JPH03247485A - Pressure sensitive copy sheet - Google Patents

Abstract

PURPOSE:To obtain a pressure sensitive copy sheet having excellent durability and adapted for a delivery slip by combining a sheet provided with a peelable developer layer on the rear surface of a transparent support, and a sheet provided with a colorant-containing microcapsule layer on the front surface of the support. CONSTITUTION:A pressure sensitive copy sheet 1 is combined with a sheet A provided with a peelable developer layer 3 on the rear surface of a transparent sheet 2 and a sheet B provided with a colorant-containing microcapsule layer 5 on the front surface of a support 4. When the sheet 1 receives a pressure (p) by writing, a typewriter, etc., the microcapsule 5 on the surface of the sheet B is damaged, the discharged colorant is reacted with the developer 3 existing on the rear surface of the sheet A to generate an image (b) at the place, the part of the developer is simultaneously peeled to be transferred onto the damaged microcapsule 5 on the sheet B to generate an image (b). Since the sheet 1 is formed to protect the layer 3 by the support 2, it has excellent durability. Since the part of the layer 3 is transferred, the damaged microcapsule is printed thereon.

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a pressure-sensitive copying sheet, and particularly to a pressure-sensitive copying sheet that has excellent durability and is suitable for delivery slips.

"Prior art" Combination of electron-donating color formers such as crystal violet lactone and benzoyl leucomethylene blue with electron-accepting color developers such as activated clay, phenol-formaldehyde condensates, and polyvalent metal salts of aromatic carboxylic acids. etc. 2
Pressure-sensitive copying sheets that utilize color reactions of various chromogenic substances are well known.

In general, these pressure-sensitive copying sheets are made by coating a support with color former-containing microcapsules prepared by a phase separation method, interfacial polymerization method, 1n-situ polymerization method, etc.; The base sheet coated on the body and the middle sheet coated with the microcapsules and developer on different sides of the support are combined as appropriate and are used in various fields.

In addition, a so-called self-coloring pressure-sensitive copying sheet in which the above-mentioned microcapsules and a color developer are coated as a laminated or mixed layer on the same side of a support, or a release sheet in which an adhesive layer is provided on the back side of a base sheet, is also available. There are also known pressure-sensitive copying adhesive sheet sets, etc., which are made by appropriately combining a structure bonded with a top sheet and a middle circumferential sheet.

However, although these pressure-sensitive copying sheets allow easy copying, they tend to have problems with durability when used outdoors, such as on delivery slips. For example, (1) If the base material is ordinary paper, it will easily tear with weak force. Particularly, when the paper is wet, it tends to tear easily.

■The color developer coating layer provided on the base material is easily destroyed by mechanical forces such as friction.

In recent years, in order to solve these problems, there have been an increasing number of cases in which water-resistant and tear-resistant synthetic paper or film is used as a base material. However, although this method also greatly improves the durability of the base material itself, the adhesion between the color developer coating layer and the base material is insufficient, so when removing cellophane tape etc. pasted on the printed area, The coating layer is likely to be destroyed and become unreadable.

Another technique is to cover the recording sheet with a transparent sheet in order to prevent the coating layer from peeling off. However, although this method also solves the above problems, it cannot be said to be sufficient considering the effort and cost of pasting the transparent sheet.

``Problems to be Solved by the Invention'' The present invention provides a pressure-sensitive copying sheet that has excellent durability and is suitable for delivery slips.

"Means for Solving the Problem" As a result of research to achieve the above object, the present inventors have developed a sheet with a color developer layer provided on the back side of a transparent support, a color developer-containing microcapsule layer, or a color developer layer. We previously filed an application for pressure-sensitive copying sheet I (Patent Application No. 172069), which basically consists of a combination of microcapsules containing a color developer and a sheet provided with a self-coloring transfer layer containing a color developer. When a sheet having a microcapsule layer is used, the sheet cannot record. Furthermore, when a sheet having a self-coloring transfer layer is used, the sheet can be used for recording, but since it is self-coloring, the sheet is often stained during handling after recording. As a result of further research, the present inventors discovered a pressure-sensitive copying sheet having the following structure.

The present invention relates to a pressure-sensitive copying sheet having a basic configuration of a sheet having a peelable color developer layer on the back side of a transparent support and a sheet having a color former-containing microcapsule layer on the surface of the support. be.

"Function" The pressure-sensitive copying sheet 1 of the present invention comprises a sheet A) in which a releasable color developer layer 3 is provided on the back surface of a transparent support 2 as shown in FIG.
The feature is that the sheet B is combined with a support 4 and a color former-containing microcapsule layer 5 provided on the surface thereof.

When this pressure-sensitive copying sheet 1 is subjected to pressure P from writing or a typewriter, the coloring agent-containing microcapsules 5 on the surface of the sheet 8 are destroyed. As a result, the released color forming agent reacts with the color developer 3 present on the back side of sheet A to produce an image at that location, and at the same time, a part of the color developer layer peels off and the surface of sheet B is exposed. It is transferred onto the destroyed color forming agent-containing microcapsules 5 to form an image.

Since the pressure-sensitive copying sheet 1 of the present invention has a structure in which the color developer layer 3 is protected by the transparent support 2, it has excellent durability. In addition, since a portion of the color developer layer 3 is transferred,
Recording can be performed on the destroyed color former-containing microcapsules.

The pressure-sensitive copying sheet of the present invention is bundled with a pressure-sensitive adhesive or adhesive and used as a delivery slip 6 having a layered structure as shown in FIGS. 2 to 7, for example.

The delivery slip 6 in FIG. 2 consists of a sheet C in which a peelable color developer layer 8 and a partial adhesive layer 9 are provided on the back side of a transparent support 7, and a color former-containing microcapsule II on the surface of a support 10. A sheet D having a partial release agent layer 12 is bonded to the adhesive layer 9 and a release agent layer 12, and a sheet E made of high-quality paper is further provided on top.

When this delivery slip 6 is written on a high-quality paper E with a writing instrument P such as a ballpoint pen, the coloring agent-containing microcapsules 11 on the surface of the writing instrument D are destroyed by the pressure of the writing. As a result, the released color forming agent reacts with the color developer 8 present on the back surface of the sheet C to form an image at that location. At the same time, a part of the color developer layer peels off and the surface of the sheet 0 is It is transferred onto the destroyed color forming agent-containing microcapsules 11 to form an image.

The completed delivery slip 6 is, for example, Sheet D and Sea) E.
is peeled off and used as a slip, and C) is affixed to the package via the partial adhesive layer 9, and the copy image is viewed through the transparent support 7. Sheet C like this
Since the color developer layer 8 is used while being protected by the transparent support 7, durability that could not be obtained with conventional structures can be obtained without any effort or cost.

3 and 4 are cross-sectional views showing an expanded embodiment of the delivery slip of FIG. 2. FIG.

The delivery slip 6 in FIG. 3 has a transparent support 7 as a sheet C.
A layer 13 containing pigment as a main component is provided on the back surface of the second layer, and a removable color developer layer 8 and a partial adhesive N9 are further provided.
It is used in the same way as the delivery slip shown in the figure. The structure in which the layer 13 mainly composed of pigment is provided has the advantage that the base of the attached baggage is difficult to see and the copied image is clearly visible, and is more preferable than the slip shown in FIG. 2.

The delivery slip 6 shown in FIG. 4 has a structure 14 in which a color developer is contained in the layer mainly composed of pigment of the sheet C shown in FIG.
A clearer image can be recorded than in FIG. 3, and this is a more preferable form.

5 to 7 are cross-sectional views showing an embodiment in which the delivery slip 6 of FIG. 4 is further developed.

The delivery slip 6 in FIG. 5 includes a sheet F in which a color developer-containing pigment layer 16 is provided on the back surface of a transparent support 15, a releasable color developer layer 17 and a partial adhesive layer 18, and a support Seat 1 with a color developer layer 20 and a partial release agent layer 21 provided on the surface of the body 19
-H is bonded to the adhesive layer 18 and the release agent layer 21, and between the sheet F and the sheet H, a sheet G in which color forming agent-containing microcapsules 23 and 24 are provided on both sides of the support 22 is interposed, and further It has a structure in which a sheet I made of high-quality paper is provided at the top.

When the delivery slip 6 is written on the sheet I with a writing instrument P such as a ballpoint pen, the pressure of the writing destroys the coloring agent-containing microcapsules 23 and 24 on the front and back sides of the sheet G, and the coloring agent is released. The color former is the color developer layer 1 of Sheet F and Sea) H.
At the same time, a part of the color developer layer 17 of C) F is peeled off and transferred onto the destroyed color former-containing microcapsules 23 on the surface of sheet G. and create an image.

After recording, Sheet 1-H and Sheet I are peeled off and used as a slip, etc., and the set of Sheet F and Sheet G is attached to the luggage via the partial adhesive layer 18, and the copied image is passed through the transparent support 15. used visually. Incidentally, the sheet G can be separated and used as a slip, etc. when transporting luggage.

The delivery slip 6 shown in FIG. 6 has color former-containing microcapsules 26 on the front surface and a back carbon layer 27 on the back surface instead of the sheet G) in which color former-containing microcapsules are provided on both sides of FIG. A sheet (C) J) with a color developer layer provided on the support and a sheet (C) K) with a partial release agent layer 29 provided on high-quality paper instead of a sheet (sheet H) with a color developer layer provided on the support. This is the configuration used.

In addition, the delivery slip 6 shown in FIG. 7 also has a backing carbon paper (sheet L) between the sheet J and the sheet of the slip shown in FIG.
).

Examples of sheets that can be interposed between the partial adhesive sheet (sheet I) and the partial release sheet (sheet H or sheet K) include (
a) Sheet in which color former-containing microcapsules are provided on both sides of the support (for example, Sheet G), (b) Sheet in which color former-containing microcapsules are provided on the front surface and a back carbon layer is provided on the back surface (for example, Sheet J), (C ) In addition to the back carbon sheet (for example, C) L), (b) a soil sheet with a color former-containing microcapsule layer on the back side of the support, (e) a color developer layer on the front side of the support, and a color forming layer on the back side. (F) A lower sheet with a color developer layer provided on the surface of the support, ((to) a color developer layer on the surface of the support, and a back carbon layer on the back surface.) For example, a sheet provided with such a material may be used, and the necessary number of these sheets can be selected as appropriate.

Another form of the present invention is one in which one or more backing carbon papers are further stacked on top of the front sheet E or sheet I, or in place of sheet E or sheet 2, an upper sheet, a middle circumferential sheet, There is also a structure in which pressure-sensitive copying sets are stacked together with a lower sheet.

As described above, the pressure-sensitive copying sheet of the present invention is extremely useful as a delivery slip, but its use is not limited to delivery slips.

The color forming agent and color developer referred to in the present invention do not simply refer to an electron-donating color forming agent and an electron-accepting color developing agent, but include all combinations of chromogen substances that react with each other to form a color, such as a color forming agent. Examples include cases in which the agent and developer are used interchangeably, and cases in which a ligand compound and a metal salt are used.

Examples of the electron-donating coloring agent include the following substances known in the field of pressure-sensitive copying paper.

3.3-Bis(p-dimethylaminophenyl)=6-dimethylaminophthalide, 3-(P-dimethylaminophenyl)-3-(1,2-dimethylindol-3-yl)phthalide, 3,3 -bis(1,2-dimethylindol-3-yl)-5dimethylaminophthalide, 3.3-
Triallylmethane dyes such as bis(9-ethylcarbazol-3-yl)-6-dimethylaminophthalide, 4
．． 4'-bis-dimethylaminobenzhydrylbenzyl ether, N-herophenyl leukoolamine, N-
Diphenylmethane dyes such as 2,4,5-1-lichlorophenylleucoolamine, thiazine dyes such as benzoylleucomethylene blue and p-nioropenzoylleucomethylene blue, 3-methyl-spiro-dinaphthopyran, 3-phenyl-spiro-dinaphthopyran, Spiro-based dyes such as 3-proby-spirogibendubiran, lactam dyes such as rhodamine-B-anilinolactam, rhodamine (0-chloroanilino)lactam, rhodamine (O-chloroanilino)lactam, 3-dimethylamino-
7-Methylfluorane, 3, diethylamino-6-methyl-7-chlorofluorane, 3-(N-ethyl-p-)
Luidino)-7-methylfluorane, 3-diethylamino-7-N-methylaminofluorane, 3-diethylamino-7-dibenzylamiofluoran, 3-(N-ethyl-p-toluidino)-6-methyl- 7-phenylaminofluorane, 3-diethylamino-6-methyl-7
-phenylaminofluorane, 3-(N-cyclohexyl-N-methylamino)6-methyl-7-phenylaminofluorane, 3-piperidino-methyl-7-phenylaminofluorane, 3-diethylamino-6- Methyl-
Fluoran dyes such as 7-xylidinofluorane and mixtures thereof.

Examples of the electron-accepting color developer include the following substances known in the field of pressure-sensitive copying paper.

Acid clay, activated clay, acpargite, zeolite,
Clays such as bentonite, as well as phenolic resins,
Polyvalent metal salts of various aromatic carboxylic acids as described in Japanese Patent Publication No. 51-25174, zinc salts of 2,2' bisphenolsulfone compounds as described in Japanese Patent Publication No. 54-106316, etc. Coloring agents and mixtures thereof.

Examples of the combination of a metal salt and a ligand compound include the following combinations of substances known in the field of pressure-sensitive copying paper.

Nickel stearate and N,N'-dibenzyludithioxamide, nickel laurate and α-benzylglyoxime, tricaprylmethylammonium vanadate and dodecylamine 8-hydrooxyquinoline sulfonate, benzyl lauryl molybdate. Dimethylammonium and lauryl protocatechuate, titanium stearate and lauryl gallate, iron naphthenate and benzyl gallate, polyferrophenylmethylsiloxane and methylene dith (8-oxyquinoline), copper palmitate and N,N
'-bis-2-octanoyloxyethyldiethyldithiooxamito, cobalt laurate and di-0-tolylguanidine, hinokitiol and polyvanadophenylmethylsiloxane, organoiron phosphate described in JP-A-58-38191, Combinations of lauryl gallate, etc., and mixtures thereof.

Color former-containing microcapsules are prepared by dissolving the color former in oil and preparing a core material by coacervation method (for example, the method shown in U.S. Pat. Kosho 3B-1
No. 9574, Special Publication No. 42-446, Special Publication No. 42-77
No. 1, the method shown in Special Publication No. 49-45133),
The 1s-situ polymerization method is encapsulated and produced by a conventionally known method such as the method shown in Japanese Patent Publication No. 36-9168, Japanese Patent Publication No. 51-9079, and Japanese Patent Publication No. 53-84881.

Examples of oils include vegetable oils, mineral oils, aromatic hydrocarbons, alcohols, organic acids, esters, and organic phosphoric compounds known in the field of pressure-sensitive copying paper.
Ethers, amides, ketones, carbonates, etc. are used, and antioxidants, ultraviolet absorbers, etc. are added to this oil as necessary.

The color former-containing microcapsule layer of the present invention is provided by preparing the thus produced microcapsules into a capsule ink or coating liquid and applying it to a support.

Capsule ink or coating liquid can be either aqueous or non-aqueous, and in the case of an aqueous type, an aqueous capsule dispersion,
It is prepared by adding a binder, a capsule protectant, a surfactant, an antifoaming agent, a pigment, a preservative, an ultraviolet absorber, etc. as necessary. On the other hand, in the case of a non-aqueous capsule dispersion, binders, capsule protectants,
A surfactant, a pigment, an ultraviolet absorber, a photopolymerization initiator, a wax, a dryer, a thickener, a gelling agent, etc. are added, and the ink is prepared as an evaporative drying type, an ultraviolet curing type, an oxidative polymerization type ink, etc.

The amount of the color former to be included in the capsule cannot be determined unconditionally depending on the substance's solubility in oil or color forming ability, but it is preferably 1 to 200 parts by weight per 100 parts by weight of oil. The amount is 2 to 100 parts by weight. In addition, the amount of capsule ink or coating liquid applied to the support is not limited to this, but from the viewpoint of color development and economical efficiency, it is 1 to 1.
It is 15 g/rrT, more preferably 2 to 10 g/rrT.

Binders used in water-based capsule inks or coating solutions include water-soluble binders and latex binders. Examples of water-soluble binders include proteins such as gelatin, albumin, and casein, cereal starch, pregelatinized starch, Starches such as oxidized starch, etherified starch, and esterified starch, celluloses such as carboxymethyl cellulose and hydroxyethyl cellulose, agar, sodium alginate, gum arabic, etc. There are water-soluble natural polymer compounds such as Group I, and water-soluble synthetic polymer compounds such as polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, polyacrylamide, maleic acid copolymers, etc. Latex binders include, for example, Styrene-butadiene latex, acrylonitrile-butadiene latex, acrylic ester latex,
Examples include vinyl acetate latex, methyl methacrylate-butadiene latex, and carboxy-modified (eg, acrylic acid) latex thereof.

Binders used in non-aqueous couple inks or coating fluids include oil-soluble binders, such as rosin, (gum rosin, wood rosin, tall oil rosin), shellax, copal, dalman, gilt night, zein. Natural resins, cured rosins, ester gums and other rosin esters, such as
Semi-synthetic resins such as maleic acid resin, fumaric acid resin, duplex rosin, polymerized rosin, rosin-modified pheno resin, methylcellulose, ethylcellulose, hydroxypropylcellulose, ethylhydroxyethylcellulose, cellulose acetate propionate, cellulose acetate butyrate, nitrocellulose, etc. , phenolic resin, xylene resin, urea resin, melamine resin, ketone resin, chromine/indene resin, petroleum resin, terpene resin, cyclized rubber, chlorinated rubber, alkyd resin, polyamide resin, acrylic resin, polyvinyl chloride, vinyl chloride/acetic acid copolymer,
Examples include synthetic resins such as polyvinyl acetate, polyvinyl butyral (butyral resin), polyvinylpyrrolidone, chlorinated polypropylene resin, epoxy resin, and polyurethane.

These binders are selected depending on the type of medium to be used, and the method disclosed in, for example, Printing Ink Technology CMC Co., Ltd. edition can be suitably employed.

Pigments include zinc oxide, titanium oxide, aluminum hydroxide, calcium carbonate, magnesium carbonate, calcium sulfate, colloidal silica, zeolite, bentonite,
Inorganic pigments such as kaolin and calcined kaolin, melamine resin particles, urea resin particles, hollow particles of styrene-methacrylate copolymer (VONCOAT PT-207-
3. (manufactured by Dainippon Ink and Chemicals) and the like.

As the non-aqueous medium used when preparing a non-aqueous coating liquid or ink, those known in the printing industry can be appropriately used, and specific examples include benzene, toluene, xylene, cyclohexane, hexane, ligroin, Methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve, diene gellicol monobutyl ether,
Diethylene glycol monobutyl acetate, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, n-hexonol, cyclohexanol, 2-ethylhexyl alcohol, polyethylene glycol acrylate, propylene glycol dimethacrylate, pentaerythritol acrylate, trimethylolpropanedi acrylate, pentaerythritol tetraacrylate, hexanediol acrylate, 1,2-butanediol acrylate,
Reaction products of epoxy resin and acrylic acid, reaction products of methacrylic acid, pentaerythritol and acrylic acid, condensates of maleic acid, diethylene glycol and acrylic acid, methyl methacrylate, butyl methacrylate, styrene, vegetable oils (linseed oil, sunflower oil) etc., semi-drying oils such as soybean oil, dehydrated castor oil, polymerized oils, maleated oils, vinylated oils, urethanized oils), mineral oils (machine oils, spindle oils), and the like.

The releasable color developer layer of the present invention is formed by printing an aqueous or non-aqueous ink.

In addition to the developer and water, the water-based ink also includes a binder (water-soluble binder as described above, latex binder), oil-encapsulated microcapsules, pigment (pigment as described above), surfactant, and dispersant as necessary. , thickeners, ultraviolet absorbers, antioxidants, fluorescent dyes, etc.

Non-aqueous inks contain, in addition to a color developer and a non-aqueous medium, a binder (oil-soluble binder as described above), oil-encapsulated microcapsules, pigment (pigment as described above), ultraviolet absorber, and antioxidant, as required. , fluorescent dyes and various auxiliary agents known in the ink field such as photopolymerization initiators, waxes, dryers, thickeners, and gelling agents are added to prepare evaporative drying type, ultraviolet curing type, oxidative polymerization type inks, etc. be done.

It should be noted that among the color developers used in the preparation of the peelable color developer ink, organic color developers with excellent color development properties are more preferable, and among them, aromatic carboxylic acid metal salts have excellent color development properties and print storage stability. Excellent and particularly preferred. Furthermore, it is preferable to add oil-encapsulated microcapsules to the removable color developing ink, since this has the effect of increasing color development.

Incidentally, oil-containing microcapsules can be obtained by encapsulating the above-mentioned oils by the above-mentioned method, but when used in non-aqueous inks, melamine-formaldehyde resin, which has excellent solvent resistance, is used as a wall film. Particularly preferred are capsules containing:

Moreover, an antioxidant, an ultraviolet absorber, etc. can be further added to the microcapsule oil, if necessary.

Examples of the non-aqueous medium used in the non-aqueous color developing ink include the above-mentioned non-aqueous medium used in the preparation of the non-aqueous capsule ink. For this reason, it is preferable to include the color developer in a dispersed state in the ink. Therefore, when using an organic color developer, it is preferable to use a medium that is difficult to dissolve the color developer among the above-mentioned media.

The binder for the strippable color developing ink is selected depending on the type of ink medium, and how to use it is, for example,
The method disclosed in Printing Ink Technology CMC Co., Ltd. edition etc. can be appropriately adopted.

Pigments include silica, colloidal silica, kaolin,
Inorganic materials known in the art, such as calcined kaolin, calcium phosphate, calcium carbonate, magnesium carbonate, calcium sulfate, aluminum hydroxide, zinc oxide, titanium oxide, melamine resin particles, urea resin particles, polystyrene resin particles, etc.
Examples include organic pigments.

Peelable color developing ink is usually prepared by mixing and stirring a color developer in water or a non-aqueous medium, further micronizing the mixture using a ball mill, sand grinder, etc., if necessary, and then mixing other components.

Each material constituting the color developing ink usually has an ink solid content of 10
1 to 99 parts by weight of color developer, 0 parts by weight of binder
．． 1 to 30 parts by weight, 0 to 80 parts by weight of pigment, and 0 to 80 parts by weight of oil-encapsulated microcapsules, preferably 30 to 85 parts by weight of color developer, 1 to 10 parts by weight of binder, and 0 to 10 parts by weight of pigment. 40 parts by weight, and 10 to 40 parts by weight of oil-encapsulated microcapsules. The releasability of the ink is most influenced by the type and amount of the binder, and in the present invention, the amount is determined in consideration of the adhesion to the substrate and the releasability. Incidentally, although the amount of color developer ink applied is not limited to this, it is usually 0.3 to 5.
g/if.

As the adhesive used to constitute the adhesive layer of the present invention, those known in the art, such as rubber-based, acrylic-based, polyether-based, ethylene-vinyl acetate-based adhesives, etc. can be used, and emulsion type, It is usually applied as a solvent-type or non-solvent type (hot-melt type or ultraviolet curing type) coating liquid at a dry weight of 5 to 50 g/rrf.

A release layer for protecting the adhesive layer is provided on the color former-containing microcapsule layer as in Sheet D, on the developer layer as in Sheet H, or on the support as in Sheet. Used to configure layers. As the release agent, condensation polymerization type silicone or addition polymerization type silicone can be used, and as an emulsion type, solvent type, or solventless type (ultraviolet curing type) coating liquid, the dry weight is usually 0.01 to 10.
It is applied so that it becomes g/rrr.

The layer 13, which is provided on a transparent support and whose main component is a pigment, contains a pigment (such as the pigment described above), a binder (such as a water-soluble binder or a latex binder as described above), and, if necessary, a dispersant and a fluorescent brightener. , an aqueous coating liquid containing ultraviolet absorbers, antioxidants, antifoaming agents, etc., with a dry weight of 1 to 10
It is formed by coating it on a support so that it is about g/rrf, preferably 2 to 7 g/rrf. Furthermore, by containing a color developer 14 (FIG. 4) in this layer, an even clearer colored image can be seen.

Unlike the releasable color developer layer, the color developer layer constituting H) is set to have good adhesion to the support, but this layer usually contains a color developer and a binder (such as the water-soluble binder described above). ,
It is formed by applying a water-based paint prepared by adding pigments (such as those described above), surfactants, dispersants, thickeners, antifoaming agents, etc. as necessary in addition to the latex binder). .

The back carbon layer constituting Sheets J, Sea) L, etc. usually contains pigments such as carbon black, ultramarine blue, navy blue, and lake red; fluid oils such as mineral oil, grease, vegetable non-drying oil, and petroleum-based vaseline; carnauba Hot-melt ink is printed by blending waxes such as wax, paraffin, synthetic wax, montan wax, and mineral wax, and the amount of ink is set at 0.5 to 1 Og/rrf.

In the present invention, methods known in the art are used as coating machines and printing machines used to coat each coating solution or ink onto a support. Coating machines include air knife coating, roll coating, blade coating, and par coating. Examples of printing machines include letterpress printing, intaglio (gravure) printing, planographic (offset) printing, screen printing, and the like.

The transparent support used in the present invention may be any material as long as records can be read through the sheet, and sheets used for this include ethylene resin, propylene resin, styrene resin, vinyl chloride resin,
Examples include synthetic resin sheets such as ester resins, polyamide resins, acrylic resins, nitrile resins, urethane resins, and cellulose resins.

Further, examples of the opaque support used in the present invention include paper, impregnated paper, synthetic paper, laminated paper, metal-deposited paper, and the like.

The sheet created as described above is further subjected to ruled line printing and desensitization printing, and then processed into a slip.

"Examples" Examples will be given below to further clarify the effects of the present invention, but the present invention is not limited to these Examples. Parts and % in the examples represent parts by weight and % by weight, respectively, unless otherwise specified.

Example 1 Oil microcapsules of ethylene-maleic anhydride copolymer (trade name: EMA-
31, manufactured by Monsando) to 200 parts of a 3.0% aqueous solution of 20% caustic soda to adjust the pH to 6.0, and 100 parts of alkyldiphenylethane (trade name: Hysol 5AS-296゜Japan Petrochemical). After emulsifying the product (manufactured by ①), the temperature of this system was raised to 55°C.

Separately, add 1 part of melamine to 45 parts of 37% formaldehyde aqueous solution.
5 parts were added and reacted at 60'C for 15 minutes to prepare an aqueous prepolymer solution. This prepolymer aqueous solution was added dropwise to the emulsification, stirred, heated to 80°C, kept at that temperature for 1 hour, lowered the pH to 3.5 with 0°2N hydrochloric acid, and further heated to 90°C. After holding for a period of time under
．． 200 parts of a 20% aqueous solution (manufactured by Mitsui Toatsu Kagaku ■) was added over 30 minutes, and the dispersion was then filtered, washed with ethanol, and dried to obtain powdered oil-encapsulated microcapsules.

・Ink U 3.5-di(tert-butyl) zinc salicylate 50 part, ethyl cellulose (ethyl cellulose Nα
14. Vercules) 5 parts, ethanol 36 parts, n
- After pulverizing 40 parts of hexyl alcohol and 40 parts of water in a ball mill, the above oil-containing microcapsules 5
0 parts and 30 parts of synthetic silica (Mizukasil P-527, manufactured by Mizusawa Chemical Industry Co., Ltd.) were added to obtain a color developing ink.

Ichinyu J [60 parts of zinc oxide, 45 parts of a mixed melt of 3.5-(α-methylbenzyl)zinc salicylate and α-methylstyrene/styrene copolymer (melt ratio 80/20), A dispersion obtained by pulverizing 15 parts of polyvinyl alcohol aqueous solution (solid content) and 90 parts of water in a ball mill for 24 hours was added to hollow particles of styrene-methacrylate copolymer (trade name: rV
ONc.

A developer coating solution prepared by adding 195 parts of AT, PT-207-3J, manufactured by Dainippon Ink and Chemicals Co., Ltd.) and 60 parts of carboxy-modified styrene-butadiene copolymer latex (solid content) was applied to a 50 μm polypropylene film ( Product name:
Toyobo Bailen Film, manufactured by Toyobo ■) with a dry weight of 5
It was coated with a bar coater so that it was g/rrf.

Next, print ruled lines on the film side of the sheet, and
The above releasable color developing ink was partially printed on the coated surface side.

Subsequently, an adhesive (trade name: BPS4940, manufactured by Toyo Ink ■) was applied to the release agent-coated surface of sheet D produced as described below using a collator so that the dry weight was 20 g/n. After partially smearing the film, it was bonded to the above-mentioned film which had been printed with ruled lines.

Aromatic polyvalent isocyanate (product name: Coronate-L
1 (manufactured by Nippon Polyurethane Co., Ltd.) and dissolved this into 2%
The mixture was added to 600 parts of an aqueous polyvinyl alcohol solution and emulsified to give an average particle size of 8.0 μm, and this system was reacted at 80° C. for 4 hours to obtain a capsule dispersion. 50 parts of starch particles and 20 parts (solid content) of carboxy-modified styrene-butadiene copolymer latex were added to this dispersion, and the concentration was 18.
% to obtain a microcapsule coating liquid.

The obtained capsule coating solution was spread on a 40 g/rd base paper using an air knife coater so that the solid content was 3.0 g/n.

Subsequently, a release agent prepared by adding 1% by weight of PL-3 as a catalyst to silicone (trade name: KS-770゜manufactured by Shin-Etsu Silicone ■) and diluting it to 20% by weight with toluene was used to remove the line-printed material. The above sheet was partially smeared to obtain C)D.

A delivery slip having the structure shown in FIG. 4 was created by overlaying high-quality paper (sheet E) with ruled lines printed on top of the delivery copy Kurikasaku Rin Sheet C1 and Sheet D.

Evaluation 1: Printed on the obtained delivery slip using a typewriter. Subsequently, Sheet D and Sheet E were removed and used as a slip, and Sheet C was pasted on the baggage. Furthermore, even when the pasted slip got wet with rain, there was no decrease in mechanical strength as seen with conventional paper.

"Effects" As is clear from the examples, the pressure-sensitive copying sheet of the present invention was extremely excellent in terms of durability.

[Brief explanation of drawings]

FIG. 1 is a sectional view illustrating a pressure-sensitive copying sheet of the present invention. Further, FIGS. 2 to 7 are cross-sectional views each showing an example of a delivery slip using the pressure-sensitive copying sheet of the present invention. A: Sheet A (color developing sheet) B: Sheet B (capsule sheet) C: Sheet C (partial adhesive sheet) D = Sheet D (partial release sheet) E: Sheet E (high quality paper) F: Sheet F (partial) G: Sheet G (double-sided capsule sheet) H: Sheet H (release sheet) I: Sheet I (high-quality paper) J: Sheet J (capsule backing carbon sheet)
K (partial release sheet) L: Sheet L (back carbon sheet) P: Writing instrument a: Print b: Recorded image 1: Pressure-sensitive copying sheet 2: Transparent support 3: Release color developer layer 4: Support 5: Color former-containing microcapsule layer 6: Delivery slip 7.15: Transparent support 8.17: Peelable color developer layer 9.18: Partial adhesive layer 10, 19.22.25.2B, 30: Support body 11
, 23.24.26: Color former-containing microcapsule layer 12, 21.29: Partial release agent layer 13: R material layer 14.16: Color developer-containing pigment layer 20: Color developer layer 27.31: Back carbon layer

Claims (3)

[Claims] (1) A pressure-sensitive copying sheet whose basic structure is a combination of a sheet in which a peelable color developer layer is provided on the back side of a transparent support and a sheet in which a color former-containing microcapsule layer is provided on the surface of the support. (2) The pressure-sensitive copying sheet according to claim (1), further comprising a layer containing a pigment as a main component between the transparent support and the releasable color developer layer. (3) The pressure-sensitive copying sheet according to claim (2), wherein the layer containing the pigment as a main component contains a color developer.