JPH06115264A - Photothermal conversion type heat mode recording material - Google Patents

Abstract

PURPOSE:To prevent color muddiness due to transfer of a photothermal conversion layer together with an ink layer and to provide excellent color reproducibility by sequentially providing at least a support, a cushion layer, an intermediate layer and the conversion layer in this order in a photothermal conversion type heat mode recording material. CONSTITUTION:A photothermal conversion type head mode recording obtains an ink image by opposing an ink surface of a photothermal conversion type heat mode recording material 3 and an image receiving surface of a photothermal conversion type heat mode image receiving material 4 and irradiating an image pattern with a light. In this recording, the material 3 sequentially has at least a support, a cushion layer, an intermediate layer, a photothermal conversion layer and an ink layer in this order. A thickness of the intermediate layer is set to 0.5mum or less. As the intermediate layer, a material is necessarily so selected that an adhesive powers of the conversion layer, the intermediate layer and the intermediate layer, the cushion layer at the time of ink transferring become larger combination that ink peeling strength at the time of ink transferring.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermal conversion type heat mode recording material capable of obtaining a high-definition image, and more particularly to a recording material requiring faithful color reproducibility.

[0002]

2. Description of the Related Art Conventionally, as thermal transfer recording, a thermal transfer recording material having a heat-meltable coloring material layer or a coloring material layer containing a heat sublimable dye provided on a substrate and an image receiving material are opposed to each other, and a thermal head There is a method of transferring and recording an image by pressing a heat source controlled by an electric signal from a head or the like from the ink sheet side. Thermal transfer recording has features such as noiseless, maintenance-free, low cost, easy colorization, and digital recording, and is used in many fields such as various printers, recorders, facsimiles, computer terminals, and the like.

In recent years, the resolution has been high in the medical and printing fields,
There is a demand for a recording method capable of high-speed recording and so-called digital recording capable of image processing. However, in the conventional thermal transfer recording method using a thermal head or a current-carrying head as a heat source, it is difficult to increase the density in terms of the life of the head heating element.

To solve this problem, thermal transfer recording using a laser as a heat source is disclosed in JP-A-49-15437, 49-17743 and 57.
-87399, 59-143659, etc. In thermal transfer recording using a laser as a heat source, the resolution can be increased by narrowing the laser spot. But,
When recording with a laser, scanning type recording is generally performed, and in terms of recording speed, scanning type recording is slower than batch exposure using a mask material or a recording method using a line head. There is a drawback that.

In order to increase the recording speed, it is necessary to increase the laser scanning speed. As a laser scanning method, a so-called plane scanning method, in which a polygon mirror or a galvanometer mirror and an fθ lens are combined to perform main scanning of laser light, and sub-scanning is performed by moving a recording medium,
Laser exposure is performed while rotating the drum, and there is cylindrical scanning in which the rotation of the drum is the main scan and the movement of the laser light is the sub-scan, but there is little energy loss in the optical system, and cylindrical scanning that enables high-density recording is heat. Suitable for mode recording.

However, another problem arises because the recording medium is fixed on the drum for recording. With the conventional transfer method using a thermal head, it is possible to press the recording medium with the platen to obtain good adhesion, but it is difficult to fix the recording medium and the recording medium to the drum to obtain a sufficient adhesion pressure for transfer. Further pressing from the outside by a contact member can be considered, but it is not realistic in a mechanism that rotates the drum at high speed. Generally, the vacuum contact method is the most effective, but even with this method, sufficient contact pressure cannot be obtained as compared with the conventional thermal head recording method.
Japanese Patent Application 03-343684, 04-142799, 04-228778, 04-22
It is described in 8779 that by providing a cushioning layer on a recording medium or a recording medium, the adhesiveness required for transfer can be obtained even in a vacuum contacting method. Further, for colorization, it is necessary to separate the ink layer and the light-heat conversion layer, but in order to prevent color turbidity, a structure in which the ink layer and the light-heat conversion layer can be completely separated is disclosed in Japanese Patent Application No. 04-94422 and 04-94422. -149472. As a result of repeated studies on a recording medium having a cushion layer, a photothermal conversion layer, and an ink layer on a support as described above, a portion having poor adhesion (that is, a recording medium due to transfer with high energy or dust or unevenness of the support) There is a problem that a heat insulating layer such as air occurs between the recording medium and the recording medium, and the photothermal conversion layer scatters or peels off from the cushion layer at the area where the photothermal conversion layer heats excessively, which adversely affects the color reproducibility. Had. In order to facilitate the separation of the ink layer and the light-heat conversion layer, if the ink layer is made of a solvent-soluble material and the light-heat conversion layer is made of a solvent-insoluble material (such as a water-soluble material), the cushion layer and the light-heat conversion layer will be separated. When the recording medium is peeled from the recording medium, the photothermal conversion layer is partly peeled due to uneven peeling, which also causes color turbidity.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to prevent color turbidity due to transfer of a light-heat conversion layer together with an ink layer and to provide good color reproducibility. In the provision of seats.

[0008]

It has been found that the above object of the present invention can be achieved by the following or the following structure.

In the photothermal conversion type heat mode recording, the ink surface of the photothermal conversion type heat mode recording material and the image receiving surface of the photothermal conversion type heat mode image receiving material are opposed to each other, and an ink image is obtained by irradiating light imagewise. A photothermal conversion type heat mode recording material, which comprises at least a support, a cushion layer, an intermediate layer, a photothermal conversion layer and an ink layer in this order.

The photothermal conversion type heat mode recording material as described in 1 above, wherein the intermediate layer has a thickness of 0.5 μm or less.

The present invention will be described in more detail below.

Description of Each Layer of Photothermal Conversion Heat Mode Recording Material (A) Support Any support may be used as long as it has good dimensional stability and withstands heat during image formation. 63-1
The films or sheets described in 93886, page 2, lower left column, lines 12 to 18 can be used. Further, when the laser light is irradiated from the recording material side to form an image, the support of the recording material is preferably transparent. The support of the recording material need not be transparent as long as laser light is applied from the image receiving material side to form an image. The thickness of the support is not particularly limited, but usually 2 to 300 μm, preferably 5 to 200
μm.

A backing layer may be provided on the back surface of the support (the surface opposite to the surface on which the ink layer is provided) in order to impart functions such as running stability, heat resistance and antistatic property. The backing layer may be a resin such as nitrocellulose dissolved in a solvent, or a binder resin and 20 to 30 μm.
It can be formed by coating the surface of the support with a coating solution for a backing layer in which fine particles of m are dissolved or dispersed in a solvent.

(B) Cushion Layer The cushion layer is provided for the purpose of increasing the close contact between the recording material and the image receiving material. The cushion layer is a layer having thermal softening property or elasticity, and a material that can be sufficiently softened and deformed by heating, a material having a low elastic modulus, or a material having rubber elasticity may be used. Specifically, natural rubber, acrylate rubber, butyl rubber, nitrile rubber, butadiene rubber, isoprene rubber, styrene-butadiene rubber, chloroprene rubber, urethane rubber, silicone rubber, acrylic rubber, fluorine rubber, neoprene rubber, chlorosulfonated polyethylene, Epichlorohydrin, EPDM (ethylene / propylene / diene rubber), elastomers such as urethane elastomers, polyethylene, polypropylene,
Polybutadiene, polybutene, high impact ABS resin, polyurethane, ABS resin, acetate, cellulose acetate, amide resin, polytetrafluoroethylene, nitrocellulose, polystyrene, epoxy resin, phenol-formaldehyde resin, polyester resin, high impact acrylic resin , Styrene-butadiene copolymer,
Resins such as ethylene-vinyl acetate copolymer, acrylonitrile-butadiene copolymer, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, vinyl chloride resin with plasticizer, vinylidene chloride resin, polyvinyl chloride, polyvinylidene chloride Can be mentioned.

Further, these materials may be applied at the time of forming the support so that the support itself has a cushioning property.

The cushion layer may be formed by coating the above material dissolved in a solvent or dispersed in a latex form with a blade coater, roll coater, bar coater, curtain coater, gravure coater, or the like.
An extrusion lamination method using hot melt, a method of laminating a film sheet and a base material, or the like can be applied.

The cushion layer promotes the close contact between the transfer medium and the transfer medium by vacuum softening or by heat softening or decrease in elastic modulus during light irradiation. The preferable thickness of the cushion layer is 1 to 50 μm.

(C) Intermediate layer As the intermediate layer, materials are selected so that the adhesive strength between the photothermal conversion layer and the intermediate layer and between the intermediate layer and the cushion layer during ink transfer is greater than the ink peel strength during ink transfer. There is a need. Generally polyester, urethane,
Conventionally known adhesives such as gelatin can be used. If the intermediate layer is poor in cushioning property and heat softening property, the effect of the cushioning layer is reduced, so it is preferable that the intermediate layer is as thin as possible. It can be said that it is preferable that the intermediate layer is thin, whether it is the room temperature deformation of the cushion layer during vacuum contact or the heat softening of the cushion layer due to heat conduction during light irradiation. However, a certain amount of film thickness is necessary to obtain sufficient adhesiveness. The preferable film thickness is 0.5 μm or less, but it is not limited to this if the intermediate layer fulfills the purpose of the cushion layer.

(D) Photothermal conversion layer The photothermal conversion layer can be provided adjacent to the ink layer.
When the photothermal conversion substance is not substantially transparent, it is desirable to provide a photothermal conversion layer separately from the ink layer in consideration of the color reproducibility of the transferred image.

When a photothermal conversion substance is used, it varies depending on the light source, but a substance that absorbs light and efficiently converts it into heat is preferable. For example, when a semiconductor laser is used as a light source, a substance having an absorption band in the near infrared. Preferred are carbon black, graphite, phthalocyanine dyes, squarylium dyes, croconium dyes, azulenium dyes, nitroso compounds and their metal complex salts, polymethine dyes, dithiol metal complex salt dyes, triarylmethane dyes. Indaniline metal complex dyes, naphthoquinone dyes, anthraquinone dyes and the like can be used. Specifically, JP-A 63-139191 and JP-A 3-1
Examples thereof include compounds described in No. 03476. As the binder in the photothermal conversion layer, a resin having a high glass transition point (Tg) and high thermal conductivity, such as polymethylmethacrylate,
Polycarbonate, polystyrene, ethyl cellulose,
Nitrocellulose, polyvinyl alcohol, polyvinyl chloride, polyamide, polyimide, polyetherimide,
A general heat resistant resin such as polysulfone, polyether sulfone, or aramid can be used. Among these, the water-soluble polymer has good releasability from the ink layer,
It is also preferable in that it has good heat resistance at the time of light irradiation and has less so-called scattering against excessive heating. When a water-soluble polymer is used, it is desirable that the photothermal conversion substance be modified to be water-soluble (by introduction of a sulfo group) or dispersed in water. Among the water-soluble resins, gelatin is preferable because it has less aggregation of the water-soluble infrared absorbing dye, stable coating of the photothermal conversion layer, storage of the recording medium, color turbidity due to aggregation of the infrared absorbing dye, and deterioration of sensitivity. Further, since increasing the peelability between the photothermal conversion layer and the ink layer leads to an improvement in sensitivity, it is effective to incorporate various releasing agents into the photothermal conversion layer. Examples of the release agent include silicone-based release agents (polyoxyalkylene-modified silicone oil, alcohol-modified silicone oil, etc.), fluorine-based surfactants (perfluorophosphate ester-based surfactants), and various other surfactants. Is effective.

The thickness of the photothermal conversion layer is preferably 0.1 to 3 μm, more preferably 0.2 to 1.0 μm. The content of the photothermal conversion substance in the photothermal conversion layer is usually 0.3 to 3.0, more preferably the absorbance at the wavelength of the light source used for image recording.
You can decide to be 0.7-2.5.

The light-heat conversion layer may be formed as a vapor deposition film in addition to the above, and carbon black, gold, silver, aluminum, chromium, nickel, antimony, tellurium described in JP-A-52-20842 can be used. Examples include vapor-deposited layers of metal black such as bismuth and selenium.
The light-heat converting substance may be the color material itself of the ink layer, and is not limited to the above, and various substances can be used.

(E) Ink Layer The ink layer means a layer which is melted or softened when heated and is transferable for each layer containing a coloring material and a binder, and does not need to be transferred in a completely molten state. .

Examples of the coloring material include pigments such as inorganic pigments and organic pigments, and dyes.

Examples of the inorganic pigments include titanium dioxide, carbon black, graphite, zinc oxide, Prussian blue, cadmium sulfide, iron oxide and chromates of lead, zinc, barium and calcium.

The organic pigments include azo-based, thioindigo-based, anthraquinone-based, anthanthrone-based, triphendioxazine-based pigments, vat dye pigments, phthalocyanine pigments (eg copper phthalocyanine) and their derivatives,
Examples include quinacridone pigment. Also, as organic dyes, acid dyes, direct dyes, disperse dyes, oil-soluble dyes,
Examples include metal-containing oil-soluble dyes and sublimable dyes.

The content of the coloring material in the ink layer is not particularly limited, but is usually in the range of 5 to 70% by weight, preferably 10 to 60% by weight.

Examples of the binder for the ink layer include a heat-melting substance, a heat-softening substance, and a thermoplastic resin, and those used in known heat-melting ink materials can be applied as they are.

Specific examples of the heat-fusible substance include vegetable waxes such as carnauba wax, wood wax, auricurie wax and espal wax;
Animal waxes such as beeswax, insect wax, shellac wax and whale wax; petroleum waxes such as paraffin wax, microcrystal wax, polyethylene wax, ester wax, acid wax; and waxes such as mineral wax such as montan wax, ozokerite and ceresin. In addition to these waxes, palmitic acid, stearic acid,
Higher fatty acids such as margaric acid and behenic acid; higher alcohols such as palmityl alcohol, stearyl alcohol, behenyl alcohol, marganyl alcohol, myricyl alcohol, eicosanol; cetyl palmitate,
Higher fatty acid esters such as myricyl palmitate, cetyl stearate, myricyl stearate; acetamide,
Examples include amides such as propionic amide, palmitic acid amide, stearic acid amide, and amide wax; and higher amines such as stearylamine, behenylamine, and palmitylamine. Further, as the thermoplastic resin, ethylene copolymer, polyamide resin, polyester resin, polyurethane resin, polyolefin resin, acrylic resin, vinyl chloride resin, cellulose resin, rosin resin, polyvinyl alcohol resin Resins such as resins, polyvinyl acetal resins, ionomer resins, petroleum resins; natural rubber, styrene butadiene rubber,
Elastomers such as isoprene rubber, chloroprene rubber and diene copolymers; ester gums, rosin maleic acid resins, rosin phenol resins, rosin derivatives such as hydrogenated rosins; and phenol resins, terpene resins, cyclopentadiene resins, aromatic hydrocarbons Examples thereof include polymer compounds such as resins. By appropriately selecting the heat-meltable substance and the thermoplastic substance, a heat-softenable ink layer having a desired heat-softening point or heat-melting point can be formed. Primary transfer to a smooth image receiving sheet,
Furthermore, it is also possible to secondarily transfer only the ink image to the desired rough paper (printing paper = art paper, coated paper, high-quality paper, etc.), in which case a styrene / (meth) acrylic acid (ester) resin is used as the ink. Used as a layer binder (Patent application
If a polyolefin-based elemental image-receiving layer is used as the image-receiving layer, the primary transfer sensitivity is high and the secondary transfer of images can be performed with high efficiency (Japanese Patent Application No. 04-142801).

As other additives, a plasticizer for increasing sensitivity by plasticizing the ink layer, a surfactant for improving coatability of the ink layer, a submicron to a micron for preventing blocking of the ink layer are added. It is possible to add order particles (matting material).

The preferable thickness of the ink layer is 0.2 to 2 μm, more preferably 0.3 to 1.5 μm. (F) Image Receiving Sheet It is desirable that the image receiving sheet also has a support and a cushion layer as in the ink sheet (light-heat conversion heat mode recording material) described above. An image receiving layer is provided on the cushion layer to form an image receiving sheet. It is desirable that the support has excellent dimensional stability. The cushion layer can be made of the same material as the ink layer, but its function is slightly different. The function of improving the adhesiveness by elastically (plastically) deforming at the time of vacuum contact is the same as that of the ink sheet, but in order to be thermally deformed at the time of light irradiation, heat conduction is performed to the cushion layer via the ink layer and the image receiving layer. Therefore, it is slightly disadvantageous as compared with the ink sheet cushion layer. Therefore, the cushion layer of the image receiving sheet is preferably a resin having a lower softening temperature. Specifically, the softening point is 150
A thermoplastic resin or a thermoplastic elastomer having a temperature of ℃ or less is preferable. When the image is once transferred to the intermediate transfer image-receiving sheet and retransferred to the rough paper by laminating or the like, the cushion layer needs to be heat-softened at the laminating temperature and have a film thickness equal to or larger than the unevenness of the rough paper. For the image receiving layer, a resin having a good affinity with the ink binder is preferable, and a resin that can be used as the ink layer binder can be used as it is. It is preferable that the thickness of the image receiving layer is as thin as not to impair the function of the cushion layer. Specifically, it is 5 μm or less, but it is not limited to this when the image receiving layer has a cushion layer function. When only the ink image is secondarily transferred to the rough paper, the above-mentioned ink layer binder and image receiving layer binder may be used. When the ink image is secondarily transferred to the rough paper together with the image receiving layer, a peeling layer may be provided between the image receiving layer and the cushion layer in order to efficiently perform the secondary transfer. In order to obtain running property, antistatic property, antiblocking property, and good coating property, it is possible to use the same technique described for the ink sheet.

Preparation of ink sheet and image receiving sheet, image formation

[0033]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 (Preparation of Ink Sheet) A 75 μm thick transparent PET (polyethylene terephthalate, T-100 made by Diamond Foil Hoechst) was sequentially coated with a cushion layer, an intermediate layer, a photothermal conversion layer and an ink layer having the following compositions. It was processed into an ink sheet. The coating was performed with a wire bar.
(The solvent remains the same).

Cushion layer-> coated so that the dry film thickness is 5 μm Polyester (Toyobo, Byron 200) 30 parts Surfactant (Sumitomo 3M, FC-431) 0.3 part Ethyl acetate 56 parts Toluene 14 parts Intermediate layer-> Dry film thickness Coated to a thickness of 0.15 μm Polyester (Reciprocal Chemistry, Pluscoat Z-446) 5 parts Ethanol 50 parts Water 50 parts Photothermal conversion layer Gelatin 64 parts Saponin 3 parts Citric acid 0.5 parts Glyoxal (hardener) 0.3 parts Sodium acetate 3 Part IR absorbing dye (IR-1) 30 parts water 93.0 parts

[0036]

[Chemical 1]

This was applied so that the absorbance at 830 nm was 1.0. The dry film thickness was about 0.25 μm.

Ink layer Magenta pigment MEK dispersion 40 parts Styrene / acrylic resin (Sanyo Kasei, SBM100) 48 parts EVA (Mitsui DuPont Polychemical, EV40Y) 5 parts DOP (dioctyl phthalate) 3 parts Fine particles (Toshiba Silicone, Tospearl 108 ) 3 parts Surfactant (Asahi Glass, S-382) 1 part MEK (methyl ethyl ketone) 1900 parts Cyclohexanone 100 parts The dry film thickness was 0.4 μm.

(Preparation of image receiving sheet) Transparent PET with a thickness of 75 μm
(Above, T-100) EVA (above, P1407C) is laminated to a thickness of 30 μm, and the base is coated with an image receiving layer coating solution having the following composition, and a dry film thickness of 1 μm is applied. The image receiving sheet was used.

Styrene / acrylic resin (Sanyo Kasei, SBM100) 92 parts EVA (Mitsui DuPont Polychemical, EV40Y) 5 parts Fine particles (Toshiba Silicone, Tospar 108) 3 parts MEK (methyl ethyl ketone) 700 parts Cyclohexanone 200 parts (thermal transfer) Above The ink layer of the ink sheet and the image-receiving layer of the image-receiving sheet are faced to each other and wound around a drum, vacuum-contacted at 200 Torr, and irradiated with a semiconductor laser having an oscillation wavelength of 830 nm to irradiate 33 m
When exposure was performed under the condition of W, 1 / e ² = 6 μm and the ink sheet was peeled from the image receiving sheet, transfer was possible with a sensitivity of 200 mJ / cm 2. This image had no light-heat conversion layer attached and had no color turbidity. This image is 150 ℃ for art paper
It was possible to completely transfer the entire image-receiving layer by laminating with.

Comparative Example 1 When the same procedure as in Example 1 was carried out except that the intermediate layer was not provided, the sensitivity was almost the same, but due to the unevenness of the image-receiving layer cushion layer, there was poor adhesion to the ink sheet, In the portion where the laser light intensity is high (the central portion of the beam), the photothermal conversion layer was scattered, causing color turbidity. Further, when the ink sheet was peeled from the image receiving layer, if uneven peeling occurred, the photothermal conversion layer peeled from the cushion layer, resulting in color turbidity.

[0042]

According to the present invention, it is possible to provide an ink sheet which can prevent color turbidity due to transfer of the photothermal conversion layer together with the ink layer and can provide good color reproducibility.

[Brief description of drawings]

FIG. 1 is a perspective view showing winding of a photothermal conversion type heat mode image receiving material and a recording material according to the present invention around a drum-shaped decompressor.

FIG. 2 is an overall configuration diagram showing a drum-shaped decompressor and the periphery of the decompressor.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Pressure roll 2 Decompression hole (2-1 shows an open state, 2-2 shows a closed state) 3 Heat mode recording material (3-1 is yellow, 3-2
Is magenta, 3-3 is cyan, and 3-4 is black recording material) 4 Heat mode image receiving material 5 Heat mode recording material replenishing means 6 Heat mode image receiving material replenishing means 7 Decompressor holding part 8 Optical writing means 9 Casing body

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Koichi Nakatani Konica Stock Company, Hino City, Hino City, Tokyo 1 (72) Inventor Sota Kawakami 1, Konica Stock Company, Sakura City, Hino City, Tokyo

Claims (2)

[Claims] 1. A photothermal conversion type heat mode recording in which an ink image is obtained by irradiating imagewise light with the ink surface of the photothermal conversion type heat mode recording material and the image receiving surface of the photothermal conversion heat mode image receiving material facing each other. The photothermal conversion heat mode recording material, wherein the photothermal conversion heat mode recording material has at least a support, a cushion layer, an intermediate layer, a photothermal conversion layer and an ink layer in this order. 2. The light-heat conversion heat mode recording material according to claim 1, wherein the thickness of the intermediate layer is 0.5 μm or less.