JPH0371136A - Transfer recording medium - Google Patents

Abstract

PURPOSE:To provide the multicolor transfer recording medium which is free from fogging and voids by using microcapsules formed with a wall material by acting bivalent or higher valency cationic inorg. ions on a high-polymer compd. having a carbonyl group. CONSTITUTION:The high-polymer compd. having carboxylic acid in the molecular structure is generally soluble in water. The H<+> ions of the carbonyl group in the high-polymer compd. molecules are substd. with the bivalent or higher valency cationic inorg. ions and the molecules are crosslinked via the carbonyl group if the bivalent or higher valency cationic inorg. ions are added to the aq. soln. As a result, the molecules precipitate as the water insoluble resin having a high glass transition point. The microcapsules having the wall material consisting of the high-polymer compd. are formed if the cores exist in a water phase at this time. Ions such as Al<3+>, Mg<2+>, Sn<2+>, Ca<2+>, and Pb<2+> can be acted as the bivalent or higher valency cationic inorg. ions. In actuality, materials which generate these ions in an aq. liquid, for example, Al(NO3)3, Mg(SO4), CuSO4, Mg(NO3)2, CuCl2, etc., are used.

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 lightweight, compact, and noiseless device.
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.

[Problem to be solved by the invention]

However, the conventional thermal transfer recording method described above is not without drawbacks. This is because in the conventional thermal transfer recording method, the transfer recording performance, that is, the print quality, is greatly affected by the surface smoothness.Good printing is performed on highly smooth transfer media, but on less smooth transfer media. In some cases, the print quality deteriorates 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 during printing cannot penetrate into the fibers of the paper 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 to obtain a multicolor image, it is necessary to repeat the transfer multiple times to overlap the colors. there were. 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, colors are rarely superimposed in a single pixel, and in the end, in conventional thermal transfer recording methods, multicolor images are created by aggregation of pixels with shifted colors. was forming. 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.

Therefore, the present applicant has proposed that when a photothermal sensitive material is used and light energy and thermal energy are applied in response to an image signal, the reaction of the material rapidly progresses and the transfer characteristics irreversibly change, resulting in an image signal. He has invented and already filed an application for an image forming method and a transfer recording medium for forming an image with different characteristics according to the characteristics and transferring it to a recording medium (Japanese Patent Application No. 6 [1-
150597).

In addition, the applicants have already filed a patent application for a combination of a phosphor that generates ultraviolet light in three wavelength ranges and a photopolymerization initiator with a corresponding photosensitive wavelength range in order to select a hue (patent application). (Sho 6l-293157).

The transfer recording medium of the application can eliminate and improve the problems and drawbacks of the conventional thermal recording method, and the present invention is a further improvement of the transfer recording medium, which has high quality and high sensitivity. An object of the present invention is to provide a transfer recording medium that can form images without fogging or white spots.

[Means for Solving the Problems 1] The present invention provides a transfer recording medium in which a recording layer made of microcapsules is provided on a support, in which the internal phase of the microcapsules contains at least a photopolymerization initiator, and light and heat. The microcapsules contain a compound with an ethylenically unsaturated double bond whose transfer characteristics change when energy is applied, and the walls of the microcapsules are made of a polymer compound with a carbonyl group in its molecular structure and an inorganic cation with a valence of 2 or more. This is a transfer recording medium made of a wall material having a structure consisting of at least ions, and the wall material is of good quality at low temperatures and has a glass transition point (
Tg) is high, so the quality of the core material of the internal phase is not deteriorated, and the reaction of the core material is not suppressed during transfer. As a result, by using the transfer recording medium, transfer recording can be performed with high sensitivity and good transferability. becomes possible.

That is, the present invention is a transfer recording medium in which the recording layer on a support is composed of microcapsules having an internal phase whose transfer characteristics change when heat and light energy are applied, and the wall material of the microcapsules is composed of molecules. It is characterized by being formed from a polymer having a carbonyl group in its structure and an inorganic cation ion having a valence of two or more.

The internal phase used in the present invention, whose transfer characteristics change upon application of heat and light energy, is a phase that contains at least a polymerizable monomer having an ethylenically unsaturated double bond and a photopolymerization initiator. It is composed of

Generally, the internal phase is often solid at room temperature.

As a method for manufacturing microcapsules having such an internal phase, after forming solid particles of the internal phase, a wall material is formed by a complex coacervation method such as gelatin-gum arabic or an in-situ polymerization method such as urea-formalin. Formed and manufactured.

However, although wall materials formed by the coacervation method can form a uniform film, they are generally made of materials with a low glass transition point, and the transfer medium is pressed against the object to be transferred and passed through a heated roller. However, in many cases, the transfer is not completed completely.
Alternatively, in order to transfer completely, it is necessary to increase the pressure of the roller.

In addition, when the internal phase is exposed to light and heat, it undergoes radical polymerization and hardens, changing the transferability.However, in radical polymerization, the polymerization rate decreases due to the presence of oxygen gas.
As a result, printing speed decreases. In this transfer medium, the internal phase is coated with a wall material to block oxygen gas and prevent a decrease in sensitivity, but the rate of gas permeation through the coating becomes extremely high when it exceeds the glass transition point. In other words, by heating, the polymerization rate of the internal phase becomes extremely high, but on the other hand, the oxygen permeability of the wall material increases, and as a result, increasing the sensitivity of the recording medium is hindered.

Normally, wall materials formed by the coacervation method are cured with aldehyde etc. to make them insoluble in solvents, but as mentioned above, when the characteristics of the transfer recording medium are influenced by the glass transition point of the wall material, However, the method of curing the wall material after it has been deposited is not necessarily the best method because the hardening agent does not penetrate sufficiently into the deposited solid film and the degree of hardening does not increase, or the degree of hardening cannot be controlled with good reproducibility. do not have.

Furthermore, since this curing treatment is generally carried out under heating, the internal phase of the microcapsules contains a compound having an unsaturated double bond and is a composition consisting of a solid mixture. In some cases, properties such as photosensitivity of the internal phase may deteriorate due to heat treatment.

In the present invention, encapsulation is not performed by hardening the wall material using the conventional coacervation method, but instead uses a polymer compound having a carbonyl group in its molecular structure as the wall material to form the wall of the capsule. A compound is cured by acting on an inorganic cation having a valence of two or more to form a wall.

The method for forming the capsule wall according to the present invention is based on the property of the polymer compound being gelled and hardened by the action of divalent or higher inorganic cations. That is, a polymer compound having a carboxylic acid in its molecular structure is generally water-soluble, and when a divalent or higher cationic inorganic ion is added to the aqueous solution, the H+ ion of the carbonyl group in the polymer compound molecule is As a result of being substituted with a cationic inorganic ion having a valence of two or more and crosslinking the molecules through carbonyl groups, a water-insoluble resin with a high Tg is precipitated. At this time, if a core is present in the aqueous phase, microcapsules having the above-mentioned polymer compound as a wall material can be formed. According to this method, high T at low temperature
It is possible to create microcapsules consisting of a wall material of Because the internal phase reaction is not inhibited by enzymes, highly sensitive transcription recording is possible.

Examples of the polymer compound having a carbonyl group in its molecular structure that can be used in the present invention include natural semi-synthetic polymer compounds such as gum arabic, pectin, casein, and xanthan gum;
Poly(meth)acrylic acid, poly(acrylic acid-acrylic ester copolymer), poly(methacrylic acid-methacrylic ester copolymer) carboxymethylcellulose,
Examples include hydrolysates of maleic anhydride copolymers such as isobutylene-maleic anhydride copolymer, methyl vinyl ether-maleic anhydride copolymer, and ethylene-maleic anhydride copolymer.

In addition, as inorganic cation ions with a valence of 2 or more, AI”,
It is possible to act on ions such as Mg", Sn", Ca", Pb2+, and in fact substances that produce these ions in aqueous liquids, such as AI (NO3)!

Mg(SO4), CuSO4, Mg(NO+)2.
CuCl2 etc. can be used.

The capsule wall can be formed using the above compound and cationic ions as follows.

First, a predetermined amount of a polymer compound having a carbonyl group is dissolved in water or the like, and particles or the like prepared as the internal phase of the capsule are spread therein. The concentration of the polymer compound varies depending on the solubility of the compound used, the number of carbonyl groups in the molecule, other molecular structures, etc., but is approximately 0.1% in water.
About 10 wt% of N is sufficient.

Next, a substance that generates divalent or higher inorganic cation ions in an aqueous solution is added in an amount that is at least chemically equivalent to the carbonyl group in the molecule of the polymer compound, and encapsulation is performed at a temperature between room temperature and 60°C. . The addition may be carried out by dropping an aqueous solution in which the polymer compound is dissolved while stirring. The particle size of the capsule and the wall thickness of the capsule can be controlled by controlling the concentration of the polymer compound dissolved in water, etc. Further, after the wall material is precipitated by the action of divalent or higher ions, by adding the ions again and continuing stirring, the capsule particles can be stabilized and the particle size can be made uniform.

The capsules obtained in the liquid can be recovered by, for example, filtering with a Nutsche filter and drying.

By the above method, the particle size is 3 to 30 μm and the capsule wall thickness is 0.
．． Capsules of about 0.01 to 1.0 μm can be formed. Further, the glass transition point of this material can be in the range of about 150° C. or higher.

Other configurations of the present invention will be described in detail below.

In the transfer recording medium of the present invention, the microcapsules supported on the support are composed of multiple types of capsules, and if each capsule has a different photosensitive wavelength range and exhibits a different hue, a full-color image can be obtained. It becomes possible to form

For ease of understanding, in the following explanation, microcapsules consist of three types: elementary bodies (A), (B), and (C).
The sensitive wavelength range of these capsules is (A) 300-36
0 nm, (B) 360-430 nm, (C) 4
30 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 initiator used in the present invention has an absorption maximum of λ = 300 to 360 nm, and includes benzyl, 4
, 4'-dimethoxybenzyl, 4.4'-dimethylbenzyl, 4,4'-dihydroxybenzyl, and other diketone compounds, and those with an absorption maximum of 360 to 430 nm, such as thioxanthone, 2-chlorothioxanthone, isopropylthioxanthone, 2.4 -thioxanthone derivatives such as diethylthioxanthone and 2,4-diisopropylthioxanthone, and those having an absorption maximum of 430 nm or more, such as 7-diethylamine-3,3°-carbonylbiscoumarin, 3,3°-carbonylbis(7-dinithylamino) A composite initiator of a coumarin derivative such as coumarin) and an S-triazine derivative or camphorquinone is used, but the present invention is not limited to the above-mentioned initiators.

The polymerizable compound having an ethylenically unsaturated double bond in the element bodies (AC, (B), (C)) is a compound having at least one ethylenically unsaturated double bond in its chemical structure, It has the chemical form of monomer oligomer and polymer. Examples include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid, and ethylene glycol and triethylene glycol. , esters with aliphatic polyhydric polyol compounds such as tetraethylene glycol, trimethylolpropane, 1,3-butanediol, pentaerythritol, dipentaerythritol,
Furthermore, urethane acrylates, urethane methacrylates, and urethane methacrylates synthesized by polyaddition reactions of polyisocyanates (which may be reacted with polyols as necessary), alcohols and amines containing ethylenically unsaturated double bonds; Examples include epoxy acrylates synthesized by addition reaction of epoxy resin and acrylic acid or methacrylic acid, polyester acrylates, and spin acrylates.

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 polyolefin, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, or copolymers thereof, as well as polyvinyl alkyl ether, polyethylene, polypropylene, polystyrene polyamide, polyurethane, chlorinated rubber, cellulose derivatives, etc. The present 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
d-3], Red 122, etc., azo lake type, monoazo type, quinacridone type pigments can be used, and cyan pigments include C, 1, Pigment No., 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° 5 6 -154 disazo type, benzimidacylon type, etc. can be used, but the present invention is not limited thereto.

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

(C) can be used as a particulate element having a particle size of about 3 to about 50 μm, preferably 7 to 15 μm when solid, or as an element (A).
), (B), and (C), even if they are liquid or solid, are physically and chemically attached to a support as microcapsules with a particle size of about 3 to about 50 μm, preferably 7 to 15 μm, to form a recording medium. shall be. The average particle size of the elements (A), (B), and (C) is preferably about 10 μm. When the microcapsules are bound onto the support using an adhesive, the binder is preferably an epoxy adhesive, a polyester adhesive, a urethane adhesive, an acrylic adhesive, a urethane acrylic adhesive, an ethylene-vinyl acetate copolymer adhesive, or the like. 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 light to be irradiated is sequentially irradiated with wavelengths to which the image forming elements (A), (B), and (C) react. For example, image forming element (A), (
If B) and (C) are colored magenta, cyan, or yellow, the wavelengths λ(M), n(C), λ(
Light 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 heat generating resistors 20b and 20c of the thermal head, for example, are caused to generate heat. Then, among the image forming elements containing a magenta coloring material, the image forming element to which both heat and light of wavelength λ (M) were applied (the hatched part in Fig. 1a; hereinafter, the cured image The formed element body is shown by hatching) is cured.

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, 20
When b and 20c generate heat, among the image forming elements containing the cyan coloring material, the image forming element to which the heat and the light of wavelength λ(C) are applied is cured. Furthermore, as shown in FIG. 1C, while irradiating light with a wavelength of
c, When 20d is heated, among the image forming elements containing the yellow coloring material, the image forming element to which heat and light of wavelength λ(Y) have been applied is cured, and the image that is not finally cured A transfer image is formed on the transfer recording layer l by the forming element.

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 particularly effective when using a transfer medium with low surface smoothness. 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 connected to a rotatable shaft 2 provided in the device main body M.
It is removably loaded into a.

9 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.
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 constant pack tension is applied to the supply roll 2 by, for example, a hysteresis brake (not shown), and this tension and the guide rollers 12a, 12b cause the transfer recording medium 1 to move toward the thermal head 3a. It is configured to be conveyed while being pressed against the object at a certain pressure and at a certain angle.

0 The recording section is composed of a heating means for applying thermal energy to the recording medium 1 and a light irradiation means for applying light energy to the transfer recording medium 1.

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 dot of 8 dots/mm.
A-4 size, line type heating resistor rows 20 are arranged, and as described above, the support lb side of the transfer recording medium 1 is applied with a predetermined pressure to the heating resistor row 20 by back tension during conveyance. It is configured to be pressed into contact. The image signal is generated from a control unit of a facsimile, an image scanner, an electronic blackboard, or the like, depending on the purpose.

On the other hand, the transfer recording layer l facing the thermal head 3a
A light irradiation means is provided on the a side. As the light irradiation means, the light emitting wavelength ranges are different from each other, and the element bodies (A) and (B
), (C) can be reacted individually, for example, Toshiba FL10A70E35/33T
15 (peak wavelength 335 nm), Toshiba FLIOA7
0E39/33T15 (peak wavelength 390 nm), Toshiba FL10A70B/33TI5 (peak wavelength 45 nm)
However, as shown in Fig. 2(b), a glass with a thickness of 2 mm (manufactured by 5CHOTT, West Germany, D
A rotating body 3C made of a cylinder made by IIRAN50) is rotatably supported by three pairs of rollers 3d, 3e, and 3f, and the roller 3d is driven and rotated by a motor to rotate at a constant speed. good.

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.

The light of phosphor +00.101.102 has a peak wavelength of 300 to 360 nm, 360 to 430 nm, and 4, respectively.
It is in the range of 30 to 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 (
Ca (PO4) 2 TI) or thallium-activated calcium zinc phosphate ((Ca-Zn) 3 (PO4
) 2: Tl'') as a main component is preferable. These fluorescent materials have high emission 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) 2P20
7.Eu) as a main component is preferable.

As the phosphor +02 having a peak wavelength in the wavelength range of 430 to 600 nm, europium activated barium magnesium aluminate (Ba, MgAl + aOz7.Eu)
Preferably, the main component is

As you can see in Figure 4, 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 has a peak wavelength of 335 nm (Graph 100), europium-activated strontium magnesium birophosphate 3 has a peak wavelength of 395 nm (Graph 101), and europium-activated barium magnesium aluminate has a peak wavelength of 453 nm. has.

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.

Manufacturing method of microcapsules: 100 g of water, a NaOH aqueous solution of isobutylene-maleic anhydride copolymer (Kureha Chemical Co., Ltd.: Isoban-10) (
(polymer concentration 20.6%) were mixed, 3.1 g of pectin was added thereto, and the mixture was stirred for 20 minutes.

The pH was then adjusted to 4.0 with a 20% sulfuric acid solution.

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. Transfer the emulsion to a 500 mJ2 beaker,
The solution temperature was set to 0° C., and the solution was stirred with a stirring blade all day and night to remove the solvent. The emulsion was poured into 0° C. water and 1β, stirred for a while, and then filtered using a Nutsche filter, and the obtained internal phase particles were dried for one day and night in a 40° C. dry air dryer.

5 g of carboxymethyl cellulose (General Science Corporation) was dissolved in 200 g of water.
The internal phase particles were developed and 1 wt% Mg (
SO4) aqueous solution was dropped to deposit the wall material. After the wall material was precipitated, 5 cc of a 10 wt% Mg (SO4) 2 aqueous solution was added and stirred for 1 hour, and then the microcapsules were filtered with a Nutsche filter and dried.

The components shown in Table 1, Table 3, Table 2, and Tables 2 and 3 were similarly made into microcapsules to produce elementary bodies (A), (B), and (C).

In addition, the average particle size of the elementary bodies (A), (B), and (C) is 8.0~
12.0μm, the glass transition point of the wall material is 140℃~160℃
It was about ℃.

Thermoplastic polyester (Nippon Gosei Kagaku Kogyo, Polyester-011) was diluted with toluene and applied to a thickness of 0.5 μm on a PET (polyethylene terephthalate) film (6 μm thick) using an applicator. Next, the element (A) was sprinkled onto the film and developed, and unbound particles were shaken off. The film was sandwiched between PET films with a thickness of 100 μm and 50 μm, and passed through a heat roller at a temperature of 110°C and a pressure of 2 to 3 kg/cm2, then the PET film was peeled off and the element body (
A transfer recording medium was prepared by firmly adhering A) to a PET film. Similarly, a transfer recording medium was prepared by mixing equal amounts of the elements (B), (C), and elements (A), (B), and (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 2 mm 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 pyrophosphate, and europium-activated barium magnesium aluminate, each at a 120-degree angle. used.

Next, as shown in the timing chart of FIG. 5, the lamp and thermal head were energized. Note that the voltage and drive signal for energizing the thermal head were controlled so that the temperature of the element body (A) was approximately 100°C. By varying the energization time τ and finding the time at which the element (A) at the point where the signal was applied stopped being transferred at all, the pulse width (defined as sensitivity) was as follows for light of ^p = 335 nm. 15m5.
Element body (B) and element body (C) have λp =, 390 nm, λ
For light with p = 450 nm it was 25 ms respectively.

Next, when the transfer recording medium formed from the elements (A), (B), and (C) was energized at the timing shown in FIG. 6, a good high-quality multicolor image could be formed.

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 200 g of water in which 5 g of polymethacrylic acid (General Science Corporation) was dissolved.
Microcapsules were prepared in the same manner as in Example 1.

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.

[Effects of the Invention] As explained above, according to the present invention, by using microcapsules in which a wall material is formed by causing a cationic inorganic ion of divalent or higher valence to act on a polymer compound having a carbonyl group, low temperature Even when cured, it becomes a wall material with a high Tg, a capsule with high sensitivity and good transferability can be obtained, and a multicolor transfer recording medium with little fogging and white spots can be provided.

[Brief explanation of 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. 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 diagram showing the relationship between wavelength and transmittance of a light source that can be used in the present invention, that is, a quartz tube carrying a phosphor. FIG. 4 is a graph showing an example of the light emission characteristics of the phosphor. FIG. 5.6 is a diagram showing a timing chart of signals applied to the light source and the thermal head in Example 2. l: Transfer recording medium 1a: Transfer recording layer 1b = Support 2: Supply roll 2a: Shaft 3a: Thermal head 3C: Rotating body 3d"f: Roller pair 3g: Light source 4a: Transfer roller 4b = Pressure roller 5: Peeling Roller 6: Winding roll 12a-d Roller 20: Heating resistor row 1 2 20a-d: Heating resistor 100, 101.102: Fluorescent material M: Main body

Claims (1)

[Claims] In a transfer recording medium in which a recording layer consisting of microcapsules is provided on a support, the internal phase of the microcapsules contains at least a photopolymerization initiator and an ethylenically unsaturated material whose transfer characteristics change upon application of light and thermal energy. Contains a compound having a double bond, and the wall of the microcapsule is made of a wall material having a structure consisting of at least a polymer compound having a carbonyl group in its molecular structure and an inorganic cation ion with a valence of two or more. A transfer recording medium characterized by: