JPS5845084A - Recording sheet - Google Patents

Abstract

PURPOSE:To permit a multi-color recording by using pressure and light by a method in which micro capsules with a photo-setting resin and a first reacting substance and micro capsules with a high-boiling organic solvent and a second reacting substance are mixed together and coated on a supporter. CONSTITUTION:Micro capsules, containing a photo-decomposing resin having photo sensitive groups (e.g., cinnamic acid residue radical, cinnamylidene residue radical, etc.) or a photo-polymerizable type resin having acryloyl group, acryl group, etc., and an electron donative compound, is mixed with micro capsules, containing an aromatic compound (e.g., alkyl naphthalene, etc.), a high-boiling organic solvent, e.g., esters (e.g., phthalates, etc.), etc., and an electron donative compound capable of producing a color different from said electron donative compound, and then the mixture is coated on a supporter and an adequate binder and a pigment, etc., are added to the coated layer. The recording sheet thus obtained is combined with an image receiving sheet containing an electron attractive compound and light and pressure are continuously applied to them to obtain a multi-color recording image on the image receiving sheet.

Description

[Detailed Description of the Invention] Regarding the kima sheet where the multi-colored kama appears, more specifically, by applying the original pressure t1@h, different hues can be obtained. This relates to record sheets.

Among the various recording methods, there is pressure-sensitive marking paper that is easily available. A p-color recording image is obtained when the Hiro reactant and co-reactant come into contact and react, and one or both of them are isolated from each other with microcapsules, etc., and the pressure of correction, typesetting, etc. The microcapsules are designed to break and come into contact with each other, and various reactants, such as electron-donating compounds tS, can be added to suit the color development of the pressure-sensitive paper. Although the color can be changed arbitrarily, the color image obtained is limited to a single hue. This is a pressure-sensitive recording system in which microcapsules containing the reactants used in the paper are uniformly coated over the entire surface of the backing of the support, and it is not possible to partially change the hue to record. There is no turtle.

On the other hand, when it is desired to record documents in nine different hues, nine methods have been proposed for recording the nine different hues.

Tokukai No. 2356 of 1983: @ contains several different reactants, etc., and the fracture strength under pressure tR is graded. It has been shown that by varying the degree of pressure applied by coating, the co-reactant can be spread onto nine supports to obtain a sickle image of nine different hues. However, it is very difficult to control the membrane strength or particle size of microcapsules during production because it changes the destruction of microcapsules. It is actually very difficult and is not suitable for general kamagi.

Japanese Patent Publication No. 48-401$3 discloses that a color-developing tube containing a co-reactant for the part to be changed, and 1 m of phosphoric acid solution etc.
It has been shown that recorded images of different hues can be obtained by denaturing the co-reactant with a phosphoric acid solution, but the difference in hue is small because the reactants are the same. There are nine drawbacks when the stability of the pipe-covered portion over time is poor. Japanese Patent Publication No. 51-39865 discloses nine examples utilizing the color development specificity of a co-reactant to a reactant. That is,
Various microcapsules encapsulating the reactants were coated at different locations on the back side of the support, and nine sheets and three camphor coreactants were coated on the surface of the support in a single layer or a laminated layer7. −
A method for obtaining multicolor recording by overlapping and pressing is shown, and in the %lIi@l5-sssez publication,
Microcapsules encapsulating SS were applied to the back side of the support, and heated mixtures of reactants and co-reactants were partially printed on the surface of the nine sheets and the support in different combinations, and the nine sheets were overlapped. The method of pressurizing them together is the real trick! 85B
Publication No. 39814 discloses that a microcapsule containing a co-reactant is coated on the back side with m, mL97-) and a reactant t*m that develops a different color upon contact with the co-reactant. The method of overlapping the sheet and applying pressure is shown.
Ru. However, with these methods, it is not possible to obtain an image that differs only in certain fixed areas because of partial printing or processing in advance.In fact, after printing, Furthermore, when recording images of different hues are to be obtained, it is often desirable to be able to obtain a multicolor recorded image by freely applying 1111a to arbitrary parts rather than just a limited number of nine parts.

The present inventors conducted research on a recording sheet that can obtain a recorded image of nine hues in any part, and found that microcapsules containing a photocurable resin and a reactant that develops color upon contact with a co-reactant; In addition, the target O recording sheet can be obtained by coating a support with microcapsules containing a high boiling point organic solvent and a reactant that develops a color different from the reactant.

The present invention will be explained in more detail.

The recording sheet of the present invention consists of a former hardened noodle microcarb containing mainly a photocurable resin and a reactant, and a high boiling point 1f
The IAS medium and the reactant contained in the original hardened filter microcancelles are mixed with ordinary microcapsules encapsulating the reactant tPi which develops a different hue, and the mixture is coated on a support, and when it reacts with the reactant □, In combination with the scratches contained on the co-reactant formed on the colored substance, a multicolor recorded image is obtained on the scratches by continuously applying pressure and force. Furthermore, when using pressure and light, there are cases where pressure is applied and exposure is applied, and cases where pressure is applied after exposure, and each is used in different ways.

When exposure is performed after pressurization by kneading pressure or the like, it can be used in the same manner as general pressure-sensitive writing paper.

That is, when the coated surface of the Kireki sheet according to the present invention and the injured sheet are overlapped and pressure is applied with a lead wire, a ballpoint pen, a typewriter, etc., the former hardened lid microcapsules on the Kakki sheet are formed. Ordinary microcapsules are destroyed at the same time, and more than 211 reactants contained in each microcapsule are leached out and come into contact with the co-reactant of the recipient sheet, resulting in the development of 41 different hues for each reactant. occurs in the same area, and a recorded image is obtained on the damaged sheet as mixed colors. Furthermore, if you want to record in 9 hues other than ii5 return, when you irradiate the Ik cloth surface of the recording sheet with light, the light will pass through the at of the 7th color of the light, and the inclusions of Kakuhardihi Takiki By curing the layer and turning it into a strong resin, the axillary microcapsules become rigid microcapsules that no longer break under pressure. On the other hand, ordinary microcapsules are unaffected by 1%A, so they are written in a single color again*
*1 When placed over an image-receiving sheet and pressurizing any part again, only the normal microcapsules are destroyed, and a single hue is recorded based on the reactant contained therein. In this way, a multicolored recorded image is obtained.

Therefore, when using the recording sheet of the present invention, -jI! Correct text in any part with a different hue from the tilted mourning record l1I4a,
Duplicate copying of additional sentences, etc. can be easily performed.

Further, between the recording sheet of the present invention and the image-receiving sheet, a damaged layer having the same composition as that of the image-receiving sheet is formed on the surface, and a coating layer having the same composition as the coating layer of the cough recording sheet is formed on the back surface. I'm having a hard time inserting it. That is, the coated surface of the recording sheet of the present invention is overlapped with the surface of the original to be copied.

If the original is made of a material that is particularly transparent to ultraviolet rays, then the original should be placed on the original side... Expose from the side of the recorded line recording sheet. The exposure time is preferably set to ms depending on the combination of the line recording sheet and the original. When exposed to light, the patterns and characters on the manuscript absorb light and the line recording sheet is not exposed to light, but other areas are exposed to light in the form of circles that transmit or reflect light. The contents of the capsule harden and become rigid microcapsules that do not break under pressure. Next, when the entire surface is pressurized by passing the image receiving sheet containing the co-reactant and the coated roll through a stacking roll or the like so as to face the coating, nine parts of the line recording sheet surface are not exposed to light, that is, the parts of the original's designs and characters. Both the photoscleroma microcapsules and the normal 1-microcapsules that meet the corresponding portions are destroyed, and the reactants that are part of the inclusions are leached out, producing a colored image on the image-receiving sheet. This color development is caused by reactants that develop different hues contained in the two types of microcapsules, and is shown as a color mixture. On the other hand, in the photosensitive area, the photocurable microcapsules are not destroyed, but only the regular microcapsules are destroyed, so that a single colored color can be obtained on the favorite sheet.

In this way, on the image-receiving sheet, the same designs and characters as the original can be obtained on a background of a single hue, but with a hue different from that of the background.

As a light source, sunlight, a xenon lamp, a low-pressure and high-pressure mercury lamp, a firefly lamp, etc. are used. There is almost no deterioration in the properties of the recording sheet during manufacture or during one hour of normal handling, such as occurs under indoor light or indirect sunlight.

The photocurable m-resin encapsulated in the photocurable microcapsules used in the present invention includes cinnamic acid residues, cinnamylidene residues, α, β-unsaturated ketone residues, coumarin residues, anthracene residues, α- 7z2k MaV imide residue, benzophenone residue, original dimerized resin with photosensitive groups such as stilbene residue A, diazonium salt residue, quinonediazide residue,
azide residue, dithiocarbame) residue Ji, photodegradable m* fat with photosensitive groups such as benzoin residue, acryloyl group,
Ex-polymerized deaf resins having allyl groups, vinyl groups, epoxy 1, etc. can be used as desired, but liquid ones are advantageously used. As a photopolymerization initiator for polymerizing the photocurable resin, commonly used known compounds may be used, such as benzoin alcohol ether, benzophenone, Michler ketones, thioxanthone, acetophenone, etc. Anthraquinone 1.5 is a photosensitizing agent that has the effect of broadening the sensitizing wavelength range of the initiator.
=-L) When Rofluorene, etc., and stabilizers such as radical polymerization inhibitors, modifiers, relatively low molecular weight oligomers, diluents such as Hiromonomers, etc. are simultaneously incorporated to improve storage stability. There is also. In addition, oily solvents with a high boiling point that improve the layered nature of the reactants to be encapsulated at the same time, such as lunar 7-talenes, alkyl biphenyls,
Alkylidene biphenyls, ester steels, etc. are sometimes used as tS disintegrants, but it is inappropriate to use them in large amounts because they have an adverse effect on the immediate hardening process.

The high boiling point organic SM used in the present invention includes solvents equivalent to those used in general pressure-sensitive recording paper, such as aromatic compounds such as alkylnaphthalene, alkyldiphenylalkane, and argylbiphenyl; Examples include ester a such as tarric acid ester and glycol ester, chlorinated halafine, toluene, xylene, flaxseed m, Jl[m&etc.

Reactants and co-reactants suitable for use in the present invention refer to reactive compounds that react with each other to produce a colored substance when brought into vh contact with each other, such as when the colored substance is a colorless electron-donating compound. and a colorless electron-accepting compound, the electron-donating compound is used as the reactant and the electron-accepting compound is used as the co-reactant. Another example of such a combination of reactive compounds is a ligand and a polyvalent metal compound. A more detailed explanation of reactive compounds
do. As an electron-donating compound, 3,3-bis(p-
dimethylaminophenyl)-6-dimethylaminophthalide, 3.3-bis(p-dimethylaminophenyl)7thalide, 5-(p-dimethylaminophenyl)-3-(1
, 2-dimethylindol-3-yl) phthalide and other triarylmethane compounds, 4.4-bisdimethylaminobenzhydrin benzyl ether and other diphenylmethane compounds 11. 3-dimethylamino-7-medoxyfluorane, 3 - Xanthine compounds III such as diethylamino-7-chlorofluorane, 3-diethylamino-7-dipendylfluorane, etc. - thiazine compounds such as benzoylleucomethylene blue, 3-methyl-spirodinaphthobilane, 3-globilus bibenzodibenzobilane Examples include subia-based compound proboscises such as. Examples of electron-accepting compounds include acid clay, activated clay, kaolin, zeolite, inorganic acid substances such as bentonite, p-coolesol, p-octylphenol, p-cyclohexylphenol, p-phenylphenol, α-naphthylphenol, tilephenol, Substituted phenol compounds such as p-chlorophenol, phenol-formalin condensates, phenolic resin compounds such as [condensed 7z nor-formalin condensates], and round metal salt-modified phenols obtained by modifying them with polyvalent metals such as zinc and nickel. Tree-based compounds, p-butylbenzoic acid, p-hydroxybenzoic acid, 2,5-dihydrocybenzoic acid, salicylic acid, 5,'t@rt
- Aromatic carboxylic acid compounds such as butylsalicylic acid, 3.5-di-t@rt-butylsalicylic acid, 3.5-di(α-methylbenzyl)salicylic acid, and polyvalent metals such as zinc and nickel. Examples include metal salts of aromatic carboxylic acid compounds in the form of metal salts, mixtures of aromatic carboxylic acid compounds and polyvalent metal compounds such as zinc acetate and propionate zinc, and the like.

Nine, as a ligand, 8-quinolitool, gallic acid,
Gallic acid dodecyl ester, l,10-phenanthroline, O-7 22 diamine, diphenylthiourea, guanidine, dotetraxinaphthoic acid, dipivaloylmethane, trifluoroacetyl acetone, etc. are also used with metal compounds. These include, but are not limited to, ferric stearate, magnesium stearate, zinc stearate, zinc N-7xnyl-N-ethyldithiocarbamate, etc. When the recording sheet of the present invention is used, It is also possible to perform multiple 1zons with 9. In other words, when the original is exposed and exposed, the nine-print recording sheet and the image-receiving sheet are overlapped, and pressure is applied with a rubber roll or the like, a copy of the original is obtained on the image-receiving sheet, but even after one press, it is still a liquid-like image. The photocurable resin and reactant remain in the broken capsule of the recording sheet, and are superimposed again with another image-receiving sheet.
- By repeating the process, a copy image of the original is obtained on another image-receiving sheet. In this way, it is possible to perform several *, Vt-.

Photo-curing microcapsules used in the present invention are encapsulated in photo-curing resin microcapsules in which the amount and type of photo-curing resin, original polymerization initiator, etc. are varied to change the degree of curing and the reactants.
It is also possible to record with two or more hues by using several colors.

The microcapsules used in the present invention can be manufactured by methods known in the art. For example, U.S. Patent No. 2.80
Phase separation method from aqueous solution as shown in G. 45 '1, specification No. 2.800.458, etc., Japanese Patent Publication No. 38 Sho.
-19574, @42-446, @42-77
Interfacial polymerization method as shown in Bulletin No. 1, etc.,
9168, 1--IU method by polymerization of seven polymers, disclosed in JP-A-51-9079, etc., British Patent Application No. 1141, No. 95
Examples include, but are not limited to, the melting and dispersion cooling method shown in No. 2.807, No. 965074, etc., and the spray drying method shown in U.S. Patent No. 31i14oy, British Patent No. 930422, etc. Well, φ.

Examples of suitable wall film forming materials include gelatin, gum arabic, starch, alginate, ethylcellulose, carboxyethylcellulose, polyvinyl alcohol, polyethylene, polyester, polyurethane, polyethyleneimine, etc. In particular, a material that sufficiently transmits ultraviolet light is more preferable.

In order to hold the various microcapsules constituting the recording sheet of the present invention on a support, a water-soluble binder and latex are generally used.

For example, gelatin, casein, carboxymethylcellulose, hydroxymethylcellulose, oxidized starch,
Esterified dengue, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, vinyl acetate-acrylic acid copolymer, acrylonitrile-butadiene copolymer,
Examples include water-retaining polymers such as vinylidene chloride copolymers and latexes. These are selected from the viewpoints of film surface strength, dispersibility, etc., and used alone or in combination.

The microcapsule coating layer of the recording sheet of the present invention is further coated with capsule preservatives such as cellulose powder, starch particles, plastic particles, Merck, calcium carbonate, f oxide, etc.
Inorganic pigments such as L lead and titanium oxide, organic pigments such as urea-formalin resin, dispersant 1 antifoaming agent, etc. may be added.

Methods for manufacturing the image-receiving sheet used in the present invention include a method in which the co-reactant is dissolved and dispersed in a tf# medium and impregnated into a support; There are methods of coating and printing on the entire surface or an expanded area using various coaters and various printing machines, but it is obvious that the method is not limited to these methods.

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.
Examples include a method of coating a portion of the support with a t*, flexo printing machine, gravure printing machine, or the like.

The support can be arbitrarily selected from transparent, translucent, and opaque. For example, one piece of paper, each piece of wood cloth, synthetic paper, metal foil,
A plastic coater film, etc., or a composite sheet made by combining these may also be used.

Hereinafter, the present invention will be described in detail with reference to Examples.

Note that "parts" indicate parts by weight.

Example (1) A photocurable porcelain microcapsule dispersion filter containing a reactant was prepared as follows.

A 100% aqueous solution of styrene-water-maleic acid copolymer dissolved in S with a small amount of sodium hydroxide at a pH of 4.0.
In the part, the reactant electron-donating compound, i.e. 3
-(4-diethylamino-2-ethoxypher)-3
2.4 parts of -('1-ethyl-2-methylindyl-3-yl)24-aza7thallide and benrylate base resin [Commercial i4! 80 parts of Aloex, manufactured by Toagosei Chemical Industry Co., Ltd., were emulsified.

On the other hand, 1 melamine 10 parts, 37j 1 formalmari? Aqueous solution 2
5 parts and 65 parts of water were adjusted to pH 9 with sodium hydroxide, and SO
After heating to 9°C for 15 minutes, a transparent melamine-formalin initial condensate was obtained. This initial condensate was added to the emulsion to bring the temperature to 60°C, and the mixture was stirred for 4 hours and then cooled to room temperature.

The solid content of the obtained microcapsule dispersion was 45%.

(2) Microcapsule dispersions containing reactants with different color hues were prepared as follows.

Styrene-maleic anhydride copolymer was dissolved with a small amount of sodium hydroxide to pH 4.0 (05 to 100% aqueous solution).
In part, 3-diethylamine-7-chlorofuran Z,
Understand B@ and Kukkaishi Hysol N-2911 (product name,
80 parts of Nippon Petrochemical Oil) were emulsified. On the other hand, melamine 10i1, 25 parts of 37N formalin water flNIL,
65 parts of water was adjusted to pH 9.0 with sodium hydroxide, and 65 parts of water was adjusted to pH9.0 with sodium hydroxide.
When heated to .degree. C., a melamine-formalin initial condensation proboscis was obtained in 15 minutes. This initial condensate was added to the emulsion and stirred for 4 hours while maintaining the temperature at 60°C, and then cooled to room temperature. ...The hardness of the obtained microcapsule dispersion was 45.

Nine-light-cured linden microcapsule concentrated liquid 11 obtained in (1)
0 parts, the usual microcapsule dispersion 110i1S obtained in (2), 150 parts of the 10jl polyvinyl alcohol aqueous solution, 40 parts of wheat dengue, 1 360 parts of water, and after thorough stirring, the Meyer paper was applied to 401/d base paper. Use -
Apply the coating so that the coating amount is 61/d and record the
I9.

(3) 3. ! 66 parts of an aqueous dispersion of i-Gt@rt-butylsalicylic acid and 80 parts of zinc oxide, 48% 8B
B9fylx40i1$S water I B6 parts t, 8 parts were stirred and applied to Sof/ll10 base paper using a Mayer bar in a coating amount of 6f/- to obtain an image receiving sheet.

<4) An example of using a combination of the Kuki sickle sheet obtained in (2) and the Kuju sheet obtained in (3) is shown below.

Typewriter
When printing was performed on the image receiving sheet, a bluish-purple printed image was obtained. Next, xenon light is irradiated on the coated surface of the printed chain kamarit using a litho-xenofax FX-150, and after overlapping it again with the recorded image-receiving sheet, it is printed on a typewriter using a ballpoint pen. A similar red corrected image was obtained on the image receiving sheet nine times after performing the print O correction.

Handwritten notes on the coated surface of the biffi recording sheet and the transparent inside.
Stack the manuscript so that it is facing the writing side of the document.
After irradiating the image receiving sheet with xenon light, the image receiving sheet obtained in (3) 1) Overlap the coated surfaces 1 Passing between the rubber rolls and applying pressure, the original is printed on the image receiving sheet. A duplicate image of the same characters appeared as a bluish-purple color, while other parts were colored red.

Claims (1)

[Claims] Microcapsules encapsulating a reactant that develops a color upon contact with the original hardened resin shield and co-reactant, and microcapsules encapsulating a reactant that develops a color #AK different from the high-boiling point organic material and the underarm reactant are the supports. A record sheet indicating that t% mold has been placed on the sheet.