JPH043065A - Photosensitive and thermosensitive transfer sheet - Google Patents

Abstract

PURPOSE:To allow the formation of high-grade color images on a body to be transferred for which special processing is not required by using porous microcapsules contg. a polymerizable monomer, a photopolymn. initiator and a dye precursor as essential components. CONSTITUTION:A porous microcapsule layer formed by dispersing the polymerizable monomer 3, the photopolymn. initiator 2 and the dye precursor 4 as the essential components into a binder contg. color developers is formed on a base. The object to be transferred is brought into contact with the porous microcapsule layer after irradiation with light and heat energy is applied from the side not coated with the porous microcapsule layer. The inclusions, therefore, bleed out of the fine pores of the porous microcapsules and are released into the binder. These inclusions develop colors and become dyes by coming into contact with the color developers contained in the binder. These dyes are transferred to the object to be transferred. The high-grade images are formed easily to the objects to be transferred, such as paper, cloth and films.

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 in printers and copying machines as outputs of computers, etc., and in particular to a transfer sheet using porous microcapsules. The present invention relates to a transfer sheet for light and heat sensitive recording materials, which allows high quality color images to be recorded on plain paper, cloth, etc. using a simple developing method.

[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 using a simple method.

The present invention is based on a porous microorganism that contains a photopolymerization initiator and a dye precursor as main components, which initiate the polymerization of a polymerizable monomer using light energy, on a support such as a polyethylene terephthalate (PET) sheet. This is a light and heat sensitive transfer sheet on which a porous microcapsule layer is formed in which capsules are dispersed in a binder containing a color developer. The color developer is something that develops color from the dye precursor into a dye by coming into contact with the dye precursor in the porous microcapsules.

When this light- and heat-sensitive transfer sheet is irradiated with light, the polymerizable monomer is polymerized and cured depending on the amount of irradiation. After irradiation with light, the object to be transferred is brought into contact with the porous microcapsule layer of the light- and heat-sensitive transfer sheet, and is heated from the side of the light- and heat-sensitive transfer sheet that is not covered with the porous microcapsule layer using a heat source such as a heat roller or a thermal head. By applying thermal energy, the inclusions extrude from the pores of the porous microcapsules according to the polymerization and curing level, are released into the binder, come into contact with the color developer contained in the binder, develop color, and become a dye. Transferred to the transferred object. As described above, a high-quality image can be easily formed regardless of the material to be transferred, such as paper, cloth, or film.

Furthermore, the photopolymerization initiator in the porous microcapsules
Three types of photopolymerization initiators are used that are selective to the wavelength of light energy necessary to receive and take light energy and generate chemical species for polymerizing polymerizable monomers, and none of them overlap. Using different wavelengths, the dye precursors that are combined with each color develop into a dye, cyan, cyan,
By including a mixture of three types of porous microcapsules, which are magenta and yellow dye precursors, in the porous microcapsule layer, a color image can be similarly obtained.

[Conventional technology]

Conventional heat-sensitive transfer sheets are generally made by coating a support on a resin film such as polyethylene terephthalate (PET) with a heat-melt ink containing a colorant dispersed in a heat-melt binder. A thermal transfer sheet is used, but in such a thermal transfer recording sheet, the PF3 fusible ink in the heated area melts and peels off from the support, so only binary recording is possible, and gradation is difficult to express. When performing this, an area modulation method such as a dither method or a density pattern method was used.

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

In addition, in the recording method using microcapsules,
4.58-23025, etc., there is a method in which microcapsules are cured 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 expressing gradation with thermal transfer sheets, it is done using the area gradation method, which not only requires complex signal processing but also reduces the resolution, making it difficult to create high-quality images. I couldn't record it.

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.

Therefore, in order to solve these conventional drawbacks, the present invention has been developed to create continuous tone, high-quality color images using a simple method, and to record on any material such as paper, cloth, or film. The purpose is to provide a photosensitive and heat-sensitive transfer sheet.

(Means for Solving 41 Problems) In order to solve the above-mentioned problems, the present invention provides polymerizable monomers, polymerizable monomers, etc. - A color developer that generates a dye precursor by contacting porous microcapsules encapsulating a photopolymerization initiator and a dye precursor as main components with the dye precursor to initiate polymerization using light energy. polyvinyl alcohol (pVA), polyethylene glycol (P
A layer formed by dispersing EG) in a binder is used as a photosensitive thermal transfer sheet.

Furthermore, three types of photopolymerization initiators are used that are selective to the wavelength of light energy necessary for the photopolymerization initiator to receive and take light energy and generate chemical species for polymerizing the polymerizable monomer. Specifically, the three types are 5a, 5b, 5
When expressed as c, each has the following characteristics.

6a: A photopolymerization initiator that is exposed to a characteristic wavelength λ in the range of 550 to 750 nm and generates chemical species for polymerizing polymerizable polymers.

6b: A photopolymerization initiator that is sensitive to a characteristic wavelength λ2 in the range of 450 to 650 nm and generates chemical species for polymerizing the polymerizable monomer.

6C: A photopolymerization initiator that is exposed to light at a characteristic wavelength in the range of 350 to 550 nm and generates chemical species for polymerization of polymerizable monomers.

However, λ, 1>λ2>λ3, and 6a is λ2゜λ,
6b is not sensitive to wavelengths of λ3. It is not sensitive to the wavelength of λ2, and 6C is not sensitive to the wavelength of λ1. In addition to these three types of porous microcapsules that are not sensitive to the wavelength of λ2, three types of dye precursors that become cyan, magenta, and yellow when colored and turned into dyes are added. For example, three types of porous microcapsules contain dye precursors that become dyes of different colors, such as cyan for 6a, magenta for 6b, and yellow for 6C. A mixture of these three types of porous microcapsules is dispersed in a binder containing the color developer and used as a porous microcapsule layer.

[Effect]

The photosensitive heat-sensitive transfer sheet obtained like a dermis is irradiated with light in accordance with an image signal to harden the porous microcapsules. The degree of curing is 811 m depending on the amount of light irradiation, and the uncured contents are cured from the side of the PET film where the porous microcapsule layer is not formed using a heat source such as a heated roller or thermal head to harden the pores of the porous microcapsules. The dye precursor is released, contacts and reacts with the color developer contained in the binder, becomes a dye, and is transferred to the transfer object.

By mixing porous microcapsules containing photopolymerization initiating agents with different curing wavelengths and cyan, magenta, and yellow dye precursors, high-quality color image recording is possible on paper. cloth,
It can be easily formed on a transfer target such as a resin film L.

Hereinafter, the present invention will be explained based on the drawings and according to examples.

FIG. 1 shows a schematic diagram of the porous microcapsule of the present invention. A porous microcapsule is a porous membrane whose porous membrane 1 has many pores, and the contained substances can be released by stimulation of heat. The photopolymerization initiator 2, which is an inclusion, absorbs light, generates a polymerization initiation species for polymerizing the polymerizable monomer 3, and polymerizes and hardens the polymerizable monomer 3. This photopolymerization initiator 2 can function as a single chemical substance, or it can be used as a photosensitizer that absorbs light and gives energy to the polymerization initiator, and as a photopolymerization initiator that receives energy from the photosensitizer. There are two types in which functions are expressed using two types of chemical substances as polymerization initiators that generate polymerization initiating species for polymerizing -3. It is possible to polymerize and harden the porous microcapsules by irradiating them with light, and the degree of polymerization can be adjusted by adjusting the amount of irradiation, and the level of curing can be changed accordingly. After irradiation with light, the porous membrane 1 is brought into contact with a heat source such as a heat roller or a thermal head to enlarge the pores of the porous membrane 1, harden it, and release the contents in accordance with the health. In other words, unirradiated capsules release a considerable portion of their contents, while capsules that have been sufficiently irradiated with light have polymerized and hardened contents and do not release them. The intermediate level of the light irradiation capsule releases its contents in accordance with its level of polymerization curing.

FIG. 2 shows a schematic diagram of the photosensitive and angry heat transfer sheet of the present invention. The support 5 is made of a heat-resistant resin film of about 10 gI+1, such as polyethylene terephthalate (PET). On this support, porous microcapsules 6 are dispersed in a binder containing a color developer 7 to form a porous microcapsule layer 8.

As the color developer 7, any one or a mixture of aromatic carboxylic acid metal salts such as salicylic acid and its derivatives, clays such as acid clay, activated clay, and bentonite, and phenolic compounds such as α-naphthol, β-naphthol, and bisphenol A can be used. Use.

As the binder, one or a mixture of polyvinyl alcohol, methylcellulose, carboxymethylcellulose, styrene-butadiene latex, polyethylene glycol, etc. is used.

Porous due to light? Polymerization hardening of the exit capsule is CR
When the porous microcapsules in the porous microcapsule layer are irradiated with light from a laser or a lamp in response to an image signal from a T or the like, the porous microcapsules in the porous microcapsule layer are hardened. The object to be transferred is brought into contact with the light-sensitive and heat-sensitive transfer sheet on which a latent image has been formed with light, and a heat source is brought into contact with the light- and heat-sensitive transfer sheet from the side on which the porous microcapsule layer is not formed. The dye precursor in the capsule is released, reacts with the color developer, develops color, and is transferred to the object.

FIG. 3 shows a schematic diagram of the formation of a color recorded image using the light and heat sensitive transfer sheet shown in FIG. CR
In response to an image signal such as from a laser or lamp, λ7. Wavelength of λ2, λ3 (λ,: 550-750n
λ2: a specific wavelength in the range of 450 to 650 nm, λ1+ a specific wavelength in the range of 350 to 550 r+m. However, λ1 1>λ2>λ3. ) is irradiated with light, depending on the respective wavelength,
Each of the porous microcapsules 6a, 6b, and 6C in the porous microcapsule layer 8 is cured depending on the wavelength. By contacting the heat source 9 from the side on which the porous microcapsule layer 8 of the light-sensitive and heat-sensitive transfer sheet on which the latent image has been formed with visible light is formed, the encapsulation in the uncured porous microcapsules is removed. By releasing a substance and reacting with a color developer, the dye precursor develops color and is transferred to the transfer object. This forms a color record. The material to be transferred may be paper, cloth, plastic film, etc., and it is not necessary to use a specially processed and dedicated material to be transferred.

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

Example-1 (Porous microcapsules) Crystalline violet lactone 1 as a dye precursor
．． 4 parts by weight were added to 25 parts by weight of trimethylolpropane triacrylate (TMPTA) using a ball mill.
Dispersed for 4 hours. Apart from this, hexamethylene diisocyanate (
N, N,
- A solution dissolved in 1 part by weight of dimethylformamide (DMF) was added to a dispersion in which a dye precursor was dispersed using a ball mill to obtain a porous microcapsule encapsulating solution.

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. Got the capsule.

(Light- and heat-sensitive transfer sheet) A color developer that develops color by reacting with crystalline oleenotolactone as a dye precursor (4,4'-isobropylidenophenol: zinc salicylate: methyl P-hydroxybenzoate: 5 25) Add 30 parts by weight to 50 parts by weight of a 3% (W/W) polyvinyl alcohol (Kuraray Bobal 117) aqueous solution using a ball mill.
Spread out time. 10 parts by weight of the porous microcapsules obtained above were further dispersed in the dispersion liquid, and coated on 8-line polyethylene terephthalate (PET) as a support using a bar coater and exposed to light.

A color image was obtained in the following manner using the light- and heat-sensitive transfer sheet obtained as described above.

Light from a 300° xenon short arc lamp passed through an ultraviolet light cant filter and was irradiated onto the light and heat sensitive transfer sheet for 1 minute to form a latent image. The object to be transferred is placed facing the surface coated with the porous microcapsule layer of the photosensitive/thermal transfer sheet on which the latent image has been formed, and a thermal head printing/recording device is used to transfer color from the back side of the photosensitive/thermal transfer sheet. An image was formed on the transfer target.

As a result, the photosensitive transfer notebook can form a latent image using visible light and develop with heat, and can also control continuous gradation expression by adjusting the light irradiation intensity, and can be applied to any transferred material. However, we were able to obtain high-quality images using a simple method.

Example 2 (Blue porous microcapsules) 4 parts by weight of cyan dye precursor] were mixed with trimethylolpropane triacrylate (TMPT) using a ball mill.
A) Dispersed in 25 parts by weight for 24 hours.

Separately, 5 parts by weight of hexamethylene diisocyanate (HMDA) as a porous microcapsule membrane monomer A, 0.1 part by weight of a complex compound of methylene flu as a blue sensitizer and triphenyl-nm butyl boron as a polymerization initiating species generator. NN, -dimethylformamide (D
MF>1 part by weight was dissolved in a ball mill and added to a dispersion in which a cyan dye precursor was dispersed to obtain a porous microcapsule enclosing liquid A. This porous microcapsule encapsulating liquid was mixed with 3% (W/W) polyvinyl alcohol (
Kuraray Bovar 224) was added to 78 liquids of water 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. Microcapsules were obtained.

(Red porous microcapsules) 1.4 parts by weight of a magenta dye precursor was added to trimethylolpropane triacrylate (TMP) using a ball mill.
It was dispersed in 25 parts by weight of TA) for 24 hours.

In addition, 5 parts by weight of hexamethylene diisocyanate (HMDA) as a porous microcapsule membrane monomer A, 0 parts of a complex compound of safranin as a red sensitizer, and triphenyl-n-butylboron as a polymerization initiating species generator.
．． 1 part by weight of N,N-dimethylformamide (DMF
) was dissolved to 1 part by weight and added to a dispersion liquid containing a magenta dye precursor in a ball mill to obtain iB encapsulated in porous microcapsules. This porous microcapsule-encapsulated IB was mixed with 3%<W/W) polyvinyl alcohol (
It was added to 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.
Knee zinc was performed under stirring for 1 hour to form a porous microcapsule membrane, and then i! ! Red porous microcapsules were obtained by filtration.

(Yellow porous microcapsules) 1.4 parts by weight of a yellow dye precursor was mixed with trimethylolpropane triacrylate (TMP) using a ball mill.
It was dispersed in 25 parts by weight of TA) for 24 hours.

Separately, hexamethylene diisono-2-ate (J(MDA) 5
Part by weight, 0.1 part by weight of a complex compound of acridine yellow as a red sensitizer and triphenyl-nm butyl boron as a polymerization initiating species generator was dissolved in 1 part by weight of N,N,-dimethylformamide (DMF). First, the material was added to a dispersion of yellow dye nIN in a ball mill to form porous microcapsules 1c. This porous microcapsule enclosing liquid C 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 to prepare porous microcapsule membrane monomer B with a concentration of 2.9% diethylenetriamine.
3 parts by weight were added, and the mixture was aged for 1 hour with stirring to form a porous microcapsule membrane, and yellow porous microcapsules were obtained by filtration.

(Light-sensitive and heat-sensitive transfer sheet) Add 5 parts by weight of each of the porous microcapsules of each color obtained as above, add 15 parts by weight of color developer to 3% (
W/W> Polyvinyl alcohol (Kuraray Bovar 117
) The dispersion was further dispersed in 211 parts of an aqueous solution using a ball mill for 24 hours, and then coated on 8-polyethylene terephthalate (PET) as a support using a bar coater and dried to form a light- and heat-sensitive transfer sheet. And so.

Using the light- and heat-sensitive transfer sheet obtained as described above, a color image was obtained on a transfer object in the following manner.

Light from a 300-degree xenon short arc lamp is applied to the photosensitive 1 thermal transfer sheet using an optical filter that transmits 650 nm light for the blue porous microcapsules, and a 550 nm light transmittance for the red porous microcapsules. For the yellow porous microcapsules, an optical filter that transmits light of 450 nm was used to perform spectroscopy according to the color image, and irradiation was performed for 1 minute to form a latent image. The object to be transferred is placed facing the porous microcapsule layer of the photosensitive and thermal transfer sheet on which the latent image has been formed, and the color is transferred onto the object from the back side of the photosensitive and thermal transfer sheet using a thermal head printing and recording device. , created a color image.

As a result, photosensitive and thermal transfer sheets can control color separation based on photosensitive wavelength and continuous gradation expression based on light irradiation intensity, and can print high-quality color images on paper, cloth, etc. without requiring special processing.
It was possible to easily form the image on a transfer target such as a film.

〔Effect of the invention〕

As described above, the present invention provides a polymerizable monomer and a photopolymerization initiator and a dye precursor that are initiated by polymerization light energy of the polymerizable monomer on a support of a heat-resistant film of about 10 al such as polyethylene terephthalate (PET). Using a light- and heat-sensitive transfer sheet provided with a microcapsule layer in which at least one type of porous microcapsules containing body as a main component is dispersed in a binder containing a color developer, light of each sensitive wavelength is applied according to the image signal. By irradiating with , the porous microcapsules of each color in the irradiated portion of each photosensitive wavelength are cured corresponding to each photosensitive wavelength. In addition, the porous f-microcapsules of each color in the unexposed area are transferred by application of heat, which causes the inclusions to pass through the pores of the film of the porous microcapsules and be released, react with the color developer, and develop a color. It can be recorded on the body. 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 dye precursors of each color in the contents of the porous microcapsules of each color released in this way pass through a binder containing a color developer that reacts with the dye precursor of each color to develop color.
A high-quality color image can be formed on a transfer object such as paper, cloth, or film that does not require special processing by transferring color onto the transfer object using a heat source such as a thermal head or heat roller. A light-sensitive and heat-sensitive transfer sheet can be provided.

[Brief explanation of the drawing]

Figure 1 is a schematic diagram of the porous microcapsules of the present invention, Figure 2 is a schematic diagram of an evil light and heat transfer sheet using the porous microcapsules of Figure 1 of the present invention, and Figure 3 is a schematic diagram of the porous microcapsules of the present invention. FIG. 2 is a color recording schematic diagram of a light- and heat-sensitive transfer sheet using porous microcapsules of three colors each containing yellow dye precursors. 1...Porous film 2...Photopolymerization initiator 2a,...S, Photosensitive photoinitiator 2b...λ2 Photosensitive photopolymerization initiator 2c...λ, Photosensitive photoinitiator 3...・Polymerizable 7-mer 4...Dye precursor 4a...Cyan dye precursor 4b...Magenta dye precursor 4C...Yellow dye precursor 5...Support 6...Porous microcapsules 6a...・λ, photosensitive porous microcapsule 6b・・λ
2 sensitive porous microcapsules 6C...λ, negative photosensitive porous microcapsules...color developing side 8...porous microcapsule layer 9...heat source 10...transferred object 11a... Cyan coloring part"y) b anger micro door FW't, km saih
i National pronunciation party 6 syllables transfer sheet ``Shicho outside'' Genyu Z Figure 1b ・Magenta coloring area 1C ・Yellow coloring area

Claims (2)

[Claims] (1) In a light- and heat-sensitive transfer sheet comprising a support and a porous microcapsule layer in contact with one of the supports, the porous microcapsule layer has a polymerizable monomer, and polymerization of the polymerizable monomer is initiated by light energy. Contains a photopolymerization initiator and a dye precursor as main components,
The degree of curing is adjusted by the amount of light irradiation, and the dye precursor is cured by contacting the porous microcapsules that release uncured capsule contents through the porous pores by applying heat. A light- and heat-sensitive transfer sheet comprising a layer dispersed in a binder containing a color developer that develops color and becomes a dye. (2) The porous microcapsule layer is a porous microcapsule that is exposed to a specific wavelength λ_1 in the range of 550 to 750 nm, and a polymerizable monomer is polymerized to become a polymer, and a specific wavelength λ_2 in the range of 450 to 650 nm. Porous microcapsules that are exposed to light and polymerizable monomers become polymers, and 350 to 550
It is formed by mixing any one or two or more porous microcapsules that are exposed to a specific wavelength λ_3 in the nm range and polymerizable monomers polymerize to become a polymer,
Each of the specific wavelengths has a relationship of λ_1>λ_2>λ_3, and each of the specific wavelengths λ_1, λ_2, and λ_3 is 5
The photosensitive and heat-sensitive transfer sheet according to claim 1, wherein the distance is determined to be 0 nm or more.