, mold release agents and the like can be added.

The wet development transfer sheet is preferably formed by sequentially laminating an alkali-soluble thermoplastic resin layer, an oxygen barrier layer, and a photosensitive resin layer on a support, and particularly,
By making the adhesive strength between the thermoplastic resin layer and the support smaller than the adhesive strength between other layers, the unnecessary support after transfer can be easily broken and the surface of the thermoplastic resin layer can be destroyed. Since it can be removed without doing so, the photosensitive resin layer after removing the support can be uniformly exposed.

The thickness of the thermoplastic resin layer is 6 to 100 μm.
Is preferable, and a range of 6 to 50 μm is more preferable. If the thickness of the thermoplastic resin layer is less than 6 μm, it is impossible to completely absorb the irregularities on the substrate of 1 μm or more, and if it exceeds 100 μm, the developability and the manufacturability are deteriorated, which is not preferable.

In the photosensitive transfer material of the present invention, an oxygen barrier layer can be provided between the above-mentioned photosensitive resin layer and thermoplastic resin. The oxygen-blocking layer is a layer having a function of blocking oxygen, and by doing so, polymerization of the photosensitive resin by exposure can proceed without being obstructed by oxygen even in the air. Also, the film thickness is 0.05 to 5
Since it can be made as thin as μm, it does not adversely affect the resolution. The material for forming the oxygen barrier layer may be any material that is dispersed or dissolved in water or an aqueous alkali solution and exhibits low oxygen permeability, and known materials can be used. For example, polyvinyl ether / maleic anhydride polymers described in JP-A-46-2121 and JP-B-56-40824, water-soluble salts of carboxyalkyl cellulose, water-soluble cellulose ethers, water-soluble salts of carboxyalkyl starch, Polyvinyl alcohol, polyvinyl pyrrolidone, various polyacrylamides, various water-soluble polyamides, water-soluble salts of polyacrylic acid, gelatin, ethylene oxide polymers,
Examples thereof include water-soluble salts of the group consisting of various starches and the like, styrene / maleic acid copolymers, maleate resins, and combinations of two or more thereof. Among them, a combination of polyvinyl alcohol and polyvinylpyrrolidone is particularly preferable.

Further, the above polyvinyl alcohol preferably has a saponification rate of 80% or more. The content of the polyvinylpyrrolidone is 1 to 1 per solid content of the oxygen barrier layer.
75 mass% is preferable, 1-60 mass% is more preferable, 10-50 mass% is the most preferable. 1
If it is less than 75% by mass, sufficient adhesiveness to the photosensitive resin layer cannot be obtained, and if it exceeds 75% by mass, the oxygen barrier ability is lowered. The oxygen barrier layer has a small thickness of about 0.1 to 5 μm, especially 0.5 to
2 μm is preferable. If it is less than about 0.1 μm, the oxygen permeability is too high, and if it exceeds about 5 μm, it takes too much time during development or removal of the oxygen barrier layer.

The support on which each of the above layers is coated is preferably one having a thermoplastic resin layer and a releasability that does not hinder the transfer, and is chemically and thermally stable and is suitable. A flexible material is preferable. Specifically, a thin film sheet of Teflon (registered trademark), polyethylene terephthalate, polycarbonate, polyethylene, polypropylene or the like or a laminate thereof is preferable.

In order to secure good releasability between the support and the thermoplastic resin layer, it is preferable that surface treatment such as glow discharge is not performed and an undercoat layer such as gelatin is not provided. The thickness of the support is appropriately 5 to 300 μm, and 2
0 μm to 150 μm is preferable.

A cover film is preferably provided on the photosensitive resin layer in order to protect it from dirt and damage during storage. The cover film may be made of the same material as or a material similar to that of the support, but it is required that it can be easily separated from the photosensitive resin layer. As a material used for the cover film, for example, silicone paper, a polyolefin sheet, a polytetrafluoroethylene sheet, or the like is preferable. Among them, polyethylene or polypropylene film is more preferable.

The cover film has a thickness of about 5 to 100 μm.
m is preferable, and 10-30 μm is more preferable.

In the wet development transfer sheet of the present invention, an alkali-soluble thermoplastic resin layer is first coated on the support and dried to form a thermoplastic resin layer, and the thermoplastic resin layer is coated with the thermoplastic resin layer. An oxygen barrier layer solution using a solvent that does not dissolve the resin layer is applied and dried to form an oxygen barrier layer, and the photosensitive resin layer coating solution is applied on the oxygen barrier layer using a solvent that does not dissolve the oxygen barrier layer. It can be formed by applying a coating solution and drying it to form a photosensitive resin layer. Alternatively, a photosensitive resin layer is provided on the cover film, while a thermoplastic resin layer and an oxygen blocking layer are provided on the support, and they are bonded so that the oxygen blocking layer and the photosensitive resin layer are in contact with each other. Alternatively, or alternatively, a photosensitive resin layer and an oxygen barrier layer are provided on the cover film, while a thermoplastic resin layer is provided on the support, and the oxygen barrier layer and the photosensitive resin layer are respectively provided in the same manner as above. It can be manufactured by laminating them so that they are in contact with each other. As a method for applying the alkali-soluble thermoplastic resin layer, the oxygen barrier layer, the photosensitive resin layer and the like, spinner, roll coater, bar coater, curtain coater and the like methods are used.

In order to form the black matrix on the image receiving sheet, first, the cover film of the wet development transfer sheet is removed, the wet development transfer sheet is overlaid on the image reception sheet to transfer the photosensitive resin layer, and then the mask is formed. Radiation is radiated from the front side and / or the back side of the image receiving sheet via. Transfer of the wet development transfer sheet onto the image receiving sheet is usually performed under pressure and / or heating. For this transfer, using a known laminator such as a laminator, a vacuum laminator and an auto-cutter laminator capable of improving productivity, the photosensitive resin layer is attached, and then the support is peeled off to form an image-receiving sheet. The photosensitive resin layer is transferred to.

Then, the photosensitive resin layer only in the black matrix portion is cured by irradiating the surface and / or the back surface of the image-receiving sheet to which the photosensitive resin layer has been transferred, through a mask to cure the pixel (R). , G, B) corresponding portions remain uncured, and the pixels (R, G, B
B) The photosensitive resin layer on the corresponding portion is removed, leaving only the black matrix portion. After that, heat treatment may be performed if necessary. In the exposure step of the above method, when there is a portion in the black matrix region that is not desired to be insolubilized, the exposure can be performed through a photomask that masks the portion. The exposure may be performed under vacuum or in a non-oxygen atmosphere such as nitrogen gas or argon gas, or may be heated before or during the exposure or after the exposure.

Examples of radiation include electron beams and ultraviolet rays. As a light source used for irradiation of radiation, light in the ultraviolet to visible region can be used depending on the photosensitivity of the photosensitive resin layer. , Xenon lamp, carbon arc lamp,
A known one such as an argon laser can be used. Also,
As described in JP-A-6-59119, 400n
An optical filter having a light transmittance of 2% or less at a wavelength of m or more may be used together. The radiation dose is selected according to the conditions when a photo- and / or heat-reactive composition is used in the formation of pixels (R, G, B) described below.

In the next wet development, for example, alkaline development, a dilute aqueous solution of an alkaline substance is used as the developing solution, but a solution containing a small amount of an organic solvent miscible with water may be used. Suitable alkaline substances include alkali metal hydroxides (eg sodium hydroxide, potassium hydroxide), alkali metal carbonates (eg sodium carbonate, potassium carbonate), alkali metal bicarbonates (eg sodium hydrogen carbonate). , Potassium hydrogen carbonate),
Alkali metal silicates (eg sodium silicate,
Potassium silicate) alkali metal metasilicates (eg sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, morpholine, tetraalkylammonium hydroxides (eg tetramethylammonium hydroxide) or phosphoric acid Mention may be made of trisodium. The concentration of the alkaline substance is 0.01 to 30% by mass.
And the pH is preferably 8-14.

Suitable organic solvents miscible with water include methanol, ethanol, 2-propanol, 1-
Propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-
Examples include butyl ether, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, and N-methylpyrrolidone. . The concentration of the organic solvent miscible with water is generally 0.1 to 30% by weight.

A known surfactant may be added to the developing solution. The developing solution can be used as a bath solution or a spray solution. In order to remove the uncured portion of the photosensitive light-shielding material layer, a method such as rubbing with a rotating brush in a developing solution or rubbing with a wet sponge can be combined. The liquid temperature of the developing solution is usually preferably around room temperature to 40 ° C. It is also possible to include a water washing step after the development processing.

Further, the development may be carried out by treating the alkali-soluble thermoplastic resin layer, the oxygen barrier layer and the photosensitive resin layer at the same time. In order to reduce the deterioration of (1), it is preferable to develop the photosensitive resin layer after first dissolving and removing the alkali-soluble thermoplastic resin layer and the oxygen barrier layer. When the photosensitive resin layer is developed later, it is preferable that the developer used for removing the alkali-soluble thermoplastic resin layer and the oxygen blocking layer is selected so as not to deteriorate the photosensitive resin layer. This method is carried out by selecting the developing solution in consideration of the difference in the dissolution rate between the alkali-soluble thermoplastic resin layer and the oxygen blocking layer and the photosensitive resin layer, or by selecting the liquid temperature, the spray pressure and the rubbing time. It can be carried out by appropriately combining development processing conditions such as pressure. By this method, uneven development of the black matrix can be suppressed.

Next, the laser thermal transfer sheet used in the present invention will be described. The laser thermal transfer sheet realizes thermal transfer images with sharp halftone dots, and B2 size recording (515
mm × 728 mm, but B2 size is 543 mm × 76
5 mm) is effective and suitable for a system that is capable.
This thermal transfer image can be a halftone dot image corresponding to the number of printed lines with a resolution of 2400 to 2540 dpi. Since each halftone dot has almost no bleeding or chipping and its shape is extremely sharp, it is possible to clearly form halftone dots in a high range from highlight to shadow. As a result, it is possible to output high-quality halftone dots with the same resolution as the image setter or CTP setter, and it is possible to reproduce halftone dots with good approximation to the set value, and at the same time, the halftone dots are pixels, that is, red ( R), green (G), and blue (B) are made to correspond.

In addition, since this thermal transfer image has a sharp halftone dot shape, halftone dots corresponding to a laser beam, and thus pixels can be faithfully reproduced, and the dependence of recording characteristics on ambient temperature and humidity is extremely small, so that it is wide. Hue in a temperature / humidity environment
Repeated reproducibility with stable concentration can be obtained.
Since this thermal transfer image has good repeatability, a highly accurate CMS (color management system) can be realized.

Further, since the dot shape of this thermal transfer image is sharp, the pixels can be reproduced well. The heat generated by the laser light is transmitted to the transfer interface without being diffused in the surface direction, and the image forming layer is sharply broken at the interface of the heated portion / non-heated portion. Therefore, the photothermal conversion layer in the thermal transfer sheet is made thin and the mechanical properties of the image forming layer are controlled.
By the way, in the simulation, it is estimated that the photothermal conversion layer instantaneously reaches about 700 ° C., and if the film is thin, it is likely to be deformed or broken. When the deformation / destruction occurs, the light-heat conversion layer is transferred to the image-receiving sheet together with the transfer layer, and the transferred image becomes non-uniform, which causes actual damage. On the other hand, in order to obtain a predetermined temperature, the photothermal conversion substance must be present in a high concentration in the film, which causes problems such as deposition of dye and migration to an adjacent layer. Therefore, it is preferable to thin the light-heat conversion layer to about 0.5 μm or less by selecting an infrared absorbing dye having excellent light-heat conversion characteristics and a heat-resistant binder such as polyimide.

Further, generally, when the photothermal conversion layer is deformed or is deformed by high heat, the image forming layer transferred to the image receiving layer causes thickness unevenness corresponding to the sub-scanning pattern of laser light, Therefore, pixels (R, G,
B) becomes non-uniform and the apparent transfer density decreases. This tendency is more remarkable as the thickness of the image forming layer is smaller. on the other hand,
When the thickness of the image forming layer is large, dot sharpness is impaired and sensitivity is also lowered. In order to achieve both of these contradictory performances, it is preferable to improve the transfer unevenness by adding a low melting point substance such as wax to the image forming layer. Also,
By adding inorganic fine particles instead of the binder, the film thickness can be increased appropriately so that the image forming layer is sharply broken at the interface between the heated and non-heated parts, and transfer is performed while maintaining the sharpness and sensitivity of the dots. The unevenness can be improved.

In general, low melting point substances such as wax are
There is a tendency to seep out or crystallize on the surface of the image forming layer,
Problems may occur in the image quality and the temporal stability of the thermal transfer sheet. In order to deal with this problem, it is preferable to use a low melting point substance having a small Sp value difference from the polymer of the image forming layer, which enhances compatibility with the polymer and separates the low melting point substance from the image forming layer. Can be prevented. It is also preferable to mix several kinds of low melting point substances having different structures to cause eutectic and prevent crystallization. As a result, pixels with sharp dot shapes and less unevenness (R, G, B)
Alternatively, pixels (R1, G1, B1) can be obtained. Further, generally, when the coating layer of the thermal transfer sheet absorbs moisture, the mechanical properties and thermophysical properties of the layer change, and the humidity dependency of the recording environment occurs. In order to reduce this temperature / humidity dependency, it is preferable that the dye / binder system of the photothermal conversion layer and the binder system of the image forming layer are organic solvent systems. Further, as the image-receiving sheet to which the pixels are thermally transferred, it is preferable that the film is formed by applying polyvinyl butyral after treatment with a silane coupling agent. There is a method of introducing a polymer hydrophobizing technique into polyvinyl butyral in order to reduce the water absorption of this film. Examples of the polymer hydrophobizing technique include reacting a hydroxyl group with a hydrophobic group as described in JP-A-8-238858, and crosslinking two or more hydroxyl groups with a hardener.

Usually, the image forming layer is also heated to about 500 ° C. or more during printing by laser exposure, and some of the pigments used in the past are thermally decomposed. This can be prevented by adopting it in the image forming layer. And due to the high heat during printing,
When the infrared absorbing dye migrates from the photothermal conversion layer to the image forming layer, in order to prevent the hue from changing, the photothermal conversion layer is combined with a strong holding infrared absorbing dye / binder as described above. It is preferable to design. Generally, high-speed printing causes energy shortage, and a gap corresponding to the laser sub-scanning interval is generated. As described above, increasing the dye concentration in the photothermal conversion layer and thinning the photothermal conversion layer / image forming layer can increase the efficiency of heat generation / transfer. Further, it is preferable to add a low melting point substance to the image forming layer for the purpose of increasing the effect of filling the gap by slightly flowing the image forming layer during heating and the adhesiveness to the film on the image receiving sheet. Further, in order to increase the adhesiveness between the film on the image receiving sheet and the image forming layer and to ensure that the transferred pixels (R, G, B) have sufficient strength, for example, as described above, the image forming layer is used as a binder of the film. The same resin as can be used.

The image receiving sheet and the thermal transfer sheet are preferably held in the laser recording device by vacuum contact. This vacuum contact is important because the image transfer behavior is very sensitive to the clearance between the image receiving surface of the image receiving sheet and the image forming layer surface of the thermal transfer sheet because an image is formed by controlling the adhesive force between the two. If the clearance between the materials is widened due to foreign matter such as dust, image defects and image transfer unevenness will occur. In order to prevent such image defects and image transfer unevenness, it is preferable that the thermal transfer sheet is provided with uniform unevenness so that the air can flow smoothly and uniform clearance can be obtained.

As a method of making unevenness on the thermal transfer sheet, there are generally post-treatments such as embossing and addition of a matting agent to the coating layer, but addition of a matting agent is preferred for simplifying the manufacturing process and stabilizing the material over time. . The matting agent needs to be thicker than the coating layer thickness, and when the matting agent is added to the image forming layer, the image in the portion where the matting agent is present may be lost. It is preferably added to the conversion layer, whereby the image forming layer itself has a substantially uniform thickness, and an image free of defects can be obtained on the image receiving sheet.

In order to surely reproduce the sharp dots as described above, the recording device side to which the laser thermal transfer sheet is applied is also required to have a highly accurate design. The basic configuration is the same as that of the conventional laser thermal transfer recording device. This conventional configuration is a so-called heat mode recording system in which a recording head equipped with a plurality of high-power lasers irradiates a fixed thermal transfer sheet and an image receiving sheet with laser for recording. Among them, the following aspects are preferable configurations. However, the K color must be created by the wet development transfer method. The thermal transfer sheet and the image receiving sheet are supplied by a fully automatic roll supply. The image receiving sheet and the thermal transfer sheet are fixed to the recording device by vacuum suction.
A large number of vacuum suction holes are formed in the recording apparatus, and the sheet is sucked onto the image receiving sheet by reducing the pressure under the image receiving sheet with a blower or a pressure reducing pump. Since the thermal transfer sheet is attracted to the image receiving sheet, the size of the thermal transfer sheet is made larger than that of the image receiving sheet.

In this apparatus, it is assumed that a large number of sheets of B2 size can be stacked and accumulated on the discharge table. Therefore, a method is adopted in which air is ejected between the two sheets to lift the sheet discharged later. A configuration example of this device is shown in FIG. The sequence of the thermal transfer sheet in the above apparatus will be described. 1) The sub-scanning axis of the recording head 2 of the recording apparatus 1 is returned to the origin by the sub-scanning rail 3, the main-scanning rotation axis of the recording drum 4 and the thermal transfer sheet loading unit 5. 2) The image receiving sheet roll 6 is unwound by the conveying roller 7, and the leading edge of the image receiving sheet is fixed on the recording drum 4 by vacuum suction through the suction hole provided in the recording drum. 3) The squeeze roller 8 comes down onto the recording drum 4, and while the image receiving sheet is being held down, the image receiving sheet is stopped by the rotation of the drum when the image receiving sheet is further conveyed by a prescribed amount, and is cut into a prescribed length by the cutter 9. 4) Further, the recording drum 4 makes one round to complete the loading of the image receiving sheet. 5) Next, in the same sequence as the image receiving sheet, the first color-red-color thermal transfer sheet R is unrolled from the thermal transfer sheet roll 10R, cut and loaded. 6) Next, the recording drum 4 starts to rotate at a high speed, the recording head 2 on the sub-scanning rail 3 starts to move, and when the recording start position is reached, the recording head 2 irradiates the recording laser on the recording drum 4 according to the recording image signal. To be done. The irradiation is terminated at the recording end position, and the sub-scanning rail operation and the drum rotation are stopped. Return the recording head on the sub-scanning rail to the origin. 7) Only the thermal transfer sheet R is peeled off while leaving the image receiving sheet on the recording drum. Therefore, the tip of the thermal transfer sheet R is hooked with a claw, pulled out in the discharge direction, and discarded from the waste port 32 to the waste box 35. 8) Repeat 5) to 7) for the remaining two colors. The recording order is red, followed by green and blue. That is, the second color-green-color thermal transfer sheet G is the thermal transfer sheet roll 1
From 0G, the third color-blue-color thermal transfer sheet B is sequentially fed out from the thermal transfer sheet roll 10B. The order of these thermal transfer sheets R, G or B is arbitrary. 9) When the three colors are completed, the recorded image receiving sheet is finally discharged to the discharge tray 31. The method of peeling from the drum is the same as that of the thermal transfer sheet of 7), but since it is not discarded unlike the thermal transfer sheet, it is returned to the discharge table by switchback when it reaches the disposal port 32. When discharged to the discharge table, air 34 is jetted from below the discharge port 33 to enable stacking of a plurality of sheets.

Conveying roller 7 at either the supplying portion or the conveying portion of the thermal transfer sheet roll and the image receiving sheet roll.
In addition, it is preferable to use an adhesive roll having an adhesive material on the surface.

By providing the adhesive roll, the surfaces of the thermal transfer sheet and the image receiving sheet can be cleaned.

As the adhesive material provided on the surface of the adhesive roll, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, polyolefin resin, polybutadiene resin, styrene-butadiene copolymer (SB
R), styrene-ethylene-butene-styrene copolymer (SEBS), acrylonitrile-butadiene copolymer (NBR), polyisoprene resin (IR), styrene-
Examples thereof include isoprene copolymer (SIS), acrylic acid ester copolymer, polyester resin, polyurethane resin, acrylic resin, butyl rubber, polynorbornene and the like.

The surface of the adhesive roll can be cleaned by contacting the surfaces of the thermal transfer sheet and the image receiving sheet, and the contact pressure is not particularly limited as long as it is in contact.

Surface roughness of the image forming layer surface of the thermal transfer sheet
The absolute value of the difference between Rz and the surface roughness Rz of the back surface is 3.0μ.
It is preferable that the absolute value of the difference between the surface roughness Rz of the image receiving sheet and the surface roughness Rz of the surface of the back surface thereof is 3.0 μm or less. With such a configuration, image defects can be prevented in cooperation with the above-mentioned cleaning means, a conveyance jam can be eliminated, and dot gain stability can be further improved.

In the present specification, the surface roughness Rz refers to JIS
Rz (maximum height) is the average surface roughness of 10 points, and the average surface of the portion extracted from the curved surface of the roughness by the reference area is the reference surface Is the input value of the distance between the average value of and the average value of the depth of the valley bottom from the deepest to the fifth. For measurement, Tokyo Seimitsu Co., Ltd.
Use a stylus-type three-dimensional roughness meter (Surfcom 570A-3DF) manufactured by K.K.
The measuring direction is vertical, the cutoff value is 0.08 mm, the measuring area is 0.6 mm × 0.4 mm, the feed pitch is 0.005 mm, and the measuring speed is 0.12 mm / s.

The absolute value of the difference between the surface roughness Rz of the surface of the image forming layer and the surface roughness Rz of the surface of the back surface layer of the thermal transfer sheet is
It is preferable that the absolute value of the difference between the surface roughness Rz of the image receiving sheet and the surface roughness Rz of the surface of the back surface layer thereof is 1.0 μm or less from the viewpoint of further improving the above effects.

Further, as another embodiment, it is preferable that the surface roughness of the surface of the image forming layer and the surface of the back surface of the thermal transfer sheet and / or the surface roughness Rz of the front and back surfaces of the image receiving sheet is 2 to 30 μm. With such a configuration, the image defect can be prevented in cooperation with the above-mentioned cleaning means, the conveyance jam can be eliminated, and the dot gain stability can be further improved.

The glossiness of the image forming layer of the thermal transfer sheet is
It is also preferably 80 to 99.

The glossiness greatly depends on the smoothness of the surface of the image forming layer, and can affect the uniformity of the film thickness of the image forming layer. Higher gloss is more uniform as an image forming layer and is more suitable for use in high-definition images. However, if smoothness is high, resistance during transportation becomes larger, and both are in a trade-off relationship.
When the glossiness is in the range of 80 to 99, both can be compatible and balanced.

The Vickers hardness Hv of the tacky material used for the tacky roll is 50 kg / mm ² (≈490 MPa) or less so that dust as a foreign substance can be sufficiently removed and image defects can be suppressed. Is preferred.

Vickers hardness means that the facing angle is 13
The hardness is a hardness measured by applying a static load to a 6-degree regular pyramid-shaped diamond indenter, and the Vickers hardness Hv is obtained by the following formula.

Hardness Hv = 1.854 P / d ² (kg / mm ² ) ≈1
8.1692MPa, where P: magnitude of load (Kg), d: diagonal length of square of depression (mm)

Further, in the present invention, the elastic material at 20 ° C. of the adhesive material used for the above-mentioned adhesive roll has
It is preferably 200 kg / cm ² (≈19.6 MPa) or less, since dust as a foreign substance can be sufficiently removed and image defects can be suppressed as in the above case. Although the outer drum system has been mainly described above, an inner drum system or a flat bed system may be used, and when a rigid body such as glass is used as the image receiving sheet, the flat bed system is used.

Next, the outline of the mechanism of multicolor image formation by thin film thermal transfer using a laser will be described with reference to FIG. An image forming laminate 30 is prepared in which the image receiving sheet 20 is laminated on the surface of the image forming layer 16 containing the red (R), green (G) or blue (B) pigment of the thermal transfer sheet 10. The thermal transfer sheet 10 has a support 12, a photothermal conversion layer 14 thereon, and an image forming layer 16 further thereon, and the image receiving sheet 20 includes a support 22 and an image receiving layer 24 thereon. The image receiving layer 24 is laminated on the surface of the image forming layer 16 of the thermal transfer sheet 10 so as to be in contact with the image forming layer 16 (see FIG. 1).
(A)). When laser light is imagewise chronologically irradiated from the support 12 side of the thermal transfer sheet 10 of the laminate 30, the laser light irradiation region of the photothermal conversion layer 14 of the thermal transfer sheet 10 generates heat, and the image forming layer 16 is generated. The adhesive force with is reduced (FIG. 1 (b)). After that, when the image receiving sheet 20 and the thermal transfer sheet 10 are peeled off, the laser light irradiation area 16 ′ of the image forming layer 16 is transferred onto the image receiving layer 24 of the image receiving sheet 20 (FIG. 1 (c)).

The laser light used for light irradiation is preferably multi-beam light, and particularly preferably multi-beam two-dimensional array. The multi-beam two-dimensional array uses a plurality of laser beams when recording by laser irradiation, and the spot arrays of these laser beams have a plurality of rows along the main scanning direction and a plurality of spots along the sub scanning direction. It means a two-dimensional plane array consisting of rows. By using a laser beam having a multi-beam two-dimensional array, the time required for laser recording can be shortened.

The laser beam to be used can be used without particular limitation as long as it is a multi-beam, and solid state gas such as argon ion laser beam, helium neon laser beam, helium cadmium laser beam and YAG laser beam can be used. Direct laser light such as laser light, semiconductor laser light, dye laser light, and excimer laser light is used. Alternatively, light obtained by converting these laser lights into a half wavelength through a second harmonic element can also be used. In the multicolor image forming method, it is preferable to use semiconductor laser light in consideration of output power, easiness of modulation, and the like. In the multicolor image forming method, it is preferable to irradiate the laser light under conditions such that the beam diameter on the photothermal conversion layer is in the range of 5 to 50 μm (particularly 6 to 30 μm), and the scanning speed is 1 m / sec. Above (especially 3m /
It is preferable to set it to 2 seconds or more).

The thickness of the image forming layer in each of the red, green and blue thermal transfer sheets is usually 0.1 to 5 μm.
And preferably 0.3 to 4 μm, and more preferably 0.5 to 3 μm. If the thickness of the image forming layer in the thermal transfer sheet of each color is less than 0.1 μm, the density may decrease due to transfer unevenness during laser recording. On the other hand, if it exceeds 5 μm, the transfer sensitivity or resolution may deteriorate. May occur.

As a method of forming a multicolor image, as described above, the thermal transfer sheet may be used to repeatedly form a multicolor image on the same image receiving sheet, or images may be once formed on a plurality of image receiving sheets. After formation, a multicolor image may be formed by retransferring to another substrate. Further, a transparent protective layer may be further provided on the formed multicolor image.

Thermal transfer recording using laser light irradiation is a method in which an image forming layer containing a pigment is transferred to an image receiving sheet by converting a laser beam into heat and the thermal energy is used to form an image on the image receiving sheet. If there is a pigment at the time of transfer,
The state change of the dye or the image forming layer is not particularly limited, and includes any of a solid state, a softened state, a liquid state, and a gas state, but the solid state or the softened state is preferable. Thermal transfer recording using laser light irradiation includes, for example, conventionally known fusion type transfer, transfer by ablation, sublimation type transfer and the like. Above all, thin film transfer type, melting
The ablation type is preferable in that it produces an image with a good hue.

Pixels (R, G, B) or pixels (R) of the color filter using the above three types of laser thermal transfer sheets.
1, G1, B1) is applied as a printed matter by applying a plate making system, a PD system can be applied. The specific connection example of the system is given below. When proofing a printed matter from a plate-making system (for example, Celebra manufactured by Fuji Photo Film Co., Ltd.), the system connection is as follows. A CTP (Computer To Plate) system is connected to the plate making system. A final printed matter is obtained by applying the printing plate thus output to a printing machine. The above-mentioned recording device is connected to the plate-making system as a multicolor image, while the PD system (registered trademark) is connected as proof drive software for bringing colors and halftone dots closer to the printed matter. The contone (continuous tone) data converted to raster data by the plate making system is converted to binary data for halftone dots and CTP.
It is output to the system and finally printed. On the other hand, the same contone data is also output to the PD system. The PD system converts the received data by using a three-dimensional (R, B, G) table so that the color of the printed material matches. Finally, it is converted into binary data for halftone dots so as to match the halftone dots of the printed matter, and output to a recording device holding a laser thermal transfer sheet and an image receiving sheet carrying a black matrix to form color filter pixels. To be done. The three-dimensional table is experimentally created in advance,
Save it in the system. The experiment for making is as follows. Prepare an image in which important color data is printed via the CTP system and an image output from a recording device via the PD system, compare the colorimetric values, and create a table to minimize the difference.

The thermal transfer sheet and the image receiving sheet which are preferably used in the recording apparatus of the above system will be described below. [Thermal Transfer Sheet] The thermal transfer sheet has at least a photothermal conversion layer and an image forming layer on a support, and further has other layers as necessary.

(Support) The material of the support of the thermal transfer sheet is not particularly limited, and various support materials can be used according to the purpose. The support is preferably rigid, has good dimensional stability, and can withstand heat during image formation. Preferred examples of the support material include polyethylene terephthalate, polyethylene-2,6-naphthalate, polycarbonate, polymethylmethacrylate, polyethylene,
Polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, styrene-acrylonitrile copolymer, polyamide (aromatic or aliphatic), polyimide,
Examples thereof include synthetic resin materials such as polyamideimide, polysulfone, and polyethersulfone. Of these, biaxially oriented polyethylene terephthalate and polyether sulfone are preferable in consideration of mechanical strength and dimensional stability against heat. When used in the production of a color proof utilizing laser recording, the support of the thermal transfer sheet is preferably made of a transparent synthetic resin material that transmits laser light. The thickness of the support is preferably 25 to 130 μm, particularly preferably 50 to 120 μm. Center line average surface roughness R of the support on the image forming layer side
a (Surface roughness measuring instrument (Surfcom, Tokyo Seiki Co., Ltd.)
(Measured in accordance with JIS B0601) is preferably less than 0.1 μm. Young's modulus in the longitudinal direction of the support is 200 to 1200 Kg / mm ² (≈2 to
12 GPa) and Young's modulus in the width direction is 250 to
It is preferably 1600 Kg / mm ² (≈2.5 to 16 GPa). The F-5 value in the longitudinal direction of the support is preferably 5 to 50 Kg / mm ² (≈49 to 490 MP.
a), the F-5 value in the width direction of the support is preferably 3 to 30.
Kg / mm ² (≈29.4 to 294 MPa), and the F-5 value in the longitudinal direction of the support is generally higher than the F-5 value in the transverse direction of the support. This is not the case when it needs to be raised. The heat shrinkage ratio of the support in the longitudinal direction and the width direction at 100 ° C. for 30 minutes is preferably 3% or less, more preferably 1.5% or less, 8
The heat shrinkage ratio at 0 ° C. for 30 minutes is preferably 1% or less, more preferably 0.5% or less. The breaking strength in both directions ^{5~100Kg / mm 2 (≒ 49~980MPa)} , modulus 100~2000Kg / mm ² (≒ 0.98~1
9.6 GPa) is preferred.

The support of the thermal transfer sheet is subjected to a surface activation treatment and / or an attachment of one or two or more undercoat layers in order to improve the adhesion to the photothermal conversion layer provided thereon. Good. Examples of the surface activation treatment include glow discharge treatment and corona discharge treatment. It is preferable that the material of the undercoat layer has high adhesiveness to both surfaces of the support and the photothermal conversion layer, has low thermal conductivity, and has excellent heat resistance. Examples of the material of such an undercoat layer include styrene, styrene-butadiene copolymer, gelatin and the like. The total thickness of the undercoat layer is usually 0.01 to 2 μm. If necessary, various kinds of functional layers such as an antireflection layer and an antistatic layer may be attached to the surface of the thermal transfer sheet opposite to the side where the photothermal conversion layer is attached, or surface treatment may be performed.

(Back Layer) Light-to-heat conversion layer of thermal transfer sheet,
A back layer can be provided on the opposite side of the image forming layer.
As the antistatic agent used in the back layer, nonionic surfactants such as polyoxyethylene alkylamine and glycerin fatty acid ester, cationic surfactants such as quaternary ammonium salt, and anionic interfaces such as alkyl phosphate. A compound such as an activator, an amphoteric surfactant and a conductive resin can be used.

Further, the conductive fine particles are used as an antistatic agent.
You can also As such conductive fine particles,
For example, ZnO, TiO₂ , SnO₂ , Al₂O₃ , I
n₂O ₃ , MgO, BaO, CoO, CuO, Cu₂O,
CaO, SrO, BaO₂, PbO, PbO₂ , MnO₃
 , MoO₃ , SiO₂ , ZrO₂ , Ag₂O, Y₂O₃,
Bi₂O₃, Ti₂O₃, Sb₂O₃, Sb₂O_Five, K₂Ti
₆O₁₃, NaCaP₂O ₁₈, MgB₂O_FiveOxides such as Cu
Sulfides such as S and ZnS; SiC, TiC, ZrC, V
Carbides such as C, NbC, MoC, WC; Si₃N_Four, Ti
N, ZrN, VN, NbN, Cr₂N and other nitrides; Ti
B₂ , ZrB₂, NbB₂ , TaB₂ , CrB, Mo
B, WB, LaB_Five Boride; TiSi₂ , ZrSi
₂ , NbSi₂, TaSi₂ , CrSi₂ , MoSi
₂ , WSi₂ And other silicides; BaCO₃ , CaCO₃ , S
rCO₃ , BaSO_Four , CaSO_Four Metal salts such as SiN
_Four -SiC, 9Al₂O₃ -2B₂O₃ Complex such as
These may be used alone or in combination of two or more.
Yes. Of these, SnO₂ , ZnO, Al₂O₃ , T
iO₂, In₂O₃ , MgO, BaO and MoO₃Is preferred
Well, SnO₂ , ZnO, In₂O₃And TiO₂ Garasara
Preferred, SnO₂ Is particularly preferable.

The antistatic agent used in the back layer is preferably substantially transparent so that it can transmit laser light.

When a conductive metal oxide is used as an antistatic agent, the particle size is preferably as small as possible in order to minimize light scattering, but the ratio of the refractive index of the particles to the binder is used as a parameter. It should be determined and can be determined using Mie's theory. Generally, the average particle size is in the range of 0.001 to 0.5 μm, preferably 0.003 to 0.2 μm. Here, the average particle diameter is a value that includes not only the primary particle diameter of the conductive metal oxide but also the particle diameter of the higher-order structure.

In addition to the antistatic agent, various additives and binders such as surfactants, slip agents and matting agents can be added to the back layer.

As the binder used for forming the back layer, for example, homopolymers and copolymers of acrylic acid type monomers such as acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, nitrocellulose,
Cellulosic polymers such as methyl cellulose, ethyl cellulose, cellulose acetate, polyethylene,
Polypropylene, polystyrene, vinyl chloride copolymers, vinyl chloride-vinyl acetate copolymers, polyvinylpyrrolidone, polyvinyl butyral, copolymers of vinyl compounds and vinyl compounds such as polyvinyl alcohol, polyesters, polyurethanes, polyamides, etc. Examples thereof include condensation type polymers, rubber type thermoplastic polymers such as butadiene-styrene copolymer, polymers obtained by polymerizing and crosslinking photopolymerizable or thermopolymerizable compounds such as epoxy compounds, and melamine compounds.

(Light-to-heat conversion layer) The light-to-heat conversion layer contains a light-to-heat conversion substance, a binder, and optionally a matting agent,
Further, other components are contained if necessary. The photothermal conversion substance is a substance having a function of converting irradiated light energy into heat energy. Generally, it is a dye (including a pigment; the same applies hereinafter) capable of absorbing laser light. When an image is recorded with an infrared laser, an infrared absorbing dye is preferably used as the photothermal conversion substance. Examples of the dyes include black pigments such as carbon black, pigments of macrocyclic compounds having absorption in the visible to near infrared region such as phthalocyanine and naphthalocyanine, and laser absorbing materials for high density laser recording such as optical disks. Examples thereof include organic dyes (cyanine dyes such as indolenine dyes, anthraquinone dyes, azulene dyes, phthalocyanine dyes), and organometallic compound dyes such as dithiol nickel complexes. Among them, the cyanine dye exhibits a high extinction coefficient with respect to light in the infrared region. Therefore, when it is used as a photothermal conversion substance, the photothermal conversion layer can be thinned, and as a result, the recording sensitivity of the thermal transfer sheet can be improved. It is preferable because it can be further improved. As the photothermal conversion substance, an inorganic material such as a particulate metal material such as blackened silver can be used in addition to the dye.

The binder contained in the light-heat conversion layer has at least a strength capable of forming a layer on the support,
Resins with high thermal conductivity are preferred. Furthermore, when the resin is a heat-resistant resin that does not decompose even by the heat generated from the photothermal conversion substance during image recording, the smoothness of the surface of the photothermal conversion layer after light irradiation is achieved even when high-energy light irradiation is performed. Is preferable because it can be maintained. Specifically, the thermal decomposition temperature (T
A resin having a temperature increase rate of 10 ° C./min by the GA method (temperature at which 5% mass is reduced in an air stream) of 400 ° C. or higher is preferable, and a resin having a thermal decomposition temperature of 500 ° C. or higher is preferable. More preferable. Further, the binder is 200 to 400 ° C.
It preferably has a glass transition temperature of 250 to 35
More preferably it has a glass transition temperature of 0 ° C. If the glass transition temperature is lower than 200 ° C., fog may occur in the formed image, and if it is higher than 400 ° C., the solubility of the resin may be lowered and the production efficiency may be lowered.
The heat resistance of the binder of the photothermal conversion layer (for example, thermal deformation temperature or thermal decomposition temperature) is preferably higher than the materials used for other layers provided on the photothermal conversion layer.

Specifically, acrylic acid resins such as polymethylmethacrylate, polycarbonate, polystyrene,
Vinyl chloride / vinyl acetate copolymer, vinyl resin such as polyvinyl alcohol, polyvinyl butyral, polyester, polyvinyl chloride, polyamide, polyimide, polyetherimide, polysulfone, polyether sulfone, aramid, polyurethane, epoxy resin, urea / melamine Resin etc. are mentioned. Among these, the polyimide resin is preferable.

Particularly, the polyimide resins represented by the following general formulas (I) to (VII) are soluble in an organic solvent, and use of these polyimide resins is preferable because the productivity of the thermal transfer sheet is improved. It is also preferable in that the viscosity stability, long-term storage stability and moisture resistance of the coating solution for the light-heat conversion layer are improved.

[0079]

[Chemical 1]

In the above general formulas (I) and (II), Ar
¹ represents an aromatic group represented by the following structural formulas (1) to (3), and n represents an integer of 10 to 100.

[0081]

[Chemical 2]

[0082]

[Chemical 3]

In the general formulas (III) and (IV), Ar
² represents an aromatic group represented by the following structural formulas (4) to (7), and n represents an integer of 10 to 100.

[0084]

[Chemical 4]

[0085]

[Chemical 5]

In the general formulas (V) to (VII), n and m
Indicates an integer of 10 to 100. In formula (VI), n:
The ratio of m is 6: 4 to 9: 1.

As a standard for determining whether or not the resin is soluble in an organic solvent, 10 parts by mass or more of the resin is dissolved at 25 ° C. with respect to 100 parts by mass of N-methylpyrrolidone. When it is dissolved in 10 parts by mass or more, it is preferably used as a resin for the photothermal conversion layer. More preferably, the resin is 100 parts by mass or more with respect to 100 parts by mass of N-methylpyrrolidone.

Examples of the matting agent contained in the photothermal conversion layer include inorganic fine particles and organic fine particles. The inorganic fine particles include silica, titanium oxide, aluminum oxide, zinc oxide, magnesium oxide, barium sulfate, magnesium sulfate, aluminum hydroxide, magnesium hydroxide, metal salts such as boron nitride, kaolin, clay, talc, zinc white, Lead white, Sieglite, quartz, diatomaceous earth, barlite, bentonite, mica, synthetic mica, etc. may be mentioned. As the organic fine particles, fluororesin particles,
Examples thereof include resin particles such as guanamine resin particles, acrylic resin particles, styrene-acrylic copolymer resin particles, silicone resin particles, melamine resin particles, and epoxy resin particles.

The particle size of the matting agent is usually 0.3 to 30 μm.
m, preferably 0.5 to 20 μm, and the addition amount is preferably 0.1 to 100 mg / m ² .

If necessary, a surfactant, a thickener, an antistatic agent, etc. may be added to the photothermal conversion layer.

The light-heat conversion layer is prepared by dissolving a light-heat conversion substance and a binder, and adding a matting agent and other components to the solution, if necessary, to prepare a coating solution, coating the solution on a support, and drying. It can be provided. Examples of the organic solvent for dissolving the polyimide resin include n
-Hexane, cyclohexane, diglyme, xylene,
Toluene, ethyl acetate, tetrahydrofuran, methyl ethyl ketone, acetone, cyclohexanone, 1,4-dioxane, 1,3-dioxane, dimethyl acetate,
N-methyl-2-pyrrolidone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, γ
-Butyrolactone, ethanol, methanol and the like. The coating and drying can be carried out by using ordinary coating and drying methods. Drying is usually performed at a temperature of 300 ° C. or lower, and preferably at a temperature of 200 ° C. or lower. When polyethylene terephthalate is used as the support, it is preferably dried at a temperature of 80 to 150 ° C.

When the amount of the binder in the light-heat conversion layer is too small, the cohesive force of the light-heat conversion layer is lowered, and when the formed image is transferred to the image-receiving sheet, the light-heat conversion layer is easily transferred together with it, and the image This will cause color mixing. On the other hand, when the amount of the polyimide resin is too large, the layer thickness of the photothermal conversion layer is increased in order to achieve a constant light absorption rate, and the sensitivity is likely to be lowered. The solid content mass ratio of the photothermal conversion substance and the binder in the photothermal conversion layer is preferably 1:20 to 2: 1, and more preferably 1:10 to 2: 1.
Further, it is preferable to make the light-heat conversion layer thin, because the heat transfer sheet can have high sensitivity as described above. The photothermal conversion layer preferably has a thickness of 0.03 to 1.0 μm, and preferably 0.0 to 1.0 μm.
More preferably, it is 5 to 0.5 μm. In the photothermal conversion layer, the absorption wavelength of laser light is preferably in the range of 700 to 1500 nm, particularly preferably 750 to 1000 nm. Also, a wavelength of 830n
It is preferable that the optical density of 0.7 to 1.1 with respect to the light of m improves the transfer sensitivity of the image forming layer.
It is more preferable to have an optical density of 0.8 to 1.0 with respect to the light of the wavelength. When the optical density at a wavelength of 830 nm is less than 0.7, it becomes insufficient to convert the irradiated light into heat, which may lower the transfer sensitivity.
On the other hand, when it exceeds 1.1, the function of the photothermal conversion layer is affected during recording, and fogging may occur.

(Image Forming Layer) The image forming layer is transferred onto the image receiving sheet to form pixels (R, G, B) or pixels (R1, G).
1, B1) to contain at least a pigment,
Further, it contains a binder for forming a layer, and optionally other components. Pigments are generally roughly classified into organic pigments and inorganic pigments, the former having particularly excellent transparency of the coating film, and the latter generally having properties such as excellent hiding properties, so that they can be appropriately selected depending on the application. Good. In addition, metal powder, metal oxide powder, fluorescent pigment, etc. may also be used. Examples of suitable pigments include azo pigments, phthalocyanine pigments, anthraquinone pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, and nitro pigments. The pigments used in the image forming layer are listed below according to hues, but the pigments are not limited to these. These pigments may be used alone or in combination.

1) Red pigment C.I. I. Pigment Red 97, C.I. I. Pigment Red 122, C.I. I. Pigment Red 149,
C. I. Pigment Red 168, C.I. I. Pigment Red 177, C.I. I. Pigment Red 18
0, C.I. I. Pigment Red 192, C.I. I. Pigment Red 215, CI No. 12085, CI No. 12120,
Organic pigments such as CI No. 12140 and CI No. 12315 2) Green pigment C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, CI No.42053, CI No.42085, CIN
Organic pigments such as o.42095 3) Blue pigment C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 1
5: 6, C.I. I. Pigment Blue 22, C.I. I. Pigment Blue 60, C.I. I. Pigment Blue 6
4, organic pigments such as CI No. 42052, CI No. 42090

4) Yellow Pigment Pigment Yellow (Pigment Yellow)
12 (C.I. No. 21090) Example) Permanent Yellow (Permanent Yellow) DHG (Clariant Japan KK)
Manufactured by Toyo Ink Mfg. Co., Ltd., Irg
alite Yellow (Irgarite yellow)
LCT (Ciba Specialty Chemicals Co., Ltd.)
), SYMLER FAST YELLOW (Shimla Fast Yellow) GTF 219 (Dainippon Ink and Chemicals, Inc.) Pigment Yellow (Pigment Yellow)
13 (CI. No. 21100) Example) Permanent Yellow (Permanent Yellow) GR (manufactured by Clariant Japan Co., Ltd.),
Lionol Yellow (Rionol Yellow)
1313 (manufactured by Toyo Ink Mfg. Co., Ltd.) Pigment Yellow (Pigment Yellow)
14 (CI. No. 21095) Example) Permanent Yellow (Permanent Yellow) G (manufactured by Clariant Japan KK), L
ionol Yellow 1
401-G (manufactured by Toyo Ink Mfg. Co., Ltd.), Seika
Fast Yellow
2270 (manufactured by Dainichiseika Kogyo Co., Ltd.), Symler
Fast Yellow (Shimla First Yellow) 4400 (manufactured by Dainippon Ink and Chemicals, Inc.) Pigment Yellow (Pigment Yellow)
17 (C.I. No. 21105) Example) Permanent Yellow (Permanent Yellow) GG02 (Clariant Japan KK)
Manufactured by SYMLER FAST Yellow (Shimla First Yellow) 8GF (manufactured by Dainippon Ink and Chemicals, Inc.) Pigment Yellow
155 Example) Graphtol Yellow (Graph Thor Yellow) 3GP (Clariant Japan KK) Pigment Yellow (Pigment Yellow)
180 (CI No. 21290) Example) Novoperm Yellow (Novopalm Yellow) P-HG (manufactured by Clariant Japan KK),
PV Fast Yellow (First Yellow)
HG (Clariant Japan KK) Pigment Yellow (Pigment Yellow)
139 (C.I.No. 56298) Example) Novoperm Yellow (Novopalm Yellow) M2R 70 (Clariant Japan KK)
Made)

5) Magenta Pigment Pigment Red 57:
1 (C.I.No. 15850: 1) Example) Graphtol Rubin (Graphtor Rubin) L6B (manufactured by Clariant Japan KK), L
ionol Red 6B-42
90G (Toyo Ink Mfg. Co., Ltd.), Irgalite
Rubine (Irgarite Rubin) 4BL (Ciba Specialty Chemicals Co., Ltd.), Symu
ler Brilliant Carmine 6B-229 (manufactured by Dainippon Ink and Chemicals, Inc.) Pigment Red (Pigment Red) 122
(C.I. No. 73915) Example) Hosterm Pink (Hoster Palm Pink) E (manufactured by Clariant Japan KK), Li
onogen Magenta (Rionogen Magenta)
5790 (manufactured by Toyo Ink Mfg. Co., Ltd.), Fastog
en Super Magenta RH (Dainippon Ink and Chemicals, Inc.)
Made) Pigment Red (Pigment Red) 53:
1 (CI. No. 15585: 1) Example) Permanent Lake Red (Permanent Lake Red) LCY (Clariant Japan Co., Ltd.), SYMLER LAKE RED (Shimla Lake Red) C conc (Dainippon Ink and Chemicals, Inc.) )) Pigment Red 48:
1 (C.I.No. 15865: 1) Example) Lionol Red (Lionol Red) 2B
3300 (manufactured by Toyo Ink Mfg. Co., Ltd.), Symule
r Red (Shimla Red) NRY (manufactured by Dainippon Ink and Chemicals, Inc.) Pigment Red (Pigment Red) 48:
2 (C.I.No. 15865: 2) Example) Permanent Red (Permanent Red) W2T (manufactured by Clariant Japan KK), Li
onol Red (Rionol Red) LX235
(Manufactured by Toyo Ink Mfg. Co., Ltd.), Symboler Red
(Shimla Red) 3012 (manufactured by Dainippon Ink and Chemicals, Inc.) Pigment Red 48:
3 (C.I.No. 15865: 3) Example) Permanent Red (Permanent Red) 3RL (Clariant Japan KK), Sy
muller Red 2BS (manufactured by Dainippon Ink and Chemicals, Inc.) Pigment Red 177
(C.I. No. 65300) Example) Cromophthal Red (Chromophtal red) A2B (manufactured by Ciba Specialty Chemicals Co., Ltd.)

6) Cyan Pigment Pigment Blue 15
(C.I. No. 74160) Example) Lionol Blue (Lionol Blue) 7
027 (manufactured by Toyo Ink Mfg. Co., Ltd.), Fastogen
Blue (Fastgen Blue) BB (manufactured by Dainippon Ink and Chemicals, Inc.) Pigment Blue (Pigment Blue) 1
5: 1 (C.I. No. 74160) Example) Hosterm Blue (Hoster Palm Blue) A2R (manufactured by Clariant Japan KK),
Fastogen Blue (Fastgen Blue)
5050 (manufactured by Dainippon Ink and Chemicals, Inc.) Pigment Blue (Pigment Blue) 1
5: 2 (C.I. No. 74160) Example) Hosterm Blue (Hoster Palm Blue) AFL (manufactured by Clariant Japan Co., Ltd.),
Irgalite Blue (Irgalite blue)
BSP (Ciba Specialty Chemicals Co., Ltd.)
Fastogen Blue (Fastgen Blue) GP (manufactured by Dainippon Ink and Chemicals, Inc.) Pigment Blue (Pigment Blue) 1
5: 3 (C.I. No. 74160) Example) Hosterm Blue (Hoster Palm Blue) B2G (manufactured by Clariant Japan Co., Ltd.),
Lionol Blue FG73
30 (manufactured by Toyo Ink Mfg. Co., Ltd.), Cromophta
l Blue (chromophthal blue) 4GNP (manufactured by Ciba Specialty Chemicals Co., Ltd.), Fast
gen Blue (Fastgen Blue) FGF
(Manufactured by Dainippon Ink and Chemicals, Inc.) Pigment Blue (Pigment Blue) 1
5: 4 (C.I. No. 74160) Example) Hosterm Blue (Hoster Palm Blue) BFL (manufactured by Clariant Japan Co., Ltd.),
Cyanine Blue (cyanine blue) 700-
10FG (manufactured by Toyo Ink Mfg. Co., Ltd.), Irgalit
e Blue (Irgalite blue) GLNF (manufactured by Ciba Specialty Chemicals Co., Ltd.), Fast
gen Blue FGS
(Manufactured by Dainippon Ink and Chemicals, Inc.) Pigment Blue (Pigment Blue) 1
5: 6 (C.I. No. 74160) Example) Lionol Blue (Lionol Blue) E
S (manufactured by Toyo Ink Mfg. Co., Ltd.) Pigment Blue (Pigment Blue) 60
(C.I. No. 69800) Example) Hosterperm Blue (Hoster Palm Blue) RL01 (Clariant Japan KK)
Manufactured by Toyo Ink Mfg. Co., Ltd. 7) Black pigment Pigment Black (Pigment Black)
7 (Carbon black CI No. 77266) Example) Mitsubishi carbon black MA100 (manufactured by Mitsubishi Chemical Co., Ltd.), Mitsubishi carbon black # 5 (manufactured by Mitsubishi Chemical Co., Ltd.), Black Pearls (Black Pearls) 430 (Cabot) Co. (Cabot)
Further, as a pigment that can be used in the present invention, "Pigment Handbook, edited by Japan Pigment Technology Association, Seibundo Shinkosha, 198"
9 ”,“ COLOUR INDEX, THE SOCIETY OF
DYES & COLOURIST, THIRD EDITION, 1987 ”, etc. can be referred to to select an appropriate product.

The average particle diameter of the pigment is 0.03 to
1 μm is preferable, and 0.05 to 0.5 μm is more preferable. When the particle size is less than 0.03 μm, the dispersion cost may increase or the dispersion may cause gelation,
On the other hand, if it exceeds 1 μm, the coarse particles in the pigment may hinder the adhesion between the image forming layer and the image receiving sheet, and may hinder the transparency of the image forming layer.

Examples of the binder for the image forming layer include butyral resin, polyamide resin, polyethyleneimine resin, sulfonamide resin, polyester polyol resin, petroleum resin, styrene, vinyltoluene, α-methylstyrene, 2-methylstyrene and chloro. styrene,
Styrene and its derivatives, such as vinyl benzoic acid, sodium vinylbenzene sulfonate, and aminostyrene, homopolymers and copolymers of substitution products, methacrylic acid esters and methacrylic acid such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, and hydroxyethyl methacrylate. Acid, methyl acrylate, ethyl acrylate,
Acrylic acid esters such as butyl acrylate, α-ethylhexyl acrylate and acrylic acid, butadiene,
With dienes such as isoprene, acrylonitrile, vinyl ethers, maleic acid and maleic acid esters, maleic anhydride, cinnamic acid, vinyl chloride, vinyl monomers such as vinyl acetate alone or with other monomers Copolymers can be used. Two or more kinds of these resins may be mixed and used. The image forming layer may contain a reactive compound that polymerizes or crosslinks upon receiving heat and / or light energy, for example, a monomer, an oligomer and / or a polymer, and a single substance or a composition containing a polymerization initiator if necessary. preferable. By containing these, heat resistance and chemical resistance of the image forming layer can be improved.
Further, the photo- and / or heat-responsive element or composition is
(1) It may be used in combination with a binder that is not light- and / or heat-reactive as described above, (2) it may be provided alone as an image forming layer on the photothermal conversion layer, and (3) photothermal conversion. The layer may be provided between the layer and the image forming layer which is not light and / or heat reactive, or (4) it may be provided on the image forming layer which is not light and / or heat reactive. Further, the photo- and / or heat-reactive simple substance or composition may be provided in layers on a color filter formed by wet development transfer and laser heat transfer.

The components used for the light- and / or heat-reactive simple substance or composition are listed below. The photopolymerizable monomer is preferably a compound having a boiling point of 100 ° C. or higher at normal pressure, and examples thereof include polyethylene glycol di (meth) acrylate (meaning polyethylene glycol diacrylate and polyethylene glycol dimethacrylate; the same applies hereinafter) and polypropylene. Glycol di (meta)
Acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin Polyfunctional alcohol such as tri (meth) acrylate, trimethylolpropane or glycerin Those (meth) acrylated after by addition reaction of ethylene oxide or propylene oxide, furthermore, JP-B-48-41708, the 50-
No. 6034, urethane acrylates disclosed in JP-A-51-37193, JP-A-48-64
183, Japanese Patent Publication Nos. 49-43191 and 52-304.
Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid, disclosed in each publication of No. 90 can be mentioned.

Of these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate are preferable.

Examples of the epoxy compound include glycidyl ethers of alcohols having 2 to 20 carbon atoms such as butyl glycidyl ether, octyl glycidyl ether, decyl glycidyl ether, aryl glycidyl ether and phenyl glycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether. Glycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether dibromoneopentyl glycol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether di Glycerol tetraglycidyl ether, polyglycero Le polyglycidyl polyglycidyl ethers of a polyol, such as ether, 2,6-diglycidyl phenyl glycidyl ether, 2,6,2 ', 6'
Tetramethyl-4,4'-biphenyl glycidyl ether, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated Type bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin,
Glycidyl ether type epoxy compounds such as halogenated phenol novolac type epoxy resins and brominated epoxy resins, alicyclic diepoxy acetals, alicyclic diepoxy adipates, and cycloaliphatic epoxy compounds such as vinylcyclohexenedioxide,
Glycidyl (meth) acrylate, tetrahydroxyphthalic acid diglycidyl ester, sorbic acid glycidyl ester, oleic acid glycidyl ester, linoleic acid glycidyl ester and other unsaturated acid glycidyl esters, butyl glycidyl ester, octyl glycidyl ester hexahydrophthalic acid diglycidyl ester Glycidyl ester type epoxy compounds such as alkyl carboxylic acid glycidyl esters such as esters and benzoic acid glycidyl esters, aromatic carboxylic acid glycidyl esters such as o-phthalic acid diglycidyl ester, diglycidyl p-oxybenzoic acid and dimer acid glycidyl ester ,
Tetraglycidyl diaminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl-m-
Glycidylamine type epoxy compounds such as aminophenol, diglycidylaniline, diglycidyltoluidine, tetraglycidyl-m-xylylenediamine, diglycidyltribromoaniline and tetraglycidylbisaminomethylcyclohexane, diglycidylhydantoin, glycidylglycidoxyalkylhydantoin And a heterocyclic epoxy compound such as triglycidyl diisocyanurate. Particularly preferably, a phenol novolac type epoxy resin and a cresol novolac type epoxy resin are used. Particularly preferred epoxy compounds are bisphenol A type epoxy resins and bisphenol F type epoxy resins, and commercially available products are Epototo YD128, YD8125 manufactured by Tohto Kasei, Epicron 840S, 850S, 1050 manufactured by Dainippon Ink and Chemicals.
830 are included.

An epoxy thermosetting accelerator, which is a thermosetting catalyst, can be used to thermally react the epoxy groups of the epoxy compound. As the epoxy heat curing accelerator, diethylenetriamine, triethylenetetramine,
Polyamines such as tetraethylenepentamine, iminobispropylamine (dipropyltriamine), bis (hexamethylene) triamine and 1,3,6-trisaminomethylhexane, trimethylhexamethylenediamine, polyetherdiamine and diethylaminopropylamine Aliphatic primary amines such as alicyclic polyamines such as polymethylenediamines, menthenediamines, isophoronediamines, bis (4-amino-3-methylcyclohexyl) methane and N-aminoethylpiperazine, and metaphenylenediamines , Aromatic diamines such as diaminophenylmethane, diaminophenylsulfone and aromatic diamine eutectic mixtures, polyamine epoxy resin adducts, polyamine-ethylene oxide adducts, polyamine-prones Alkyleneoxy adducts, modified amine such as cyanoethylated polyamines and ketimine,
Secondary amines such as piperidine, piperazine and morpholine and amine compounds such as tetramethylguanidine, triethanolamine, benzyldimethylamine, and tertiary amines such as 2,4,6-tris (dimethylaminomethyl) phenol, phthalic acid Anhydride, trimellitic anhydride, ethylene glycol bis (anhydro trimellitate), glycerin tris (anhydro trimellitate), pyromellitic anhydride and 3,3 ', 4,4'-
Aromatic acid anhydrides such as benzophenone tetracarboxylic acid anhydride, maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic acid Cyclic aliphatic anhydrides such as acid anhydrides, alkenyl succinic anhydrides, hexahydrophthalic anhydrides, methylhexahydrophthalic anhydrides and methylcyclohexene tetracarboxylic anhydrides, polyadipic anhydrides, polyazelaic anhydrides Acid anhydrides such as polysebacic acid anhydride, chlorendic acid anhydride and halogenated acid anhydrides such as tetrabromophthalic anhydride, 2-methylimidazole, 2-ethyl-4-methylimidazole , 2-undecylimidazole, 2 Heptadecyl imidazole, 2
-Phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2 -Undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-phenylimidazolium isocyanurate, 2,4-diamino-6- [2-methyl Imidazolyl- (1)]-ethyl-s-triazine, 2,4-diamino-6- [2-ethyl-4-methylimidazolyl- (1)]-ethyl-s-triazine,
2,4-Diamino-6- [2-undecylimidazolyl- (1)]-ethyl-s-triazine, 2-phenyl-
4-methyl-5-hydroxymethylimidazole, 2-
Phenyl-4,5-dihydroxymethylimidazole,
1-cyanoethyl-2-phenyl-4,5-di (cyanoethoxymethyl) imidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 1,3-dibenzyl-2-methylimidazolium chloride, etc. Imidazole compounds, dicyandiamide,
o-tolyl biguanide, phenyl biguanide, and α
Examples of known epoxy curing accelerators include dicyandiamide derivatives such as -2,5-dimethylbiguanide, carboxylic acids, phenols, quaternary ammonium salts, melamine derivatives, organic acid hydrazides, and methylol group-containing compounds. Particularly preferably, dicyandiamide,
1-benzyl-2-methylimidazole may be mentioned.
You may use these epoxy thermosetting accelerators individually or in mixture of 2 or more types.

If desired, a crosslinking agent or a catalyst thereof may be added to the photo- and / or heat-reactive composition. Examples of the cross-linking agent include low-molecular compounds such as polycarboxylic acids or their acid anhydrides (for example, itaconic acid, methylmaleic anhydride, dodecanedioic acid, 2-dodecenedioic acid, dodecenylsuccinic anhydride, phthalic anhydride). Compounds, tetrahydrophthalic anhydride, trimellitic anhydride, 1,2-, 1,3- and 1,4-
Cyclohexanedicarboxylic acid, hexahydrophthalic anhydride or mixtures thereof, polycarboxylic acid semiesters (polyols such as 1,6-hexanediol, trimethylolpropane and acid anhydrides such as hexahydrophthalic anhydride, methyl hexa) Reaction product of hydrophthalic anhydride), aromatic polyamine, aliphatic polyamine, triazine compound, polymercaptan, bisphenol A,
Tetrabromobisphenol A, trimethylol allyloxyphenol, polyisocyanate compounds and the like can be mentioned. As the polymer compound, phenols such as phenol novolac resin and butylated phenol resin, carboxyl group-containing unsaturated or saturated polyester, etherified And optionally urea- and / or triazine-formaldehyde resins.

Examples of the thermosetting catalyst include tetraethylammonium bromide, tetrabutylphosphonium bromide, triphenylbenzylphosphonium chloride, triethylamine, tributylamine, bismuth nitrate nitrate, lead 2-ethylhexanoate, sodium trichlorophenolate, lithium acetate and chloride. Examples thereof include tributyltin, tributyltin cyanate, titanium tetrachloride, dibutyltitanium dichloride, iron trichloride, ferrocene, toluphenylantimony, copper acetate, pyridineborane, calcium acetate, barium acetate.

The light- and / or heat-reactive simple substance or the reactive polymer used in the composition has a group having an unsaturated bond, a carboxyl group, an amino group, an epoxy group, a mercapto group, a hydroxyl group, an isocyanate group, or the like. Examples include polymers. For example, firstly, a copolymer composed of a monomer represented by the general formula (a), a monomer represented by the general formula (b) and a monomer represented by the general formula (c) can be mentioned.

[0107]

[Chemical 6]

In the above monomers, R ₁ , R ₂ , R ₃ and R ₅ each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms. R ₄ represents an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms. R ₆ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms or a halogen atom, and a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, an alkoxyl group having 1 to 2 carbon atoms or Chlorine atom and bromine atom are preferred. n shows the integer of 1-10, and 1-8 are preferable.

The copolymer of the monomer (a), the monomer (b) and the monomer (c) is not particularly limited in the monomer sequence and may be random or regular, for example, block or graft.

As the reactive polymer, secondly, (A) a repeating unit derived from at least one compound selected from the group consisting of acrylic acid and methacrylic acid, and (B) a benzyl acrylate and a benzyl methacrylate. A repeating unit derived from at least one compound selected from the group consisting of, and optionally (C) at least one compound selected from the group consisting of alkyl methacrylate containing an alkyl group having 1 to 12 carbon atoms; A copolymer containing a derived repeating unit and having a weight average molecular weight of preferably 5,000 to 50,000.
00, more preferably 10,000 to 42,000.

Specific examples of the component (C) include methyl (meth) acrylate (meaning methyl acrylate and methyl methacrylate; the same applies hereinafter), ethyl (meth) acrylate, propyl (meth) acrylate, 1-propyl ( (Meth) acrylate, butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, 2
-Methylbutyl (meth) acrylate, 3-methylbutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth)
Examples thereof include acrylate, the above-mentioned monomer (a), monomer (b) and monomer (c). Of these, methyl methacrylate and the like are preferable.

Preferred specific examples of the second reactive polymer include benzyl methacrylate / methacrylic acid copolymer (molar ratio of repeating units = 73: 27, mass average molecular weight = 40,000), benzyl methacrylate /
Benzyl acrylate / methacrylic acid terpolymer (molar ratio of repeating units = 60: 13: 27, mass average molecular weight = 32,000), benzyl methacrylate / acrylic acid / methacrylic acid terpolymer (molar of repeating units Ratio = 73: 8: 19, mass average molecular weight = 35,000
0), benzyl methacrylate / methyl methacrylate / methacrylic acid terpolymer (molar ratio of repeating units = 60: 13: 27, mass average molecular weight = 46,000)
Can be mentioned.

Examples of the photopolymerization initiator used in the present invention include α-diketones such as benzyl and diacetyl,
Acylloins such as benzoin, Acylloin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, thioxanthone-1-sulfonic acid, thioxanthone-4-sulfonic acid , Benzophenone, 4,4′-bis (dimethylamino) benzophenone, benzophenones such as 4,4′-bis (diethylamino) benzophenone, acetophenone, p-dimethylaminoacetophenone, α, α′-dimethoxyacetoxyacetophenone,
2,2'-dimethoxy-2-phenylacetophenone,
Acetophenones such as p-methoxyacetophenone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone and anthraquinones, 1,
Quinones such as 4-naphthoquinone, phenanthryl chloride, tribromomethylphenyl sulfone, tris (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) triazine, Examples thereof include halogen compounds such as the compounds described in JP-A-63-153542, peroxides such as di-t-butyl peroxide, and the like. Particularly preferably 2,2'-dimethoxy-2-phenylacetophenone, 2-methyl-
[4- (methylthio) phenyl] -2-morpholino-
1-propanone (trade name: Irgacure 907, manufactured by Ciba-Geigy) can be used. As a particularly preferred example,
2-trichloromethyl-4'-butoxystyryl-1,
3,4-oxadiazole, 2,4-bis (trichloromethyl), 6- (4'-methoxyphenyl) -s-triazine, 2,4-bis (trichloromethyl) -6-
Mention may be made of {4 ′-(N, N-diethoxycarbonylmethylamino) -3′-bromo} phenyl-s-triazine.

These photopolymerization initiators may be used alone or in combination of two or more. Examples of such a mixture of two or more kinds include a combination of a 2,4,5-triarylimidazole dimer and 2-mercaptobenzoxazole or leuco crystal violet, and US Pat.
Combination of 4,4'-bis (dimethylamino) benzophenone and benzophenone or benzoin methyl ether described in 27161, U.S. Pat. No. 4,239,985.
No. 0, a combination of benzoyl-N-methylnaphthothiazoline and 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) triazine, JP-A-57-57.
-23-602 and dimethylthioxanthone and 4-
Examples thereof include a combination with a dialkylaminobenzoic acid ester, a combination of 4,4′-bis (dialkylamino) benzophenone, a ketone and a trihalogenated methyl-containing compound described in JP-A-59-78339.

The photopolymerization initiator preferably has substantially no sensitivity to light having a wavelength of 400 nm or more. The term “substantially not sensitive” is determined by the spectral sensitivity spectrum of the photopolymerization initiator and the spectral characteristics of the thermal transfer sheet. Is defined as the ratio (A / B) of the area (B) of 400 nm or less from the lowest wavelength at which the transmittance of 10% or more, and the value of A / B is 0.1 or less.

The light- and / or heat-reactive composition may include a colorant such as a pigment, a thermal polymerization inhibitor, an adhesion promoter, and the like, if necessary.
Dispersant, plasticizer, anti-sagging agent, leveling agent, defoaming agent,
You may mix auxiliary additives, such as a flame retardant and a brightener.
Examples of the thermal polymerization inhibitor include hydroquinone and p-
Methoxyphenol, pt-butylcatechol, 2,
Aromatic hydroxy compounds such as 6-di-t-butyl-p-cresol, β-naphthol and pyrogallol, quinones such as benzoquinone and p-toluquinone, amines such as naphthylamine, pyridine, p-toluidine and phenothiazine, N- Aluminum salts or ammonium salts of nitrosophenylhydroxylamine, chloranil, nitrobenzene and the like can be mentioned. Examples of the adhesion promoter include alkylphenol / formaldehyde novolac resin, polo vinyl ethyl ether, polyvinyl isobutyl ether, polyvinyl butyral, polyisobutylene, styrene-butadiene copolymer rubber, butyl rubber,
Examples thereof include vinyl chloride-vinyl acetate copolymer, chlorinated rubber, acrylic resin-based adhesives, aromatic, aliphatic or alicyclic petroleum resins, and silane coupling agents.

The thermal transfer sheet used in the present invention is a light- and / or heat-reactive element or a single element which is light- and / or heat-reactive so as to satisfy the adhesion, heat resistance, chemical resistance, etc. between the pixels (R, G, B) and the image-receiving sheet. The blending ratio of the components in the composition should be adjusted. The following is an example of the standard of the mixing ratio of the components in the composition. The photopolymerization initiator is preferably 0.1 to 30 parts by mass with respect to the reactive monomer, and particularly preferably 0.1 to 30 parts by mass.
It is preferable to use 5 to 15 parts by mass. If it is less than 0.1 parts by mass, the sensitivity may be lowered, and if it exceeds 30 parts by mass, precipitation of crystals and deterioration of film quality may occur. The cross-linking agent is generally in the range of 0.2 to 10 parts by mass with respect to 100 parts by mass of the composition. The amount of the thermosetting catalyst used is usually in the range of 0.02 to 5 parts by mass with respect to 100 parts by mass of the composition. The epoxy compound can be used usually in an amount of 1 to 40 parts by mass, preferably 5 to 30 parts by mass, relative to 100 parts by mass of the composition. The reactive polymer is the composition 10
Usually, 10 to 95 parts by mass, preferably 20 to 90 parts by mass can be used with respect to 0 parts by mass. The above blending ratio should be appropriately selected according to the aspects (1) to (5) described later.

The light- and / or heat-reactive simple substance or composition may be mixed with (1) a binder which is not light- and / or heat-reactive to form an image forming layer, or (2) alone as a photothermal conversion layer. It may be provided as an image forming layer above, or (3) provided as a layer between the photothermal conversion layer and the image forming layer which is not light and / or heat reactive, and transferred onto the image receiving sheet together with the image forming layer by laser thermal transfer. May be configured to
(4) It may be provided on an image forming layer that is not light and / or heat reactive, or (5) provided on pixels (R, G, B) and a black matrix provided by wet development transfer and laser thermal transfer. May be. In order to form a layer such as the image forming layer of (1) to (5), each composition is used as a coating liquid. As the organic solvent used for the coating liquid,
Ketones such as methyl ethyl ketone and cyclohexanone,
Aromatic hydrocarbons such as toluene and xylene, alkoxyethanols such as methoxyethanol, ethoxyethanol, butoxyethanol, carbitol, carbitols such as butylcavitol, ethyl acetate, butyl acetate, etc.
There are acetic acid esters such as ethoxyethanol acetic acid ester, butoxyethanol acetic acid ester, carbitol acetate and butyl carbitol acetate, and methyl lactate and ethyl lactate. These organic solvents may be used alone or 2
You may use it in mixture of 2 or more types.

The light- and / or heat-reactive coating layer is usually composed of
It is dried under the conditions of 60 to 150 ° C. and 0.5 to 10 minutes. The pixels (R, G, B) or the pixels (R1, G1, B1) transferred from the thermal transfer sheet to the image receiving sheet are subjected to light irradiation processing and / or heating processing together with the black matrix. This light irradiation treatment is usually 0.1
Ultraviolet irradiation of up to 500 mJ / cm ² can be mentioned, and an ultrahigh pressure mercury lamp or the like is preferable as a light source. Also, the heat treatment is 1
50-250 degreeC and 10-120 minutes are preferable. In addition,
At least one of the light irradiation treatment and the heat treatment is performed, but it is preferable to perform both of them, and it is also possible to perform both at the same time, and the heat treatment may be performed before or after the light irradiation treatment.

The image forming layer preferably contains the pigment in an amount of 30 to 70% by mass, more preferably 30 to 50% by mass. The image forming layer is made of resin 70
It is preferably contained in an amount of 30 to 30% by mass, more preferably 70 to 40% by mass.

The image forming layer may contain the following components (1) to (3) as the other components. Waxes Examples of waxes include mineral waxes, natural waxes, and synthetic waxes. Examples of the mineral waxes include petroleum wax such as paraffin wax, microcrystalline wax, ester wax, and oxidized wax, montan wax, ozokerite, ceresin, and the like. Of these, paraffin wax is preferable. The paraffin wax is separated from petroleum and various types are commercially available depending on the melting point thereof. Examples of the natural waxes include plant waxes such as carnauba wax, wood wax, auricurie wax, and espal wax, and animal waxes such as dense wax, insect wax, shellac wax, and whale wax.

The above synthetic wax is generally used as a lubricant and is usually composed of a higher fatty acid compound. Examples of such synthetic waxes include the following. 1) Fatty acid wax A linear saturated fatty acid represented by the following general formula: CH ₃ (CH ₂ ) _n COOH In the above formula, n represents an integer of 6 to 28. Specific examples include stearic acid, behenic acid, palmitic acid, 12-hydroxystearic acid and azelaic acid.
In addition, metal salts of the above fatty acids (for example, K, Ca, Z
n, Mg, etc.). 2) Fatty Acid Ester Wax Specific examples of the fatty acid ester include ethyl stearate, lauryl stearate, ethyl behenate, hexyl behenate, and behenyl myristate. 3) Fatty Acid Amide Wax Specific examples of the fatty acid amide include stearic acid amide and lauric acid amide. 4) a linear saturated aliphatic alcohols represented by an aliphatic alcohol wax represented by the following general formula: CH ₃ (CH _{2) n} OH wherein formula, n represents an integer of 6 to 28. Specific examples include stearyl alcohol and the like.

Among the above synthetic waxes 1) to 4), higher fatty acid amides such as stearic acid amide and lauric acid amide are particularly preferable. The wax compounds may be used alone or in combination as required.

Plasticizer As the plasticizer, an ester compound is preferable, and dibutyl phthalate, di-n-octyl phthalate, di (2-ethylhexyl) phthalate, dinonyl phthalate, dilauryl phthalate, butyl lauryl phthalate, Phthalates such as butylbenzyl phthalate, adipic acid di (2-
Aliphatic dibasic acid esters such as ethylhexyl) and di (2-ethylhexyl) sebacate, tricresyl phosphate, phosphoric acid triesters such as tri (2-ethylhexyl) phosphate, polyol polyesters such as polyethylene glycol ester, epoxy Known plasticizers such as epoxy compounds such as fatty acid esters can be used. Among these, esters of vinyl monomers, particularly esters of acrylic acid or methacrylic acid, are preferable because they have a large effect of improving transfer sensitivity and transfer unevenness, and a large effect of controlling elongation at break.

Examples of the ester compound of acrylic acid or methacrylic acid include polyethylene glycol dimethacrylate, 1,2,4-butanetriol trimethacrylate, trimethylolethane triacrylate, pentaerythritol acrylate, pentaerythritol tetraacrylate, dipentaerythritol-. Polyacrylate etc. are mentioned.

The plasticizer may be a polymer, and among them, polyester is preferable because it has a large effect of addition and is difficult to diffuse under storage conditions. Examples of the polyester include sebacic acid type polyester and adipic acid type polyester. The additives contained in the image forming layer are not limited to these. The plasticizers may be used alone or in combination of two or more.

If the content of the above-mentioned additive in the image forming layer is too high, the resolution of the transferred image is lowered, the film strength of the image forming layer itself is lowered, and the adhesion between the photothermal conversion layer and the image forming layer is decreased. Transfer of the unexposed portion to the image receiving sheet may occur due to the decrease in force. From the above viewpoint, the content of the waxes is preferably 0.1 to 30% by mass, and more preferably 1 to 20% by mass of the total solid content in the image forming layer. Further, the content of the plasticizer is preferably 0.1 to 20% by mass, and more preferably 0.1 to 10% by mass of the total solid content in the image forming layer.

Others The image-forming layer further comprises, in addition to the above components, a surfactant,
Inorganic or organic fine particles (metal powder, silica gel, etc.), oils (linseed oil, mineral oil, etc.), thickeners, antistatic agents, etc. may be contained. The energy required for transfer can be reduced by including a substance that absorbs the wavelength of the light source used for image recording, except when a black image is obtained. The substance that absorbs the wavelength of the light source may be either a pigment or a dye, but in the case of obtaining a color image, an infrared light source such as a semiconductor laser is used for image recording, and there is little absorption in the visible region. It is preferable for color reproduction to use a dye having a large absorption of the wavelength of the light source. Examples of near infrared dyes include
The compounds described in JP-A-3-103476 can be mentioned.

For the image forming layer, a coating solution in which a pigment and the binder and the like are dissolved or dispersed is prepared, and the solution is applied onto the photothermal conversion layer (or when the following heat-sensitive peeling layer is provided on the photothermal conversion layer, It can be provided by coating on a layer) and drying. As the solvent used for preparing the coating solution,
Examples thereof include n-propyl alcohol, methyl ethyl ketone, propylene glycol monomethyl ether (MFG), methanol and water. Application and drying are normal application,
It can be performed using a drying method. (Cushion layer) It is preferable to provide a cushion layer having a cushion function between the support and the light-heat conversion layer. When the cushion layer is provided, the adhesion between the image forming layer and the image receiving layer at the time of laser thermal transfer can be improved and the image quality can be improved. Further, at the time of recording, even if foreign matter is mixed between the thermal transfer sheet and the image receiving sheet, the deformation effect of the cushion layer reduces the gap between the image receiving layer and the image forming layer, resulting in a reduction in the size of image defects such as white spots. You can also do it.

The cushion layer has a structure that is easily deformed when stress is applied to the interface, and in order to achieve the above effect,
It is preferably made of a material having a low elastic modulus, a material having rubber elasticity, or a thermoplastic resin which is easily softened by heating. The elastic modulus of the cushion layer is preferably 0.5 MPa to 1.0 GPa at room temperature, particularly preferably 1 M.
Pa to 0.5 GPa, more preferably 10 to 100 MP
a. In addition, in order to insert foreign matter such as dust, the penetration (25 ° C,
100 g, 5 seconds) is preferably 10 or more. The cushion layer has a glass transition temperature of 80 ° C or lower, preferably 25 ° C or lower, and a softening point of 50 to 200 ° C. It is also possible to suitably add a plasticizer to the binder in order to adjust these physical properties, for example, Tg.

Specific materials used as the binder for the cushion layer include rubbers such as urethane rubber, butadiene rubber, nitrile rubber, acrylic rubber and natural rubber, as well as polyethylene, polypropylene, polyester and styrene-butadiene copolymer. Examples thereof include polymer, ethylene-vinyl acetate copolymer, ethylene-acryl copolymer, vinyl chloride-vinyl acetate copolymer, vinylidene chloride resin, plasticizer-containing vinyl chloride resin, polyamide resin, and phenol resin. The thickness of the cushion layer varies depending on the resin used and other conditions, but is usually 3 to 100 μm,
It is preferably 10 to 52 μm.

On the light-heat conversion layer of the thermal transfer sheet,
Providing a heat-sensitive peeling layer containing a heat-sensitive material that generates gas by the action of heat generated in the photothermal conversion layer or releases adhered water etc., thereby weakening the bonding strength between the photothermal conversion layer and the image forming layer. You can Examples of such a heat-sensitive material include a compound (polymer or low-molecular compound) that itself decomposes or deteriorates by heat to generate a gas, or a compound (polymer that absorbs or adsorbs a considerable amount of easily vaporizable gas such as water). Alternatively, a low molecular weight compound) or the like can be used. You may use these together.

Examples of the polymer which decomposes or deteriorates by heat to generate a gas include self-oxidizing polymers such as nitrocellulose, chlorinated polyolefin, chlorinated rubber, polychlorinated rubber, polyvinyl chloride and polyvinylidene chloride. Such halogen-containing polymers, acrylic polymers such as polyisobutyl methacrylate where volatile compounds such as water are adsorbed, cellulose esters such as ethyl cellulose where volatile compounds such as water are adsorbed, volatile compounds such as water Examples thereof include natural polymer compounds such as adsorbed gelatin. Examples of the low molecular weight compound that decomposes or deteriorates by heat to generate a gas include a compound such as a diazo compound or an azide, which generates a gas upon exothermic decomposition. In addition, it is preferable that the above-described decomposition and deterioration of the heat-sensitive material occur at 280 ° C. or less, and particularly at 230 ° C. or less.

When a low molecular weight compound is used as the heat sensitive material of the heat sensitive release layer, it is desirable to combine it with a binder. As the binder, it is possible to use the above-mentioned polymer which itself decomposes or deteriorates by heat to generate gas, but it is also possible to use an ordinary binder having no such property. When the heat-sensitive low molecular weight compound and the binder are used in combination, the mass ratio of the former and the latter is preferably 0.02: 1 to 3: 1.
More preferably, it is 0.05: 1 to 2: 1. The heat-sensitive peeling layer preferably covers the photothermal conversion layer over substantially the entire surface thereof, and the thickness thereof is generally 0.03 to.
It is 1 μm, preferably in the range of 0.05 to 0.5 μm.

On the support, a photothermal conversion layer, a heat-sensitive peeling layer,
In the case of the thermal transfer sheet in which the image forming layers are laminated in this order, the heat-sensitive peeling layer is decomposed and deteriorated by the heat transmitted from the photothermal conversion layer to generate gas. Due to this decomposition or generation of gas, the heat-sensitive peeling layer partially disappears, or cohesive failure occurs in the heat-sensitive peeling layer, and the binding force between the photothermal conversion layer and the image forming layer is reduced. Therefore, depending on the behavior of the heat-sensitive peeling layer, a part of the heat-sensitive peeling layer may adhere to the image forming layer and appear on the surface of the finally formed image, which may cause color mixing of the image. Therefore, even if such transfer of the heat-sensitive peeling layer occurs, the heat-sensitive peeling layer is hardly colored, that is, high in visible light, so that visual color mixing does not appear in the formed image. It is desirable to show permeability. Specifically, the light absorption of the heat-sensitive release layer is 50% or less, preferably 1 with respect to visible light.
It is 0% or less. Incidentally, instead of providing an independent heat-sensitive peeling layer on the heat transfer sheet, the heat-sensitive material is added to the light-heat converting layer coating liquid to form a light-heat converting layer, so that the light-heat converting layer and the heat-sensitive peeling layer may be used together. It is also possible to have a different configuration. The coefficient of static friction of the outermost layer of the thermal transfer sheet on which the image forming layer is coated is 0.35 or less, preferably 0.20.
The following is preferable. The static friction coefficient of the outermost layer is 0.
By setting the ratio to 35 or less, it is possible to eliminate roll stains when the thermal transfer sheet is conveyed and to improve the quality of the image formed. The static friction coefficient is measured according to the method described in Japanese Patent Application No. 2000-85759, paragraph (0011). Smoother value of the image forming layer surface is 0.5 to 50 mmHg (≒ 0.0665 to 6.
65 kPa) is preferable, and Ra is 0.05 to 0.4 μ.
It is preferable that m is small, and this makes it possible to reduce a large number of microscopic voids in which the image receiving layer and the image forming layer cannot come into contact with each other on the contact surface, and is preferable in terms of transfer and image quality. R
The a value can be measured based on JIS B0601 using a surface roughness measuring device (Surfcom, manufactured by Tokyo Seiki Co., Ltd.). The surface hardness of the image forming layer is preferably 10 g or more with a sapphire needle. After the thermal transfer sheet is charged according to US Federal Test Standard 4046, the charging potential of the image forming layer 1 second after the thermal transfer sheet is grounded is -1.
It is preferably from 100 to 100V. The surface resistance of the image forming layer is preferably 10 ⁹ Ω or less at 23 ° C. and 55% RH.

An image receiving sheet used in combination with the thermal transfer sheet will be described below. [Image Receiving Sheet] (Layer Structure) The image receiving sheet has a function of carrying an image from the thermal transfer sheet, and is composed of at least a support, and preferably has one or more image receiving layers on the support, If desired, any one layer or two or more layers of an adhesive layer, a cushion layer, a peeling layer, and an intermediate layer are provided between the support and the image receiving layer. Further, it is preferable to have a back layer on the surface of the support opposite to the image receiving layer from the viewpoint of transportability. The support is generally made of glass, but a heat resistant flexible resin such as polyether sulfone may be used.
An image receiving layer is preferably provided on the support, and a configuration in which an adhesive layer is provided between the support and the image receiving layer is also preferable. Examples of the adhesive layer include a treatment layer with a silane coupling agent. The thickness of the adhesive layer is preferably 50 Å to 5 μm, more preferably 50 to 1000 Å. As the silane coupling agent, for example, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, etc. are known. It is commercially available from Shin-Etsu Chemical Co., Ltd. as a "silane coupling agent". As a method for providing the silane coupling agent on the support, there is used a method in which the silane coupling agent is applied as it is or as a coating solution onto the support by a method such as a spinner, roll coater, bar coater or curtain coater, and then dried.

(Image Receiving Layer) The image receiving layer is preferably a layer formed mainly of an organic polymer binder. The binder is preferably a thermoplastic resin, and examples thereof include acrylic acid, methacrylic acid, acrylic acid esters, homopolymers of acrylic monomers such as methacrylic acid esters and copolymers thereof, methyl cellulose, ethyl cellulose, Cellulose-based polymers such as cellulose acetate, homopolymers of vinyl-based monomers such as polystyrene, polyvinylpyrrolidone, polyvinyl butyral, polyvinyl alcohol, polyvinyl chloride, etc. and their copolymers, condensation polymers such as polyester, polyamide, etc. Rubber-based polymers such as butadiene-styrene copolymer. The binder of the image receiving layer is preferably a polymer having a glass transition temperature (Tg) of lower than 90 ° C. in order to obtain a proper adhesive force with the image forming layer. For this reason, it is possible to add a plasticizer to the image receiving layer. Also, the binder polymer has a Tg in order to prevent blocking between the sheets.
Is preferably 30 ° C. or higher. As the binder polymer of the image receiving layer, in terms of improving the adhesion to the image forming layer during laser recording, and improving the sensitivity and the image strength,
It is particularly preferable to use the same or similar polymer as the binder polymer of the image forming layer. It is also preferable to form at least one of the image receiving layers from a photocurable material. Examples of such a photocurable material include the same as the light- and / or heat-reactive simple substance or composition of the image forming layer. For example, a) a photopolymerizable monomer composed of at least one kind of polyfunctional vinyl or vinylidene compound capable of forming a photopolymer by addition polymerization, b) an organic polymer, c) a photopolymerization initiator, and optionally a thermal polymerization inhibition. A combination of additives such as agents can be mentioned.
As the above-mentioned polyfunctional vinyl monomer, unsaturated ester of polyol, particularly ester of acrylic acid or methacrylic acid (eg, ethylene glycol diacrylate, pentaerythritol tetraacrylate) is used.

Examples of the organic polymer include the image forming layer forming polymer. As the photopolymerization initiator, a general photoradical polymerization initiator such as benzophenone or Michler's ketone is used in a proportion of 0.1 to 20% by mass in the layer.

After the pixels (R, G, B) are once formed on the image receiving layer, they can be retransferred to another support such as glass.

The thickness of the image receiving layer is preferably 0.01 to 10 μm, more preferably 0.01 to 1 μm. Smoother value of the image receiving layer surface is 0.5 to 50 mmHg (≒
0.0665 to 6.65 kPa) is preferable, and Ra is 0.05.
It is preferably from 0.4 to 0.4 μm, which makes it possible to reduce a large number of microscopic voids in which the image receiving layer and the image forming layer cannot come into contact with each other on the contact surface, and is preferable in terms of transfer and image quality. The Ra value is measured by a surface roughness measuring device (Surfcom,
It can be measured based on JIS B0601 by using, for example, Tokyo Seiki Co., Ltd.). US Federal Test Standard 40
After the image receiving sheet is charged by 46, the charging potential of the image receiving layer 1 second after the image receiving sheet is grounded is preferably −100 to 100V. Surface resistance of image receiving layer is 10 ⁹ Ω at 23 ℃ and 55% RH
The following is preferable. The coefficient of static friction on the surface of the image receiving layer is preferably 0.2 or less. The surface energy of the image receiving layer surface is preferably 23 to 35 mg / m ² .

(Other Layers) Between the support and the image receiving layer,
A cushion layer may be provided. This cushion layer is effective when the support is flexible and is retransferred to glass or the like. When the cushion layer is provided, the adhesion between the image forming layer and the image receiving layer at the time of laser thermal transfer can be improved and the image quality can be improved. Further, at the time of recording, even if foreign matter is mixed between the thermal transfer sheet and the image receiving sheet, the deformation effect of the cushion layer reduces the gap between the image receiving layer and the image forming layer, resulting in a reduction in the size of image defects such as white spots. You can also do it. Furthermore, when an image is transferred and formed and then transferred to a separately prepared printing paper or the like, the image receiving surface is deformed according to the uneven surface of the paper, so the transferability of the image receiving layer can be improved, and the transferred image can also be transferred. By reducing the gloss of the product, the closeness to the printed product can be improved.

The cushion layer is constructed so as to be easily deformed when a stress is applied to the image receiving layer, and in order to achieve the above effect, a material having a low elastic modulus, a material having rubber elasticity, or easily softened by heating. Preferably, it is made of a thermoplastic resin. The elastic modulus of the cushion layer at room temperature is preferably 0.5 MPa to 1.0 GPa, particularly preferably 1 MPa to 0.5 GPa, more preferably 10 to 100.
It is MPa. In addition, in order to insert foreign matter such as dust, the penetration (25
C., 100 g, 5 seconds) is preferably 10 or more. The cushion layer has a glass transition temperature of 80 ° C or lower, preferably 25 ° C or lower, and a softening point of 50 to 200 ° C. It is also possible to suitably add a plasticizer to the binder in order to adjust these physical properties, for example, Tg.

Specific materials used as the binder of the cushion layer include rubbers such as urethane rubber, butadiene rubber, nitrile rubber, acrylic rubber and natural rubber, as well as polyethylene, polypropylene, polyester and styrene-butadiene copolymer. Examples thereof include polymer, ethylene-vinyl acetate copolymer, ethylene-acryl copolymer, vinyl chloride-vinyl acetate copolymer, vinylidene chloride resin, plasticizer-containing vinyl chloride resin, polyamide resin, and phenol resin. The thickness of the cushion layer varies depending on the resin used and other conditions, but is usually 3 to 100 μm,
It is preferably 10 to 52 μm.

The image-receiving layer and the cushion layer need to be adhered to each other until the laser recording stage, but they are preferably provided in a peelable manner in order to transfer the pixels to the image-receiving sheet. However, in the case of forming a color filter,
Although not particularly required, when transferring to another support such as a glass plate, if desired, it is preferable that the image receiving layer and the cushion layer are provided so as to be peelable. In order to facilitate peeling, it is also preferable to provide a peeling layer having a thickness of about 0.1 to 2 μm between the cushion layer and the image receiving layer. If the film thickness is too large, the performance of the cushion layer will be difficult to appear, so
It is necessary to adjust according to the type of release layer. Specific examples of the binder for the release layer include polyolefin, polyester, polyvinyl acetal, polyvinyl formal, polyparabanic acid, polymethyl methacrylate, polycarbonate, ethyl cellulose, nitrocellulose, methyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, polyvinyl chloride. Styrenes such as urethane resin, fluorine resin, polystyrene, acrylonitrile styrene and those obtained by cross-linking these resins, polyamide, polyimide, polyetherimide, polysulfone, polyethersulfone, aramid, etc., having a Tg of 65 ° C or higher and thermosetting Examples include resins and cured products of those resins. As the curing agent, general curing agents such as isocyanate and melamine can be used. Polycarbonate, acetal, and ethyl cellulose are preferable in terms of storability when a binder for the peeling layer is selected according to the above physical properties, and when an acrylic resin is used for the image receiving layer, the peeling property becomes good when retransferring the image after laser thermal transfer. Particularly preferred. In addition, separately, a layer having extremely low adhesiveness to the image receiving layer upon cooling can be used as the release layer. Specifically, a layer containing a heat-melting compound such as waxes and binders or a thermoplastic resin as a main component can be used. As the heat-fusible compound, Japanese Patent Laid-Open No.
There are substances described in JP-A-3-193886. In particular, microcrystalline wax, paraffin wax, carnauba wax and the like are preferably used. As the thermoplastic resin, ethylene-based copolymers such as ethylene-vinyl acetate-based resin and cellulose-based resin are preferably used. If desired, higher fatty acids, higher alcohols, higher fatty acid esters, amides, higher amines and the like can be added to the release layer as additives. Another structure of the peeling layer is a layer having peelability by cohesively breaking itself by melting or softening during heating. Such a release layer preferably contains a supercooling substance. As the supercooling substance, poly-ε-caprolactone,
Examples thereof include polyoxyethylene, benzotriazole, tribenzylamine, vanillin and the like. Further, in the peelable layer having another structure, a compound that reduces the adhesion to the image receiving layer is included. Examples of such a compound include silicone resins such as silicone oil; fluorine resins such as Teflon and fluorine-containing acrylic resins; polysiloxane resins; polyvinyl butyral, polyvinyl acetal, polyvinyl formal and other acetal resins; polyethylene wax, amide wax. Solid waxes such as; fluorine-based and phosphoric acid ester-based surfactants and the like. Examples of the method for forming the release layer include coating methods such as blade coaters, roll coaters, bar coaters, curtain coaters, gravure coaters, and the like in which the above materials are dissolved in a solvent or dispersed in a latex form, and extrusion lamination methods using hot melt. It can be applied and can be applied and formed on the cushion layer. Alternatively, there is a method in which a material obtained by dissolving the raw material in a solvent or dispersed in the form of a latex on a temporary base is applied by the above-mentioned method and the cushion layer is bonded and then the temporary base is peeled off.

The image-receiving sheet combined with the thermal transfer sheet may have a structure in which the image-receiving layer also serves as a cushion layer. In that case, the image-receiving sheet is a support / cushionable image-receiving layer or a support / undercoat layer. / It may have a cushioning image-receiving layer. Also in this case, it is preferable that the cushioning image-receiving layer is detachably provided so that the image can be retransferred to the actual printing paper. In this case, the image after retransfer to the actual printing paper has excellent gloss. The thickness of the cushioning image-receiving layer is 5 to 100 μm, preferably 10
Is about 40 μm.

Further, it is preferable to provide a back layer on the surface of the image receiving sheet opposite to the surface of the support on which the image receiving layer is provided, since the transportability of the image receiving sheet is improved. It is preferable to add an antistatic agent such as a surfactant or tin oxide fine particles, and a matting agent such as silicon oxide or PMMA particles to the back layer in order to improve transportability in the recording apparatus. The above additives can be added not only to the back layer but also to the image receiving layer and other layers, if necessary. Although it is not possible to specify the type of additive depending on its purpose,
For example, in the case of a matting agent, particles having an average particle size of 0.5 to 10 μm can be added to the layer in an amount of about 0.5 to 80%. As the antistatic agent, the surface resistance of the layer is 23 ° C., 50
% 10 ¹² Omega less RH for, more preferably 10 ⁹ Omega
As described below, various surfactants and conductive agents can be appropriately selected and used. In addition, the pixel (R, G, B) or the pixel (R1,
When G1 and B1) and the black matrix are formed as they are, it is preferable to use the above additives within the range in which the transparency is ensured. It is not necessary to retransfer the pixels (R, G, B) or the pixels (R1, G1, B1) and the black matrix formed on the image receiving sheet to another transparent support such as glass.

As the binder used in the back layer, gelatin, polyvinyl alcohol, methyl cellulose, nitrocellulose, acetyl cellulose, aromatic polyamide resin, silicone resin, epoxy resin, alkyd resin, phenol resin, melamine resin, fluorine resin, polyimide resin. , Urethane resin, acrylic resin, urethane modified silicone resin, polyethylene resin, polypropylene resin, polyester resin, Teflon resin, polyvinyl butyral resin, vinyl chloride resin, polyvinyl acetate, polycarbonate, organic boron compound, aromatic ester, fluorinated polyurethane A general-purpose polymer such as polyethersulfone can be used. Crosslinking using a water-soluble crosslinkable binder as the binder of the back layer is effective in preventing the matting agent from falling off and improving the scratch resistance of the backcoat. It is also effective in blocking during storage. As the cross-linking means, any one of heat, actinic rays and pressure or a combination thereof can be adopted without any particular limitation, depending on the properties of the cross-linking agent used. In some cases, an optional adhesive layer may be provided on the side of the support on which the back layer is provided in order to impart adhesiveness to the support.

As the matting agent preferably added to the back layer, organic or inorganic fine particles can be used. As an organic matting agent, polymethylmethacrylate (PMM
A), polystyrene, polyethylene, polypropylene,
Examples thereof include fine particles of other radical polymerization type polymers, fine particles of condensation polymers such as polyester and polycarbonate. The back layer is preferably provided in an amount of about 0.5 to 5 g / m ² . If it is less than 0.5 g / m ² , the coating property is unstable and problems such as powder drop of the matting agent are likely to occur.
Further, when it is applied over 5 g / m ² , the particle size of a suitable matting agent becomes very large, and the embossing of the image receiving layer surface occurs due to the back coat during storage, and especially thermal transfer for transferring a thin image forming layer In this case, the recorded image is likely to be missing or uneven. The number average particle diameter of the matting agent is preferably 2.5 to 20 μm larger than the film thickness of only the binder of the back layer. Among matting agents, particles having a particle size of 8 μm or more are required to be 5 mg / m ² or more, and preferably 6 to 600 m.
g / m ² . This improves especially foreign matter failures. Also, the value σ obtained by dividing the standard deviation of the particle size distribution by the number average particle size.
By using a narrow particle size distribution such that / rn (= coefficient of variation of particle size distribution) is 0.3 or less, it is possible to improve defects caused by particles having an abnormally large particle size. The desired performance can be obtained with a small amount of addition. More preferably, this coefficient of variation is 0.15 or less.

An antistatic agent is preferably added to the back layer in order to prevent foreign matter from adhering to the back layer due to frictional charging with the transport roll. Examples of the antistatic agent include cationic surfactants, anionic surfactants, nonionic surfactants, polymeric antistatic agents, conductive fine particles, and "1129".
Compounds described in “Chemical products of No. 0”, Kagaku Kogyo Nipposha, pp. 875-876, etc. are widely used. Among the above substances, metal oxides such as carbon black, zinc oxide, titanium oxide and tin oxide, and conductive fine particles such as organic semiconductors are preferably used as the antistatic agent that can be used in the back layer. It is particularly preferable to use the conductive fine particles because the antistatic agent is not dissociated from the back layer and a stable antistatic effect is obtained regardless of the environment. In addition, various activators are added to the back layer in order to impart coatability and releasability.
It is also possible to add a release agent such as silicone oil or fluorine resin. The back layer is particularly preferable when the softening point of the cushion layer and the image receiving layer measured by TMA (Thermomechanical Analysis) is 70 ° C. or lower.

The TMA softening point is determined by observing the phase of the object to be measured, while raising the temperature of the object to be measured at a constant temperature rising rate while applying a constant load. In the present invention, the temperature at which the phase of the measurement object begins to change is defined as the TMA softening point. The measurement of the softening point by TMA can be performed using a device such as Thermoflex manufactured by Rigaku Denki Co., Ltd.

The thermal transfer sheet and the image receiving sheet can be used for image formation as a laminate in which the image forming layer of the thermal transfer sheet and the image receiving sheet or the image receiving layer thereof are superposed. The laminate of the thermal transfer sheet and the image receiving sheet can be formed by various methods. For example, it can be easily obtained by stacking the image forming layer of the thermal transfer sheet and the image receiving sheet or the image receiving layer thereof and passing them through a pressure heating roller. In this case, the heating temperature is preferably 160 ° C or lower, or 130 ° C or lower.

As another method for obtaining a laminated body, the above-mentioned vacuum adhesion method is also suitably used. In the vacuum contact method, the image receiving sheet is first wound on the drum provided with suction holes for vacuuming, and then a thermal transfer sheet having a size slightly larger than that of the image receiving sheet is pressed while the air is uniformly pushed out by the squeeze roller. It is a method of vacuum adhesion to. As another method, there is also a method in which an image receiving sheet is mechanically attached while being pulled on a metal drum, and a thermal transfer sheet is similarly mechanically pulled and attached so as to be in close contact therewith. Among these methods, the vacuum contact method is particularly preferable because it does not require temperature control of a heat roller or the like and facilitates quick and uniform lamination.

[0153]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples.
In the text, "part" means "part by mass" unless otherwise specified. Example 1 -1. Preparation of wet development transfer sheet for K color A coating solution H1 having the following composition was coated on a polyethylene terephthalate film temporary support having a thickness of 100 μm and dried to provide a thermoplastic resin layer having a dry film thickness of 20 μm.

[0154]   <Coating liquid H1 for thermoplastic resin layer>   ・ Methyl methacrylate / 2-ethylhexyl acrylate / benzylmethac     Relate / methacrylic acid copolymer   (Copolymerization composition ratio (molar ratio) = 55 / 28.8 / 11.7 / 4.5,     Weight average molecular weight = 90000) ... 15 parts   ・ Polypropylene glycol diacrylate ・ ・ ・ ・ 6.5 parts   (Average molecular weight = 822)   ・ Tetreethylene glycol dimethacrylate ・ ・ ・ ・ 1.5 parts   ・ P-toluenesulfonamide ・ ・ ・ ・ 0.5 parts   ・ Benzophenone ・ ・ ・ ・ 1.0 parts   ・ Methyl ethyl ketone ・ ・ ・ ・ 30 parts

Next, a coating solution B1 having the following composition was applied onto the thermoplastic resin layer and dried to give a dry film thickness of 1.
An oxygen barrier layer having a thickness of 6 μm was provided. <Coating liquid B1 for oxygen barrier layer> -Polyvinyl alcohol ... 130 parts (PVA205 (saponification rate = 80%); Kuraray Co., Ltd.)-Polyvinylpyrrolidone (PVP, K-90; GAF Corporation) ...・ ・ 60 parts ・ Fluorosurfactant ・ ・ ・ ・ 10 parts (Surflon S-131 manufactured by Asahi Glass Co., Ltd.) ・ Distilled water ・ ・ 3350 parts

On the support having the thermoplastic resin layer and the oxygen barrier layer, a K-color photosensitive solution having the following formulation was applied and dried to form a K-color photosensitive resin layer having a dry film thickness of 2 μm. Formed. <Prescription> benzyl methacrylate / methacrylic acid copolymer: 73/27 (mol), viscosity: 0.12) 60 parts pentaerythritol tetraacrylate 43.2 parts Michler's ketone 2.4 parts 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer 2.5 parts Carbon black 5.6 parts Methyl cellosolve acetate 560 parts Methyl ethyl ketone 280 parts Further, polypropylene (thickness 1
2 μm) of the covering sheet was pressure-bonded to prepare a K-color wet development transfer sheet. -2. Preparation of laser thermal transfer sheet 1-1. Preparation of cushion layer Composition of coating liquid for forming cushion layer Vinyl chloride-vinyl acetate copolymer 25 parts (MPR-TSL manufactured by Nisshin Chemical Co., Ltd.) Plasticizer 6 functional acrylate monomer 12 parts (Nippon Kayaku Co., Ltd. ), DPCA-120, molecular weight 1947) Surfactant 0.4 parts (Megafuck F-177, Dainippon Ink and Chemicals, Inc.) Methyl ethyl ketone 75 parts The coating amount was adjusted so that the dry film thickness was about 20 μm.

1-2. Preparation of Photothermal Conversion Layer 1) Preparation of Photothermal Conversion Layer Forming Coating Liquid The following components were mixed with stirring with a stirrer to prepare a photothermal conversion layer forming coating liquid. Composition of coating liquid Infrared absorbing dye (NK-2014, manufactured by Nihon Sensitive Dye Co., Ltd.) 10 parts Binder (Ricacoat SN-20, manufactured by Shin Nippon Rika Co., Ltd.) 200 parts N-Methyl-2-pyrrolidone 2000 parts Surfactant 1 part (MegaFac F-177, manufactured by Dainippon Ink and Chemicals, Inc.) 2) Formation of a photothermal conversion layer on the surface of a support A spin coater (whirler) for coating the above coating solution on the above cushion layer coated surface. After applying using
It was dried in an oven at 0 ° C. for 2 minutes to form a photothermal conversion layer on the support. The obtained photothermal conversion layer has a wavelength of 700
In the range of up to 1000 nm, there was an absorption maximum near 830 nm, and its absorbance (optical density: OD) was measured with a Macbeth densitometer, and was OD = 1.0. When the cross section of the photothermal conversion layer was observed with a scanning electron microscope, the film thickness was 0.3 μm on average.

1-3. Preparation of image forming layer 3) Preparation of coating liquid for forming image forming layer Each of the following components was applied to a paint shaker (Toyo Seiki Co., Ltd.).
Glass), and then the glass beads are removed,
A red pigment-dispersed mother liquor was prepared. Pigment dispersion mother liquor composition 20 mass% n-propyl alcohol solution of binder (acrylic acid: diethylene glycol monoethyl ether acrylate: styrene = 32: 6: 62 (molar ratio), mass average molecular weight 10,000) 12.6 parts Pigment Irgadine Red BPT (red) 24 parts Dispersion aid (Solspers S-20000, manufactured by ICI Corporation) 0.8 part n-Propyl alcohol 110 parts Glass beads 100 parts The following components are mixed while stirring with a stirrer, and red A coating liquid for forming an image forming layer was prepared. Coating liquid composition The above pigment dispersion mother liquor 20 parts Polymerization initiator Michler's ketone 0.1 part Thermosetting monomer pentaerythritol tetraacrylate 2.0 parts n-Propyl alcohol 60 parts Surfactant 0.05 parts (MegaFac F-176PF, large Similarly, a copper phthalocyanine (green) pigment having a green color and a sudan blue (blue) having a blue color were used to prepare an image forming coating solution. 4) Formation of a red image forming layer on the surface of the photothermal conversion layer After applying the coating liquid on the surface of the photothermal conversion layer,
The coated material was dried in an oven at 100 ° C. for 2 minutes, and the red image forming layer (pigment 64.2% by weight,
Polyvinyl butyral 33.7% by weight) was formed. The absorbance (optical density: OD) of the obtained image forming layer was measured with a Macbeth densitometer TD504 (B), and OD =
It was 0.7. The film thickness was 2 μm on average when measured in the same manner as above. Through the above steps, a thermal transfer sheet was prepared in which a cushion layer, a photothermal conversion layer, and a red image forming layer were provided in this order on the support.
Similarly, a thermal transfer sheet having a green image forming layer and a blue image forming layer was prepared.

-3. Preparation of image-receiving sheet A glass substrate having a thickness of 1.1 mm was used as a support for the image-receiving sheet, and the surface thereof was surface-treated with a 0.3% aqueous solution of a silane coupling agent (KBE-903 manufactured by Shin-Etsu Chemical Co., Ltd.). . Then, an image receiving layer (thickness: 1 μm) from the following image receiving layer coating solution using a spin coater on the treated surface
Was set up. Image receiving layer coating solution Polyvinyl butyral (Denka Butyral # 2000-L, manufactured by Denki Kagaku Kogyo KK) 16 parts Surfactant 0.5 part (Megafuck F-177, manufactured by Dainippon Ink and Chemicals, Inc.) n- Propyl alcohol 100 parts-4. Formation of color filter 2 K of wet development transfer sheet for K color is formed on the image receiving sheet using a laminator (VP-II manufactured by Taisei Laminator Co., Ltd.).
G / cm ² (≈196 kPa), heating (130 ° C.) for bonding, and subsequent peeling at the interface between the support and the thermoplastic resin layer, the support was removed. Then, the back surface of the image-receiving sheet is exposed to ultraviolet rays of 400 mJ / cm ² , and then 1%.
The thermoplastic resin layer and the oxygen barrier layer were dissolved and removed using a triethanolamine aqueous solution. At this time, the photosensitive resin layer was not substantially developed. Next, the photosensitive resin layer was developed using a 1% aqueous sodium carbonate solution to remove unnecessary portions, and a black matrix having a line width (c in FIG. 3) of 20 μm was formed on the glass substrate. The image-receiving sheet (25 cm × 35 cm) was adsorbed on a flat bed having a suction hole for vacuum adsorption having a diameter of 1 mm (one area density in an area of 3 cm × 3 cm). Then 30c
An m × 40 cm thermal transfer sheet R was stacked so as to be evenly protruded from the image receiving sheet, and the squeeze roller was squeezed to bring the thermal transfer sheet into close contact with the suction holes so that air was sucked into the image transfer sheet. . The degree of pressure reduction when the suction hole was blocked was −150 mmHg (≈81.13 kPa) with respect to 1 atm. Then, the above flat bed is moved, and a wavelength of 830 n is applied to the surface of the laminate on the flat bed from the outside.
m of semiconductor laser light is focused so as to form a spot of 7 μm on the surface of the photothermal conversion layer, and is moved in the direction perpendicular to the moving direction of the flat bed (main scanning direction) (sub scanning), The laser image recording was performed. Laser recording was performed by irradiating an image corresponding to the color filter image shown in FIG. 3 from the side of the thermal transfer sheet imagewise with laser light. a is 150 μm, b is 100 μm
m and d were set to 3 μm. The laser irradiation conditions are as follows. Laser power: 110 mW Main scanning speed: 4 m / sec Sub scanning pitch (sub scanning amount per channel): 10
μm Temperature, humidity: 25 ° C., 50% RH The layered body on which the laser image recording described above was removed from the flat bed and the image receiving sheet and the thermal transfer sheet R were peeled off by hand, and the laser irradiation part of the image forming layer was detected. It was confirmed that only the image was transferred from the transfer sheet to the image receiving sheet. Images were transferred on the laser thermal transfer sheets G and B in the same manner as described above to form pixels (R1, G1, B1) on the image receiving sheet. Next, this image-receiving sheet was subjected to a heat treatment at 200 ° C. for 20 minutes and an exposure treatment of 400 mJ / cm ^{2 with an} ultrahigh pressure mercury lamp to cure the black matrix and the pixels (R1, G1, B1).
Then, a liquid crystal color filter polishing device (SANSHI)
The surface of the black matrix and the pixels (R1, G1, B1) was subjected to polishing treatment with PL-201-TL manufactured by N Co., Ltd. to produce a color filter having a flat surface. Comparative Example In Example 1, a line width (c in FIG. 3) was obtained by using a K color laser thermal transfer sheet instead of the K color wet development transfer sheet.
With a 20 μm black matrix as pixels (R1, G
1, B1), and the pixel (R, G, B) was formed in the same manner as above except that d was set to 0 μm in the formation of the pixel (R1, G1, B1). To create a color filter. The laser thermal transfer sheet for K color was prepared in the same manner as in the preparation of the laser thermal transfer sheet R, except that the coating liquid for black image forming layer described below was used in place of the coating liquid for image forming layer. Preparation of Coating Solution for Black Image Forming Layer The following components were placed in a kneader mill, and a shearing force was applied while adding a small amount of solvent to carry out a pretreatment for dispersion. A solvent was further added to the dispersion to finally prepare the following composition, and the mixture was subjected to sand mill dispersion for 2 hours to obtain a pigment dispersion mother liquor. [Black pigment dispersion mother liquor composition] Composition 1 • Polyvinyl butyral 12.6 parts (“S-REC B BL-SH”, manufactured by Sekisui Chemical Co., Ltd.) • Pigment Black (Pigment Black) 7 (carbon black C.I. 77266) 4.5 parts ("Mitsubishi Carbon Black MA100", Mitsubishi Chemical Co., Ltd., PVC blackness: 1) -Dispersion aid 0.8 parts ("Solspers S-20000", ICI Co., Ltd.)- n-Propyl alcohol 79.4 parts Composition 2-Polyvinyl butyral 12.6 parts ("S-REC B BL-SH", Sekisui Chemical Co., Ltd.)-Pigment Black (pigment black) 7 (carbon black CI No. .77266) 10.5 parts ("Mitsubishi Carbon Black # 5", manufactured by Mitsubishi Chemical Corporation, PVC blackness: 0) Dispersion aid 0.8 parts ( "SOLSPERSE S-20000", ICI (Ltd.)) - n-propyl alcohol 79.4 parts

Next, the following components were mixed with stirring with a stirrer to prepare a coating liquid for black image forming layer. [Composition of coating liquid for black image-forming layer] -Black pigment dispersion mother liquor 185.7 parts Composition 1: Composition 2 = 70:30 (parts) -Polyvinyl butyral 11.9 parts ("S-REC B BL-SH", Sekisui Chemical Co., Ltd.) Kogyo Co., Ltd.-Wax compound (stearic acid amide "Nutron 2", manufactured by Nippon Seika Co., Ltd.) 1.7 parts (behenic acid amide "Diamid BM", manufactured by Nippon Kasei Co., Ltd.) 1 0.7 parts (lauric acid amide "Diamid Y" manufactured by Nippon Kasei Co., Ltd.) 1.7 parts (palmitic acid amide "Diamid KP" manufactured by Nippon Kasei Co., Ltd.) 1.7 parts (erucic acid amide " Diamid L-200 ", manufactured by Nippon Kasei Co., Ltd. 1.7 parts (oleic acid amide" Diamid O-200 ", manufactured by Nippon Kasei Co., Ltd.) 1.7 parts, rosin 11.4 parts (" KE -311 ”, Arakawa Chemical ( (Components: Resin acid 80-97%; Resin acid component: Abietic acid 30-40%, Neoabietic acid 10-20%, Dihydroabietic acid 14%, Tetrahydroabietic acid 14%) ・ Surfactant 2 .1 part ("Megafuck F-176PF", solid content 20%, manufactured by Dainippon Ink and Chemicals, Inc.)-Inorganic pigment 7.1 parts ("MEK-ST", 30% methyl ethyl ketone solution, Nissan Chemical Co., Ltd.) N-propyl alcohol 1050 parts / methyl ethyl ketone 295 parts The black image forming layer coating solution was applied onto the surface of the photothermal conversion layer in the same manner as in the formation of the thermal transfer sheet having the red image forming layer to form a black image. A thermal transfer sheet having a forming layer was produced.

The color filters obtained in Examples and Comparative Examples were evaluated as follows and shown in Table 1. <Evaluation method> a. Positional accuracy is evaluated by the difference between the recording reference position and the recording position. ⊚: less than 1 μ O: less than 1 to 2 μm Δ: less than 2 to 3 μm x: 3 μm or more b. Edge shape ◎: straight end. The angle is 90 degrees and there are no debris. ◯: Some deformation is seen at the end, but it is almost straight and there are no fragments or the like. Δ: Deformation is seen at the edges and the corners are rounded. X: Deformation at the end is large, the corners are rounded, and fragments and the like are generated.

[0162]

[Table 1]

In the example, there was no gap between the black matrix and the pixels (R, G, B) and there was no step at their contact parts, and the edge shape was good, but in the comparative example, the reference position Is 2 to 3 μm or 3 μm or more, a gap is seen between the black matrix and the pixels (R, G, B), and a step due to overlapping is seen at their contact portions, and the edge shape is also good. There wasn't.

[0164]

According to the present invention, since a laser thermal transfer sheet and a wet development transfer sheet are used, a large size (A2 /
The color filter of B2) can be provided inexpensively and accurately. In the present invention, the black matrix is formed by the wet development transfer sheet, and the laser thin film thermal transfer method is used during the formation of the actual halftone dot recording to transfer the RGB pixels to the image receiving sheet. Also, under different temperature and humidity conditions,
Even when laser recording is performed with high energy by laser light having a multi-beam two-dimensional array, RGB pixels are good, and RGB pixels with stable transfer density are installed between the black matrix without gaps and without steps. It is possible to provide a color filter having an excellent edge shape.

[Brief description of drawings]

FIG. 1 is a diagram illustrating an outline of a mechanism of multicolor image formation by thin film thermal transfer using a laser.

FIG. 2 is a diagram showing a configuration example of a laser thermal transfer recording device.

FIG. 3 shows an example of forming pixels of a color filter.

[Explanation of symbols]

1 recording device 2 recording head 3 Sub-scanning rail 4 recording drum 5 Thermal transfer sheet loading unit 6 Image-receiving sheet roll 7 Conveyor rollers 8 squeeze roller 9 cutter 10 Thermal transfer sheet 10R, 10G, 10B Thermal transfer sheet roll 12 Support 14 Photothermal conversion layer 16 Image forming layer 20 Image receiving sheet 22 Support for image receiving sheet 24 Image receiving layer 30 stacks 31 discharge stand 32 Waste port 33 outlet 34 air 35 waste box 41 color filter 42 Red filter pixel 43 Green filter pixels 44 Blue filter pixel 45 Black Matrix

Claims (4)

[Claims] 1. A mask is formed on the front surface and / or the back surface of the image receiving sheet after a wet development transfer sheet having a black (K) photosensitive resin layer is superposed on the image receiving sheet to transfer the photosensitive resin layer. Via a laser beam and then wet-developed to form a black matrix, and then three types of laser thermal transfer sheets having red (R), green (G) or blue (B) image forming layers are used as image receiving sheets. Laser light is imagewise irradiated from the side of the superimposed thermal transfer sheet to form an image consisting of R, G and B between the black matrices on the image receiving sheet or between the black matrices and on the peripheral edge of the black matrix. And method of forming a color filter. 2. A method comprising the steps of heat-treating an image-receiving sheet carrying an image composed of R, G and B and a black matrix prepared by the method of claim 1, and then polishing the surface of the image-receiving sheet. The method of forming a color filter according to claim 1. 3. Three types of laser thermal transfer sheets having at least a photothermal conversion layer and a red (R), green (G) or blue (B) image forming layer on a support, and at least black (K) on the support. 3. A color filter forming material for use in the method for forming a color filter according to claim 1 or 2, which comprises a wet development transfer sheet having a photosensitive resin layer according to 1). 4. A color filter manufactured by the method for forming a color filter according to claim 1.