JPS5845090A - Self-chromogenic type recording sheet - Google Patents

Abstract

PURPOSE:To obtain a chromogenic recording sheet permitting the combined use of light and pressure by a method in which micro capsules, obtained by encapsulating individually a photo-setting resin and a co-reactant, a high-boiling organic solvent and a reactant capable of producing color different from said co- reactant, and a co-reactant in micro capsules, are coated on the same surface of a support. CONSTITUTION:Micro capsules containing a photo-setting resin (e.g., photodimerization or polymerization type resin, etc.) and a photo-polymerization initiator capable of polymerizing said resin (e.g., benzoinalkylether, benzophenone, etc.), micro capsules containing a high-boiling organic solvent and a reactant capable of producing color different from that of said reactant, and micro capsules containing an electron donative compound (e.g., acid clay, substituted phenolic compounds, etc.) and a colorless electron attractive substance capable of becoming a chromogenic substance when combined are coated on the same surface of a supporter. The recording sheet thus obtained is capable of producing different color hues by means of light and pressure.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a recording sheet (Kll self-coloring silver sheet) that allows multicolor recording.

Among various recording methods, one of the most convenient is pressure-sensitive recording paper that uses pressure. Color recording is obtained when the Hiro reactant and co-reactant come into contact and react.On the other hand, both the Fi and Fi are isolated from each other with microcapsules, etc., and are used to record paper, writing pressure, typing pressure, etc. The microcapsules are designed to rupture under pressure and come into contact with each other. Although the hue of a colored image on pressure-sensitive recording paper can be adjusted arbitrarily by mixing various reactants, such as electron-donating compounds, depending on diazo, copyability, etc., the coloring image obtained is Limited to one hue. This is because the eyelid coating, which contains reactants and the like used in pressure-sensitive recording paper, is uniformly applied to the entire back surface of the support, so it is not possible to record with a partial change in hue.

On the other hand, there are many cases in which documents are recorded in nine different hues and are round, and several methods and tastes have been proposed for recording rounded and multi-colored documents.

Japanese Patent Publication No. 55-2356 discloses that a number of microcapsules containing different types of Kyusakai compounds and having different breaking strength under pressure are mixed and coated on a support. It has been shown that by varying the degree of pressure, it is possible to apply a co-reactant and obtain recorded images of different hues on the nine-branched body. However, in order to change the breaking strength of the microcapsules, it is very difficult to control the membrane strength of the microphone-capsule during manufacturing and the particle size, and when recording, the voltage is changed and the peaks are recorded at a constant pressure. This is actually very difficult and is not suitable for general recording paper.

Japanese Patent Publication No. 48-4053 discloses that when a co-reactant is prepared in the area where the coloring hue is desired to be changed, a phosphoric acid solution is applied onto a nine support, and the co-reactant is modified to produce a different hue than K. However, since the reactants are the same, the difference in hue is small, and the 8 o'clock stability of the area coated with phosphoric acid liquid is poor. Special public@5.
Japanese Patent No. f-39565 discloses an example in which the color development specificity of a co-reactant to a reactant is utilized. That is, a sheet in which various microcapsules containing different reactants are coated at different locations on the back surface of the support and a sheet in which three types of co-reactants are coated in a single layer or a stack on the surface of the support are prepared. A method for obtaining multicolor recording by overlapping and applying pressure is shown, and Japanese Patent Application Laid-Open No. 1I855-95592 discloses a sheet coated with microcapsules containing a solvent on the back side of a support, and a sheet coated with microcapsules containing a solvent on the back surface of the support. A method of partially printing different combinations of mixtures of co-reactants and co-reactants and overlapping and pressing nine sheets was also developed in 1988-3.
Publication No. 9814 discloses a method in which nine sheets are coated on the back surface with microcapsules containing a coreactant, and nine sheets are coated on the surface with reactants that develop different colors upon contact with the coreactant. A method of pressurizing is shown. However, in all of these methods, the partial printing is done in advance, and the difference is only in a certain part, and the hue is 01il! The bell statue is not available.

In addition, these methods require a combination of a sheet containing a reactant and a sheet containing a co-reactant, which is inconvenient. In fact, after recording once, if you want to obtain a recorded image with nine different hues, or if you want to be able to obtain a multicolored recorded image by freely recording any part rather than a limited part. -It becomes more.

The present inventors have conducted research on a recording sheet that can obtain recorded images of different hues in arbitrary parts with a single sheet, and as a result, the inventors have conducted research on a recording sheet that contains a photocurable resin and a reactant that develops color when it comes into contact with a co-reactant. Mic-capsules, microcapsules containing a high-boiling point organic solvent and a reactant that develops a color different from the wrinkle reactant, and microcapsules containing a dispersed weight of a co-reactant or a skeleton co-reactant on the same surface of a support. A self-coloring phoenix recording sheet for papermaking purposes was obtained by mixing and coating.

The present invention will be explained in more detail.

The self-coloring seed recording sheet of the present invention is a photocurable resin microcapsule mainly containing a photocurable MS resin and a reactant, and a reaction that produces a color with a hue of a high boiling point organic solvent and a reactant encapsulated in the photocurable disc microcapsule. A normal microphone containing the body - a co-reactant that reacts with the capsule and the skeleton reactant to produce a colored substance is encapsulated in a microscopic capsule or a normal microphone 1 Kabul, and 94 are heated. However, by coating on the same side of a support and using pressure and light, a multicolor record can be obtained on a single recording sheet.

Furthermore, when using pressure and light, there are cases where pressure is applied first and then exposed, and cases where pressure is applied first and then exposed, and each is used in different quantities.

When the paper is exposed to light after being pressurized by pressing or the like, it can be used in the same manner as general self-coloring pressure-sensitive writing paper. That is,
KlE line on the coated surface of the self-coloring waterfall recording sheet according to the present invention,
Alternatively, if you overlap it with plain paper and press it with a lead wire, a ballpoint pen, a typewriter, etc., the light-cured microcapsules on the recording sheet will form a normal! The microcapsules are simultaneously destroyed, and two or more reactants contained in each microcapsule leak out and come into contact with nearby co-reactants, resulting in the development of different hues unique to each reactant. The aS appears on the cough record sheet as a yellowish color.

Furthermore, if you want to record with a different hue in areas other than one recording area,
When the coated surface of the recording sheet is irradiated with light, the light passes through the walls of the photocurable microcapsules, hardens the photocurable resin contained therein, and transforms it into a strong resin. It becomes a v-microcapsule and no longer breaks even when pressurized. On the other hand, normal blue microcapsules are not affected in any way, so if you put pressure on any part of the scissors/sickles sheet with the memo directly on it, or by overlaying plain paper and pressurizing any part again, only the normal microcapsules will be destroyed. , recorded as a single hue based on the contained reactants. In this way, a multicolored recorded image is obtained.

Incidentally, it is possible to stack a plurality of self-coloring sheets according to the present invention and press them together to produce a large number of sheets.

That is, the self-coloring cover recording sheet of the present invention and the original are superimposed. At this time, if the document support is made of a material that easily transmits light, especially ultraviolet rays, the coated side of the recording sheet and the side of the document that is not chained or printed, that is, the back side, should face each other. Expose from the stacked original side. If the support for the original manuscript is difficult to transmit the light of the book, the uncoated side of the Ikki Kama sheet using a support similar to transparent round wire and the printed or printed side of the Mukuro manuscript. Stack them so that they are facing each other, and expose the sheet side to light. It is desirable to adjust the exposure time depending on the combination of the scissors and sickles sheet and the original.

When exposed to light, light is absorbed in the basket marks, printed patterns, and characters of the manuscript manuscript, and the scissors recording sheet is not exposed to light, but other areas are exposed to light because the light passes through or reflects in lines, and these areas are coated. photocuring - the microcapsule encapsulation is cured.

When the exposed Bakuki Kama sheet is pressed with a roll or the like, both the photocurable microcapsules and the normal microcapsules corresponding to the designs and characters on the manuscript are destroyed, and the reaction that is part of the inclusions is destroyed. The body leaches out and comes into contact with nearby co-reactants, resulting in a colored image. This color development *d is caused by reactants that develop different hues contained in two types of microcapsules, and is shown as a color mixture. - In the exposed area, the photocurable microcapsules are not destroyed, but only the normal microcapsules are destroyed, so a colored image of a single hue can be obtained.

In this way, on the cough sheet, the same design and characters as the original are obtained on a background of a single hue, but in a hue different from that of the background.

By using several types of photocurable microcapsules in which the degree of curing and reactants are varied by changing the amount and type of photocurable resin and photopolymerization initiator encapsulated in the photocurable microcapsules used in the present invention, It is also possible to record in more hues than colors.

The high boiling point organic compound used in the present invention may be a solvent equivalent to a solvent used in general pressure-sensitive recording paper, such as aromatic compounds such as alkylnaphthalene, alkyldiphenylalkane, rubiphenyl in alcohol, atalic acid, etc. ester,
Examples include esters such as glycol esters, chlorinated buffins, toluene, xylene, amide oil, cottonseed oil, and the like.

The photocurable resins encapsulated in the photocurable microcapsules used in the present invention include cinnamic acid residues, cinnamylidene residues, α, β-unsaturated ketone residues, coumarin residues, anthracene residues, α- Photosensitivity of photodimerizable resins with photosensitive groups such as phenylmaleido residues, benzophenone residues, and stilbene residues, diazonium salt residues, quinonediazide residues, azide residues, dithiocarnolyte residues, benzoin residues, etc. A photopolymerizable resin having an acrylic group, an allyl group, a vinyl group, an epoxy group, etc. can be optionally used, but a light heavy mold resin is preferred. As for the shape, a liquid one is advantageously used. 9. Known compounds that are commonly used as photopolymerization initiators for polymerizing photocurable resins may be used, such as benzoin alkyl ether, benzophenone, 2-hiraketones, thioxanthates, and acetophenones. For example, anthraquinone, 5-nitrofluorene, etc. are used as photosensitizing aids that have the effect of broadening the sensitizing wavelength range of the photopolymerization initiator, and stabilizers and modifiers such as radical polymerization inhibitors are used to improve storage stability. In some cases, a relatively low molecular weight oligomer or a diluent agent may be incorporated at the same time. In order to improve the solubility of the reactants to be simultaneously incorporated, high-boiling oily solvents such as alkylnaphthalenes, alkyl biphenyls, alkyl ten biphenyls, and esters are used.
A% is sometimes used as a solubilizing agent, but it is not uniformly used in large amounts because it has a negative effect on the degree of curing.

The reactants and co-reactants used in the present invention refer to reactive compounds that react with each other upon contact and produce a colored substance. For example, a colored substance is a colorless electron-donating compound and a colorless electron-donating compound. in combination with an electron-accepting compound, an electron-donating compound is used as the reactant,
An electron-accepting compound is used as a co-reactant. A more specific explanation will be given of the single-reactive compound, which includes a combination of a ligand and a polyvalent metal compound. As an electron-donating compound, 3,3-bis(P-
dimethylaminophenyl)-6-dimethylanno7thallide, 3.3-bis(P-dimethylaminophenyl)phthalide, 3-(P-dimethylaminophenyl)-3-(1
, 2-dimethylindol-3-yl) phthalide and other triarylmethane compounds, 4,4'-bisdimethylacetylbenz(drypenzyl ethyl) and other diphenylmethane compounds, 3-dimethylacetate, 7-medoxyfluorane, Xanthine compounds such as 3-diethyl amanor 7-chlorofluorane, 3-diethyl amanor 7-dipendyl fluorane, thiazine compounds of benzoyl leucomethylene blue, 3-methyl subirodinaphthobilane, 3-propyl dibenzo Examples include spiro compounds such as pyran.

Examples of electron-accepting compounds include inorganic acidic substances such as acid clay, activated clay, kaolin, zetaite, and bentonite;
-Cresol, P-octylphenol, P-cyclohexylphenol, P-phenylphenol, α-su7
Substituted phenol compounds such as tilphenol, /l phenol, and P-chlorophenol, phenol resin compounds such as phenol-pol-19f8 compounds, and substituted phenol-formalin condensates, and their use in zinc, nickel, etc. Metal salt-modified phenolic resin compound modified with a polyvalent metal, P-butylbenzoic acid, P-hydroΦcybenzoic acid, 2
．． 5-dihydroxybenzoic acid, salicylic acid, 5-1er
Aromatic carboxylic acid compounds such as t-butylsalicylic acid, 3.5-di-t-M-butylsalicylic acid, and 3.5-di”(-monomethylbenzyl)salicylic acid, and their use with polyvalent metals such as zinc and nickel. Examples of metal salts include metal salts of nine aromatic carboxylic acid compounds, and mixtures of aromatic carboxylic acid compounds and polyvalent metal compounds such as zinc acetate and zinc pionate.

In addition, as a ligand, 8-quinolitool, gallic acid, gallic acid dodecyl ester, 1,10-phenan) II
9-,'0-phenylenesiaiy diphenylthiourea, guanidine, hydroxynaphthoic acid, dibipatriylmethane, trifluoroacetylacetonate; metal compounds include ferric stearate, magnesium stearate, zinc stearate, N- Examples include, but are not limited to, phenyl-N-ethyldithiocarbamate/acid zinc.

The microcapsules used in the present invention can be manufactured by methods known in the Todoroki industry. For example, U.S. Patent No. 28004
57, the method of phase separation from an aqueous solution as shown in the specification of No. 2800458, etc., the method of phase separation from an aqueous solution as shown in Gyutokoku No. 38-19574, No. 4 Tate No. 6 of the same Sho 42-4, No. 771 of the same Sho 42-771, etc. interfacial polymerization methods such as JP-B No. 86-9168, JP-A-51-9079, etc., in-5-itu method by polymerization of monomers, British Patent No. 95280? No. 965074, etc., and the melting and dispersion cooling method disclosed in US Pat. No. 3,111,407.
Examples include, but are not limited to, the spray drying method shown in British Patent No. 930,422 and the like. In addition, as wall film forming materials and binding materials, gelatin, ara, beer gum starch, sodium alginate, ethyl cellulose, carboxyethyl hexa-acetate, polyvinyl alcohol, polyethylene, boria dendritic acid, polyester, polyphretown, polyethylene imine, etc. are used. but,
It is more preferable to use a material that sufficiently transmits light, especially ultraviolet light.

Ultraviolet light is generally used as the light for curing the photo-curable FIV Ikuto capsule used in the present invention. As light sources, sunlight, xenon lamps, low-pressure and high-pressure mercury lamps, fluorescent lamps, etc. are used. The degradation of the properties of the self-coloring recording sheet of the present invention due to exposure to light such as that occurring under room light or indirect sunlight during manufacturing and during normal handling is unlikely to occur.

In order to hold the recording layer of the self-coloring system II'/-) of the present invention on a support, water-soluble binders and latexes are generally used.

N, tb, gelatin, casein, carboxymethylcellulose, human dimethylcellulose, saponified starch,
Esterified starch, polyvinyl alcohol, polyvinyl vinylidene, polyacrylic acid, vinyl acetate-acrylic acid copolymer, Atari m! Examples include water** polymers and latexes such as toly-butadiene copolymers and vinylidene chloride copolymers. These are selected from the viewpoints of surface strength and dispersibility and are used alone or in combination.

The recording layer of the recording sheet of the present invention further contains cellulose powder, dengue/particles, a capsule preservative made of plastic particles, inorganic pigments such as Merck, calcium carbonate, zinc oxide, titanium oxide, and urea. Even if organic pigments such as formalin 11, dispersants, antifoaming agents, etc. are added, it will not work.

As a coating method, for example, an air knife coater, a blade coater, a gutswier coater, etc. are used to coat the entire surface of the support.
Examples include a method in which a part of the support is covered with K11k cloth in a flexographic printing machine, a gravure printing machine, etc.

As the support, transparent, transparent, or opaque materials can be arbitrarily selected, such as paper, various kinds of nonwoven fabrics, synthetic paper, metal foil, plastic film, etc., or a composite sheet of a combination of these can also be used.

Hereinafter, the present invention will be specifically explained with reference to Examples, where "parts" indicate parts by weight.

Example 1 (1) A photocured resin microcapsule dispersion containing a reactant was prepared as follows.

A styrene-leic acid anhydride copolymer was dissolved in 11I with a small amount of sodium hydroxide, and a 5T aqueous solution of 9P H4,0 was prepared.
In 00 parts, the electron-donating compound which is a reactant, namely 3-(4-diethylamino-2-ethyl)
-3-(1-Ethyl-2-methylindol-3-yl)-4-aza 7-talide &4 parts and 0.2 parts of benzoin ethyl ether dissolved in acrylate-based photocurable resin [
80 parts of NIA-X (trade name, manufactured by Toagosei Chemical Industry Co., Ltd.) were emulsified.

On the other hand, 10 parts of Metsumaf, 25 parts of aqueous formalin solution, and 65 parts of water were adjusted to pH 9 with sodium hydroxide, heated to 60°C, and a transparent paper and initial condensate of formalin and formalin were obtained in 15 minutes. It was done. This initial shrinkage 5 food was added to the emulsion to bring the temperature to 60°C, stirring was continued for 4 hours, and then the mixture was cooled to room temperature.

The solid content of the obtained microgastric capsule dispersion was 45 饱.

(1) Contains a reactant that has a different hue from (1)! 9. Prepare a capsule dispersion as follows.

5-Aqueous solution of styrene-leic anhydride copolymer dissolved with a small amount of sodium hydroxide at pH 4.0 10
0 parts of 3-diethylamino-two-curroturuorane 2
．． 8 stone Hysol N-296 (product name:
Emulsify 80 parts of Nippon Petrochemical Oil). On the other hand, 72
7,710 parts, 25 parts of a 37-bag formalin aqueous solution, and 65 parts of water were adjusted to pH 9.0 with sodium hydroxide, heated to 60°C, and became transparent in 15 minutes, yielding a melamine-formalin initial condensate.

The initial condensation product of keratin was added to the emulsion, and the emulsion was stirred for 4 hours while maintaining the emulsion at 60°C.After 9 hours, the emulsion was cooled to room temperature.

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

(3) 110 parts of the photocurable reduced microcapsule dispersion obtained in (1), 110 parts of the normal microcapsule dispersion obtained in (2), 309G of 3.5-di-art-butyl slithylic acid. 66 parts of aqueous dispersion and 10% polyvinyl alcohol aqueous solution zso@.

50 parts of wheat starch and 200 parts of water were added and thoroughly stirred to prepare a coating liquid. A coating liquid consisting of 50 g of zinc oxide, 20 parts of 48% 88B latex, and 100 parts of water was coated to a total volume of 217 ml, and the dry coating amount of the above coating liquid was applied to 95,017 ml of base paper using a Meyer parlor in a dry coating amount of 8.0 t/ml. A self-coloring layer recording sheet was obtained.

(4) When printed on the obtained 9 self-coloring Kama sheets using an IBM typewriter 82011 without the tie-remen, bluish-purple characters were obtained.

The Ik4ii surface of the wrinkled recording sheet with this colored image was irradiated with Senon light using a Cenofax FX-150 during re-saw, and later printed again using the same typewriter to obtain a colored image of 9 and ζ. A bluish-purple and red colored image was obtained on a single Kikama sheet.

Example 2 (1) A photocurable microcapsule containing a reactant was prepared as follows.

10-water of ethylene-anhydrous maleic copolymer @i11
0Gg, urea tog, 7 to 1/71 part and water 200
The mixture was heated to form a solution, and the pH was adjusted to 15 using an aqueous sodium hydroxide solution.

The reactant is a 4-electron donating compound, i.e. 3-diethylamino-6-methyl-4-di-sulfur, 2 parts, benzoin ethyl ether (L 5g) dissolved in an epoxy acrylate photocurable resin (trade name: riboxy,
Showa Kobunshi III (manufactured by Showa Kobunshi III) was emulsified and dispersed in the above mixed aqueous solution to obtain an oil-in-water emulsion with oil droplets of 4 to 8 electrons. Then 37 thiformaldehyde aqueous solution 25
After adding m, the liquid temperature was kept at 55°C, stirring was continued for 4 hours, and then cooled to room temperature to complete encapsulation.

(2) (Microcapsules encapsulating a reactant that develops a color different from the reactant in I) were prepared as follows.

3-diethylamino-7 to 3-diethyl 72 or 6-methyl-7-anilite fluoran in (1) above,
- Encapsulation was carried out under pressure in the same manner as in 11) except that 8 stone... Isol N296 was used in the epoxy acrylate photocurable resin kawasho in which benzoin ethyl ether and benzoin ethyl ether were dissolved.

(3) Microcapsules containing coreactants were prepared as follows.

In place of the 3-diethylamino-7-chlorofluorane in (2) above, the co-reactant 3,5-di-tert-
Encapsulation was carried out in the same manner as in the case except for (9) using 9.0 parts of butylsalicylic acid and 115 parts of Octix zinc (Nihon Kagaku Sangyo ■Ill).

(4) Prepare a Kamefu liquid with the following composition and apply it to paper with a basis weight of 50F/s/using a Meyer parser so that the dry coating amount is 9 fowl.

Reactant-encapsulated photocurable microcapsule dispersion (above (1)
22 parts reactant encapsulating microphone capsule dispersion (according to (2) K above) 18 parts co-reactant encapsulating microphone capsule dispersion (according to (3) K above) 44 parts 1G-polyacrylic acid Water soluble 1 [26 parts water
50 copies of the nine self-coloring recording sheets obtained in this way were stacked with the back side of the handwritten document on semi-transparent paper as a manuscript, and the manuscript side was printed using a Soxenofax FX-150. When irradiated with xenon light, the self-coloring deaf recording sheet was passed between rubber rolls and pressed, and a black copy of the same characters as the original appeared on the recording sheet.

In addition, the parts other than the letters are colored red.

469-

Claims (1)

[Claims] Iku capsule contains a reactant that develops a color when it comes in contact with light, an II chemical resin, and a co-reactant, and contains a reactant that develops a color different from the high boiling point organic knowledge and the reactant! 1. A Maroki coloring recording silver sheet, characterized in that a support is coated with a kidney capsule and a dispersion tube of a co-reactant or a microcapsule containing the co-reactant.