JPH03280055A - Photosensitive thermosensitive recording material - Google Patents

Abstract

PURPOSE:To allow high-speed recording and continuous gradation with low energy and to obtain high-resolution images by forming the latent images of images by light energy and subjecting dyes to color development by thermal transfer to obtain the images. CONSTITUTION:A microcapsule layer 8 formed by dispersing porous microcapsules 3 which contain a dye precursor 4, a polymerizable monomer 5 to be cured by light energy and a photopolymn. initiator 6 and are synthesized by using an interface polymn. method into a binder is constituted on one surface of a base 2. The porous microcapsules 3 transmit the dye precursor contg. therein when impressed with heat energy. The polymerizable monomer 5 can control the transmission quantity of the dye precursor 4 released from the porous microcapsules 3 by a difference in the degree of polymn. by photoirradiation. The thermal transfer is executed on the recording sheet provided with a color developer layer on a base, such as paper, in such a manner, by which the ground fogging is obviated and the continuous gradation is possible. The high-quality image is thus obtd.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a light and heat sensitive recording material that can be used for printers and copying machines as outputs of computers, etc. The present invention relates to a light- and heat-sensitive recording material capable of digital recording.

[Summary of the invention]

In the present invention, a color developer layer in which a color developer that reacts with a dye precursor to develop color from the dye precursor is dispersed in a binder is provided on one side of a support such as paper. A photosensitive method for recording by thermal transfer using a heat-sensitive transfer sheet having a microcapsule layer in which porous microcapsules containing a dye precursor, a polymerizable polymer, and a photopolymerization initiator are dispersed in a binder on a support. It is a heat-sensitive recording material.

The purpose of this is to irradiate this microcapsule layer with visible light or ultraviolet light to draw a latent image, and then thermally transfer it using a heat roller, infrared rays, or the like to obtain a high-quality recorded image that is capable of continuous gradation.

[Conventional technology]

Conventional heat-sensitive recording materials are generally those in which a thermochromic dye is coated on a support such as paper, and the color is developed by heat from a thermal source or the like for recording. Furthermore, carbonless paper is a typical recording material to which microcapsules are applied, and the resolution depends on the pressurized area of a pressurized object such as a ballpoint pen.

In addition, as a recording material that applies light energy and microcapsules, Japanese Patent Application Laid-Open No. 58-88739 and Japanese Patent Application Laid-Open No. 58-17432 disclose a photosensitive and pressure-sensitive recording sheet that uses light to create a latent image of an image using high pressure. By destroying the microcapsules, the contents of the microcapsules are released, and the dye reacts with a color developer to develop color and produce an image.

Further, in Japanese Patent Application Laid-Open No. 60-214990, after an image is formed by heat, the image is fixed and recorded by curing the photocurable resin inside the uncolored microcapsules with light energy.

[Problem to be solved by the invention]

With conventional recording materials using thermochromic dyes, it is difficult to express gradation without using a pseudo gradation method such as a dither method, and natural color development of the dye has been a problem during long-term storage.

In addition, with angry light pressure-sensitive recording sheets, since the microcapsules are destroyed by high pressure, there are problems such as unevenness in the image due to uneven pressure in the pressurized area, an increase in the size of the device, and the inability to record at high speed. Ta. In the fixing type using light energy, the resolution of the image depends on the heating element that is the thermal energy source, so there is a problem that a high-resolution image cannot be obtained.

[Means to solve the problem]

In order to solve the above problems, in the present invention, a latent image of an image is formed using light energy, and the dye is colored by thermal transfer to obtain an image, thereby enabling high-speed recording, continuous gradation, and high resolution with low energy. The purpose of the present invention is to provide a light- and heat-sensitive recording material that can produce images of high quality.

[Effect]

The porous microcapsules of the photosensitive and thermosensitive recording material of the present invention contain a dye precursor and a polymerizable monomer,
Depending on the degree of polymerization of the polymerizable monomer in the porous microcapsules due to light irradiation, the amount of dye precursor that permeates through the porous microcapsules is controlled, making it possible to express continuous gradations.

Therefore, the light and heat sensitive recording material of the present invention is irradiated with ultraviolet or visible light corresponding to an image signal from a CRT or the like, and a latent image corresponding to the image signal is formed on the polymerizable layer, and a heat roller or a thermal head Alternatively, an amount of dye precursor corresponding to the image signal is transmitted through the porous microcapsule by heat from infrared rays, etc., and transferred to the recording sheet, where it reacts with the color developer in the color developer layer to develop color, producing continuous gradation and high resolution. Image recording of image quality is achieved.

〔Example〕

This will be explained below based on the drawings. FIG. 1 is a schematic cross-sectional view showing a heat-sensitive transfer sheet in the present invention. FIG. 2 is a schematic cross-sectional view showing the exposure state of the heat-sensitive transfer sheet, and FIG. 3 is a schematic cross-sectional view showing the heat-sensitive transfer state. In the present invention, polyethylene terephthalate (
Porous microcapsules 3 containing a dye precursor 4, a polymerizable monomer 5 that is cured by light energy, and a photopolymerization initiator 6 on one side of a support 2 such as PET) film and synthesized using an interfacial polymerization method. The structure includes a microcapsule layer 8 in which is dispersed in a binder.

Here, the porous microcapsules 3 have the effect of transmitting the dye precursor contained therein by applying thermal energy, and the polymerizable monomer 5 contained in the porous microcapsules 3 is irradiated with light. Since the amount of permeation of the dye precursor 4 released from the porous microcapsules 3 can be controlled by the difference in the degree of polymerization, this has the effect of controlling the amount of permeation of the dye precursor 4 depending on the irradiated light energy.

When the microcapsule layer 8 is irradiated with irradiation light 9 such as ultraviolet rays or visible light according to an image signal from a CRT or the like, the polymerizable molecules 5 are polymerized according to the energy and released from the porous microcapsules 3. dye precursor 4
It becomes possible to control the amount of permeation. When heated by the heating element 16, the binder 7 in the microcapsule layer 8
is melted, and the dye precursor 4 whose permeation amount is controlled depending on the degree of polymerization of the polymerizable monomer 5 is released from the porous portion of the porous microcapsule 3, and the dye precursor 4 is released from the porous portion of the porous microcapsule 3, and the dye precursor 4 is released from the porous portion of the porous microcapsule 3, and the dye precursor 4 is released from the porous portion of the porous microcapsule 3. It is transferred to layer 12 and reacts with color developer II in the color developer layer to develop color. Therefore, color development of the dye corresponding to the energy amount of the irradiated light 9 is observed in the color developer layer 12, and a continuous gradation high-quality image is recorded.

Examples of the constituent materials of the film of the porous microcapsule using the interfacial polymerization method in the present invention include polyamide, polyester, polyurea, polyurethane, and the like.

As constituent compounds of these porous microcapsule films, examples of polycarboxylic acid chloride include malonyl dichloride, succinic acid dichloride, glutaric acid chloride, adipoyl chloride, sebacoyl chloride, fumaryl chloride, itaconyl chloride, terephthalic acid chloride,
Compounds such as phthaloyl chloride, isophthaloyl chloride, 1.3-naphthoic acid chloride, and 4.4°-biphenyl-dicarboxylic acid chloride can be used. Further, as the carboxylic acid anhydride, compounds such as maleic anhydride, benzoic anhydride, and pyromellitic dianhydride, which are dehydrated condensates of two carboxylic acid molecules or dicarboxylic acids, can be used. As the polyvalent amine, 1,2-diaminopropane,
1,3-diaminopropane, 1,4-diaminobutane,
1.5-Diaminopenkune, L, 6-cyaminohexane, 12-diaminocyclohexane, 1,7-diaminooctane, 1,8-diaminooctane, 1,9-diaminononane, 1.10-diaminodecane, 112- Diaminododecane, 1,2-diamino-2methylpropane,
3,3“-diamino-N-methyldipropylamine,
1.8-Methanediamine, 4.4'-ethylene-di-m-)luidine, 24, 6. -trimethyl-1,3-
phenylenediamine, 2,3,5.6-tetramethyl-
1,4=phenylenediamine, 2.4-diaminotoluene, 2.6-diaminotoluene, 3,4-diaminotoluene, 2,6-diaminotoluene, 1.2
-Dianilinoethane, 4,4° -methylene dianiline, 2,7-diaminotoluene, 37-diamino-2-methoxyfluorene, 1,5-diaminonaphthalene, 1,
8-diaminonaphthalene, 2,3-diaminonaphthalene, 3,4-diaminohensiphenone, 1,2-diaminoanthraquinone, 1,4-diaminoanthraquinone, 2
゜6-diaminoanthraquinone, 3,5-diamino 12
．． 4-4 lyazole, 2,3-diaminopyridine, 2,
6-diaminopyridine, 3,4-diaminopyridine, 4
．． 5-diaminopyridine, 4.5-diaminopyrimidine, 4.6-diamin2-mercaptopyrimidine, 5,
6-diamino 1,3-dimethyluracil hydrate, diaminomaleonitrile, 9. Examples include lO-diaminophenanthrene, dimethylenetriamine, 2.4.6-)riaminopyrimidine, 4,5.6-)riaminopyrimidine, and trianterene. As polyvalent isocyanate,
m-phenylene diisocyanate, p-phenylene diisocyanate, 26-tolylene diisocyanate, 2.
44 lylene diisocyanate, naphthalene-1,4-diidisocyanate, diphenylmethane-4,4°-diisocyanate, 3,3゛ dimethoxy-4,4゛-biphenyl diisocyanate, 3,3°-dimethyldiphenylmethane-4,4°-diisocyanate , xylylene-1,4-diisocyanate, 4.4°-diphenylpropane diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanate, butylene-1,2-diisocyanate, ethyridine diisocyanate, cyclohexylene-1 , 2-cyidicyanate, cyclohexylene-1,4-diisocyanate, 4,4°-methylenebiss(cyclohexyl isocyanate), isophorone diisocyanate, trimethylhexamethylene diisocyanate, 1.3-(isocyanatomethyl)cyclohexane, 1.4- (Methyl isocyanate)cyclohexane, p-4°4',4''-triphenylmethane triisocyanate, toluene-2,4,6-)cyidicyanate, polymethylene polyphenylisocyanate, 4.
4°-dimethyldiphenylmethane-2,23,3゛-
In addition to tetraisocyanate and the like, compounds having the following structures can also be used.

Further, as polyhydric alcohols, 1,2-butanediol, 1.3-butanediol, 1.4-butanediol, 2.3-butanediol, 1.5bentanediol,
2,4-bentanediol, 2-methyl-2,4-bentanediol, 3-methyl-1,5-bentanediol, 2,2,4-trimethyl-1,3-bentanediol, 1,6-hexanediol , 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octanediol, 12.6-hexanediol, and the like.

Examples of leuco dyes used as pigments for expressing images include crystal violet lactone, rhodamine B lactam, malachite green, and 3-dialkylamino-7-
Examples include dialkyl amyl fluorane and benzoyl leucomethylene blue.

Color developers for coloring the leuco dye include aromatic carboxylic acid metal salts such as salicylic acid and its derivatives, clays such as acid clay, activated clay, and bentonite;
Phenol compounds such as α-naphthol, β-naphthol, bisphenol A, etc. can be used.

As the binder, polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, styrene-butadiene latex, etc. can be used.

As the polymerizable monomer, a monomer having at least two or more ethylenically unsaturated groups in the molecule or a polymer having ethylenically unsaturated properties at the terminal or side chain can be used. Compounds included in these include polyesters having acrylate or methacrylate terminals, epoxy resins having acrylate or methacrylate terminals, and acrylic esters or methacrylic esters of polyhydric alcohols. Specifically, the compounds included in these include diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate,
Triethylene glycol dimethacrylate, tripropylene glycol diacrylate, tripropylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate,
Hexanediol diacrylate, hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolbroban trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate ,
In addition to dipentaerythritol hexamethacrylate, ethylcarpitol acrylate, ethylcarpitol methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, and the like, the following acrylates can be mentioned.

-8 A-+M-Nh+M-A, A-4X-Y+-
nX-A Here, A: diacrylic acid, M: dihydric alcohol, N: dibasic acid, X: polyhydric alcohol, Y: polybasic acid.

As the photopolymerization initiator, quinone, acyloin, diazoanthrone, diazonium salt, diazophenanthrone, disulfide, aromatic azide, aromatic ketone, aromatic azosulfonate, aromatic carbazide, etc. can be used.

Examples of the present invention are shown below, but the present invention is not limited thereto.

(Preparation of recording sheet) For the color developer side, use a color developer solution in which 20 parts by weight of each of bisphenol A and silica powders are dispersed in an aqueous solution of 5% (W/W) polyvinyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) using a ball mill. was coated onto a support such as paper using a bar coater (Bar Coater #20 manufactured by Yoshimitsu Seiki Co., Ltd.) to prepare a recording paper.

(Example 1) 1.4 parts by weight of a leuco dye that develops a magenta color was dispersed for 24 hours in 25 parts by weight of a photoresist resin Aronix 309 (Toagosei Chemical Department) using a ball mill. Separately, 5 parts by weight of terephthalic acid dichloride as capsule membrane monomer 1 and 0.75 parts by weight of benzoin methyl ether as a photopolymerization initiator were dissolved in 25 parts by weight of diisopropylnaphthalene as oil. Add to this the dispersion in which the leuco dye was previously dispersed using a ball mill, and
Capsule inclusions were created. Furthermore, this liquid was added to 3% (W/
W) polyvinyl alcohol (Kuraray Bovar 224)
It was mixed with an aqueous solution and emulsified and dispersed using a homogenizer. This emulsified dispersion was cooled with ice water and continued to be stirred with a mechanical stirrer. When the emulsified dispersion reaches a temperature equivalent to that of ice water, the capsule monomer 2 is 2.93
An aqueous solution containing parts by weight of diethylenetriamine and 3 parts by weight of sodium carbonate as a neutralizing agent was added.

Interfacial polymerization was carried out in this state for about 24 hours to obtain a capsule dispersion solution, and porous microcapsules were obtained by filtration.

5% of the same amount of porous microcapsules synthesized in this way
(W/W) Polyvinyl alcohol (Kuraray Bovar 11
7) It was dispersed in an aqueous solution and coated on a PET film using a bar coater to obtain a heat-sensitive transfer sheet.

Characteristics of the prepared photosensitive window thermal recording paper were evaluated using a 300W xenon short arc lamp (manufactured by Ushio ITS: UYX-3).
00) is used to irradiate the thermal transfer sheet to form a latent image using a thermal hand printing device (manufactured by Taishoku Denki: TH-Ml).
) was used to perform thermal transfer onto a recording sheet, and the resulting image was used.

As a result, an image was formed on the recording sheet according to the light irradiation time, and continuous gradation recording was also possible. In addition, in areas where color development was not required, the polymerizable monomer was cured by light irradiation and the dye was in a state where no color development occurred, so it was possible to obtain a good image without background fading.

(Example 2) The same procedure as in Example 1 was carried out using 5.32 parts by weight of Millionaire MT (Japan Polyurethanes) as the capsule membrane monomer I and 2.20 parts by weight of diethylenetriamine as the capsule membrane monomer 2. Porous microcapsules were synthesized by a method (in this case, no neutralizing agent was required) and coated on a PET film to prepare a heat-sensitive transfer sheet.

As a result of examining the characteristics against light irradiation, Example 1
Similarly, continuous gradation recording was possible and high quality images could be obtained.

(Example 3) Using the cyan-colored leuco dye in Example 2, Sumidur N was added as the capsule membrane monomer 1.
Porous microcapsules were synthesized in the same manner as in Example 2 using 9.744 parts by weight of 3200 (manufactured by Bayer Urethane) and 2.45 parts by weight of hexamethylene diamine as the capsule membrane monomer 2, and then placed on a PET film. It was coated to make a heat-sensitive transfer sheet.

As a result of examining the characteristics with respect to light irradiation, we were able to obtain high-quality images with continuous gradation recording, similar to the previous example.

(Example 4) A leuco dye that develops a yellow color was used,
The mixture was dispersed for 24 hours using a ball mill in 25 parts by weight of trimethylolpropane trimethacrylate as a photosensitive resin. Further, porous microcapsules were synthesized in the same manner as in Example 2, except that 25 parts by weight of Aroninx 309 was used as the oil, and coated on a PET film to form a heat-sensitive transfer sheet.

As a result of examining the characteristics with respect to light irradiation, it was possible to perform continuous gradation recording and obtain high-quality images as in the other examples.

(Example 5) Porous microcapsules were synthesized in the same manner as in Example 2 using 4.6 parts by weight of dianhydride pyromellitic acid as the capsule membrane monomer 1, and coated on a PET film to form a heat-sensitive transfer sheet. did.

As a result of examining the characteristics against light irradiation, we were able to obtain high-quality images with very little background blur and continuous gradation recording.

〔Effect of the invention〕

In the present invention, a dye precursor, a photopolymerization initiator, and a polymerizable monomer are encapsulated in porous microcapsules synthesized by an interfacial polymerization method on a support such as PP or T film, and porous microcapsules are dispersed in a binder. By thermally transferring a heat-sensitive transfer sheet with a capsule layer to a recording sheet with a color developer layer on a support such as paper, we can produce high-quality light and heat-sensitive recording materials with no background fog and continuous gradation. can be provided.

[Brief explanation of drawings]

FIG. 1 shows a schematic cross-sectional view of the leisurely transfer sheet of the present invention, FIG. 2 is a schematic cross-sectional view showing the exposure state of the heat-sensitive transfer sheet of FIG. 1, and FIG. FIG. 3 is a schematic cross-sectional view showing a state of thermal transfer in a material. 1...Thermal transfer sheet 2...Support 3...Porous microcapsules 4...Dye precursor 5...Polymerizable monomer 6...Photopolymerization initiator 7 ... Binder 8 ... Microcapsule layer 9 ... Irradiation light 10 ... Photocured microcapsules 11 ...
Color developer 12...Color developer layer 13...Support, color development section 5, recording paper or higher

Claims (4)

[Claims] (1) A color developer layer that reacts with a dye precursor to form a color is provided on one side of a support, and a porous layer containing the dye precursor, a polymerizable monomer, and a photopolymerization initiator is provided on another support. 1. A light- and heat-sensitive recording material, characterized in that a microcapsule layer is prepared by synthesizing quality microcapsules using an interfacial polymerization method and dispersed in a binder, and the dye precursor is colored by thermal transfer. (2) The photosensitive and thermosensitive recording material according to claim 1, wherein the capsule membrane material of the porous microcapsules synthesized by the interfacial polymerization method is selected from among the combinations of compounds shown below. a) A reaction product resulting from a combination of a polyhydric carboxylic acid chloride and a polyhydric amine; b) A combination of a polyhydric carboxylic acid chloride and a polyhydric alcohol. c) Combination of carboxylic acid anhydride and polyvalent amine. d) Combination of polyvalent isocyanate and polyvalent amine. e) Combination of polyhydric isocyanate and polyhydric alcohol. F) Combination of polyvalent isocyanate and water. (3) The light and heat sensitive recording material according to claim 1, wherein the dye precursor is a leuco dye. (4) The light and heat sensitive recording material according to claim 1, wherein the polymerizable monomer is a compound that is crosslinked and cured by light energy.