JPS6254248A - Plain paper transfer type photosensitive and pressure-sensitive recording sheet - Google Patents

Abstract

PURPOSE:To permit the coating of plural color forming components into a single layer on a base and the transfer of a desired color onto plain paper by combining a sheet which is formed by coating a component consisting of microcapsules mainly including a photosetting resin and reactant, specific co- reactant to form a coloring material by reacting with the reactant and wax on the same plane of a base and the plain paper. CONSTITUTION:The sheet formed by coating the component consisting of at least one among 1, 2, 3, i.e., 1 the microcapsules essentially including the co- reactant and reactant resin of the microcapsules which include essentially the photosetting resin and reactant and form the coloring material by reacting with the reactant, 2 the microcapsules including the co-reactant and 3 pulverous powder co-reactant and the wax on the base is combined with the plain paper. The multi-color transfer record is thereby taken onto the plain paper.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a photosensitive and pressure sensitive recording sheet that can be transferred onto plain paper using a photocurable capsule sound.

Q-11 Conventional technology The conventionally known tp pressure-extraction paper is made by dissolving an electron-donating, colorless coloring agent in a nonvolatile oil, etc. A top paper made by coating the back side of the support and a bottom paper made by coating the surface of the support with an electron-receptive colorless developer are coated with each coat. - When printing the surface of the upper paper facing each other under pressure using a typewriter, it is possible to obtain a colored layer on the lower paper.Furthermore, gold dust can be used instead of the above coloring agent and color developer. There is also pressure-sensitive copying paper that uses a coloring reaction caused by a chelate-forming reaction between a compound and a ligand.・These pressure-sensitive copying papers have the inconvenience of having to use a combination of upper paper and lower paper when the situation is severe. There is.

In addition, there is a type of self-coloring pressure-sensitive copying paper in which both of the above-mentioned corresponding reaction components are coated on the same side of a support;
II image cannot be obtained. Zarani, self-coloring pressure-sensitive copying paper is lacquered II! It is already known that even if pages are printed on plain paper and a printed image is printed, a colored image is obtained only on the coated layer, and no copy image on plain paper is obtained at all.

The term "plain paper" as used herein refers to a support on which there is no reactant or co-reactant, such as an electron-donating color former or an electron-accepting color developer, or as defined in the claims. The paper is characterized by the fact that it is a degraded paper containing a metallic compound and/or an inorganic pigment.

On the other hand, the color former (reactant or co-reactant) is placed on the same side of the support.
Pressure-sensitive photographic paper containing a color developer (co-reactant or reactant) and capable of forming a copied image on plain paper is disclosed in JP-A-54-126111 and JP-B-Sho 53. −
There is one disclosed in Japanese Patent No. 16728.

JP-A-54-126111 discloses that a coating liquid prepared by cooling a solid coloring agent and solid M1gAl1 in wax is coated on a support.

It is clearly stated that the coating liquid exhibits a coloring reaction and becomes colored immediately after mixing the color former and the color developer.

That is, it relates to a pressure-sensitive transfer material having a colored coating layer, such as so-called expanded carbon paper, and because the coating layer is colored, there are disadvantages in appearance.

Japanese Patent Publication No. 53-16728 relates to chelate coloring, in which a support is coated with a fully encapsulated reactant, and then a co-reactant is dissolved in a solvent and coated thereon. Since a solvent is used, the wall of the microcapsule must be made of a material that is resistant to solvents. However, there are many disadvantages both environmentally and economically.

(C) Problems to be Solved by the Invention 7. Japanese Patent Laid-Open No. 56-121790, which is an improved version of the publication published in the prior art for the purpose of transfer to plain paper,
There is a publication No. 7-207088.

JP-A-56-121790 discloses a plain paper transfer type pressure-sensitive copying paper in which a mixture of an electron-donating color former, an electron-accepting color developer, and waxes is coated on the same side of a support. The waxes are similar in that they use two types of waxes: amide wax and other waxes.

JP-A-57-207088 discloses a plain paper transfer type pressure-sensitive copying paper in which a single layer of a ligand, a metal compound, and a wax is coated on the back side of a support.

These plain paper transfer type pressure-sensitive copying papers have good transferability to plain paper, and can be used for either full-surface coating or partial coating on a support, if necessary.

However, the above method is limited to single-color transfer to plain paper. In other words, the coloring component coated on the support is 1 M
You can achieve that goal by applying all 4 cloths, even if you apply a multi-food coloring ingredient! The color when it is simply transferred is only a mixed color.

The present inventors arrived at the present invention through intensive research aimed at transferring a desired color onto plain paper by coating a support with a single layer of a plurality of color-forming components.

υ) Means for Solving the Problems The present inventors conducted intensive research to solve these drawbacks, and as a result, were able to provide a plain paper transfer type photosensitive and pressure sensitive recording sheet.

That is, on the same surface of the support, (1) microcapsules mainly encapsulating the photocurable resin and the reactant, (2) the reaction microcapsules, microcapsules encapsulating the co-reactant, and the finely powdered co-reactant. By combining plain paper with a sheet coated with at least one of the following ingredients and (3) waxes, it was possible to provide a plain paper transfer type photosensitive and pressure sensitive recording sheet.

Furthermore, by using a translucent or translucent support, it was possible to improve the transferability and improve the efficiency of recording.

In addition, by making the plain paper coated with a metal compound and/or a hot pigment, it was possible to reduce the transfer density to dust and improve the shelf life. As the metal compound, oxides, hydroxides, and charcoal salts are preferable6. Conventionally, microcapsules have been used to encapsulate liquid or solid substances so that they are separated from other substances under normal conditions. The overall purpose is to destroy the microcapsules by giving an external attack when necessary, extracting the contents, and reacting or mixing them with other substances. For this reason, if the entire support coated with microcapsules is pressurized, all of the microcapsules in the pressurized area will inevitably break and the contents will inevitably leak out.

The photocurable microcapsules contained in the photosensitive photocurable resin used in the present invention are destroyed by applying pressure to the microcapsules and controlled by light. That is, when it is desired to take out the contents, the microcapsules are destroyed and the contents ooze out by applying an external impact in the same way as with ordinary microcapsules. However, when you want to enclose the contents as they are, when you put money into the microcapsules, the light that passes through the wall material of the microcapsules hardens the photocurable resin that is part of the contents, converting the contents from liquid to hard. into a resin.

As a result, the microcapsule becomes a rigid capsule, and even if an external impact is applied, the microcapsule will no longer be destroyed, and the contents will no longer ooze out. By using photocurable microcapsules having such characteristics, the plain paper transfer type photosensitive pressure sensitive recording sheet used in the present invention can be obtained.

In other words, there are two unique types of microcapsules: photocurable microcapsules that encapsulate a reactant and photocurable microcapsules that encapsulate a co-reactant that produces a colored substance upon contact with the reactant; The light-sensitive pressure-sensitive recording sheet coated with the light-sensitive pressure-sensitive material and the original are completely overlapped. At this time, if the document support is made of a material that easily transmits light, especially ultraviolet rays, the coated side of the light-sensitive and pressure-sensitive recording sheet and the written or printed side of the document, that is, the surface, should be stacked so that they face each other. Expose from the original side. In addition, if the support of the document is difficult to transmit light, such as a shaft, the coated surface of the light-sensitive and pressure-sensitive recording sheet using a transparent or nearly transparent support should face the writing or printing surface of the document. The recording sheets are stacked one on top of the other and exposed from the recording sheet side. It is desirable to adjust the exposure time depending on the combination of the H self-recording sheet and the original. When exposed to light, the written or printed designs and characters on the manuscript absorb light, and the recording sheet is not exposed to light.
Other parts are sensitive because light is transmitted or reflected;
The inclusions of the photocurable microcapsules coated in this area are cured. When the recording sheet (18) after exposure is stacked and pressed with a roll, etc., the microcapsules in the parts corresponding to the designs and characters of the original are destroyed, and the reactants and co-reactants come into contact, producing colored substances. , the same designs and characters as the original are transferred and recorded.

When the plain paper transfer type photosensitive pressure sensitive recording sheet of the present invention is used,
As is already clear, normal manuscripts of Bozitaig can be used, which can optionally be handwritten documents or printed materials such as books. In addition, only the microcapsules in the parts of the manuscript that correspond to the designs and characters are destroyed and a colored image is formed on the plain paper.
It does not change color at all and has extremely good storage stability.

The plain paper transfer type photosensitive and pressure sensitive recording sheet of the present invention has the following characteristics. For example, a recording sheet' (c
- When the prepared microcapsules are exposed and pressurized using the exposure method described above, only the recorded image can be clearly recorded, and each microcapsule of the reactant and co-reactant other than the recording part becomes a rigid capsule, so the background background is No transcription occurs at all. This has the advantage that when microcapsules containing a co-reactant are used, it is possible to overcome the drawback that the solution in which the co-reactant is dissolved in the background surface is transferred to the surface under pressure, causing conspicuous stains. be.

Furthermore, a characteristic feature is that the reactants (or co-reactants) and the co-reactants (or reactants), which are two or more color-forming components, each contain photocuring resins or photopolymerization initiators with different absorption wavelengths. With such microcapsules, rigid encapsulation can be controlled by the wavelength of light that exposes each microcapsule, and multicolor transfer recording can be performed.

Furthermore, in the plain paper transfer type photosensitive pressure sensitive recording sheet of the present invention, it is also possible to instantaneously create a so-called desensitized area by light.

In other words, if the areas that do not need to be recorded are exposed to light before using the recording sheet, the photocurable capsules in the exposed areas will harden and the colored recorded image will remain even if pressure is applied to that area during recording. It is also possible to prevent this from occurring.

On the other hand, the plain paper transfer type photosensitive pressure sensitive recording sheet according to the present invention can also be used as a plain paper transfer type photosensitive pressure sensitive copying paper. In this case, a copy image can be obtained by placing the coated surface on plain paper and applying pressure from the non-coated paper surface using car pressure, a typewriter, or the like. The transfer density of recorded images and copied images obtained on plain paper by transfer is extremely high. By adding waxes to the coating layer, it is possible to improve the degree of transfer by copying. This is because when the microcapsules are destroyed by pressure, the solvent in the internal phase is absorbed into the support surface of the coated paper, reducing transferability, and the wax in the coating layer has a water- and oil-repellent effect. This is due to the fact that the internal phase solvent is transferred to plain paper, leading to improved transferability.

Further, the plain paper transfer type photosensitive pressure sensitive recording sheet of the present invention can perform multicolor recording transfer as described below by using two or more types of color forming components tl of either reactants or co-reactants. It has the characteristic that it can be done. For example, by making each of the coloring components of a multimodal species contain a photocurable resin or a photopolymerization initiator with different absorption wavelengths, and using microcapsules containing each of them, irradiation with light with different absorption wavelengths can be used. A multicolored recorded image corresponding to each coloring component is obtained on paper. Furthermore, microcapsules that do not contain a photocurable resin may be used. For example, when two types of coloring components are used, one type of coloring component is microencapsulated containing the photocurable resin, and another one is microcapsulated. Types are microencapsulated without containing photocurable resin. By exposing these two microcapsules to light, a two-color recorded image can be obtained on plain paper.

Further, the plain paper transfer type photosensitive pressure sensitive recording sheet of the present invention is characterized in that by making the support transparent or semitransparent, exposure to light and pressure can be carried out completely continuously. That is, when the coated side of the recording sheet and plain paper are overlapped and integrated and exposed to light from the non-coated side of the recording sheet, the light transmitted through the support acts on the coated side and hardens the necessary parts. .

Subsequently, pressure is applied while the sheet is integrated, and after the pressure is applied, the recording sheet and plain paper are peeled off, and the recorded image is transferred to the surface of the plain paper.

If the support is made transparent or translucent in this way, three steps are required: exposing the recording sheet using an opaque support to light from the coated side, overlaying it with plain paper, and applying pressure. It has the advantage of requiring only two steps compared to the previous method.

Specific examples of the support include plastic films such as polyethylene terephthalate film (PET film), vinyl chloride film, polypropylene film, polyethylene film, and polyimide film, transparent materials such as cellophane, and translucent materials such as tracing paper. It will be done.

Other transparent materials such as paper, various nonwoven fabrics, synthetic paper, metal foil, etc., or a composite sheet 1 made of a combination of these may also be used without any limitation.

Furthermore, since the plain paper to be combined with the plain paper transfer type photosensitive pressure sensitive recording sheet of the present invention is a plain paper fully coated with metal compounds and/or inorganic pigments, it has the characteristics of high transfer density and improved storage stability. be. That is, the reaction of the colored substance transferred to the plain paper is further promoted by the metal compound and/or the inorganic pigment. Moreover, the coloring substance is fixed and the storage stability is further improved.

For example, metal compounds include oxides, hydroxides, and carbonates. Particularly preferred are zinc oxide, cadmium oxide, magnesium oxide, salivary lead hydroxide, magnesium hydroxide, calcium hydroxide, zinc carbonate, calcium carbonate, and magnesium carbonate. Furthermore, there is a good case of zinc chloride.

Examples of the mineral-free pongee materials include silicic acid, aluminum silicate, zinc silicate, lead silicate, tin silicate, colloidal hydrated aluminum silicate, zeolite m, bentonites, kaolin, and talc.

The photocurable resin and I- contained in the photocurable microcapsules used in the present invention include cinnamic acid residue, cinnamic acid residue, a, β-unsaturated ketone residue, coumarin residue, and anthracene residue. group, a photodimerizable resin having a photosensitive group such as an α-phenylmaleimide residue, a benzophenone residue, a stilbene residue, a diazonium salt residue, a quinone diphosphate residue,
Photodegradable resins with photosensitive groups such as azide residues, dithiocarbamate residues, and benzoin residues, photopolymerizable resins with acryloyl groups, allyl groups, vinyl groups, epoxy groups, etc. are optionally used, but are preferred. is a photopolymerizable resin. As for the shape, a liquid one is advantageously used. Also,
Examples of known compounds commonly used as photopolymerization initiators for total polymerization of photocurable resins: penzoin argyl ether, benzophenone, Michler ketones,
Thioxanthones, acetophenones, etc., and photosensitizing aids that have the effect of broadening the sensitizing wavelength range of the photopolymerization initiator, such as anthraquinone, 5-nitrofluorene, etc.
In order to improve storage stability, stabilizers such as radical polymerization inhibitors, modifiers, diluents such as relatively low molecular weight oligomers or monomers, etc. may all be included at the same time.

In addition, in order to improve the solubility of the reactants to be encapsulated at the same time, oily solvents with high boiling points, such as EVA, alkylnaphthalenes, alkylbiphenyls, alkyritene biphenyls, and esters, are sometimes used as solubilizing agents; It is inappropriate to use it for polyvalents because it has an adverse effect on the polyvalents.

The reactants and co-reactants used in the present invention refer to reactive compounds that react when they come into contact with each other to produce a colored substance, for example, a colored substance is a colorless electron-donating compound and a colorless electron-donating compound. When the reactant is an electron-donating compound, the co-reactant is the whole compound, and when the reactant is an electron-accepting compound, the co-reactant is the co-reactant. The body represents an electron-donating compound. Another example of such a combination of reactive compounds is a ligand and a polyvalent metal compound. The reactive compound will be explained in more detail. As an electron donating compound, 3
．． 3-bis(P-dimethylaminophenyl)-6-dimethylminophthalide, 3゜3-bis(P-dimethylaminophenyl)phthalide), 3-(P-dimethylaminophenyl)-3-(1,2- Triarylmethane compounds such as dimethylindol-3-yl) phthalide, 4.4
'-Bisdimethyl, diphenylmethane compounds such as minobenzhydrin benzyl ether, 3-dimethylamine-7-medoxyfluorane, 3-dienalamino-7-
Xanthine compounds such as chlorofluoran and 3-diethylamino-7-dibenzylaminofluorane, thiazine compounds such as benzoylleucomethylene blue, and spiro compounds such as 3-methyl-spiro-dinaphthopyran and 3-propyl-spiro dibenzopyran. etc.

The electron-accepting compound and 1 to 1 include inorganic acidic substances such as acid clay, activated clay, kaolin, zeolite, and bentonite;
Phenol-based compounds such as P-cresol, P-octylphenol, P-cyclohexylphenol, P-phenylphenol, α-naphthylphenol, cumylphenol, P-chlorophenol, phenol-formalin condensate, substituted phenol-formalin condensation phenolic resin compounds such as phenolic resin compounds and metal salt-modified phenolic resin compounds obtained by modifying them with polyvalent metals such as zinc and nickel, P-butylbenzoic acid, P-hydroxybenzoic acid, 2
．． 5-dihydroxybenzoic acid, surityl, 5-ter
Aromatic carbonate compounds such as t-butylsalicylic acid, 3,5-tert-butylsalicylic acid, and 3,5-di(α-methylbenzyl)salicylic acid, and their combinations with zinc,
Examples include metal salts of aromatic carboxylic acid compounds made with polyvalent metals such as nickel, and mixtures of aromatic carboxylic acid compounds and polyvalent metal compounds such as zinc acetate and zinc propionate.

The ligand and polyvalent metal compound of the present invention include ammonium tannic acid tometavanadate, tannic acid and ferric monoxide, naphthol As caustic soda and 4-benzamide 2, respectively.
, Stable diazonium salt of 5-jethoxyaniline, phthalonitrile and sulfuric acid, water-soluble chelate reaction substance described in Japanese Patent Publication No. 43-23710; Japanese Patent Publication No. 50-1788
Sodium orthovanadate, sodium metavanadate, etc. described in Publication No. 9 and protocatechuate, ethyl protocatechuate, gallic acid, ethyl gallate, dodecyl gallate, pyrogallol-4-carboxylic acid, hyrogallol tannin, tannic acid Aromatic hydroxy compounds such as, ferric naphthene and zinc OIO-diisopropyldithiophosphate, iron stearate and zinc dimethyldithiocarbamate, copper palmitate, etc., described in Japanese Patent Publication No. 49-43566! :N,N-bis-2-octanoyloxyethyldiethyldithiooxamide, a combination of cobalt naphthenate and N-lauroyl-DL-glutamic acid, and the ligand is a nitrogen base compound, Japanese Patent Publication No. 54-6926 Vanadium salts such as vanadyl acetate, vanadyl acetylacetonate, and vanadyl acetylacetonate, and gallic acid esters such as -n-zolo'pyl gallate, g-n-butyl gallate, and n-octyl gallate, 4
tert-butylcatechol, 3,5-di-tert
- Alkylcatechols such as butylcatechol and 3-6-rheinprobylcatechol, 2,3-dihydroxynaphthalene, 2,3,4-trihydroxyacetophenone, pyrogallol, 2,2'-thiobis(P-cresol), etc. Mention may be made of oil-soluble chelate reactants such as thiocatechols, halogenated catechols such as quercetin, tetrachlorocatechol, and tetrabromocatechol.

The waxes of the present invention include beeswax, spermaceti wax, Chinese wax,
Animal waxes such as lanolin, candelilla wax,
Vegetable waxes such as carnauba wax, real wax, rice wax, and sugarcane wax; mineral waxes such as montan wax, osikerite, ceresin, and lignite wax; petroleum waxes such as paraffin wax and microcrystalline wax; montan wax derivatives;
Modified waxes such as halafine wax derivatives and microcrystalline wax derivatives, hydrogenated waxes such as castor wax and opal wax, low molecular weight polyethylene and its derivatives, synthetic waxes such as acra wax and distearyl ketone, caproic acid amide, caprylic acid amide Saturated fatty acids such as pelargon amide, capric amide, lauric amide, tridecyl amide, myristic amide, stearic amide, behenamide, ethylene bisstearamide, mite-based waxes, caproleic acid amide, myristrein amide, etc. Unsaturated fatty acid amide waxes such as amide, oleic acid amide, elaidic acid amide, linoleic acid amide, erucic acid amide, ricinoleic acid amide, and rirun cough amide can be used alone or in combination.

The microcapsules used in the present invention can be manufactured by methods known in the art. For example, U.S. Patent No. 28004
57, the phase separation method from an aqueous solution as shown in the specification of No. 2800458, etc., Japanese Patent Publication No. 38-19574,
1n-situ using the interfacial polymerization method as shown in Makai No. 42-446, Makai No. 42-771, etc., using a monomer chassis as shown in Japanese Patent Publication No. 36-9168, Japanese Unexamined Patent Publication No. 51-9079, etc. The melting and dispersion cooling method shown in British Patent No. 952807, British Patent No. 965074, etc.
US Patent No. 3111407, UK Patent No. 930422
Examples include, but are not limited to, the spray drying method shown in No. In addition, gelatin, gum arabic, starch, sodium alginate, ethyl cellulose, carboxydiethyl cellulose, polyvinyl alcohol, polyethylene, polyamide, polyester, polyurethane, polyethyleneimine, etc. are used as wall J-forming materials. For example, it is more preferable to use a material that allows all of the light to pass through.

Ultraviolet light is generally used as the light for softening the original value type microcapsules used in the present invention. As the light source, sunlight, xenon lamps, low-pressure and pressure-measuring water lamps, fluorescent lamps, etc. are used. Deterioration of the properties of light and pressure sensitive recording sheets due to exposure to light such as that which occurs in room lights or indirect sunlight during manufacturing and during normal handling times is rarely seen.

In order to hold all the photosensitive and pressure sensitive layers of the plain paper transfer type photosensitive pressure sensitive i-recording sheet of the present invention on the support, a water bathable binder or latex is generally used.

Examples include gelatin, casein, carboxymethylcellulose, hydroxymethylcellulose, oxidized starch, esterified starch, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, vinyl-acrylic acid copolymer, acrylonitrile-butadiene copolymer, vinylidene chloride. Examples of system 1 include water bathable polymers such as polymers and latexes. These are selected based on film surface strength, dispersibility, etc., and used alone or in combination.

The photosensitive pressure sensitive layer of the Shin 1m paper transfer type photosensitive pressure sensitive M6 recording sheet of the present invention further contains cellulose protective agents such as cellulose powder, starch particles, glasstic particles, Merck, calcium charcoal, zinc oxide, titanium fluoride, etc. , organic pigments such as urea-formalin resin, separation agents, antifoaming agents, etc. may be added.

As a coating method, for example, an air knife coater, a blade coater, a gravure coater, etc. are used to coat the entire surface of the support.
Methods of coating a portion of the support using a flexographic printing machine, a gravure printing machine, etc. are available.

0) Function The music paper transfer type photosensitive and pressure sensitive recording sheet of the present invention comprises microcapsules containing a photocurable resin and a reactant, and a reaction with the reactant.1. Microcapsules containing a co-reactant that forms a color viewing substance (or microcapsules containing both a co-reactant and a photocurable resin, or the co-reactant itself) and a support mainly composed of waxes. It is coated on the same side of paper and has the characteristic of being able to perform transfer recording, especially multicolor transfer recording, on plain paper.

Conventional photo-curing resin) Microcapsules encapsulating only the reactant that does not contain Iilk) The second type will result in a mixed color transfer record, but by incorporating the photo-curing resin, the microcapsules containing the reactant can be exposed to light. By forming the microcapsule into a rigid capsule and controlling the destruction of the microcapsule, transfer recording of a desired color can be achieved.

Further, by making the support of the recording sheet transparent or translucent, there is an effect that the steps from exposure to pressure can be simplified.

Furthermore, if a metal compound or/and inorganic pigment is used as a thread on plain paper, there is an effect that the transfer density can be improved.

Prompt) Examples The present invention will be explained in detail below with reference to Examples.

Note that "parts" indicate parts by weight.

Example 1 (1) Photocurable microcapsules containing reactants were prepared as follows.

10% water bath solution of ethylene-maleic anhydride copolymer 10
0 parts, 10 parts of urea, 1 part of resorcinol, and 200 parts of water were mixed to form a solution, and the pH was adjusted using an aqueous sodium hydroxide solution.
Adjusted to 3.5.

An epoxy acrylate photocurable resin (in which the reactants, electron donating compounds, 7.2 parts of 3-diethylamino-6-methyl-7-anilinofluorane and 0.5 parts of benzoin ethyl ether) Trade name: Lipoxy, manufactured by Showa Kobunshi Co., Ltd., 172.8 parts was emulsified and dispersed in the above mixed water bath solution to form an oil-in-water emulsion with oil droplets of 4 to 8 microns.Next, 37 thiformaltehyde aqueous solution 25
The solution was kept at 55°C and stirred for 4 hours, then cooled to room temperature to complete the encapsulation.

(2) Photocurable microcapsules containing coreactants were prepared as follows.

In place of the 3-diethylamino-6-methyl-7-anilinofluorane in (1) above, an electron-accepting compound as a co-reactant, namely 9.0 parts of 3,5-di-tert-butylsalicylic acid and octycus zinc (The capsules were made in the same manner except that 11.5 parts of Nichifu Kagaku Shogyo (Hasei) was used).

(3) Prepare a thickening solution with the following composition, tsubo: t 50 f/
n? It was coated on paper using a Meyer bar.

Photocurable microcapsules containing reactants 10 parts Photocurable microcapsules containing coreactants 20 parts Paraffin wax 10 parts Wheat starch
20 parts SBR latex
10 copies The coated side of the plain paper transfer type photosensitive and pressure sensitive recording sheet thus obtained was stacked with the surface of the handwritten document on semi-transparent paper as the original, and the photosensitive recording sheet was printed from the original side.
After irradiating xenon light using the Xenofax FX-150', a plain paper transfer type photosensitive pressure sensitive recording sheet is stacked on plain paper and passed between the rubber rolls with a knife and pressed down to create a transferred image of the same characters as the original on the plain paper. appeared as black. In addition, no coloring occurred in areas other than the letters, and the background remained white.

On the other hand, instead of the paper with a basis weight of 50 μm used above, a thickness of 50 μm is used.
It was coated on a polyethylene terephthalate film of m.

K so that the inclined surface of the recording sheet obtained here is in contact with the plain paper.
J, next, turn the back side of the manuscript onto the uncorrupted side of the recording sheet. In the same manner as above, only the original is irradiated with xenon light, the original is removed, and the original is passed between 70' rubber rolls and pressurized. Thereby, a transferred image can be obtained on plain paper. As described above, by setting the recording sheet and plain paper, it is possible to continuously irradiate and press the original, and it is also simpler than using a recording sheet coated with paper.

Example 2 (1) A valent-type microcapsule containing a ligand as a reactant was prepared as follows.

Hydroxylation of a small amount of styrene maleic anhydride copolymer)
10 parts of dodecyl gallate, polyoxypropylene glycol monoether aog, benzoin ethyl ether o, ag, epoxy acrylate photocurable resin (
Product name: Lipoxy, Akihiko Nippon Ball! J! Then, 59.7 parts of the mixed solution was added and emulsified. When 10 parts of melamine, 25 parts of 37 thiformaldehyde water bath solution, and 65 parts of water were adjusted to pH 9 with sodium hydroxide and heated to 60°C, the mixture became transparent in 15 minutes, and a melamine-formaldehyde initial condensate was obtained. Add this initial condensate to the emulsion and lower the temperature to 6.
When the temperature was kept at 0°C and stirring was continued, the formation of capsules was confirmed in 30 minutes, so the mixture was cooled to room temperature.

(2) Photocurable microcapsules containing coreactants were prepared as follows.

Microencapsulated gold was carried out in the same manner as in (1) above, except that 8 parts of vanadosiloxane was used instead of 10 parts of dodecyl gallate in formula (1), and 80 parts of dioctyl phthalate was used instead of polyoxypropylene glycol monoether. Ta.

(3) The following coating liquid was prepared using the microcapsules obtained in (1) and (2) above.

Photocurable microcapsules containing dodecyl gallate 35 parts Photocurable microcapsules containing vanadosiloxane 1
5 parts paraffin wax 15 parts wheat starch 20 parts 8 BR latex 15 parts However, the above parts are parts by weight of dry solids. With this formulation, the basis weight is 50 f/lr using a Mayer bar? Coated on paper.

Using the plain paper transfer type photosensitive and pressure sensitive recording sheet prepared here, exposure and pressure were applied in the same manner as in Example 1 to perform transfer recording.
A black transferred image was obtained.

In addition, it was possible to simplify the process in the same manner as in Example 1 by changing the base paper for coating to a 50 μm polyethylene terephthalate film.

Example 3 (1) Preparation of photocurable microcapsules containing reactant (colorless dye that develops black color) Microencapsulation was carried out in the same manner except that a photopolymerization initiator having λmax was used.

(2) Preparation of photoif-type microcapsules containing a reactant (colorless dye that develops red color) Instead of the photopolymerization initiator benzoin ethyl ether used in (1) of Fuse i+111, λmax was set at around 400 nm.
Microencapsulation was carried out in the same manner except that 3-diethylnamino-7-chlorofluoran was used in place of the photopolymerization initiator 3-diethylamine-6-methyl-7-chlorofluoran.

(3) Preparation of photocurable microcapsules encapsulating a co-reactant A receptor compound, i.e. 3°5-tert-
The same procedure was carried out except that 9.0 parts of butylsalicylic acid, 11.5 parts of Octixzinc (Nihon Kagaku Zagyo ■W), and a photopolymerization initiator with a λmax around 300 nm were used instead of the photopolymerization initiator benzoin ethyl ether. Microencapsulated.

(4) Preparation of photocurable microcapsules encapsulating co-reactants Same as above (3) except that instead of the photopolymerization initiator with λmax around 300 nm, a photopolymerization initiator with λmax around 400 nm was used. and microencapsulated.

(5) A coating solution having the following composition was prepared and applied to paper having a basis weight of 5022 cm using a Meyer bar.

Paraffin wax: 20 parts Wheat starch: 40 parts SBR latex: 20 parts Using the thus obtained plain paper transfer type light-sensitive and pressure-sensitive recording sheet, transfer recording in two colors, black and red, was carried out in the following manner.

First, the surface of the original document 1 made of a translucent sheet is completely overlapped with the coated surface of the recording sheet. Light around 400 nm was irradiated from the side of the original 1 using a spectral filter.

Here, the photocurable microcapsules in (2) and (4) above, which are sensitive to wavelengths around 400 nm, became rigid capsules in the background portion of the original 1. After exposure, the unexposed areas of the recording sheet retain red and black colors. Subsequently, the entire surface of the original 20 made of a translucent sheet and the coated surface of the recording sheet are molded. In this case, the original 2 needs to be created to form a black image. Then, using a spectral filter, the original 2 was irradiated with light having a wavelength of around 300 nm from the side.

At this time, the above (1) that is felt at a wavelength around 300 nm
All of the photocurable microcapsules in (3) above, which were in the background area of the document 2 other than the unexposed area, became rigid capsules. Through two exposures, in each unexposed area, black and red reactant photocurable microcapsules and corresponding coreactant photocurable microcapsules are held on the coated surface with pressure-sensitive gold. It turns out.

When the recording sheet thus exposed twice was stacked on plain paper and passed between rubber rolls and pressed, a two-color transferred image of black and red could be obtained on the plain paper.

Example 4 (1) Photocurable microcapsules containing reactants were prepared as follows.

10% aqueous solution of ethylene-maleic anhydride copolymer 10
0 parts, 10 parts of urea, 1 part of resorcinol, and 200 parts of water were mixed to form a solution, and the pH was adjusted using sodium hydroxide droplets.
Adjusted to 3.5.

Epoxy acrylate photocurable resin (trade name) in which 7.2 parts of 3-diethylamino-6-methyl-7-anilinofluorane and 0.5 parts of hendiine ethyl ether are dissolved. 172.8 parts of lipoxy (manufactured by Showa Kobunshi ■) were emulsified and dispersed in the above mixed aqueous solution to obtain an oil-in-water type emulsilon with oil droplets of 4 to 8 microns. Then 37% formaldehyde aqueous solution 25
The solution was kept at a temperature of 55° C. and stirred for 4 hours, then cooled to room temperature to complete the encapsulation.

(2) Microcapsules containing coreactants were prepared as follows.

An electron-accepting compound that is a co-reactant in place of the 3-diethyl-6-methyl-7-nilinofluorane, benzoin ethyl ether, and epoxy acrylate photocurable resin in (1) above, that is, P-phenyl-phenol resin 35 Encapsulation was carried out in the same manner except that 1 part, 53 parts of 1,1-diphenylethane, and 1,1-diphenylethane were used.

(3) Prepare a coating liquid with the following composition and have a basis weight of 50 fan?
It was coated on paper using a Mayer bar.

Photocurable microcapsules encapsulating reactants 10 parts Microcapsules encapsulating coreactants 20 parts Paraffin wax 10 parts Wheat starch
20 parts SBR latex
10 copies The coated surface of the plain paper transfer photosensitive and pressure-sensitive recording sheet thus obtained was stacked with the surface of the handwritten document on semi-transparent paper as a manuscript, from the manuscript side, using a Riso Xenofax FX-150'i. After being completely irradiated with xenon light, the plain paper transfer type photosensitive pressure sensitive recording sheet was placed over plain paper and passed between rubber rolls and pressed, and a transferred image of the same characters as the original appeared on the plain paper as black. In addition, no coloring occurred in areas other than the letters, and the background remained white.

Also, the basis weight used above is 50 tan? 50 instead of paper
When a μm polyethylene terephthalate film was used, the process could be simplified in the same way as in Example 1.

Example 5 (1) Photocurable microcapsules containing a ligand as a reactant were prepared as follows.

10 parts of dodecyl gallate, 30 ff of polyoxypropylene glycol monoether (S, benzoin ethyl ether 0 A mixed solution of .3 parts and 59.7 parts of epoxy acrylate photocurable resin (product name: RIBOXY, Showa Kobunshi ■W) was added and emulsified. 10 parts of melamine, 25 parts of 37 thiformaldehyde aqueous solution, and 65 parts of water. was adjusted to p19 with sodium hydroxide and heated to 60°C. It became transparent in 15 minutes, and a melamine-formaldehyde initial condensate was obtained. This initial condensate was added to the emulsion, and the liquid temperature was lowered to 60°C.
When the temperature was kept at 0° C. and stirring was continued, the formation of capsules was confirmed in 30 minutes, so the mixture was cooled to room temperature.

(2) Microcapsules containing coreactants were prepared as follows.

In place of 10 parts of dodecyl gallate in the above (1), 8 parts of vanadosiloxane, and in place of polyoxypropylene glycol monoether, 80 parts of dioctyl fluoride,
Microencapsulation was performed in the same manner as in (1) above except that benzoin ethyl ether and epoxy acrylate photocurable resin were removed.

(3) The following coating liquid was prepared using the microcapsules obtained in (1) and (2) above.

Paraffin wax 15 parts Wheat Kung Kung 20 parts 8BR latex 15 parts However, the above parts are parts by weight of dried solids. With this formulation, using a Mayer bar, the basis weight is 50 f/W? Coated on paper.

Using the plain paper transfer type photosensitive and pressure sensitive recording sheet prepared here, exposure and pressure were applied in the same manner as in Example 1 to perform transfer recording.
A black transferred image was obtained.

Also, - the tsubo i 50 f/n used above? When a 50 μm polyethylene terephthalate film was used instead of the paper, the process could be simplified in the same way as in Example 1.

Example 6 (1) Preparation of photocurable microcapsules containing reactants In place of 3-diethylamino-6-methyl-7-anilinofluorane used in Example 1 (1), evening-colored crystal fist was used. Microcapsules were prepared using violet lactone.

(2) Preparation of microcapsules encapsulating reactants 8 parts of red 3-diethylamino-7-chlorofluorane and 1 part of red 3-diethylamino-7-chlorofluorane were used in place of 8 parts of vanadosiloxane and 80 parts of dioctyl phthalate used in (2) of Example 2. .ktJc microencapsulated using 80 parts of 1-diphenylethane.

(3) Preparation of microcapsules containing all coreactants f2
) in place of 8 parts of 3-diethylamino-7-chlorofluorane and 80 parts of 1,1-diphenylethane, 35 parts of P-phenyl-phenol resin and 53 parts of 1,1-diphenylethane were used to prepare microcapsules. .

(4) Prepare a coating liquid with the following composition and have a basis weight of 50 f/n?
It was coated on paper using Meyer Par.

10 parts of the photocurable microcapsules of (1) above 10 parts of the microcapsules of (2) above 20 parts of paraffin wax 15 parts of wheat dengue 25 parts of SBR latex
15 copies of the coated surface of the plain paper transfer photosensitive and pressure sensitive recording sheet and the polka dot pattern printed on the semi-transparent sheet were overlapped and exposed to xenon light from the pattern side using a reso xenon fac δFX-150'r. After full irradiation, the coated side of the plain paper transfer type photosensitive and pressure sensitive recording sheet was placed over plain paper and pressed through the rubber roll, resulting in a transferred image consisting of a pattern of purple polka dots on a red background. Ta.

Example 7 (1) Preparation of plain paper (sanko paper) 150% of the metal compound or inorganic pigment listed in the table was added to a solution of 4.5 parts of dispersant sodium pyrophosphate dissolved in 95.5 parts of water.
1 part (W) under stirring and well dispersed.

Subsequently, 200 parts of 10% polyvinyl alcohol was gradually added with stirring. Furthermore, 20 parts of 50% SDR latex are added in the same manner. This coating solution was coated on high-quality paper with a total basis weight of 40 t/lri using a Mayer bar so that the coated amount was 6 to 7 mm (solid content).

(2) Example 1 of manufacturing a plain paper transfer type photosensitive and pressure sensitive recording sheet
．． In the same manner as in Example 2 and Example 4, a recording sheet was prepared by coating a 50 μm polyethylene terephthalate film using a Mayer bar so that the smear was 10 f/y.

(3) Printing and evaluation Overlap the coated side of (2) above with the coated side of the valley coated paper of (1), and place the sticky original from the non-coated side of (2) on the Lin-Xenofax I” X-15 (l using xenon light ff
i irradiation, followed by 10Ky/
It was pressurized at a pressure of -. The solid area was blocked from xenon light, the capsule containing the photocurable resin remained uncured, and a solid transfer image could be obtained on the coated paper by applying pressure.

The resulting transferred image was measured using an optical densitometer (Macbeth RI) model 514. Furthermore, using a xenon long life fade meter, under an atmosphere of 40°C and 60% R, H,
A light fastness test was conducted by irradiating for 3 hours, and the storage stability was determined.

The results are listed in the table as optical density and residual rate (%).

In addition, the values for the high-quality paper used in (1) are also listed.

*Uses high-quality paper as the image-receiving paper, not as a material.As is clear from the table, coated paper coated with metal compounds or inorganic pigments has a lower density when compared to high-quality paper. It also shows that the survival rate is high.

O) Effects of the invention The plain paper transfer type photosensitive and pressure sensitive recording sheet of the present invention can be made into plain paper by coating a mixture of multiple types of microcapsules mainly containing a photocurable resin and a reactant on a support. It is capable of multi-color transfer recording, and is of extremely high industrial significance in the present day when there is a demand for copy recording of colored images.

Claims (1)

[Scope of Claims] 1. On the same surface of the support, (1) microcapsules mainly containing a photocurable resin and a reactant; (2) [1] which reacts with the reactant to form a colored substance; Microcapsules mainly containing a coreactant and a photocurable resin [2] Microcapsules containing a coreactant [3] At least one of [1], [2], and [3] among the finely powdered coreactants ,as well as(
3) A plain paper transfer type photosensitive and pressure sensitive recording sheet characterized by combining a sheet coated with a component consisting of wax and plain paper. 2. The plain paper transfer type photosensitive pressure-sensitive recording sheet according to claim 1, wherein the support is a transparent or translucent support. 3. Claim 1, characterized in that the plain paper is a plain paper coated with a metal compound and/or an inorganic pigment.
A plain paper transfer type photosensitive and pressure sensitive recording sheet as described in 2. 4. The plain paper transfer type photosensitive and pressure-sensitive recording sheet according to claim 1 or 3, wherein the metal compound comprises an oxide, hydroxide, or carbonate.