JPH03280057A - Photosensitive thermosensitive recording material - Google Patents

Abstract

PURPOSE:To obtain color images having continuous gradation and high quality by a simple method by providing a microcapsule layer contg. specific porous microcapsules and recording color images on plain paper. CONSTITUTION:The porous microcapsules 6a to 6c of respective colors are irradiated with light of respective photosensitive wavelengths according to image signals. The porous microcapsules 6a to 6c of the respective colors of the parts irradiated with the respective photosensitive wavelengths are cured by corresponding to the respective photosensitive wavelengths. The inclusions are released through the fine pores of the films of the porous microcapsules 6a to 6c by the impression of heat. Further, the degree of polymn. of a polymerizable monomer is controlled by controlling the intensity of the irradiation with the light of the respective photosensitive wavelengths, by which the amt. of the inclusions to be released of the porous microcapsules 6a to 6c is controlled. The dyes 7a to 7c of the respective colors in the released inclusions in the microcapsules of the respective colors are transferred onto the plain paper by using a thermal head, heat roller, etc. The high-grade color images are thus recorded on the plain paper.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a light and heat sensitive recording material, and in particular a light and heat sensitive recording material that is capable of recording high quality color images on plain paper using a simple developing method. It is related to.

[Summary of the invention]

In recent years, with the development of the information industry, there has been a growing demand for image recording to obtain color recording from information equipment terminals in a simple manner.

In the present invention, a polymerizable monomer and a photopolymerization initiator and a dye that initiate the polymerization of the polymerizable monomer by visible light energy are included as main components on a support, and the portion irradiated with light is cured. The unexposed areas are then thermally exposed by forming a latent image using visible light using a light- and heat-sensitive recording material provided with a microcapsule layer containing porous microcapsules whose contents can be released by application of heat. The purpose is to transfer the dye onto plain paper using a head, heat roller, etc. to obtain a high-quality color image.

(Prior art) Conventional heat-sensitive transfer sheets are generally made by applying a heat-melt ink in which a colorant is dispersed in a heat-melt binder to a support on a resin film such as polyethylene terephthalate (PET). A coated slow transfer sheet is used, but such a thermal transfer recording sheet can only perform binary recording because the hot melt ink in the heated area melts and peels off from the support. When performing gradation expression, area gradation methods such as dither method and density pattern method were used.

In addition, the electrophotographic color recording method uses a photoreceptor,
Complex elements such as a charging device, a photosensitive device, and each color of toner must be incorporated into a single device, and multiple processes must be repeated.

In addition, recording methods using microcapsules include JP-A-58-88739, JP-A-58-17432, and JP-A-5.
8-23024, JP-A-58-23025, etc., there is a method in which microcapsules are hardened with light, and the microcapsules are destroyed using pressure to release the dye precursor contained therein. .

[Problem to be solved by the invention]

As mentioned above, when using thermal transfer sheets, gradation is expressed using the area VR adjustment method, which not only requires complex signal processing but also reduces resolution, making it difficult to achieve high quality. Unable to record image.

In addition, with electrophotography, the equipment becomes complicated and large.
The recording energy consumed also increased, making it impossible to easily record color images.

Furthermore, in the recording method using microcapsules, a very large pressure is required to destroy the microcapsules during the development process, making the apparatus complicated.

Furthermore, since a large pressure is used, not only the apparatus but also the recording material such as receiving paper on which the image is formed are limited, making it impossible to easily record color images. Furthermore, the receiving paper on which the image is formed must be a special paper coated with a color developer that reacts with a dye precursor to develop color, making it impossible to easily record a color image.

SUMMARY OF THE INVENTION In order to overcome these conventional drawbacks, it is an object of the present invention to provide a light- and heat-sensitive recording material that can produce continuous-tone, high-quality color images in a simple manner.

[Means to solve the problem]

In order to solve the above-mentioned problems, the present invention has a polymerizable monomer and polymerization of the polymerizable monomer on a support of a heat-resistant film of about 10 μm made of polyethylene terephthalate (CPET) using visible light energy of 580 to 78 Qnm. , a blue porous microcapsule encapsulating a blue light polymerization initiator and a blue dye as main components, a polymerizable monomer, and polymerization of the polymerizable monomer.
A red porous microcapsule encapsulating a photopolymerization initiator and a red dye as main components, a polymerizable monomer, and the polymerization of the polymerizable monomer are initiated by visible light energy of 60 to 620 nm. A microcapsule layer containing at least two types of yellow porous microcapsules containing a photopolymerization initiator and a yellow dye as main components, which are initiated by light energy, was provided.

[For production]

Each photosensitive wavelength of the porous microcapsules of each color of the light and heat sensitive recording material obtained as described above (580 to 780 nm for blue porous microcapsules, 460 to 620 nm for red porous microcapsules, and 460 to 620 nm for yellow porous microcapsules) In the case of microcapsules, light of 380 to 520 nm) is irradiated in accordance with the image signal, and the porous microcapsules of each color in the irradiated portion of each photosensitive wavelength are cured in accordance with each photosensitive wavelength. Further, in the unexposed portions of the porous microcapsules of each color, the inclusions can be released by passing through the pores of the film of the porous microcapsules by applying heat. Furthermore, by controlling the irradiation intensity of light of each photosensitive wavelength, the degree of polymerization of the polymerizable monomer can be controlled, and the amount of released substances contained in the porous microcapsules can be controlled. The dyes of each color in the contents of the porous microcapsules released in this way are transferred onto plain paper using a thermal head, heat roller, etc., and a high-quality color image is recorded on the plain paper. I can do it.

〔Example〕

Hereinafter, the present invention will be explained based on the drawings.

FIG. 1 shows a schematic diagram of the porous microcapsule of the present invention. The porous microcapsule has a porous microcapsule membrane 1 having many pores, and the contents contained in the porous microcapsule can be released by heat stimulation. The sensitizer 3 in the porous microcapsule absorbs the sensitive wavelength, reacts with the polymerization initiating species generator 4, generates a polymerization initiating species that polymerizes the polymerizable monomer 5, and polymerizes the polymerizable monomer 5. harden. Furthermore, since the degree of polymerization can be controlled by the energy of the photosensitive wavelength, the amount of inclusions released from the porous microcapsules due to heat can be controlled by the degree of polymerization.

FIG. 2 shows a schematic diagram of the light and heat sensitive recording material of the present invention. The support 10 is made of a heat-resistant resin film of about 10 μm such as polyethylene terephthalate (PET). A structure in which a porous microcapsule layer 9 containing porous microcapsules 6a, 6b, and 6c of each color containing sensitizers 8a, 8b, and 8c that are sensitive to visible light of different wavelengths is provided on this support. It becomes.

FIG. 3 shows a schematic diagram of color transfer recording using the light and heat sensitive recording material 11 of FIG.

In response to an image signal from a CRT or the like, λ1. λ8. The wavelength of λ (λ1: 580
~780nm, λ! ;460-620nm, λ, :
When irradiated with light (380 to 520 nm), the porous microcapsules 6a, 5b, and 5c of each color in the porous microcapsule layer are cured according to the respective wavelengths. The heat-sensitive photosensitive recording material 11 on which a latent image has been formed with visible light is placed so that the receiving paper 13 and the porous microcapsule layer 9 of the light-sensitive heat-sensitive recording material 11 face each other, and the porous microcapsules of the photosensitive heat-sensitive recording material 11 are Uncured porous microcapsules 6a of each color are formed by applying heat from the back side of the layer 9 using a thermal head 14 or the like;
The dyes 7a, 7b, 7c of each color in 6b, 6c pass through the pores of the film of the porous microcapsule, and form colored portions 15a, 15b, 15 of each color corresponding to the image signal on the receiving paper 13.
C is transferred and a color image can be recorded.

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

[Example 1] (Porous Microcapsules) 1.4 parts by weight of Crystal Violeft as a dye was dispersed for 24 hours in 25 parts by weight of trimethylolpropane triacrylate (TMPTA) using a ball mill. In addition, 5 parts by weight of hexamethylene diisocyanate (HMDA) as a porous microcapsule membrane monomer A, and 0.1 part by weight of a complex compound of methylene blue as a sensitizer and triphenyl-n-butylboron as a polymerization initiating species generator. was dissolved in 1 part by weight of N,N,-dimethylformamide (DMF) and added to a dispersion in which crystal violet was dispersed using a ball mill to obtain a porous microcapsule-encapsulating liquid.

This porous microcapsule encapsulating liquid was added to a 3% (W/W) polyvinyl alcohol (Kuraray Bovar 224) aqueous solution, and emulsified and dispersed using a homogenizer. This emulsified dispersion was stirred with a mechanical stirrer, 2.93 parts by weight of diethylenetriamine was added as porous microcapsule membrane monomer B, and aged with stirring for 1 hour to form a porous microcapsule membrane, which was then filtered. Porous microcapsules were obtained by

(Photosensitive and thermosensitive recording material) 5 parts by weight of the porous microcapsules obtained as described above were dispersed in 20 parts by weight of a 5% (W/W) polyvinyl alcohol (Kuraray Bovar 117) aqueous solution, and 8 μm polyethylene as a support was dispersed. It was coated onto terephthalate (PET) using a bar coater to obtain a light and heat sensitive recording material.

A color image was obtained in the following manner using the light and heat sensitive recording material and receiving paper obtained as described above.

The light and heat sensitive recording material was irradiated with light from a 300 W xenon short arc lamp through an ultraviolet cut filter for 1 minute to form a latent image. The porous microcapsule layer of the light- and heat-sensitive recording material on which the latent image has been formed is placed face-to-face with 40 g/m'' high-quality paper, and the image is transferred from the back side of the light- and heat-sensitive recording material using a thermal head printing and recording device. was developed.

As a result, light- and heat-sensitive recording materials can form latent images using visible light and develop using heat, and can also control continuous gradation expression based on light irradiation intensity, making it possible to easily create high-quality images. I was able to get it.

[Example 2] (Blue porous microcapsules) Binasiatool chloride 1.4 as cyan dye
Part by weight was dispersed in 25 parts by weight of trimethylolpropane triacrylate (TMPTA) for 24 hours using a ball mill. Separately, hexamethylene diisocyanate (HM
DA) 5 parts by weight, 0.1 parts by weight of a complex compound of methylene blue as a blue sensitizer and triphenyl-n-butylpolone as a polymerization initiating species generator, into 1 part by weight of N,N,-dimethylformamide (DMF). The dissolved material was first added to a dispersion of binaciatool chloride in a ball mill to form a liquid containing porous microcapsules. 3% (W/W) of this porous microcapsule enclosing liquid A
) was added to an aqueous solution of polyvinyl alcohol (Tararebovar 224) and emulsified and dispersed using a homogenizer. This emulsified dispersion was stirred with a mechanical stirrer, 2.93 parts by weight of diethylenetriamine was added as porous microcapsule membrane monomer B, and aged under stirring for 1 hour to form a porous microcapsule membrane, which was then filtered. Blue porous microcapsules were obtained.

(Red Porous Microcapsules) 1.4 parts by weight of pararosaniline as a magenta dye was dispersed for 24 hours in 25 parts by weight of trimethylolpropane triacrylate (TMPTA) using a ball mill. In addition, 5 parts by weight of hexamethylene diisocyanate (HMDA) as a porous microcapsule membrane monomer A, and 0.1 part by weight of a complex compound of safranin as a red sensitizer and triphenyl-n-butylporone as a polymerization initiating species generator. Parts are N, N, -dimethylformamide (
DMF) was dissolved in 1 part by weight and added to a dispersion in which valarozaniline was dispersed in a ball mill to obtain a porous microcapsule encapsulating liquid B. This porous microcapsule enclosing liquid B was added to a 3% (W/W) polyvinyl alcohol (Kuraray Bovar 224) aqueous solution and emulsified and dispersed using a homogenizer. While stirring this emulsified dispersion with a mechanical stirrer, 2.93 parts by weight of diethylenetriamine was added as porous microcapsule membrane monomer B.
Aging with stirring was performed for 1 hour to form a porous microcapsule membrane, and red porous microcapsules were obtained by filtration.

(Yellow porous microcapsules) 701.4 parts by weight of Orami as a yellow dye was dispersed for 24 hours in 25 parts by weight of trimethylolpropane triacrylate (TMPTA) using a ball mill.

Separately, 5 parts by weight of hexamethylene diisocyanate (HMDA) as porous microcapsule membrane monomer A, a complex compound of acridine yellow as a red sensitizer and triphenyl-n-butylboron as a polymerization initiating species generator. 0.1 part by weight of N,N,-dimethylformamide (DMF>1 part by weight) was dissolved and added to a dispersion in which Auramine 0 was dispersed in a ball mill to obtain a porous microcapsule encapsulating liquid C.

3% (W/W) of this porous microcapsule encapsulating liquid C
The mixture was added to an aqueous solution of polyvinyl alcohol (Kuraray Bovar 224) and emulsified and dispersed using a homogenizer. This emulsified dispersion was stirred with a mechanical stirrer, 2.93 parts by weight of diethylenetriamine was added as porous microcapsule membrane monomer B, and aged under stirring for 1 hour to form a porous microcapsule membrane, which was then filtered. yellow porous microcapsules were obtained.

(Photosensitive and thermosensitive recording material) 5 parts by weight of the porous microcapsules of each color obtained as described above were dispersed in 20 overlapping parts of a 5% (W/W) polyvinyl alcohol (Kuraray Bovar 117) aqueous solution, and used as a support. This was coated onto 8 μm polyethylene terephthalate (PET) using a bar coater to obtain a light and heat sensitive recording material.

A color image was obtained in the following manner using the light and heat sensitive recording material and receiving paper obtained as described above.

Light from a 300W xenon shield lamp is applied to the light and heat sensitive recording material using an optical filter that transmits 650 nm light to the blue porous microcapsules, and a 550 nm light transmittance to the red porous microcapsules. Optical Filter The yellow porous microcagucell was subjected to spectroscopy using an optical filter that transmits 450 nm light according to the color image, and was irradiated for 1 minute to form a latent image. The porous microcapsule layer of the light and heat sensitive recording material tq on which this latent image has been formed is placed face to face with 40 g/m'' high quality paper, and a thermal hefed printing device is used to transfer color from the back side of the light and heat sensitive recording material. , a color image was developed.

As a result, photosensitive and thermosensitive recording materials can control color separation based on photosensitive wavelength and continuous gradation expression based on light irradiation intensity.
We were able to obtain high-quality color images using a simple method.

〔Effect of the invention〕

As described above, the present invention involves initiating the polymerization of a polymerizable monomer and the polymerizable hexamer on a heat-resistant film support of about 10 μm made of polyethylene terephthalate (PET) using visible light energy. Using a light- and heat-sensitive recording material provided with a microcapsule layer containing at least two types of porous microcapsules containing a photopolymerization initiator and a dye as main components, visible light of each sensitive wavelength is emitted in response to an image signal. By irradiation, the porous microcapsules of each color in the irradiated portion of each photosensitive wavelength are cured corresponding to each photosensitive wavelength. Further, in the unexposed portions of the porous microcapsules of each color, the inclusions can be released by passing through the pores of the film of the porous microcapsules by applying heat. Furthermore, by controlling the irradiation intensity of light of each photosensitive wavelength, the degree of polymerization of the polymerizable monomer can be controlled, and the amount of released substances contained in the porous microcapsules can be controlled. The dyes of each color in the contents of the porous microcapsules released in this way are transferred onto receiving paper using a thermal head, heat roller, etc., and a high-quality color image is recorded on plain paper. It is possible to provide a light- and heat-sensitive recording material that can.

[Brief explanation of the drawing]

FIG. 1 shows a schematic diagram of a porous microcapsule of the present invention, and FIG. 2 shows a schematic diagram of a light and heat sensitive recording material using the porous microcapsule of FIG. Further, FIG. 3 shows a schematic diagram of color transfer recording using the light and heat sensitive recording material shown in FIG. 1... Porous microcapsule membrane 2... Dye 3... Sensitizer 4... Polymerization initiating species generator 5... Polymerizable monomer 6a... Porous microcapsule sensitive to wavelength λ1 6b.
・Porous microcapsules 6C sensitive to wavelength λ8...Porous microcapsules 7a sensitive to wavelength λ...Cyan dye 7b...Magenta dye 7C...Yellow dye 8a...Sensitive to wavelength λ1 Sensitizer 8b...wavelength λ, bad sensitivity photosensitizer 8C...wavelength λ, bad sensitivity photosensitizer 9...porous microcapsule layer 2a 2b 2c 13 14 5a 5b 5c ・Support, photosensitive and thermosensitive Recording material - Cured porous microcapsules sensitive to wavelength λ1 - Cured porous microcapsules sensitive to wavelength λ and ills - Cured porous microcapsules sensitive to wavelength λ3 - Receiving paper - Thermal head heating element - Cyan color transfer section - Magenta color transfer area/yellow color transfer area and above

Claims (5)

[Claims] (1) A polymerizable monomer and a photopolymerization initiator and a dye that initiate the polymerization of the polymerizable monomer using visible light energy are included as main components on the support, and the portions irradiated with light are cured and the unused portions are cured. In the exposed area, inclusions can be released through the porous pores of the film by applying heat, and the degree of polymerization in the area irradiated with light can be controlled by controlling the intensity of light irradiation. 1. A light- and heat-sensitive recording material, characterized in that it is provided with a microcapsule layer containing porous microcapsules that can control the amount of material released, and is capable of recording color images on plain paper. (2) A photopolymerization initiator is a compound that itself undergoes a chemical change due to light energy and generates polymerization initiation species.
Alternatively, it is composed of a sensitizer that undergoes a chemical change due to light energy and a polymerization initiation species generator that reacts with the chemically changed sensitizer to generate polymerization initiation species, and has a photosensitive wavelength of 580 to 780 nm. 2. The light and heat sensitive recording material according to claim 1, wherein a blue polymerization initiator is used. (3) Photopolymerization initiators are compounds that themselves undergo chemical changes due to light energy and generate polymerization initiation species;
Alternatively, it is composed of a sensitizer that undergoes a chemical change due to light energy and a polymerization initiation species generator that reacts with the chemically changed sensitizer to generate polymerization initiation species, and has a photosensitive wavelength of 460 to 620 nm. 2. The light and heat sensitive recording material according to claim 1, wherein a red polymerization initiator is used. (4) Photopolymerization initiators are compounds that themselves undergo chemical changes due to light energy and generate polymerization initiation species;
Alternatively, it is composed of a sensitizer that undergoes a chemical change due to light energy and a polymerization initiation species generator that reacts with the chemically changed sensitizer to generate polymerization initiation species, and has a photosensitive wavelength of 380 to 520 nm. 2. The light and heat sensitive recording material according to claim 1, wherein a yellow polymerization initiator is used. (5) A photopolymerization initiator is a compound that itself undergoes a chemical change due to light energy and generates polymerization initiation species;
Alternatively, it is composed of a sensitizer that undergoes a chemical change due to light energy and a polymerization initiation species generator that reacts with the chemically changed sensitizer to generate polymerization initiation species, and has a photosensitive wavelength of 580 to 780 nm. A blue polymerization initiator with a photosensitive wavelength of 460 to 620 nm, a red polymerization initiator with a photosensitive wavelength of 3
A yellow polymerization initiator having a wavelength of 80 to 520 nm, and at least two different porous microcapsules containing different polymerization initiators having different photosensitive wavelengths separated by at least 50 nm or more are separated from each other by 50 nm or more. The light and heat sensitive recording material according to claim 1, characterized in that it contains at least one type of light and heat sensitive recording material.