JPH10272845A - Method and material for forming high-gloss image in melting type thermal transfer recording - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image recording method and a material for forming a high-grade multicolor image which make the most of the formation of an image receiving body for a non-image part and give a high gloss only to an image part, in regard to an image recorded by a melting type thermal transfer recording system. SOLUTION: In a method for forming a high-grade multicolor image which makes the most of the formation of an image receiving body for a non-image part and gives a high gloss only to an image part, the image is recorded by a melting type thermal transfer system of a thermal peeling method on an image receiving layer of an image forming material which has on a substrate the image receiving layer having a property of release from the substrate and being excellent in adhesion to the image formed by melting type thermal transfer recording of the thermal peeling method, then an image receiving body and the image forming material are held in lamination, subjected to heating and/or pressing treatment and then cooled sufficiently and the image forming material is peeled from the image receiving body. Thereby only an image part of the image forming material is transferred, together with the image receiving layer, onto the image receiving body. In this image forming material, the image receiving layer contains at least one kind of resin out of water-soluble nylon resin, a copolymer thereof and halogenated polyolefin resin and an inorganic or organic particulate pigment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a multicolor image by a thermal transfer recording method, and an image forming material used directly for the method. The present invention relates to a method for forming a high-quality multi-color image in which only the image portion has high gloss while utilizing the formation of the image receiving member in the non-image portion by the fusion type thermal transfer recording, and an image forming material directly used for carrying out the method.

[0002]

2. Description of the Related Art In recent years,
As full-color image recording systems, systems such as thermal transfer (fusible thermal transfer, sublimation thermal transfer), electrophotography, and inkjet have been put to practical use.

[0003] However, the sublimation type thermal transfer changes the thermal energy of a heat source such as a thermal head, and
Because the amount of dye to be sublimated and transferred can be changed,
It has the feature of being able to reproduce the gradation of an image by density modulation.However, in order to form an image, an image receiver having a dedicated image receiving layer for receiving a sublimation dye is required as a recording image receiver, and plain paper or plastic film is required. However, recording on a medium having no image receiving layer is not possible. Further, the sublimation dye also has a problem in light fastness, and has a drawback that it is not suitable for outdoor use or long-term storage. The ink-jet method has the feature that large-size (A0 or larger) recording is possible, and the one using pigment ink can be used outdoors. Is required.

On the other hand, the fusion type thermal transfer system has a feature that a special image receiving layer is not required as an image receiving body, but on the other hand, if the surface of a recording image receiving body (image receiving surface) is not excellent in smoothness, a high heat transfer method is required. It had the disadvantage that it was not possible to print quality images. For example, when printing is performed on paper having poor smoothness, the image is transferred only to the convex portions of the paper surface, and the image is not transferred to the concave portions. Was.

Therefore, Japanese Patent Application Laid-Open No. Hei 4-220380 discloses
As disclosed in JP-A-7-137470 and the like, by devising the structure of the thermal transfer recording medium and the material used for the ink layer, high-quality recording free of transfer loss on paper having poor surface smoothness can be achieved. Method for obtaining the same, and JP-A-58-16
As disclosed in Japanese Patent No. 2355 or the like, an intermediate transfer medium is provided in a thermal transfer recording apparatus, a recorded image is primarily transferred onto the intermediate transfer medium, and then re-transferred onto an image receiving body, whereby surface smoothness is improved. To obtain a high-quality recorded image free from transfer defects even on paper of inferior quality, as disclosed in Japanese Patent Application Laid-Open No. 7-290731, etc., with a donor sheet having a peelable thin film (fused thermal transfer recording material). An image-receiving material (image-forming material according to the present invention) having a possible image-receiving layer (image-receiving layer according to the present invention) is uniformly laminated, and then thermal energy is applied imagewise to bond the thin film of the donor sheet. A method of causing an imagewise decrease in force, forming an image on the image receiving layer (peeling development), and then transferring the image formed on the image receiving layer from the image receiving material to a permanent support (image receiving body in the present invention). ,So far It is draft.

However, JP-A-4-220380, JP-A-7-137470, and JP-A-58-1
The method disclosed in Japanese Patent Application Laid-Open No. 62355/1992 has an advantage that only an image can be recorded on an image receiving body, as well as a conventional fusion-type thermal transfer recording method, and provides a method for an image receiving body having poor smoothness as compared with the related art. Although the recording quality has been improved, satisfactory recording quality has not been achieved on all printing papers (coated paper, high-quality paper, lower grade paper, newsprint, etc.) with a wide range of smoothness, and high gloss images cannot be obtained. I can't get it.

In the method disclosed in Japanese Patent Application Laid-Open No. 7-290731, the image-receiving layer of the image-receiving material is configured to be peelable, so that the image recorded on the image-receiving layer together with the image-receiving layer It is transferred onto a permanent support. Therefore, this method can perform recording without transfer dropping even on a printing paper having a wide range of smoothness, but cannot form a high gloss image because an image alone cannot be recorded on a permanent support. Although it is possible, both the image portion and the non-image portion become high gloss, and the non-image portion forms a high-quality multicolor image having only the image portion having high gloss while utilizing the formation of the permanent support. There was a problem that you could not do that.

[0008]

An object of the present invention is to provide a mold having a releasability between a support and the support.
And an image forming material having an image receiving layer exhibiting a releasability between the image receiving layer and a re-transfer image receiving member, while having an adhesive force with an image formed by a hot-melt type thermal transfer recording. Then, the binder is opposed to the ink layer of the melt-type thermal transfer recording material provided with an ink layer of a thermal-transferable property mainly composed of a thermoplastic resin, and imagewise heating is performed from the back side of the melt-type thermal transfer recording material or the back side of the image forming material. Then, before the ink is cooled and solidified, the fusion type thermal transfer recording material is peeled off from the image forming material, and after the image is recorded on the image receiving layer of the image recording material, only the image portion is the same as the image receiving layer. A thermal transfer recording method for retransferring a portion corresponding to the image portion onto the image receiving body,
The problem is solved by an image forming material having a specific image receiving layer used therein.

Conventionally, there are two types of image recording methods for a fusion type thermal transfer recording material: a cold release type in which an ink is solidified and the molten type thermal transfer recording material (ink ribbon or the like) is peeled off from a recording medium; There is a hot peeling method in which a fusion type thermal transfer recording material is peeled off from a recording medium.

However, in the case of the cold peeling method, the ink layer surface of the fusion type thermal transfer recording material and the image receiving layer surface of the retransferable image forming material are overlapped, and the ink is transferred to the image receiving layer using a thermal head or a laser. When transferring to
In order to selectively transfer the ink layer corresponding to the imagewise heating section and obtain high image quality, both the shear breaking force and elongation of the ink layer coating film are small, and the affinity and wettability with the image receiving layer It is necessary to choose the one with high. Therefore, the affinity between the image transferred to the image receiving layer and the image receiving layer becomes strong, but if the adhesion strength between the support and the image receiving layer is not greater than the shear breaking force of the ink layer coating film, When the ink is transferred to the image receiving layer, the ink peels off at the interface between the support and the image receiving layer, and as a result, it is difficult to transfer the image onto the image receiving layer. Further, when the adhesion strength between the support and the image receiving layer is larger than the shear breaking force of the ink layer coating film, the cohesive failure of the ink occurs when the ink is finally re-transferred to the image receiving body (printing paper, etc.), and the ink is selectively removed. It is difficult to retransfer only the image portion together with the image receiving layer.

On the other hand, in the present invention, a material containing a thermoplastic resin as a main component is used as a binder of the ink layer, and after the imagewise heating and before the ink is cooled and solidified, the fusion type thermal transfer recording material is subjected to a specific image receiving process. Transferring the image onto the image receiving layer of the image forming material by peeling off from the image forming material having the layer (hot peeling method), and thereafter, transferring only the image portion on the image receiving layer to the image portion of the image receiving layer It is possible to re-transfer the entire portion corresponding to.

That is, a thermoplastic resin system is selected as a binder for the ink layer, and before the ink is cooled and solidified (when the ink is in a molten state), the fusion type thermal transfer recording material is placed on the image receiving layer of the image forming material. Transfer, the resulting image can be transferred onto the image receiving layer even if the adhesion strength between the support and the image receiving layer is smaller than the shear breaking force of the ink layer coating film after cooling and solidification. I found it. Therefore, finally, only the image portion on the image receiving layer is transferred to the image receiving member (printing paper or the like) together with the portion corresponding to the image portion of the image receiving layer.
It is possible to retransfer to

Hereinafter, the present invention will be described in more detail. First, the fusion type thermal transfer recording material will be described. The fusion-type thermal transfer recording material used in the present invention basically has a configuration in which an ink layer containing a binder containing a hot-release type thermoplastic resin as a main component is laminated on a support. An intermediate layer (release layer, deformable layer, light-to-heat conversion layer) may be provided between the ink layer and the ink layer.

The binder used for the ink layer of the fusion type thermal transfer recording material is mainly composed of a thermoplastic resin suitable for the hot peeling method. good. Examples of the resin include an ethylene-vinyl acetate copolymer, an ethylene- (meth) acrylic acid copolymer, and an ethylene- (meth) acrylic acid alkyl ester copolymer (where the alkyl group is methyl, ethyl, butyl, hexyl, Heptyl, octyl,
About 1 to 16 hydrocarbons such as 2-ethylhexyl, nonyl, dodecyl, hexadecyl and the like), ethylene-acrylonitrile copolymer, ethylene-styrene copolymer such as ethylene-styrene copolymer; polylauri (meth) Acrylates; vinyl chloride (co) polymers such as polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl alcohol copolymer and the like. Among them, especially ethylene-vinyl acetate copolymer,
It is preferable because it has high viscosity at the time of melting and excellent temporary adhesiveness.

Examples of the waxy substance include natural waxes such as wood wax, beeswax, carnauba wax, candelilla wax, montan wax and ceresin wax; petroleum waxes such as paraffin wax and microcrystalline wax; Synthetic waxes such as ester wax, polyethylene wax, Fischer-Tropsch wax, α-olein-maleic anhydride copolymer wax; higher fatty acids such as myristic acid, palmitic acid, stearic acid and behenic acid; higher aliphatic acids such as stearyl alcohol and docosanol Alcohols; esters of higher fatty acid monoglyceride, fatty acid esters of sucrose, fatty acid esters of sorbitan, and the like; amides such as stearamide, oleylamide, and bisamides. That.

As the colorant used in the ink layer, any of those conventionally used as colorants for this type of hot-melt ink can be used, and various inorganic and organic pigments and dyes can be used as appropriate. .

The method of imagewise heating the ink layer includes a method of imagewise heating the ink layer with a thermal head or the like, and a method of imagewise heating the image layer with light by imparting a light-to-heat conversion function to a fusion-type thermal transfer recording material. Available.

An apparatus that enables the hot peeling method is disclosed in Japanese Patent Application Laid-Open No. 7-81113, for example, in which an ink ribbon is separated from a heat generating portion of a thermal head to shorten a distance from an edge portion. Are available.

Next, the image forming material used in the present invention will be described. The image forming material of the present invention has an image receiving layer on a support, and in some cases, a release layer may be provided between the support and the image receiving layer for the purpose of peeling off from the interface. . Further, an antistatic layer may be provided on the surface of the support opposite to the image receiving layer and / or on the image receiving layer for the purpose of preventing charging.

As a support for the image forming material, a conventionally known sheet material such as a plastic film can be used. For example, a plastic film such as polyethylene terephthalate, polypropylene, polyethylene, polyvinyl chloride, polystyrene, polycarbonate, and triacetate, or a metal plate such as an aluminum plate and a zinc plate can be used. Further, since the ink layer melted by heat is transferred, a material having appropriate heat resistance and excellent dimensional stability is preferable, and a polyethylene terephthalate film, a polycarbonate film, and the like are preferable from the viewpoint of handling, but are not particularly limited thereto. Not something. Further, the transparency of the support is not particularly limited to this. The thickness of the support is not particularly limited, but is preferably 25 to 200 μm, and more preferably 50 to 150 μm, from the viewpoint of workability.

The material used for the image receiving layer of the image forming material contains a water-soluble nylon resin and a copolymer thereof, a halogenated polyolefin resin, and an inorganic or organic fine particle pigment. And it was effective in retransferring the image portion and the image receiving layer of the image formed portion to the image receiving member. If necessary, other resins or plasticizers, wettability improvers, antistatic agents and the like may be added to such an extent that required performance is not impaired.

The halogenated polyolefin in the present invention is obtained by halogenating a polyolefin. Examples thereof include halogenated polyethylene and its copolymer, halogenated polypropylene and its copolymer, halogenated polybutylene and its copolymer, and halogenated polyolefin. Examples thereof include polyisobutylene and a copolymer thereof. Among the halogenated polyolefins, those having a small content of impurities such as halogen molecules, hydrogen halides and other halides are preferably used, and chlorinated polyolefins are particularly preferable from the viewpoint of easy production.

In the present invention, inorganic or organic fine particle pigments include inorganic fine particles such as silicon dioxide, calcium carbonate and alumina fine particles, and organic fine particles such as polyethylene, polypropylene and polystyrene fine particles, but are not particularly limited thereto. Absent. Further, the particle size of the inorganic or organic fine particle pigment is preferably 100 nm or less, more preferably 20 nm or less. The reason for this is that when a particle size of 100 nm or more is used, the saturation of the image after retransfer decreases due to the decrease in the transparency of the coating film (the image after retransfer becomes whitish), This is because the edge is cut off and transferability is deteriorated (retransferability of a low gradation portion is deteriorated). As a result of intensive studies, it has been found that colloidal silica is preferably used as the inorganic or organic fine particle pigment.

Further, the weight ratio of the inorganic or organic fine particle pigment to the resin in the image receiving layer in the present invention is preferably 80/100.
It is 20-95 / 5, more preferably 85 / 15-90 / 10. The reason for this is that, when the weight ratio of the resin is 20 parts or more, the image reproducibility when images are recorded on the image receiving layer is reduced (missing dots in low gradation portions) and This is because, after retransfer, the edge becomes poorly cut, fringe of the image receiving layer occurs around the image portion, and the image is transferred to the non-image portion. Further, when the weight ratio of the resin is 5 parts or less, the strength of the coating film is weakened, and the coating film is easily damaged.

As for the thickness of the image receiving layer, if the coating thickness is too thin, retransfer to the image receiving body cannot be performed. If the coating thickness is too thick, the transparency and the strength of the coating film will be reduced, and the edge will be poorly cut. The fringe of the image receiving layer is generated around, or the image is transferred to the non-image area.
m, more preferably 1 to 3 μm, and these have led to realizing the effects of the present invention in a more preferable form.

A method for retransferring an image formed on an image receiving layer on an image forming material to an image receiving member will be described. As the device, a device having a mechanism such as a laminator is suitable. The device is uniformly heated to a temperature of 80 ° C to 150 ° C, and simultaneously has a linear pressure of 1 ° C.
The pressure is preferably applied at a pressure of at least kg / cm, and in the case of performing the transfer only by applying the pressure, the pressure is preferably applied at a linear pressure of at least 2 kg / cm.

[0027]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. In this example, “parts” means “parts by weight” unless otherwise specified.

[0028]Example 1  100 μm thick biaxially stretched polyethylene terephthalate
Image receiving layer comprising the following composition
Forming solution is dried by wire bar coating method.
Coating was performed so that the thickness became 1.7 μm. Nylon graft polymerized polyolefin 4.0 parts (HYTEC N-2010 (25% solution: manufactured by Toho Chemical) Colloidal silica 30.0 parts (Snowtex S (30% solution) particle size 8 to 11 nm: manufactured by Nissan Chemical) Methanol 33 3.0 parts Water 33.0 parts

Example 2 An image receiving layer forming solution having the following composition was coated on a biaxially stretched polyethylene terephthalate film support having a thickness of 100 μm by a wire bar coating method so as to have a dry film thickness of 1.7 μm. did. Halogenated polyolefin 2.2 parts (Supercron 773H (45% liquid): Nippon Paper) colloidal silica 30.0 parts (Snowtex MEK-ST (30% liquid) particle size 10-20 nm: Nissan Chemical) Toluene 33 .9 parts Methyl ethyl ketone 33.9 parts

Example 3 A solution for forming an image receiving layer having the following composition was coated on a biaxially stretched polyethylene terephthalate film support having a thickness of 100 μm by a wire bar coating method so as to have a dry film thickness of 1.7 μm. did. Nylon graft polymerized polyolefin 4.0 parts (HYTEC N-2010 (25% liquid): Toho Chemical) Colloidal silica 45.0 parts (Snowtex N (20% liquid) particle size 10 to 20 nm: Nissan Chemical) Methanol 25 .5 parts water 25.5 parts

Example 4 An image receiving layer forming solution having the following composition was coated on a biaxially stretched polyethylene terephthalate film support having a thickness of 100 μm by a wire bar coating method so as to have a dry film thickness of 1.7 μm. did. Nylon graft polymerized polyolefin 4.0 parts (HYTEC N-2010 (25% liquid: manufactured by Toho Chemical) Colloidal silica 30.0 parts (Snowtex OL (30% liquid) particle size 40 to 50 nm: manufactured by Nissan Chemical) Methanol 33 3.0 parts Water 33.0 parts

Comparative Example 1 A solution for forming an image receiving layer having the composition of Example 1 was applied to a biaxially stretched polyethylene terephthalate film support having a thickness of 100 μm by a wire bar coating method to give a dry film thickness of 0.7 μm. Coated as follows.

Comparative Example 2 On a biaxially stretched polyethylene terephthalate film support having a thickness of 100 μm, an image receiving layer forming solution having the composition of Example 1 was dried by a wire bar coating method to a dry film thickness of 5.5 μm. Coated as follows.

Comparative Example 3 An image receiving layer forming solution having the following composition was coated on a biaxially stretched polyethylene terephthalate film support having a thickness of 100 μm by a wire bar coating method so that the dry film thickness became 1.7 μm. did. Nylon graft polymerized polyolefin 12.0 parts (HYTEC N-2010 (25% liquid: manufactured by Toho Chemical) Colloidal silica 23.3 parts (Snowtex S (30% liquid) particle size 8 to 11 nm: manufactured by Nissan Chemical) Methanol 32 .3 parts water 32.4 parts

Comparative Example 4 An image receiving layer forming solution having the following composition was coated on a biaxially stretched polyethylene terephthalate film support having a thickness of 100 μm by a wire bar coating method so as to have a dry film thickness of 1.7 μm. did. Nylon graft polymerized polyolefin 16.0 parts (HYTEC N-2010 (25% liquid): Toho Chemical) Colloidal silica 20.0 parts (Snowtex S (30% liquid) particle size 8 to 11 nm: Nissan Chemical) Methanol 32 0.0 parts water 32.0 parts

Comparative Example 5 An image receiving layer forming solution having the following composition was coated on a biaxially stretched polyethylene terephthalate film support having a thickness of 100 μm by a wire bar coating method so as to have a dry film thickness of 1.7 μm. did. Nylon graft polymerized polyolefin 4.0 parts (HYTEC N-2010 (25% liquid): Toho Chemical) Colloidal silica 22.5 parts (Snowtex MP-3040 (40% liquid) particle size 300 ± 30 nm: Nissan Chemical) 36.7 parts of methanol 36.8 parts of water

Using the above-mentioned image forming materials (Examples 1 to 4 and Comparative Examples 1 to 5), the following hot-melt type thermal transfer recording material and thermal transfer recording apparatus of the peeling type, and a laminator as a retransfer apparatus were used. Test. Melt-type thermal transfer recording material: Black MDC-FLCK (Alps Electric) Cyan MDC-FLCC (Alps Electric) Magenta MDC-FLCM (Alps Electric) Yellow MDC-FLCY (Alps Electric) Thermal transfer recording device: Micro dry process printer MD-2000S (manufactured by Alps Electric) Laminator: Star Proof Flaminator SPL-005 (manufactured by Nippon Paper) Roll temperature: 110 ° C Transfer speed: 400 mm / min The evaluation results are shown in Table 1 below.

[0038]

[Table 1]

[0039]

As is clear from Table 1, when the thermal transfer recording method and the image forming material of the present invention are used, in the image recorded by the fusion type thermal transfer recording method, the non-image portion is formed while utilizing the formation of the image receiving body. Thus, a high-quality multicolor image in which only the image portion has high gloss can be formed.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Masahide Takano 1551 Higashidaira, Higashimatsuyama-shi, Saitama, Japan Image Technology Center

Claims (9)

[Claims] 1. A support and a transparent image-receiving layer showing releasability between the support and the support, and the image-receiving layer is formed on the image-receiving layer by a hot-release type thermal transfer recording method. It has an adhesive force with the transfer image to be formed, but uses an image forming material showing releasability between it and the retransfer image receiving member, and the above-mentioned hot-release type melt-type thermal transfer recording uses After performing image recording on the image receiving layer of the above, the surface of the image receiving layer having the transferred image of the image forming material is carried on the image receiving layer for retransfer, and subjected to a heating and / or pressure treatment. After cooling, the image forming material is peeled off from the image receiving member, so that only the image portion on the image receiving layer of the image forming material is retransferred onto the image receiving member together with the image receiving layer portion on which the image portion is formed. In the fusion type thermal transfer recording, characterized in that High gloss image forming method. 2. A multi-color image recording apparatus according to claim 1, wherein the non-image portion of the re-transferred image on the image receiving member has a high gloss by covering only the image portion with a transparent image receiving layer while utilizing the formation of the image receiving member. 2. A method according to claim 1, wherein a high-quality multicolor image is formed. 3. A support and a transparent image-receiving layer showing releasability between the support and the image-receiving layer, and the image-receiving layer is formed on the image-receiving layer by a hot-release type thermal transfer recording. 2. The image forming apparatus according to claim 1, wherein the adhesive layer has an adhesive force with a formed transfer image, but exhibits releasability with a retransfer image receiving body.
Or an image forming material directly used for carrying out the high gloss image forming method in the fusion type thermal transfer recording of 2. 4. The image forming material according to claim 3, wherein the image receiving layer contains at least one resin selected from the group consisting of a water-soluble nylon resin, a copolymer thereof, and a halogenated polyolefin resin. 5. The image forming material according to claim 3, wherein the image receiving layer contains an inorganic or organic fine particle pigment. 6. An image forming material, wherein the fine particle pigment according to claim 5 is colloidal silica. 7. An inorganic or organic fine particle pigment having a particle size of 100
7. The image forming material according to claim 5, wherein the thickness is not more than nm. 8. The image forming material according to claim 5, wherein the weight ratio of the inorganic or organic fine particle pigment to the resin in the image receiving layer is 80/20 to 95/5. . 9. The image forming material according to claim 4, wherein the thickness of the image receiving layer is 1 to 5 μm.