JPS63139338A - Recording medium - Google Patents

Abstract

PURPOSE:To obtain the titled medium having high sensitivity and preservative stability and excellent light fastness and capable of giving a clear and high gradient image and having less environmental dependence at the time of transferring by incorporating a coloring agent and a specific sensitizing agent which sensitizes by light energy and heat or energy capable of converting to the heat to a transfer recording layer. CONSTITUTION:The transfer layer of the titled medium contains the sensitive component which sensitizes by the light energy and the heat or the energy capable of converting to the heat. The sensitive component is composed of at least 3 kinds of a photopolymerization initiator, a monomer having an unsatd. double bond or its oligomer and a binding component. The molecular weight of said monomer or oligomer is a range of 350-3,000. The binding component is composed of a thermoplastic high polymer which has the weight average molecular weight of >=5X10<4> and the degree of dispersion of the molecular weight of <=5. The content of the high polymer contd. in the recording layer is 5-90wt.%. The photopolymerization initiator is preferably exemplified by a radial initiator such as an azo compd., an org. sulfur compd., a carbonyl compd., and a halogen compd., etc.

Description

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

(Prior 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. As one such recording method, the thermal transfer recording method uses a compact device, has no noise, and is easy to operate.
It has the feature of excellent storage stability. However, in conventional thermal transfer recording methods, the transfer recording performance, that is, the print quality, is greatly affected by the surface smoothness of the transfer medium, such as paper, or the printing speed is determined mainly by the heat supply from the thermal head. Therefore, there were problems such as high-speed recording being difficult. Furthermore, 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 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 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.

Further, US Pat. No. 4,399,209 discloses a method for forming a multicolor visible image using a color forming agent and a color developer. U.S. Pat. No. 4,399,209 uses a recording medium in which microcapsules containing a photosensitive composition and a coloring agent are arranged on a base material, and uses mainly ultraviolet light converted in accordance with a recorded image to generate microcapsules. The photosensitive composition in the capsule is cured to form a transferred image, and this transferred image is superimposed on a recording medium having a color developing layer and passed through a nip between a pair of pressure rollers to destroy the microcapsules. A transfer forming system for developing an image is disclosed. A multicolor image is obtained by image-formingly transferring a color former to an image forming sheet, where the color former reacts to form an image.

Further, US Pat. No. 4,416,966 discloses a self-contained color developer in which the color developer is present on the same support surface as the photosensitive microcapsules.
) discloses an image forming system. When the imaging sheet is passed through a pressure roll after exposure with mainly ultraviolet light converted in accordance with the recorded image, the microcapsules rupture and the internal phase is released imagewise. The color former then migrates to a developer, usually provided in a separate layer, where it reacts and forms a color image.

Both of the above two recording methods contain a photopolymerization initiator in a microcapsule, and the photopolymerization initiator is made to have different photosensitive wavelength ranges. The contents inside the microcapsules are cured using ultraviolet light. However, a common problem with these methods is that the means used for image formation mainly irradiates only ultraviolet light, that is, optical energy, onto a substrate on which microcapsules are arranged, thereby forming a transferred image on a recording medium. Therefore, in order to obtain clear recorded images at high speed, it was necessary to use a photosensitive material with high sensitivity to light or to irradiate it with high energy light.

However, high-sensitivity recording media that utilize only photoreactions have the fatal drawback of high reactivity when irradiated with light and poor storage stability near room temperature. In addition, to obtain high-energy light, the equipment must be large, and to obtain multicolor recording, the equipment must be large, and the cost of the equipment is also high.
Practically undesirable. In addition, since the above method forms an image using only light energy, it can be used when outputting an image in response to an external signal, such as in a printer, or when reading an image from a color original, as in a color copying machine. This is inappropriate when applying image information to a recording medium after converting the image into a digital signal using a color image scanner. That is, when irradiating high-energy light, it is necessary to use short wavelength light, mainly ultraviolet light, and a digitally controllable light source for ultraviolet light is currently not available. For example, optical heads such as liquid crystal shutter arrays and LED arrays have been devised as a method for obtaining digital light sources, but although these are suitable for miniaturization, liquid crystal molecules deteriorate at wavelengths in the ultraviolet region. UV light cannot be extracted.

Furthermore, since the color development method uses leuco dye, it has the drawback that the stability of recorded images is essentially poor.

Furthermore, in order to facilitate development by applying pressure after exposure, the contents of the microcapsules need to be a photosensitive composition that has a liquid phase at room temperature, resulting in poor storage stability and the resulting images remain unrefined. Due to the destruction of the reactants, there is a musty odor, which is a property that is undesirable in practice.

[Problem that the invention seeks to solve]

The present invention provides an image forming method that solves the above conventional problems,
In other words, high-quality transfer images can be formed, high-speed recording is possible,
It is capable of half-tone recording and can be effectively applied to an image forming method that can obtain a clear multicolor image without color shift without making complicated movements of the transfer medium even when obtaining a multicolor transfer image. The main purpose is to provide recording media.

A further object of the present invention is to provide a recording medium that does not require a special color developing layer and can form a clear transferred image on commonly used plain paper with low surface smoothness.

A further object of the present invention is to provide a highly sensitive recording medium that can record digital images with low power without requiring a special digital light source with high optical energy.

Furthermore, an object of the present invention is to provide a recording medium with high storage stability and high sensitivity.

A further object of the present invention is to provide a recording medium on which recorded images with excellent light resistance can be obtained.

A further object of the present invention is to provide a recording medium that can produce clear, multicolor recorded images with high gradation using a small and inexpensive device.

A further object of the present invention is to provide a recording medium that can be used in an image forming method with extremely little environmental dependence during transfer image formation.

[Means for solving problems]

The above-mentioned object of the present invention is to create a transfer recording layer whose physical properties governing its transfer characteristics change by applying at least one type of energy including light simultaneously in correspondence with image recording information. A recording medium provided on a support, wherein the transfer recording layer contains at least a colorant and a sensitive component that is sensitive to application of light energy and heat or heat-convertible energy, and the sensitive component is photopolymerized. Initiator, 1,000 polymers with unsaturated double bonds
or an oligomer and a binding component, the monomer or oligomer having an unsaturated double bond has a molecular weight of 350 or more and 3000 or less, and the binding component is a thermoplastic polymer compound. and the weight average molecular weight of the polymer compound is 5 x'to
' or more, and the molecular weight dispersity (weight average molecular weight/number average molecular weight) is 5 or less, and the content of the polymer compound in the transfer recording layer is 5 to 90% by weight. achieved by.

Transfer recording using the recording medium of the present invention, that is, formation of a transfer image, basically involves transferring at least one kind of complex energy including light to the transfer recording layer as described above and converting it into image recording information. The physical properties that govern the transfer characteristics are changed by simultaneously applying them in a corresponding manner, and the transferred image formed by the portion where the physical properties have changed is transferred to the transfer medium using, for example, heat and pressure. It will be done. Specifically, the physical properties that govern the transfer characteristics include changes in the softening temperature of the transfer recording layer and changes in tackiness based on the softening temperature. In addition to light, the plurality of types of energy used to form a transferred image include heat or electricity that can be converted into heat, ultrasonic waves, pressure, and the like.

Incidentally, as long as the transfer recording layer contains each of the above-mentioned components, an image-forming element formed by coating a support with a minute image-forming element formed by supporting each of these components in microcapsules, etc. It can take various forms, such as a layer with a distribution of particles or a layered structure formed by simply coating a composition obtained by mixing these components on a support. It is preferable that a forming element body is provided.

In order to explain a preferred example of the image forming method using the recording medium of the present invention, a case in which a transferred image is formed using light and thermal energy will be described with reference to FIGS. 1a to 1d.

The time axes (horizontal axes) in FIGS. 1a to 1d correspond to each other. Further, the transfer recording layer contains at least three types of sensitive components: a photopolymerization initiator, an oligomer or oligomer having an unsaturated double bond, and a binding component, which will be described later.

In Figure 1a, heating means such as a thermal head is heated from 0 to t3.
This figure shows the change in surface temperature of the heating means when it is thermally driven. The recording medium that is pressed against the heating means shows a temperature change as shown in FIG. 1b as the temperature of the heating means changes. The transfer recording layer of this recording medium contains a monomer or oligomer having a melting point or softening point ('Tm), and the viscosity decreases rapidly at a temperature exceeding Tm, as shown in FIG. 1c. At this time, when light is irradiated as indicated by the symbol B in the figure, the photopolymerization initiator in the transfer recording layer is activated, and the probability that the polymerizable polymer will polymerize increases dramatically. , curing progresses rapidly and the softening temperature of the transfer recording layer rises to Ts-+Ts'. This situation is shown in 1d
As shown in the figure. On the other hand, in the portions of the transfer recording layer where heating and light irradiation were not performed simultaneously and effectively, the softening temperature does not increase, as indicated by the symbol A in the figure. Therefore, for example, if the transfer recording layer is heated to Tr that satisfies Ta<Tr<Ta' (where Ta and Ta' are transfer temperatures that change depending on fluctuations in the glass transition point of the transfer recording layer) and is pressed against the transfer medium, Portions where the softening temperature has increased as the curing progresses are not transferred, and portions where the softening temperature has not increased are transferred to form an image recording.

FIG. 2a is a schematic diagram of an example of an apparatus suitable for forming an image using the recording medium of the present invention. This recording device selectively drives a single heating means equipped with a plurality of heating elements in accordance with an image signal, and at least the position of the driven heating element according to the color tone of an image to be recorded. This is for carrying out a forming method for forming a multicolored transfer image by irradiating different lights, and the one indicated by reference numeral 1 in the figure is a film (
2 is a supply roll around which the recording medium 1 is wound; 3 is a low-pressure mercury lamp, a high-pressure mercury lamp, a metal octroid, a fluorescent lamp, and a xenon lamp for uniformly irradiating the recording medium 1 with light; A light irradiation means such as a lamp, and 4 a heating means such as a thermal head which causes a control circuit 5 to generate heat pulses based on an image signal. Here, the recording medium 1 can also be an energization type recording medium that generates heat by energizing it, and in this case, the heating means 4 is preferably an energization head that generates electric pulses for energization. This heating means 4
is equipped with a plurality of heating elements (for example, the heating element may be a heating resistor when the heating means is a thermal head, or an electrode when the heating means is an energizing head). The heating elements may be arranged in a single row, or may be arranged in any other desired manner, such as in a matrix or in multiple rows. Further, the heating elements may be each separated, or may be a continuous rod-shaped energized heat generating material separated by a plurality of electrodes.

8.9 is a transfer means, 8 is a beat roll having a heater 7 inside, 9 is arranged opposite to the beat roll 8, and a transfer medium 10 such as plain paper or an OHP sheet and a recording medium 1 are sandwiched therebetween. A pinch roller 11 presses the recording medium, and a winding roll 11 winds up the recording medium after transfer recording. The recorded image 12 is transferred to the transfer medium 10 and separated from the recording medium.

Now, the recording medium 1 fed out from the supply roll 2 is given a heat pulse based on an image signal by the thermal head 4 . At the same time that a thermal pulse is applied to the recording medium 1 by the thermal head 4, light of different wavelengths is sequentially irradiated from the lamp 3 in synchronization with the thermal pulse based on a (color) image signal. The principle of the transfer image forming process is as explained in FIGS. 1a to 1d. The lamp 3 shown in the figure is shown schematically, and it is preferable to irradiate light with different wavelengths using a plurality of lamps. That is, if one lamp irradiates light of one wavelength, the same number of lamps as the types of color tones exhibited by the transfer recording layer are required.

A transferred image is formed on the transfer recording layer 1b by the thermal head 4 and the lamp 3, and this transferred image is transferred to the transfer medium 10 by the heat roll 8 and the pinch roller 9.

In this case, as described above, it is basically one selective heating means such as a thermal head that is controlled based on the image signal, and the control circuit can therefore be simple. As a result, it becomes easy to realize a compact and highly reliable apparatus and to form stable images.

Furthermore, it is also possible to control both heating and light irradiation according to the image signal. For example, heat is applied in the same manner as in the example shown in FIGS. 1a to 1d, and light is irradiated to the position corresponding to the heating resistor that generates heat. In other words, in the examples shown in Figures 1a to 1d, light is uniformly irradiated, but when both heating and light irradiation are controlled, the light irradiation position is controlled so as to match the heat generation position of the thermal head. Ru. In this way, when a wavelength-dependent image-forming element is used as the image-forming element in the transfer recording layer, the wavelength of light is sequentially changed according to the color of the image-forming element, and a temperature-dependent image-forming element is used as the image-forming element. When using, the heating temperature is changed depending on the color of the image forming element.

Control of both heating and light irradiation as described above is advantageous in increasing the contrast of changes in physical properties of a transferred image, and it becomes easy to obtain a sharp image. Furthermore, since the influence on the image when one of the two is deteriorated is halved, the device can be highly reliable.

Above, the formation of a multicolor image has been mainly explained, but if the colorant contained in the transfer recording layer 1b is one type, the coloring agent 2a
It is also possible to form monochrome images with the apparatus shown in the figure.

The recording medium of the present invention contains at least a photopolymerization initiator, a monomer or oligomer having an unsaturated double bond, and a binding component as sensitive components of the transfer recording layer. As described above, transfer recording using the recording medium of the present invention basically involves forming a transfer image using energy including light, and transferring the transfer recording layer on which the transfer image has been formed to a medium to be transferred. However, the changes in physical properties that govern the transfer characteristics caused by the application of energy including light must be as large as possible at the time of forming the transferred image, that is, the sensitivity must be high, and the transfer recording layer must be It is desirable that the image be efficiently transferred to the transfer medium.

In order to achieve such a high-sensitivity record, the present inventors have conducted intensive studies and found that there is a close relationship between the sensitivity and the molecular weight of the oligomer or oligomer having unsaturated bonds constituting the above-mentioned sensitive component. There is also a close relationship between the transfer rate of the transfer recording layer and the above molecular weight, and furthermore, using an appropriate amount of a thermoplastic polymer compound as a binding component is effective in improving sensitivity and transfer rate. This discovery led to the present invention. That is, the lower the molecular weight of the polymer or oligomer, the higher the sensitivity can be obtained, but the transfer rate is lower; conversely, the higher the molecular weight is, the higher the transfer rate is, but the sensitivity is lower.

Here, physical property changes that govern transfer characteristics include polymerization or crosslinking of monomers or oligomers as described above,
There is a change in adhesion with the transfer medium due to an increase in the glass transition point or softening point, but generally the glass transition temperature or softening temperature of polymer compounds is due to an increase in molecular weight in a relatively low molecular weight region. In the high molecular weight region, the value is generally constant regardless of the molecular weight. In the present invention, since a monomer or oligomer with a low molecular weight is used, changes in the glass transition temperature and softening temperature due to the polymerization reaction become large, and it is believed that a highly sensitive recording medium is obtained. Furthermore, by using an appropriate amount of a thermoplastic polymer compound with excellent film properties together with these polymers or oligomers, the transfer rate was also improved.

The thermoplastic polymer compound as a binding component contained in the recording medium of the present invention preferably has a high molecular weight in order to improve the film properties of the recording medium, and in order to obtain a good transfer rate, the weight average molecular weight (Mw) is It needs to be 5×104 or more. However, since this transfer rate varies depending on the shape of the sensitive component, the type of support, and the proportion of the polymer compound in the sensitive component, it is desirable to set it to 1X10' or more.

In addition, the thermoplastic polymer compound has a molecular weight dispersity (the value obtained by dividing the weight average molecular weight by the number average molecular weight (Mn)).
If the dispersion is large and contains a large amount of low molecular weight components, the film properties will be reduced, so it is necessary to set the degree of dispersion to 5 or less.

Examples of such polymer compounds include acrylic resins, styrene resins, vinyl chloride resins, and chlorinated polyolefin resins.

In addition, the thermoplastic polymer compound L is contained in the transfer recording layer.
It is necessary that the content be % to 90% by weight (hereinafter referred to as ``abundance''). If the amount of wood is less than 5wt, the film properties will deteriorate and the transfer rate will decrease. On the other hand, 90wt!
When k is exceeded, the proportion of polymerizable molecules or oligomers in the transfer recording layer decreases, resulting in a decrease in sensitivity.

In the recording medium of the present invention, the transfer rate varies depending on the type of support used, the shape of the transfer recording layer, the transfer temperature, the transfer method, etc., and the sensitivity also varies depending on the type and concentration of the photopolymerization initiator, as well as the monomers and oligomers used. Although it varies depending on the reactivity of
In order to suppress the temperature to below about 0 to 150°C and to obtain practical sensitivity using a photopolymerization initiator that is generally available at low cost, it is particularly preferable that the proportion of the above-mentioned polymer compound is in the range of 1O to 40wtX. preferable.

The polymer or oligomer having an unsaturated double bond as a sensitive component contained in the recording medium of the present invention needs to have a molecular weight of 350 or more and 3000 or less. In this range, the lower the molecular weight, the higher the sensitivity, but if the molecular weight is less than 350, only an extremely low transfer rate can be obtained. Furthermore, if the molecular weight exceeds 3000, not only the sensitivity will be extremely reduced, but also the compatibility with the above-mentioned thermoplastic polymer compound will be significantly deteriorated, making it impossible to obtain a uniform film.

Examples of such polymers or oligomers having unsaturated double bonds include epoxy acrylates, urethane acrylates, oligoester acrylates, etc. Commercially available products include, for example, Aronix M- manufactured by Toagosei Chemical Industry Co., Ltd. 1100, M-1200, M-80
60, V-88530 manufactured by Osaka Uchiki Kagaku Kogyo Co., Ltd., and the like.

The coloring agent contained in the recording medium of the present invention is a component contained in order to form an optically recognizable image, and various pigments and dyes are used as appropriate. Examples of such pigments and dyes include carbon black, yellow lead, molybdenum red,
Inorganic pigments such as Red Garla, Hansa Yellow, Benzidine Yellow, Brilliant Carmine 6B, Lake Red C,
Examples include organic pigments such as Permanent Red F5R, Phthalocyanine Blue, Victoria Blue Lake, and Fast Sky Blue, leuco dyes, and phthalocyanine dyes.

As the photopolymerization initiator in the present invention, radical initiators such as azo compounds, organic sulfur compounds, carbonyl compounds, and halogen compounds are preferable.

For example, carbonyl compounds such as benzophenone, benzyl, benzoin ethyl ether, 4-N,N-dimethylamino-4'-methoxy-benzophenone, sulfur compounds such as dibutyl sulfide, benzyl disulfide, decylphenyl sulfite, etc. Examples include peroxides such as -butyl peroxide and benzoyl peroxide, halogen compounds such as carbon tetrachloride, silver bromide, and 2-naphthalenesulfonyl chloride, and nitrogen compounds such as azobisisobutyronitrile and benzenediazonium chloride.

In addition to these components, the transfer recording layer may contain hydroquinone, p-methoxyphenol, p-tert-butylcatechol, 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol), etc. It may also contain a stabilizer and the like.

Based on the present invention, it is possible to use a recording medium coated in a single layer on a base film, but in order to prevent a decrease in sensitivity due to #12S inhibition in the atmosphere, a film made of polyethylene, polypropylene, etc. can be used for recording. It is also effective to press the adhesive onto the medium and peel it off after the transfer image is formed. On the other hand, if one image forming element is granulated and coated with a high molecular compound having low oxygen permeability, it is possible to prevent a decrease in sensitivity and further improve image resolution. Furthermore, a recording medium compatible with color recording can be obtained by microcapsulating a plurality of compositions consisting of a colorant and a photopolymerization initiator having different absorption wavelength regions and randomly supporting them on a base film.

When microcapsules are used in the image forming element constituting the transfer recording layer, the above-described material is contained in the core portion. Examples of materials used for the wall material of microcapsules include gelatin, gelatin-gum arabic, ethyl cellulose, cellulose-based urea-formalin such as nitrocellulose, nylon, tetron, polyurethane, polycarbonate, maleic anhydride copolymer, vinyldene chloride, Examples include polyvinyl chloride, polyethylene, polystyrene, and polyethylene terephthalate.

In the recording medium of the present invention, the thickness of the transfer recording layer is preferably 1 to 20 μm, particularly preferably 3 to 10 μm.

When the transfer recording layer is composed of image forming elements of microcapsules, the particle size of the macrocapsules is 1 to 20 μm.
is preferred, particularly a particle size of 3 to 10 microns. Also,
The particle size distribution of microcapsules is ±5 with respect to the number average diameter.
It is preferably 0% or less, particularly preferably ±20% or less. The thickness of the wall material of the microcapsule is preferably 0.1 to 2.0μ, particularly preferably 0.1 to 0.5μ.

As the microencapsulation method, any conventionally known method can be applied, such as simple coacervation method, complex coacervation method, interfacial polymerization method, 1n
- Situ polymerization method, interfacial precipitation method, phase separation method, spray drying method, air suspension coating method, mechanochemical method, etc. are used.

The microcapsule image forming element is bound to the substrate using a coating binder such as polyvinyl alcohol (PvA) or epoxy adhesive. The thickness of the coating binder is preferably 0.1 to 1 μm.

When using the recording medium of the present invention for multicolor image formation,
In order to reproduce a color image, the image forming element constituting the transfer recording layer needs to have wavelength dependence depending on the type of coloring material. In other words, when the transfer recording layer is composed of image forming elements of n types of colors, the reaction rate seems to change rapidly with light of different wavelengths for each colored color, that is, with n types of different wavelengths. The distribution layer of the image forming element is composed of a combination of sensitive components. As a combination of such sensitive components, for example, two-color recording is made possible by using a component that is sensitive to approximately 400 to 500 nm, such as a sensitizer, and a component that is sensitive to approximately 480 to 60 Qnm, such as a sensitizer. . In this case, although the wavelength range of 480 to 500 nm overlaps, the photosensitive range of both is a low sensitivity range, and by appropriately selecting a light source, it is possible to almost completely separate the two.

Further, by combining these with an azo compound sensitive to 340 to 400 nm or a halogen compound sensitive to 300 to 400 nm, it is possible to use a three-color image forming element, making it possible to develop full-color recording.

Further, as a combination of initiators, a combination of 02-chlorothioxanthone/ethyl p-dimethylaminobenzoate and (1) dichlorobenzophenone/ethyl p-dimethylaminobenzoate can also be used. The light source used for this combination is: ■The peak wavelength is 390n.
m fluorescent lamps and ■ fluorescent lamps with a peak wavelength of 313 nm can be used. The irradiation energy required to obtain the same reaction amount (equal transfer concentration) is, assuming that the combination of ■-■ is 1,
-■ is 4, and the combination of ■-〇 is 1. l, ■-■ is 5.

Therefore, by setting the irradiation energy of ``1'' to 1 and the irradiation energy of ``1'' to 1.1, the reactions ``■'' and ``2'' can be distinguished.

Furthermore, even if the wavelength dependencies of the sensitive components contained in image forming elements exhibiting different color tones are approximately equal, it is possible to impart wavelength dependence through the filter effect of the colorant.

For example, if the colorant is blue, this blue colorant reflects and transmits blue light wavelengths of approximately 400 to 500 nm, and green to red wavelengths of approximately 400 to 500 nm.
Absorbs light with a wavelength of 00 to 700 nm. Therefore, an imaging element containing a blue colorant is sensitive to blue light. For the same reason, if it has a red colorant, it can be sensitive to red light. Therefore, even if there is a sensitive component that is sensitive to light from blue to red, it is possible to make it wavelength dependent by using the colorant.

In the recording medium of the present invention, radical reactions in the transfer recording layer may be suppressed due to oxygen in the air. In order to prevent this, it is preferable to apply, for example, an aqueous polyvinyl alcohol solution to which a small amount of a surfactant is added as an oxygen-preventing layer on the transfer recording layer. This oxygen prevention layer is removed by washing with water after the transfer image is formed. In addition, in the case of a microencapsulated element, the wall material can have a function as an oxygen prevention layer.

The recording medium of the present invention can be manufactured, for example, as follows.

The recording medium of the present invention is prepared by melt-mixing each component such as a sensitive component, a photopolymerization initiator, a sensitizer, a stabilizer, a colorant, etc., and applying the mixture onto a substrate using an applicator or the like. In addition, when the transfer recording layer is constituted by an image forming element, the above-mentioned components are made into minute image forming elements by spray drying method etc. for each color, and then each color image forming element is formed with a binder such as a polyester resin. After sufficiently mixing the body in a solvent such as methyl ethyl ketone or ethylene glycol diacetate, the desired recording medium is prepared by solvent-vent coating on a film such as polyimide, and further drying at 80°C for 3 minutes to remove the solvent. You can get it.

When the image-forming element is composed of microcapsules, the image-forming element of microcapsules is manufactured, for example, by a method detailed in the Examples below,
In the same manner as in the case of particulate image forming elements, it is applied onto a substrate by a solvent coating method.

Further, the particulate element may be electrostatically attached to a support, and in that case, the particulate element or the support or both are corona-charged or tribo-electrified and attached.

In the present invention, methods for physically or chemically supporting the image forming element on the support include the above-mentioned solvent coating method and electrostatic adhesion method; Examples of the method include a method in which functional groups are provided on each of the surfaces where the image forming element and the support come into contact, and chemically bonded to the image forming element and the support.

The support is not particularly limited, and conventionally known supports can be used as they are.

Examples include polyester, polycarbonate, triacetylcellulose, nylon, polyimide, polyethylene terephthalate, aramid resin, etc., and these may be in the shape of a film, plate, drum, or sphere.

(Example〕 The present invention will be further explained below with reference to Examples.

Example 1 The components shown in Table 1 were dissolved in dichloromethane solvent,
6 scales thick polyethylene terephthalate (PET)
Thickness 4ILI+ on film by solvent coating method
It was applied at. An aqueous solution of polyvinyl alcohol (M = 1200) was applied onto this film by a solvent coating method to form an oxygen-preventing film (thickness: 10 mm), which was used as a sample.

Next, the sample prepared by the above method was placed on a hot plate heated to a predetermined temperature, and a high-pressure mercury lamp with an input of 2 Kw was installed at a position facing the sample, and ultraviolet light was irradiated for a predetermined period of time. After irradiation with ultraviolet light, the sample was placed on a hot plate at 100°C for 3 seconds to accelerate and homogenize the reaction, and then the polyvinyl alcohol (PVA) oxygen barrier film was removed by washing with water.

Next, the transfer recording layer of this sample had a surface smoothness of 1.
After stacking plain paper in the range of 0 to 30 seconds, the sample with the stacked papers was sandwiched between the beat roll 8 and pinch roll 9 of the device having a portion corresponding to the separation transfer section shown in Fig. 2a described above. Transported. The heat roll 8 was an aluminum roll having a 300 W heater inside and whose surface was coated with silicone rubber 2 mm thick, and the heater was controlled so as to maintain the surface at 150°C. The pinch roll 9 is a silicone rubber roll with a hardness of 50 degrees according to the JIS rubber hardness tester, and the pressure is set to 1 to 1.5 g.
/crn'.

The PUT film was peeled off from the sample transported in this manner, and the presence or absence of transfer of the exposed portion was examined.

When we performed this operation while varying the exposure time, we found that in samples with an exposure time of 70 m5 or less, transfer occurred even in the exposed area, but in samples with an exposure time of 80 ss or more, no transfer occurred in the exposed area. , this recording medium is 80
It was found that images could be formed at 11IS or higher. In addition, the transfer rate of this recording medium was determined by measuring the optical density of the transfer recording layer coated on the PET film and the optical density of the recording layer transferred to plain paper using a Macbeth RD-914 optical densitometer. , the ratio was calculated to be approximately 100%.

Separately, the sample prepared by the above method was wound into a roll and incorporated into the apparatus shown in FIG. 2a for recording.

The thermal head 4 is A-4 with 8 points/mm.
A size line type with heat generating element rows arranged at the edge part is used, and the base material 1a side of the recording medium 1 is placed in contact with the heat generating elements, and is pressed against the heat generating elements by the tension of the recording medium 1. I did it like that. A high-pressure mercury lamp 3 of about 2 W was placed at a position facing the recording medium 1 at the opposite location.

Next, the heat generation of the thermal head was controlled according to the image signal.

In this embodiment, since the transfer recording layer is treated with light and heat to increase the transfer start temperature, negative recording is performed. That is, the thermal head is controlled such that it does not conduct electricity when a mark signal (black) is present, but conducts current when it is not a mark signal (white) to generate heat.

The energizing energy during this heat generation is 0.8w/do
tx 2. Om sec. In this way, the thermal head was controlled and driven according to the image signal in the manner described above while uniformly irradiating light with a high-pressure mercury lamp.
The recording medium was synchronously conveyed by a stepping motor and a drive rubber roll at a repeating cycle of c, /line.

Next, the PVA film was removed, and after being conveyed in close contact with the recording paper by a beat roll in the separation transfer section shown in FIG. 2a, the PET film was peeled off, and a high-quality image with good fixability was formed.

Example 2 Samples were prepared in the same manner as in Example 1 using the components shown in Table 2 and changing the polymerizable monomer and binding component in the ratios shown in Table 3. Using this method, we determined the minimum exposure time and transfer rate necessary to prevent the exposed area from being transferred to plain paper. The results are shown in Table 3.

If the binding component is less than 5 wt%, the transfer rate will be extremely low, and if it exceeds 90 wt96, the exposure time required for no transfer will be as long as 150 m5, resulting in a decrease in sensitivity. On the other hand, when the binding component is in the range of 5 to 90 wt%, the transfer rate is 60% or more, and the exposure time is also +0%.
It has a high sensitivity of 0m5 or less.

Example 3 As shown in FIG. 3, the transfer recording layer 1b was formed into a microcapsule-shaped image forming element using the components shown in Tables 4 and 5 as the core IC 11d by the method shown below.

That is, a mixture of 10 parts by weight of the components shown in Tables 4 and 5 in 20 parts by weight of methylene chloride was mixed with 200 ml of water in which 1 g of gelatin and a surfactant such as a cationic or nonionic surfactant having an HLB value of at least 10 times or more were dissolved. mix, 60
8.000 to I0,0 using a homomixer under heating at °C.
Stir at 00 rpm to emulsify, and the average particle size is 26. Obtain oil droplets.

Stirring was further continued at 60° C. for 30 minutes, and methylene chloride was distilled off to bring the average particle size to lθμ. Add 20 ml of water in which 1 g of gum arabic was dissolved, cool slowly, and then add NH40H (ammonia) water to 9811.
By doing the above, a microcapsule slurry is obtained, and glutaraldehyde 20% aqueous solution], Oml, is slowly added to harden the capsule walls.

After that, solid-liquid separation was carried out using a Nutsche filter, and 35
C. for 10 hours to obtain a microcapsule-shaped image forming element.

The image forming element formed as described above had an average particle size of 10
-) are mixed in equal amounts, and adhered to a support la made of a polyethylene terephthalate film with a thickness of 6u+ using an adhesive 1f made by dropping a few drops of a surfactant per 100cc in a 5% PVA aqueous solution to form a transfer recording layer. 1b was formed, thereby obtaining a recording medium 1 as shown in the third figure.

The recording medium was wound into a roll and incorporated into the apparatus shown in FIG. 2a. The light source indicated by 3 here corresponds to the absorption characteristics of both compositions, and has an emission peak wavelength of 355 nm (
Mimi FL10A70E35) and emission peak wavelength 39
Two types of fluorescent lamps with a diameter of 0 nm (FL10A70E39 manufactured by Jikken) were arranged in parallel and could be irradiated through a 1 mm slit between them and the sample surface, as shown in FIG. 2b.

When the transfer recording layer 1b is exposed to light and heat of a predetermined wavelength, its softening temperature increases and it is no longer transferred to the recording paper 10. Therefore, as shown in the timing chart of FIG. During recording, power is not applied to the heating elements of the heating element array that correspond to the red color of the image signal, and the white color of the image signal (recording medium 1
25 m5 of electricity is applied to the portion corresponding to the white color), and the fluorescent lamp 3b is uniformly irradiated with a delay of 5+ns. The irradiation time at this time is 45 m5.

Next, when recording yellow, 50 m5 after the end of the irradiation, that is, looms after the energization time, the heating element corresponding to the yellow of the image signal in the heating element array is not energized, and the image signal is white. 25 m5 of current is applied to the portion corresponding to , and after 5 rnS, the fluorescent lamp 3C is uniformly irradiated. The irradiation time at this time was also 45 m5 as described above.

In the manner described above, the thermal head 4 is controlled according to the yellow, red, and white image signals to form a negative image on the transfer recording layer 1b, and the recording medium 1 is synchronously transferred at a repeating cycle of 200 m5/1ine. transport. Furthermore, in the transfer section, the transfer recording layer 1b on which the image has been formed is pressed against the recording paper 10 and heated, thereby making it possible to transfer the yellow and red two-color transfer images onto the recording paper 10. After that, recording medium 1 and recording paper 10
The film is peeled off and an image of the desired color is recorded.

As described above, two-color recording is performed in one shot.

Furthermore, Figure 5 shows the absorption spectrum A of the initiator having the components shown in Table 4, the absorption spectrum B of the initiator having the components shown in Table 5, and the emission spectrum of the two types of fluorescent lamps used in Figure 6. .

Comparative Example 1 A sample was prepared in the same manner as in Example 1 using the components shown in Table 6, and then irradiated with light in the same manner as in Example 1.

After a recording paper was placed on this sample, it was conveyed between a heat roll and a pinch roll kept at 110°C, the PET film was peeled off, and the presence or absence of transfer was observed. When such an operation was performed while varying the exposure time, the minimum exposure time required for the exposed area to no longer be transferred to the paper was 160 m5, and the sensitivity was lowered to 1/2 compared to Example 1. . Also,
Although transfer occurred in samples where the exposure time was 150 Ils or less, the transfer rate was as low as 40%.

Comparative Example 2 A sample was prepared in the same manner as in Example 1 using the components shown in Table 7, and then irradiated with light in the same manner as in Example 1.

After a recording paper was placed on this sample, it was conveyed between a heat roll and a pinch roll kept at 110°C, the PET film was peeled off, and the presence or absence of transfer was observed. When such an operation was carried out while varying the exposure time, the minimum exposure time required for the exposed area not to be transferred to the paper was 90 m5, which was almost the same as in Example 1, but transfer occurred. Exposure time 8
The transfer rate of samples of 0 m5 or less was as low as 20%.

Comparative Example 3 When a sample was prepared in the same manner as in Example 1 using the components shown in Table 8, the polymerizable polymer and the binding component were not compatible and the coating film turned white. In addition, when this sample was irradiated with light in the same manner as in Example 1 and the minimum exposure time required for the exposed area to no longer be transferred to paper was investigated, it took more than 4 seconds, and the sensitivity was extremely low. .

Table 1 Table 382 Table 3 Table 4 Table 5 Table 6 Table 7 Table 8 [Effects of the Invention] As explained above, the recording medium of the present invention can simultaneously absorb multiple types of energy including light. Because it has a transfer recording layer that has different properties only when applied, it is more stable against the environment than conventional recording media that use only heat or light energy, which are susceptible to environmental temperature. This has made it possible to always stably obtain highly detailed images, and has improved not only the storage stability of the recording medium itself but also the storage stability of recorded images.

Further, the recording medium of the present invention is capable of high-speed recording because it performs recording by controlling a plurality of energies including light. Furthermore, since the transferred image is formed using a plurality of types of energy, it is easy to adjust the degree of change in physical properties for forming the transferred image in stages, making it possible to perform halftone recording.

Furthermore, since the recording medium of the present invention contains a thermoplastic polymer compound having a high molecular weight, the image can be transferred to a transfer medium at a high transfer rate and a high image density can be obtained. Furthermore, since the recording medium of the present invention has high sensitivity and changes the transfer characteristics to the transfer medium, the process speed can be increased, high-speed, high-sensitivity recording is possible, and high-quality images with significantly reduced image fog can be produced. formation is now possible.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing the principle of transfer recording using the recording medium of the present invention, FIG. 2 is a schematic diagram of an apparatus for performing transfer recording using the recording medium of the present invention, and FIG. 3 is a diagram showing the principle of transfer recording using the recording medium of the present invention. FIG. 4 is a timing chart for applying heat and light, FIG. 5 is an absorption spectrum of a photopolymerization initiator according to an example of the present invention, and FIG. 6 is a diagram showing the structure of a recording medium. 3 is an emission spectrum of a light source according to an example. DESCRIPTION OF SYMBOLS 1...Recording medium, 1a-Support, 1b...Transfer recording layer, LC, LD-core, 1E-shell (wall material), 1
f... Adhesive, 2... Supply roll, 3... Lamp, 4... Thermal head, 5... Control circuit, 7...
・Heater, 8... Beat roller, 9... Pinch roller, 10-... Recording paper, 11... Winding roll, 1
2... Recorded image.

Claims (5)

[Claims] (1) By simultaneously applying multiple types of energy, including light, at least one type of energy corresponding to image recording information, a transfer recording layer whose physical properties governing the transfer characteristics change can be formed on a support. The transfer recording layer contains at least a colorant and a sensitive component that is sensitive to application of light energy and heat or heat-convertible energy, and the sensitive component contains a photopolymerization initiator, a non-photopolymerization initiator, and a It is composed of at least three types: a monomer or oligomer having a saturated double bond, and a binding component, and the molecular weight of the monomer or oligomer having an unsaturated double bond is 350 or more and 3000 or less, and the binding component is It is a thermoplastic polymer compound, and the polymer compound has a weight average molecular weight of 5×10^4 or more and a molecular weight dispersity (weight average molecular weight/number average molecular weight) of 5 or less, and the transfer recording layer A recording medium characterized in that the content of the polymer compound is 5 to 90% by weight. (2) The recording medium according to claim 1, wherein the colorant and the sensitive component are physically or chemically supported in a layered manner on a support. (3) The recording medium according to claim 1 or 2, wherein the colorant and the sensitive component are particulate bodies. (4) Claims 1 to 3, characterized in that a plurality of types of element bodies each having a different sensitivity wavelength range of a sensitive component contained in the particulate element body are supported in a mixed state on a support. A recording medium described in any of the above. (5) The recording medium according to any one of claims 1 to 4, wherein the particulate element containing the colorant and the sensitive component is encapsulated.