JPH0368948A - Transfer recording medium - Google Patents

Abstract

PURPOSE:To enable high-grade polychromatic recording by copying while nearly preventing void and fogging by incorporating a specified arom. compd. into the wall material of microcapsules on a recording layer by 5-40mol%. CONSTITUTION:Two kinds of microcapsules sensitive to light in two photosensitive wavelength regions and having different hues are supported on the recording layer of a transfer recording medium 1. The wall material of the microcapsules is made of urea-formaldehyde resin or melamine-formaldehyde resin and an arom. compd. having one or more hydroxyl groups is incorporated into the wall material by 5-40mol%. The reactivity of the wall material to a bright line having 254nm wavelength is reduced and the wavelength selectivity of the microcapsules is improved. At the time of printing with a color (B), the medium 1 is heated with a line of heating resistors 20 and irradiated with light in the photosensitive wavelength region of the microcapsules (A) and from a light source 3 to harden the microcapsules A and recording with the color B is carried out. At the time of printing with a color (A), the microcapsules (B) are hardened.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a transfer recording medium used in printers, copying machines, facsimiles, and the like.

[Background Art] In recent years, with the rapid development of the information industry, various information processing systems have been developed, and recording methods and devices suitable for each information processing system have also been developed and adopted. One such recording method is the thermal transfer recording method, which uses a light, compact device and is noiseless.
It has excellent operability and maintainability, and has been widely used recently.

This thermal transfer recording method generally uses a thermal transfer medium formed by coating a sheet-like support with a thermal transfer ink made of a heat-melting binder and a colorant dispersed therein. The thermal transferable ink layer is superimposed on the transfer medium so as to be in contact with the transfer medium, and heat is supplied from the support side of the thermal transfer medium by a thermal head to transfer the melted ink layer to the transfer medium. A transfer ink image is formed on a medium according to the shape of heat supply. According to this method, plain paper can be used as the transfer medium.

[Problems to be Solved by the Invention] However, conventional thermal transfer recording methods are not without drawbacks. This is because in conventional thermal transfer recording methods, the transfer recording performance, that is, the print quality, is greatly affected by the surface smoothness, and while good printing is performed on highly smooth transfer media, it is possible to print well on transfer media with low smoothness. In some cases, print quality may deteriorate significantly. However, even when using paper, which is the most typical transfer medium, highly smooth paper is rather special, and ordinary paper has various irregularities due to entangled fibers. Therefore, in the case of paper with large surface irregularities, the hot-melted ink cannot penetrate into the paper fibers during printing and only adheres to the concavities on the surface or the vicinity thereof, resulting in the edges of the printed image not being sharp. or part of the image may be missing, resulting in a decrease in print quality.

In addition, with conventional thermal transfer recording methods, only one color image can be obtained with one transfer, so in order to obtain a multicolor image, it is necessary to repeat the transfer multiple times to match the colors. Met. However, it is very difficult to accurately superimpose images of different colors, and it is difficult to obtain images without color shift. In particular, when focusing on a single pixel, color matching is rarely done in a single pixel, and as a result, in conventional thermal transfer recording methods, multi-colored images are produced due to a collection of pixels with misaligned colors. It was forming an image. For this reason, clear multicolor images cannot be obtained using conventional thermal transfer recording methods.

In addition, when trying to obtain multicolor images using conventional thermal transfer recording methods, it is necessary to install multiple thermal heads or to make complicated movements such as reverse feeding and stopping of the transfer medium, which requires the entire device. This method has drawbacks such as large and complicated data and a decrease in recording speed.

The present applicant uses a photothermal sensitive material, and when light energy and thermal energy are applied in accordance with the image signal, the reaction of the material rapidly progresses and the transfer characteristics irreversibly change, causing the image signal to change. He has invented an image forming method and a transfer recording medium for forming an image with the corresponding difference in characteristics and transferring it to a recording medium, and has already filed an application (Japanese Patent Application No. 1505-1981).
97).

The transfer recording medium of the application can eliminate and improve the problems and drawbacks of the conventional heat-sensitive recording method as described above, and the present invention further improves the transfer recording medium, and provides a high-quality pillar. The main object of the present invention is to provide a transfer recording medium capable of forming multicolor images with high sensitivity and less fogging and omission.

[Means for Solving the Problems] In the present invention, the recording layer on the support is composed of at least two microcapsules whose transfer characteristics change upon application of light and thermal energy, and the internal phase of the microcapsules is A compound having at least an ethylenically unsaturated double bond,
The microcapsule wall material contains a coloring agent and a photopolymerization initiator, and the microcapsule wall material has urea-formalin or melamine-formalin resin as a main component, and contains an aromatic compound having at least one hydroxyl group. Alternatively, it is a transfer recording medium characterized by containing melamine in a range of 5 to 40 mo1%, and the transfer recording medium has high sensitivity and good transfer properties, and in particular transfer with good gradation. It becomes possible to obtain images.

In the present invention, microcapsules are composed of a capsule wall and an internal phase, and the internal phase is composed of at least a compound having an ethylenically unsaturated double bond, a photopolymerization initiator, and a coloring agent, and the microcapsules are formed by applying heat and light energy. The transfer characteristics change. In addition, in the present invention, at least two types of microcapsules are those in which the photopolymerization initiator contained in the internal phase of the microcapsules has a photosensitive wavelength range of at least 2.
The microcapsules are seeded, meaning that two or more types of microcapsules exhibit different hues.

It is desirable that the wavelength range of light that sensitizes commonly used photopolymerization initiators is divided into approximately 300 to 600 nm. This is because many photoinitiators contain an aromatic ring in their molecules, and the absorption band determined by the transition of the aromatic ring is 300 nm.
The light that exists at wavelengths below 1.300 nm is sensitive to light with wavelengths below 1.300 nm, making it difficult to separate the sensitive wavelength ranges. This is because it becomes impossible to obtain.

The recording medium of the present invention aims at recording in at least two colors, and the wavelength range of 300 to 600 nIO is divided into at least two wavelength ranges, each having photosensitive characteristics in two types of wavelength ranges. It is constructed by supporting microcapsules exhibiting different hues on a support.

Although the present invention can be applied to multi-color or full-color recording using two or more colors, the following explanation will be given using two-color recording as an example for better understanding.

A recording medium is prepared by supporting two types of microcapsules A and B, which have different photosensitive wavelength ranges and exhibit different hues, on a support. Here, when printing in hue B, if the recording medium is heated and irradiated with light in the sensitive wavelength range of the microcapsules A, the microcapsules A will harden and lose their transfer characteristics, so the recording medium will be heated. When the recording paper is passed through a heating and pressing means such as a heat roller facing the transfer paper, B
The hue of the image can be recorded.

Furthermore, when recording hue A, light in the B photosensitive wavelength range may be irradiated in the same manner.

As one of the light sources for exposing such a transfer recording medium, the present inventors proposed a compact light source shown in FIG. 2 (3g) (Japanese Patent Application No. 61-93368). This light source is
An excitation light source that generates abundant 2S4 nm mercury emission lines is placed inside a cylindrical glass tube coated with several types of phosphors, and the excitation light source emits light in synchronization with the rotation of the glass tube. By energizing the excitation light source when a desired phosphor is placed at a position facing the thermal head, the transfer recording medium can be irradiated with light in a desired wavelength range.

A quartz tube can be used as a glass tube for such a light source. Quartz is preferable because it has high transparency even for ultraviolet light, especially short wavelength light, and does not attenuate the light. but,
Even if the quartz tube is coated with phosphor, the ultraviolet light that has passed through the quartz tube contains wavelengths such as 254nm.
When a transfer recording medium is irradiated with a mercury bright line of m, as mentioned above, most photopolymerization initiators are sensitive to 254 nm light, so for example, in order to cure the microcapsules of A. When irradiated with light, a bright line of 254 nm is also irradiated at the same time, causing the capsule of B to react slightly and harden. This causes white spots etc. to occur in the image.

The present inventors conducted intensive studies to solve the above problems, and found that by using urea-formalin or melamine-formalin resin containing 5 to 30 wt% of an aromatic compound having a hydroxyl group as the wall material of the microcapsules, a Reduces reactivity to wavelength emission lines,
They discovered that the wavelength selectivity of the capsule can be improved, leading to the present invention. By containing the aromatic compound in the wall material of the capsule, the aromatic ring in the photopolymerization initiator absorbs the 254nn+ bright line and prevents the internal phase from reacting to the bright line. That is, the aromatic ring of the aromatic compound contained in the wall material of the capsule absorbs the 254 nm emission line and acts as a filter, so the aromatic ring contained in the photopolymerization initiator in the internal phase absorbs the 254 nm emission line and acts as a filter. The amount of bright radiation that reaches and is absorbed can be reduced, and the curing reaction can be suppressed.

In order to achieve the above effect, the content of the aromatic compound must be 5 to 4011101% relative to the wall material.

If it is less than 5mo1%, a sufficient effect cannot be obtained;
If it exceeds 0mo1%, the content of the urea-formalin resin or melamine-formalin resin, which is the main component of the wall material, will be relatively reduced, making it difficult for the curing reaction to occur during force bonding, and as a result, the wall material will deteriorate. In order to increase the degree of curing, a high curing reaction temperature is required, which may lead to deterioration of the characteristics of the internal phase, and also cause the wall material to take on a brown color and reduce the sharpness of the image.

As a prior art, USP 673293 discloses the use of urea-formalin resin containing resorcin in wall materials, but the main purpose of this patent is to improve the adhesion of wall materials to internal phase particles. However, the amount of resorcinol contained is very small (5 mol % or less), and no effect of the aromatic ring in the present invention is suggested at all.

Since the main purpose of the aromatic ring in the present invention is to act as a filter for the 254 nm bright line, its content should be at least 5 mo1% or more of the wall material.

Here, as a means of introducing the aromatic ring into the capsule wall,
For example, a method in which a phenol resin is precipitated around the internal phase by 1n-situ polymerization, or a method in which a polymeric compound having an aromatic ring is attached by coacervation, etc. can be considered, but these resins cannot be easily deposited at relatively high temperatures. It is necessary to carry out a curing reaction.

On the other hand, in the present invention, since urea-formalin resin or melamine-formalin resin is used as the main constituent component of the wall material, the curing temperature during encapsulating by 1n-situ polymerization method etc. can be lowered, and the internal phase This suppresses characteristic deterioration and enables efficient covering.

The reaction of urea-formalin resin or melamine-formalin resin generally proceeds depending on the hydrogen ion concentration, that is, pH, and a sufficient degree of curing can be obtained at a curing reaction temperature of 100° C. or lower.

In addition, in the present invention, since the aromatic compound has a hydroxyl group, when introducing an aromatic ring into the resin, the aromatic compound is dissolved in a predetermined ratio in the aqueous phase during encapsulating. You can easily install it by just leaving it in place.

Aromatic compounds having at least one hydroxyl group according to the present invention include phenol, 0-cresol, m-cresol,
p-cresol, 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, 2-n-propylphenol, 3-n-propylphenol, 4-n-propylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol,
2-n-butylphenol, 3-n-butylphenol, 4-n-butylphenol, 2-sec-butylphenol, 4-sec-butylphenol, 2-isobutylphenol, 4-isobutylphenol, 2-te
Alkylphenol such as rt-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 2-bromophenol,
Halogenated phenols such as 3-bromophenol and 4-bromophenol; aminophenols such as 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-dimethylaminophenol, 3-dimethylaminophenol, and 4-dimethylaminophenol; Contains phenol:
resorcinol, and 5-chlororesorcinol, 5
-bromoresorcinol, 5-amylsorcinol, 5
-Methoxyresorcinol, 5-methylresorcinol, 5-ethylresorcinol, 5-n-propylresorcinol, 5-isopropylresorcinol, 5-n-
Resorcinol such as butylresorcinol, conductor: hydroquinone, and chlorohydroquinone, bromohydroquinone, 2,6-dichlorohydroquinone, 2,6-dibromohydroquinone, methylhydroquinone, 2-methyl-6-
Ethylhydroquinone, 2,6-dimethylhydroquinone,
Hydroquinone derivatives such as 2゜6-dichlorohydroquinone: naphthol, and 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 3-methylnaphthol, 3-ethylnaphthol, 3-n-propyl Naphthol, 3-isopropylnaphthol, 3-chlornaphthol, 3-bromonaphthol, and 3-methyl-1,4-dihydroxynaphthalene, 3-ethyl-1,4-dihydroxynaphthalene, 3-n-propyl-1,4- Examples include naphthol derivatives such as dihydroxynaphthalene and 3-isopropyl-1,4-dihydroxynaphthalene.

Since these aromatic compounds have different reactivities, it is necessary to optimize the amount and pH conditions when introducing them into wall materials. For the same amount of preparation, the higher the pH (4 to 7)
The amount introduced will increase. The amount of the introduced aromatic compound having a hydroxyl group can be easily quantified by analytical means such as IR and NMR.

The urea-formalin resin or melamine-formalin resin that can be used in the present invention is a resin synthesized by a polycondensation reaction of urea or melamine and formalin. Methylolation, which is a resin that gels and hardens by forming a three-dimensional network structure through the reaction between the methylol groups, and the polymerization reaction of the methylol groups are mainly controlled by pH. Therefore, urea or melamine and formalin (2 times the mole for urea, 3 times the mole for melamine) are dissolved in the aqueous phase in which the core particles are expanded, and the pH of the aqueous phase is adjusted to acidic (preferably pH 5, O ~2
．． 0), urea (melamine)-formalin resin is formed on the core particles to produce microcapsules.

If a hydroxyl group-containing aromatic compound is present in the aqueous phase at this time, the component can be incorporated into the capsule film.

That is, formalin has 0 for the hydroxyl group of the aromatic ring.
A nucleophilic substitution reaction takes place at the - or P- (7) position to generate a methylol group, which can be polymerized with the methylol group added to the urea (melamine) and incorporated into the resin.

Note that configurations of the present invention other than those described above can be implemented based on known techniques.

Hereinafter, the principle etc. that enable recording with the transfer recording medium according to the present invention will be explained in more detail in the case of full color recording.

In the transfer recording medium of the present invention, the microcapsules supported on the support are composed of a plurality of types of capsules.
If each capsule has a different photosensitive wavelength range and exhibits a different hue, it is possible to form a full-color image.

For ease of understanding, in the following explanation, microcapsules are composed of three types, elementary bodies (A), (B), and (C), and the sensitive wavelength range of these capsules is (A) 300~ 360
0m, (B) 360-430nm.

(C) 430 nm or more and the coloring material is a pigment, but the present invention does not cover other methods of dividing the photosensitive wavelength range and methods of developing hue, such as using pigments, dyes, and leuco dyes. is also applicable.

The photopolymerization initiators used in the present invention include benzyl, 4,
Diketone compounds such as 4°-dimethoxybenzyl, 4,4°-dimethylbenzyl, 4,4′-dihydroxybenzyl, and those with an absorption maximum of 360 to 430 nm, such as thioxanthone, 2-chlorothioxanthone, isopropylthioxanthone, 2.4- diethylthioxanthone,
Thioxanthone derivatives such as 2,4-diisopropylthioxanthone, and coumarins such as 7-diethylamino-3,3゛-carbonylvistamarin and 3.3°-carbonylbis(7-ethylachnocoumarin) as those having an absorption maximum of 43 Or+m or more. Although a composite initiator of a derivative and an S-triazine derivative or camphorquinone is used, the present invention is not limited to the above-mentioned initiators.

The polymerizable compound having an ethylenically unsaturated double bond in the element bodies (A), (B), and (C) is a compound having at least one ethylenically unsaturated double bond in its chemical structure. It has the following chemical forms: , monomer oligomer, and polymer. Examples include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, and ethylene glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane, l, :+-" r
Contains esters with aliphatic polyhydric polyol compounds such as tanediol, pentaerythritol, and dipentanitritol, as well as polyisocyanates (which may be reacted with polyols if necessary) and ethylenically unsaturated double bonds. Urethane acrylates and urethane methacrylates synthesized by the addition reaction of alcohols and amines; epoxy acrylates, polyester acrylates, and spin acrylates synthesized by the addition reaction of epoxy resins and acrylic acid or methacrylic acid. Examples include the following.

In addition, polymers have a backbone of polyalkyl, polyether, polyester, polyurethane, etc. in the main chain and acrylic, methacrylic, cinnamoyl, cinnamylideneacetyl, furyl acryloyl groups, etc. in the side chain. The present invention is not limited to these examples, but the present invention is not limited thereto.

Further, an element body (A) containing the above-mentioned photopolymerization initiator and a polymerizable compound having an unsaturated double bond.

(B) and (C) may further contain known additives such as binders, UV absorbers, plasticizers, and thermal polymerization inhibitors, if necessary.

As the binder, any organic polymer that is compatible with monomers, oligomers, or polymers having unsaturated double bonds may be used. Examples of such organic polymers include polyacrylic acid alkyl esters such as polymethyl acrylate and polyethyl acrylate, polymethacrylic acid alkyl esters such as polymethyl methacrylate and polyethyl methacrylate, or chlorinated polyethylene and chlorinated polypropylene. Examples include chlorinated polyolefins such as polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile or their copolymers, as well as polyvinyl alkyl ethers, polyethylene, polypropylene, polystyrene polyamides, polyurethanes, chlorinated rubbers, cellulose derivatives, etc. The invention is not limited to these.

These polymers may be used alone or in a mixture of two or more in an appropriate ratio. Furthermore, waxes may be used as binders, regardless of whether they are compatible or incompatible. Any amount of these polymers can be mixed into the total composition.

Furthermore, the magenta pigment used in the present invention includes C,1
, Pigment No., Red 57-1. Re
Azo lake pigments such as d-31, Red-122, monoazo pigments, and quinacridone pigments can be used, and cyan pigments include C, 1, Pigment No., and Blue-60.
,Blue-15-6,Blue-15゜Blue-1
Phthalocyanine pigments such as 5-2, Blue-15-3, Blue-15-4 can be used, and yellow pigments include Yellow-12, -13, -14, -17,
-55, -83°-154, disazo type, benzimidacylon type, etc. can be used, but the present invention is not limited thereto.

Next are the elementary bodies (A) and (B) consisting of the above-mentioned components.

(C) has a particle size of about 3 to about 50 μm when solid.

Preferably as a particulate element with a particle size of 7 to 15 μm, or even if the element bodies (A), (B), and (C) are solid or solid, the particle size is about 3 to about 50 ttm, preferably 7 to 15 μm. The microcapsules are physically and chemically attached to a support to form a recording medium.

The average particle size of the elements (A), (B), and (C) is preferably about 10 μm. When binding microcapsules onto a support using an adhesive, the binding agent may include an epoxy adhesive,
Polyester adhesives, urethane adhesives, acrylic adhesives, urethane acrylic adhesives, ethylene-vinyl acetate copolymer adhesives, and the like are preferably used.

Next, a specific example of an image forming method using the recording medium of the present invention will be shown based on FIG. First, the transfer recording medium 1 is stacked on the heating resistor array 20 of the thermal head, and light is irradiated so as to cover the entire area of the heating section of the thermal head. The irradiation light has a wavelength that causes the image forming elements (A), (B), and (C) to react in sequence. For example, image forming element (A),
(B).

When (C) is colored magenta, cyan, or yellow, light with wavelengths λ(M), λ(C), and λ(Y) is sequentially irradiated.

That is, first, light of wavelength λ(M) is irradiated from the transfer recording layer 1a side of the transfer recording medium 1, and the heating resistors 20b and 20c of the thermal head, for example, are caused to generate heat. Then, among the image forming elements containing the magenta coloring material, the image forming element (1a
The hatched part in the diagram. Hereinafter, the cured image forming element is indicated by hatching. ) hardens.

Next, as shown in FIG. 1b, the transfer recording layer 1a is coated with a wavelength λ(
While irradiating the light of C), the heating resistors 20a and 20b
When 20c and 20c are made to generate heat, the image forming element containing the cyan coloring material, to which the heat and the light of wavelength λ(C) are applied, is cured. Further, as shown in FIG. 1C, light of wavelength λ(Y) is irradiated and the heating resistor 20c
, 20d, among the image forming elements containing the yellow coloring material, the image forming elements to which heat and light of wavelength λ(Y) have been applied are cured, and the image forming element that has not been cured is finally cured. A transferred image is formed on the transfer recording layer 1 by the element body. This transferred image is transferred to the transfer medium 21 in the next transfer process as shown in FIG. 1d.

In the transfer process, the transfer recording medium on which the transferred image has been formed is brought into contact with the transfer medium, and the transferred image is selectively transferred to the transfer medium by heating from the transfer recording medium or the transfer medium side to form an image. do. Therefore, the heating temperature at this time is determined so that only the transferred image is selectively transferred in the transfer step. Further, in order to perform the transfer efficiently, it is also effective to apply pressure at the same time. Pressure is applied to the right, especially when a transfer medium with low surface smoothness is used. Furthermore, if the physical property that governs the transfer characteristics is the viscosity at room temperature, transfer is possible only by applying pressure.

Furthermore, heating during the transfer process is suitable for obtaining stable, durable, and durable multicolor images.

In the example explained above in FIGS. 1a to 1d, a method is shown in which an image is formed by irradiating light onto the entire area of the heating resistor row 20 of the thermal head and selectively causing the heating resistors of the thermal head to generate heat. However, by uniformly heating a certain part of the transfer recording medium (in terms of the thermal head shown in Fig. 1a,
When all heating resistors generate heat), a multicolor image can be similarly formed by selectively irradiating light. That is, light energy of a wavelength that is modulated according to the recording signal and that is selected depending on the color tone of the image forming element whose physical properties governing the transfer characteristics are desired to be changed is applied together with thermal energy.

A preferred example of a recording apparatus using the recording medium of the present invention will be described with reference to FIGS. 2(A) and 2(B).

In the figure, reference numeral 1 denotes a transfer recording medium of the present invention in the form of a long sheet, which is wound into a roll and is removably incorporated into an apparatus main body M as a supply roll 2. That is, this supply roll 2 is provided in a rotatable @2 provided in the main body M of the apparatus.
It is removably loaded into a.

Therefore, first, the leading edge of this transfer recording medium 1 is transferred to the supply roll 2.
Transfer roller 4a and pressure roller 4b pass through guide roller 12a, thermal head 3a and guide roller 12b.
From between the peeling roller 5 and the guide rollers 12c and 12d.
The winding roller 6 is directed to the winding roll 6, and its tip is locked to the winding roll 6 by means such as a gripper (not shown). Thereafter, by rotating the transfer roller 4a while applying torque to the take-up roll 6 in the direction of arrow C using a known drive means, the transfer recording medium 1 is rotated.
The film is unwound in the direction of arrow a, and is sequentially wound around the circumferential surface of the winding roll 6.

Incidentally, during the winding, a certain back tension is applied to the supply roll 2 by, for example, a hysteresis brake (not shown), and this tension and the guide rollers 12a and 12b cause the transfer recording medium 1 to move toward the thermal head. It is configured to be conveyed while being in pressure contact with 3a at a constant pressure and at a constant angle.

The recording section includes a heating means for applying thermal energy to the recording medium 1, and also transfers light energy to the recording medium! and a light irradiation means for applying the light to the light.

The heating means generates heat on the surface of the thermal head 3a according to the image signal, for example, with a width of 0.2 mm and a rate of 8 dots/rn.
Line type heating resistor row 2 for tn A-4 size
As described above, the support lb side of the transfer recording medium 1 is configured to be pressed against the heating resistor array 2o with a predetermined pressure due to the back tension during conveyance.

Note that the image signal may be used for facsimile, for example, depending on the purpose.
It is emitted from a control unit such as an image scanner or an electronic whiteboard.

On the other hand, the transfer recording layer l facing the @ mark head 3a
A light irradiation means is provided on the a side. As the light irradiation means, a rotating body 3c made of a cylinder made of quartz glass with a thickness of 2IIIm is rotatably supported by three pairs of rollers 3d, 3e, and 3f, and is rotated at a constant speed by driving and rotating the rollers 3d by a motor. It may be configured so that it rotates.

Three types of phosphors 100, 1 are provided on the inner surface of the rotating body 3c.
01 and 102 are coated at 120 degrees (3 equal parts) in the cylindrical direction, and these phosphors are excited by light from a light source 3g (for example, Toshiba germicidal lamp GL-20) disposed inside the rotating body 3c. and emit fluorescence.

Phosphor 100.101.・The peak wavelength of light 102 is 300 to 3600 m, 360 to 430 nIn, and 430 m, respectively.
~600 nm, and it is necessary that its half width be as small as possible in order to suppress crosstalk.

As the phosphor 100 having a peak wavelength in the wavelength range of 300 to 360 nm, thallium-activated calcium phosphate (
(:a (PO4) 2・TI) or thallium-activated calcium zinc phosphate ((Ca-Zn) + (PO
4) Preferably, the main component is 2:T11). These fluorescent materials have high luminescence intensity and are very preferable.

As the phosphor 101 having a peak wavelength in the wavelength range of 360 to 430 nm, europium-activated strontium magnesium birophosphate ((Sr, Mg) 2P207
-Eu) is preferred as a main component.

As the phosphor 102 having a peak wavelength in the wavelength range of 430 to 600 nm, europium activated barium magnesium aluminate (Ba, MgAl+602y·εU) is used.
Preferably, the main component is

As you can see in Figure 3, each phosphor is 100.101°10
The peak wavelengths of 2 are within the range of 300 to 360 nm, 360 to 430 nm, and 430 to 600 nm, respectively.
Exists within the range of For example, thallium-activated calcium phosphate is 335r+m (graph +00), europium-activated strontium magnesium pyrophosphate is 335r+m (graph +00).
Europium-activated barium magnesium aluminate has a peak wavelength at 95 nm (graph 101), and 453 nm.

In addition to the above materials, binders and other additives may be mixed with the phosphor 100.101.102, but at least 90% by weight of each of the phosphors 100.101.102 should be mixed with the above materials. Preferably, it is occupied by a fluorescent material.

[Example Example 1 50 g of each of the components shown in Table 1.2.3 were microencapsulated by the method shown below.

Method for manufacturing microcapsules: Mix 100 g of water with 26 g of isobutylene-maleic anhydride copolymer (Kureha Chemical Co., Ltd.: Isoban-10) (polymer concentration: 20.6%), and add 3.1 g of pectin. and stirred for 20 minutes. Then 20
% sulfuric acid solution to pH 4.0.

While stirring at 3000 rpm with a homomixer, a solution prepared by dissolving 20 g of the components shown in Table 1 in 40 g of chloroform was added over 10 to 15 seconds, and emulsification was continued for 10 minutes. The emulsion was transferred to a 500 ml beaker, and the solvent was removed by stirring with a stirring blade all day and night at a temperature of 0°C. After adding the emulsion to 0°C water and stirring for a while,
Filtration was performed using a Nutsche filter, and the resulting internal phase particles were dried in a free-air dryer at 40° C. for one day and night.

Next, after dispersing 20 g of internal phase particles in 50 g of water, 4
After adding 3 g of urea and 3 g of resorcin, the pH was set to 9 and the mixture was stirred at room temperature for 1 hour.

Furthermore, after setting pi-t to 4 with 1% sulfuric acid and adding 25 g of formalin (3H), stirring was continued for 8 hours, and then the pH was set to 2 and stirring was performed at 50° C. for 2 hours. 3N to the reaction solution
After returning to neutrality by adding Na Kano ice aqueous solution, 1000 c
It was washed by pouring it into the water of step c, filtered, and dried.

The components shown in Table 2, Table 1, Table 3, Table 2.3 were similarly made into microcapsules, and elementary bodies (A), (B), and (C) were also produced.

Thermoplastic polyester (Nippon Gosei Kagaku Kogyo, Polyester-011) was diluted with toluene and applied to a thickness of 0.5 μm using an applicator on a PET (polyethylene terephthalate) film (6 μm thick). Then, element body (A) was sprinkled on the film and spread, and unbound particles were shaken off.
Sandwiched between ET films, temperature 110℃, pressure 2-3 kg
/cm'' heat roller, the PET film was peeled off, and a transfer recording medium was prepared in which the element body (A) was firmly adhered to the PET film. Similarly, the element body (B
), (C), and elementary bodies (A), (B).

A transfer recording medium was prepared by mixing equal amounts of (C).

The transfer recording medium consisting of the element body (A) was wound into a roll and incorporated into the apparatus shown in FIG. The thermal head used was an A-4 size line type with a width of 2IIIm and 8 dots/mm, in which rows of heating elements were arranged at the edges.

As a light source, a glass tube was coated with thallium-activated calcium phosphate, europium-activated strontium magnesium birophosphate, and europium-activated barium magnesium aluminate, each at a 120-degree angle. It was used.

Subsequently, when the transfer recording medium was wound in the apparatus and the thermal head and excitation light source were energized at the timing shown in FIG. 5, a high-quality multicolor image with good gradation and no white spots was formed. did it.

Example 2 Internal phase particles were prepared using the ingredients shown in Table 1.2.3 in the same manner as in Example 1, and then capsules were prepared using the formulation shown in Table 4.

In the same manner as in Example 1, a transfer recording medium was produced by supporting the capsule on PET, and then an image was formed using the apparatus shown in FIG. 2, and a good image was formed.

Next, as shown in the timing chart of FIG. 4, the lamp and thermal head were energized. The thermal head is energized through the element body (A).

The voltage and drive signal were controlled so that the temperature of (B) and (C) was about 100°C. Element bodies (A) and (B) where signals are applied by changing the energization time τ.

The time required for no transfer of (C) was determined.

In Table 4, capsule (A) has λp=390.450
If a reaction occurs with a nm lamp (crosstalk), the selectivity of the color layer will deteriorate and the image quality will deteriorate.

Here, one of the reasons why capsules (A), (B), and (C) react to light at wavelengths other than those corresponding to each one is as follows.
This is because a mercury bright line of λ=254 nm exists in the light emitted from each lamp, and this bright line directly excites the reactive monomer.

Table 4 shows that microcapsules made from a shell material containing an aromatic compound having a hydroxyl group have improved selectivity for light of the corresponding wavelength, whereas the aromatic ring absorbs the emission line of λ = 254 nm. It can be seen that

Table 4 [Effects of the Invention] As explained above, according to the present invention, an aromatic compound having at least one hydrosyl group is contained in a range of 5 to 40 mo1% based on urea or urea. By using microcapsules made of a wall material of 100% gradation, it is possible to obtain capsules with excellent tonality, high sensitivity, and good transferability, and it is possible to provide a multicolor transfer recording medium with little fogging and white spots.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing the principle by which multicolor recording is possible using the transfer recording medium according to the present invention. 2. FIGS. 2A and 2B are diagrams showing an example of an apparatus for performing multicolor recording using a transfer recording medium according to the present invention. FIG. 3 is a graph showing an example of the light emission characteristics of a phosphor. FIG. 4.5 is a diagram omitting a timing chart of signals applied to the light source and the thermal head used in the embodiment. 1: Transfer recording medium 1a: Transfer recording layer 1b: Support 2: Supply roll 2a:! lid+ 3a: Thermal head 3C: Rotating body 3dNf: Roller pair 3g: Light source 4a: Transfer roller 4b: Pressure roller 5: Peeling roller 6: Winding roll 12aNd Ni guide roller 20: Heat generating resistor row 20a''d: Heat generating resistor Body 100, 101.102: Phosphor M: Main body

Claims (1)

[Claims] 1. A compound in which the recording layer on the support is composed of at least two types of microcapsules whose transfer characteristics change upon application of light and thermal energy, and the internal phase of the microcapsules has at least an ethylenically unsaturated double bond. , containing a coloring agent and a photopolymerization initiator, and the wall material of the microcapsules is urea-formalin or melamine-formin.
1. A transfer recording medium comprising a formalin resin as a main component and containing an aromatic compound having at least one hydroxyl group in an amount of 5 to 40 mol% based on urea or melamine.