JPH0958120A - Recording sheet and detection of forgery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermal and pressure-sensitive color forming recording sheet. SOLUTION: A thermal/pressure-sensitive color forming recording sheet 6 is obtained by laminating a support 1, a thermoplastic resin layer 2, a single self-color forming pressure-sensitive recording layer 3 obtained by independently laminating or mixing a color former and a coupler at least one of which is microencapsulated, transparent or translucent paper 4 and a thermal recording layer 5 containing a color former and a coupler forming a color upon the contact with the color former. Therefore, a thermal color forming type self-color forming pressure-sensitive recording sheet capable of performing thermal recording and pressure-sensitive recording and having sufficient friction resistance can be obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording sheet having anti-counterfeit property, and the basic anti-counterfeit property is provided by pressure-sensitive coloring. For example, a heat-sensitive / pressure-sensitive color-developing recording sheet having anti-counterfeiting property according to the present invention can be easily heat-sensitive printed by using a thermal head, and can be easily pressure-sensitive colored by an impact printer or simple pressurization. The present invention relates to a heat sensitive and pressure sensitive color type recording sheet. The release sheet having anti-counterfeiting property allows the release sheet to be colored during printing on a general label, so that it is possible to make a duplicate copy and prevent forgery. The hiding type pressure-sensitive color-developing recording sheet is to be able to write the lottery wins and rankings after the hiding layer is provided, and to prevent forgery by pressure-sensitive coloring the recording sheet after peeling off the hiding layer. Is something that can be done. Such a recording sheet can be used for slips, forms, recording paper, toys, communications, securities, cash vouchers, tickets, tickets, documents, stickers, lottery, labels, etc. It is a recording sheet having a preventive property.

[0002]

2. Description of the Related Art In recent years, thermal recording by thermal energy in a wide range of fields such as facsimiles, printers and recorders for various measuring instruments, printers for labels, printers for POS, vending machines for tickets and entrance tickets. Recording materials have come into use. Thermal recording is used for information transmission using printers and facsimiles, and since information can be sent instantaneously via a telephone line, etc. and is accurate, it is conveniently used in business offices, retail stores, and homes. There is. However, the heat-sensitive recording has a problem that it can be easily forged when it is treated as a cash voucher such as a boarding ticket because the same printing can be easily performed due to the development of personal computers, printers, and printing fonts. For the purpose of anti-counterfeiting, such recording paper is printed with a tint block for anti-counterfeiting, or is printed with micro characters for anti-counterfeiting. But we are in a situation where we can easily make duplicates. This situation is not limited to simply cash vouchers, but it is the same that it is easy to make duplicates, such as price tags or labels with product details, or speed lottery with a hidden layer that can be peeled off with silver paste ink etc. It is.

The self-coloring pressure-sensitive recording system which is the basis of the present invention has been developed from so-called carbonless copying paper, and is also called a self-coloring pressure-sensitive recording sheet or self-contined paper as a product form. . The structure is such that a microcapsule enclosing a colorless dye (hereinafter referred to as a pressure-sensitive recording color former) is provided on a support, and an electron-accepting material such as acidic clay, a phenol resin, or an organic acidic substance is further provided on the coating layer. A two-layer coating method (including a method in which the order of coating is reversed) including two steps, which are convenient for providing a conductive substance (hereinafter referred to as a pressure-sensitive recording developer), There is known a production method in which at least one component is microencapsulated, uniformly mixed, and one layer is applied (Japanese Patent Publication No. 47-16096).

As a matter of course, in the self-coloring pressure-sensitive recording sheet, both the pressure-sensitive recording color-developing agent and the pressure-sensitive recording color-developing agent are present in close proximity to the surface of the support, and the color is developed by a little friction or pressure. Therefore, it is necessary to impart abrasion resistance. As a simple method for imparting abrasion resistance, there is a method in which wheat starch particles having a particle size larger than that of the microcapsules are dispersed in the self-coloring pressure-sensitive recording layer so that the color is not carelessly developed under some pressure. However, when such a cushioning material (stilt material) is used in combination, the abrasion resistance effect is limited. That is, even in a self-coloring pressure-sensitive recording sheet with extremely improved abrasion resistance, if the printing is not a printer designed for pressure-sensitive paper, the self-coloring pressure-sensitive recording layer develops color with a paper feed roll or the like. There was a problem of being lost. Due to such poor abrasion resistance, the traces of the paper feed roll will be colored when passing through a thermal printer, for example, and if a peelable concealing layer such as silver paste ink is provided, it will self-color when peeling off the concealing layer. There was a dilemma that the pressure sensitive recording layer also developed color and was unusable.

In thermal recording, a printer that can be used is limited only by a single coloring method. Therefore, a recording paper which can be printed by both a thermal head and an impact head has been desired. One of the reasons for this is that since only one type of recording method, such as thermal recording or pressure-sensitive recording, can be easily counterfeited as described above, the development of a multifunctional recording sheet in which at least two recording methods can be used together Was desired.

Further, in the case of the self-coloring pressure-sensitive recording sheet, as in the case of the heat-sensitive recording body, a recent personal computer, printer,
Also, due to the development of printing fonts and the like, the same printing can be easily performed, so that there is a problem that it is easy to forge when handling it as a cash voucher. The fact that the copy-forgery-inhibited pattern printing for preventing forgery can be duplicated by color copying is the same as in the case of heat sensitivity.

As such a recording sheet, a double-sided recording sheet in which a pressure-sensitive recording layer and a heat-sensitive recording layer are coated on both sides of a support, or both a heat-sensitive recording layer and a pressure-sensitive recording layer on at least one side of the support are used. A multi-layer type recording sheet provided is devised, but in both cases, when passing through the printer for thermal recording, the self-coloring pressure-sensitive recording layer develops color by the paper feed roll of the printer, or the pressure-sensitive recording layer. When both the heat-sensitive recording layer and the heat-sensitive recording layer are overlapped, the oil in the capsule destroyed at the time of pressure-sensitive color development dissolves the developer for heat-sensitive recording or induces heat-sensitive color development, and the color develops in the same place because the color develops in the same place. There was a problem that it was difficult to distinguish.

[0008] Due to the development of forgery methods in social life (particularly where color copying is largely owed), the targets are not only cash vouchers such as tickets and tickets, but also labels, price tags and documents. Not leak. In other words, besides gold tickets such as admission tickets, tickets, stamps, stamps, etc., labels and manuals of books, CDs, game software etc. circulating in the world,
The price tag of the product itself, lottery tickets of all kinds, voting tickets (such as betting tickets), company's special paper, etc. can be easily made if you want to make a color copy.

Further, a self-coloring pressure-sensitive recording paper having a peeling property will be mentioned as a means for preventing forgery or an element constituting a new copy slip. As mentioned above, in the use of labels, any copy can be easily made due to the progress of color copying, but by making the release paper used with the label anti-counterfeit (that is, pressure-sensitive color development), It is possible to prevent counterfeiting itself or provide a release paper that can be used as a copy sheet. However, the adhesive layer is in contact with the release layer of the release paper, and even if the release layer is simply provided on the self-coloring pressure-sensitive recording layer, the self-coloring pressure-sensitive recording layer is included in the release layer or the adhesive layer. The self-coloring pressure-sensitive recording property is provided even though it has peeling property, depending on whether the color is not developed due to the action of the low molecular weight component, or the self-coloring pressure-sensitive recording layer develops color when the pressure-sensitive adhesive layer is peeled from the release layer and becomes unusable. It was originally difficult to have. In particular, if the release sheet is to have not only the self-coloring pressure-sensitive recording property but also the function as a copy sheet, it cannot be provided with the function as a copy sheet because of poor printability.

Further, in recent years, a speed lottery having a peelable concealing layer (often a silver paste ink layer having a high light-shielding property) in which it is easy to determine whether or not the winning is won (a type in which the winning is recognized by rubbing the releasing layer on the spot). Lottery) is beginning to be widely used in the world. However, this type of lottery can be produced only by providing a hiding layer on the paper on which the hits have been printed in advance, because the winnings are covered with the hiding layer.
That is, the probability of winning is the probability of the lottery base paper that was printed in advance, and it was impossible to change the probability according to the intention of the lottery issuer. This is because if you put another display in the lottery to check the winnings in another way, the lottery function will be lost at that point. For this reason, lottery tickets with this type of concealment layer can usually be applied only when the probability of winning is decided at a very large event. We could not meet the demand to use the lottery winning check method. The biggest reason was that it was not possible to record the winning lottery after the hidden layer was provided. For the same reason, for lottery tickets with such a hidden layer,
It was not easy to use because it was impossible to put an expiration date after printing or put in a product name.

[0011]

The first problem to be solved by the present invention is to impart anti-counterfeit property to a recording sheet by recording by two methods of pressure-sensitive recording and heat-sensitive recording. is there. Therefore, the present invention is not only capable of recording on a recording sheet itself, but also has applicability to a recording method used for heat-sensitive recording because the pressure-sensitive recording layer (self-coloring pressure-sensitive recording layer) has sufficient abrasion resistance ( A heat-sensitive / pressure-sensitive color-developing recording sheet having sufficient printer suitability, heat resistance, roll resistance, etc.) is provided. By enabling both pressure-sensitive recording and thermal recording with a single recording sheet, the color-developing method that is mainly used is for information recording, and the recording method that is not mainly used is complementary to prevent forgery. It is to develop an anti-counterfeit recording sheet that can be used for.

A second problem to be solved by the present invention is to obtain a release sheet having a pressure-sensitive self-coloring property as one of means for preventing forgery. When using an adhesive label, etc., by giving the release paper used at the same time anti-counterfeit property, the label itself can be provided with anti-counterfeit property, and the release paper can be used as a copy sheet to copy the print contents. An object is to provide a pressure-sensitive color-developing release sheet.

A third problem to be solved by the present invention is
In a lottery paper having a peelable covert layer, a covert type pressure-sensitive color-developing recording sheet capable of recording the lottery contents such as winning, ranking, product name, and expiration date after the covert layer is provided. It is in.

[0014]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have made the invention as follows.

The heat-sensitive / pressure-sensitive color forming recording sheet of the present invention comprises
At least one of the support, the thermoplastic resin layer, the color-forming agent for pressure-sensitive recording or the color-developing agent for pressure-sensitive recording is microencapsulated, and they are laminated or mixed individually to form a single-layer self-coloring pressure-sensitive recording layer ( Hereinafter, a thermosensitive recording layer containing only a self-coloring pressure-sensitive recording layer), transparent or semi-transparent paper, a thermosensitive recording color former and a thermosensitive recording color developer that develops color by contact with the thermosensitive recording color former (hereinafter , A heat-sensitive recording layer) is sequentially laminated.

In the above heat-sensitive / pressure-sensitive color-sensitive recording sheet, the color development of the self-coloring pressure-sensitive recording layer and the color development of the heat-sensitive recording layer are different in hue.

The anti-counterfeit paper of the present invention is characterized in that anti-counterfeiting or forgery detection is performed by using at least both heat-sensitive color development and pressure-sensitive color development methods using the heat-sensitive / pressure-sensitive color development recording sheet. And

According to the forgery detection method of the present invention, at least a part of the heat-sensitive / pressure-sensitive color-developing recording sheet subjected to heat-sensitive color development is subjected to pressure-sensitive color development so that only the heat-sensitive color-developing recording sheet is formed. Characterized by identifying the difference.

Further, in the forgery detection method of the present invention, at least a part of the heat-sensitive / pressure-sensitive color-developing recording sheet, which has been subjected to the pressure-sensitive color development, is heated to cause the heat-sensitive color development, whereby the pressure-sensitive color development is performed. It is characterized by recognizing the difference from the pressure sensitive recording sheet.

The heat-sensitive / pressure-sensitive color developing label of the present invention comprises a support, a thermoplastic resin layer, a self-coloring pressure-sensitive recording layer,
It is characterized in that transparent or semi-transparent paper, a thermosensitive recording layer, and the above are laminated, and an adhesive layer is provided on the surface opposite to the support.

The pressure-sensitive color-developing release sheet of the present invention is characterized in that a support, a thermoplastic resin layer, a self-color-developing pressure-sensitive recording layer, transparent or translucent paper, and a release layer are sequentially laminated.

The concealment type pressure-sensitive color-developing recording sheet of the present invention comprises a support, a thermoplastic resin layer, a self-coloring pressure-sensitive recording layer, transparent or semi-transparent paper, and a peelable concealment layer. Characterize.

Further, the recording sheet of the present invention is characterized in that transparent or translucent paper has a transparency of at least 30% or more.

[Detailed Description of the Invention] The details of the present invention will be described below for each constitution.

As the support used in the present invention, ordinary natural pulp paper such as high-quality paper, art paper, cast paper, coated paper and the like can be used, and wood pulp, synthetic pulp, filler, sizing agent, and UV absorption. Raw materials usually used in papermaking, such as agents, antioxidants, pigments, paper-strengthening agents, and dyes, can be used as necessary. Also, polyethylene, polypropylene, polyethylene terephthalate, polyamide, polyvinyl chloride, polyvinylidene chloride, plastic sheets such as polymethylpentene, and synthetic paper or nonwoven fabric made of these synthetic fibers, or these synthetic resins on one side of paper, or Laminated paper laminated on both sides may be used. Materials made of these synthetic resins may be white or colored.

In the present invention, a paper having a transparency of 30% or more, which is suitable for confirming the color development of the self-coloring pressure-sensitive recording layer, is called a transparent paper or a semitransparent paper. The transparency referred to in the present invention is expressed as a value obtained by subtracting the opacity value from 100.
The opacity value is the opacity (%) measured by JIS P8138. The thickness is a value measured by a test method for the thickness and density of paper and paperboard specified by JIS P8118. Above all, the transparent paper or semi-transparent paper of the present invention preferably has a basis weight of 10 to 55 g / m ² . The transparent paper or semi-transparent paper of the present invention includes wood pulp, synthetic pulp, filler, sizing agent, anti-UV agent, antioxidant,
Raw materials usually used in papermaking, such as paper-strengthening agents and dyes, can be used as necessary.

The basis weight of transparent or translucent paper is 10 g / m ²
If it is smaller, dimensional stability is poor and wrinkles are apt to be formed at the time of lamination, and it may be broken at the time of writing, which is not preferable. On the other hand, when the basis weight is more than 55 g / m ² , the thickness after laminating becomes large, and the color developability and readability of the important self-coloring pressure-sensitive recording layer are impaired, which is not preferable.

In the present invention, transparent paper or translucent paper having a transparency of 30% or more is suitable for confirming the color development of the self-coloring pressure-sensitive recording layer through another recording layer such as a thermosensitive recording layer, If the transparency is lower than 30%, it is not suitable because it is difficult to confirm the color development.

The transparent paper or semi-transparent paper (hereinafter collectively referred to as transparent paper) used in the present invention has a transparency of 30%.
If it is above, glassine paper, resin impregnated paper, typewriter paper, condenser paper, tracing paper, copy paper, impregnated tracing paper, Japanese paper, thin high quality paper, etc., but there is no particular limitation,
Among them, thin high-quality paper, copy paper, tracing paper, impregnated tracing paper, or Japanese paper is suitable. Nonwoven fabrics can be used as long as the transparency is within the range of the present invention. In addition, the tracing paper referred to in the present invention is a transparent paper also called natural trepe or natural trepe, which is used for the purpose of distinguishing it from the impregnation type tracing paper.

To obtain the recording sheet of the present invention, typically, a pressure-sensitive recording color-forming agent or a pressure-sensitive recording color-developing agent, in which at least one of them is microencapsulated on one surface of transparent paper, is used alone. Laminating or mixing to provide a single layer of the self-coloring pressure-sensitive recording layer, integrating the self-coloring pressure-sensitive recording layer and the support with a thermoplastic resin layer, and not providing the self-coloring pressure-sensitive recording layer It can be produced by applying a recording layer of another recording method such as a thermosensitive recording layer on transparent paper, or by combining the above steps, but the details of these steps and the order of combination are not particularly limited.

As the thermoplastic resin used in the recording sheet of the present invention, generally, a thermoplastic resin used in a thermoplastic resin coating or a thermoplastic resin laminate can be used without limitation, and examples thereof include polyethylene (low density, medium density). , High density, linear low density polyethylene), polypropylene, polytrimethylpentene, polybutene, polyester, polystyrene, polyamide, ethylene vinyl acetate copolymer, ethylene ethyl acrylate copolymer, ethylene acrylic acid copolymer, ethylene methyl acrylate Copolymer, ethylene vinyl alcohol copolymer,
General-purpose melt-extruded resins such as ethylene methacrylic acid copolymers and salts thereof, vinyl chloride, and vinylidene chloride can be used alone or in combination. The mixing method is not particularly limited, and any method can be used. For example, a kneader extruder, a heating kneading roll, a Banbury mixer, a predetermined amount of a thermoplastic resin using a kneader,
Then, various additives (release agent, slip agent, pigment, antioxidant, neutralizing agent, ultraviolet absorber, etc.) are added and melt-mixed as necessary, and then the mixture is crushed and pelletized, or Utilizing a method such as direct injection into an extruder in the so-called simple blend state and extrusion coating, or a method of using a mixed resin obtained by copolymerizing other components during polymerization of one thermoplastic resin. can do. Since the thermoplastic resin is in direct contact with the self-coloring pressure-sensitive recording layer, it is necessary to use it in consideration of the effects of the plasticizer, dispersant, antioxidant, etc. in the resin.

To integrate the support and the transparent paper having the self-coloring pressure-sensitive recording layer with the thermoplastic resin layer, a general melt extrusion die, a T die, or a multilayer simultaneous extrusion die can be used. As a pretreatment for melt extrusion, a known treatment for improving adhesion such as corona treatment or frame treatment may be performed on transparent paper or a support having a self-coloring pressure-sensitive recording layer. Further, on the back surface of the recording sheet of the present invention, curl prevention, antistatic,
A back coat layer such as a pigment coat layer or a water resistant layer can be provided, and an antistatic agent, a hydrophilic binder, a latex, a hardener, a pigment, a surfactant, an adhesive agent and the like are appropriately combined in the back coat layer. Can be included.

Application amount of thermoplastic resin (laminating amount)
Is preferably in a certain range because it affects the color developability of the self-coloring pressure-sensitive recording layer and the adhesiveness to transparent paper. For the purpose of sufficiently maintaining the adhesive strength between the transparent paper and the support, a coating amount of 8 to 40 g / m ² is preferable, which suppresses the deterioration of the coloring property due to the cushioning property of the thermoplastic resin, and provides sufficient self-coloring pressure-sensitive recording. In order to secure color development of the layer, it is necessary to control the coating amount to 30 g / m ² or less at most. If the basis weight of the transparent paper exceeds a certain range, the color developability sufficient for reading is impaired. Further, if the thermoplastic resin layer is less than a certain range, the adhesiveness of the transparent paper is insufficient, and if the thickness of the transparent paper is less than a certain range, the strength is weak and it may be broken during writing. When the transparency of the transparent paper is lower than a certain range, it is difficult for the color development of the self-coloring pressure-sensitive recording layer to pass through, and it is difficult to read the record.

The self-coloring pressure-sensitive recording layer that can be used in the present invention is not particularly limited, and any conventionally known one can be used. For example, a method of microencapsulation or a wall material of a microcapsule, a pressure-sensitive recording color former or an oil that dissolves the color former, or a pressure-sensitive recording developer, an adhesive resin,
And microcapsule protective agents.

As the microencapsulation method, a coacervation method (such as US Pat. No. 2,800,458), an interfacial polymerization method (such as Japanese Patent Publication No. 47-1763), and an in-situ polymerization method (Japanese Patent Laid-Open No. 51-9079). Gazette etc.) can be used.

As the wall material of the microcapsule, polyurethane, polyurea, epoxy resin, urea / formalin resin, melamine / formalin resin and the like can be used.

The color-forming agent for pressure-sensitive recording, the color-forming agent for heat-sensitive recording, and the color-developing agent for pressure-sensitive recording used in the present invention are not particularly limited as long as they are generally used for pressure-sensitive recording materials and heat-sensitive recording materials. Not done. For example, as a color former for pressure-sensitive recording or heat-sensitive recording, triallylmethane compounds,
Diarylmethane compounds, xanthene compounds, thiazine compounds, spiropyran compounds, diphenylmethane dyes, spiro dyes, lactam dyes, fluoran dyes, and the like can be used.

Specifically, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (crystal violet lactone), 3,3-bis (p-dimethylaminophenyl) phthalide, 3- ( p-dimethylaminophenyl) -3- (1,2-dimethylindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-methylindole-3-yl) phthalide, 3 , 3-bis (1,2-dimethylindole)
3-yl) -5-dimethylaminophthalide, 3,3-bis (9-ethylcarbazol-3-yl) -6-dimethylaminophthalide, 3,3-bis (2-phenylindole-3) -Yl) -6-dimethylaminophthalide, 3-
p-dimethylaminophenyl-3- (1-methylpyro-
Lu-3-yl) -6-dimethylaminophthalide, 3-p
-Dimethylaminophenyl-3- (1-methylpyrrol-2-yl) -6-dimethylaminophthalide 3- (p-
Dimethylaminophenyl) -3- (2-methylindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-phenylindol-3-yl)
Phthalide, 3,3-bis (1,2-dimethylindol-3-yl) -5-dimethylaminophthalide, 3,3-
Bis (1,2-dimethylindol-3-yl) -6
Dimethylaminophthalide, 3,3-bis (9-ethylcarbazol-3-yl) -5-dimethylaminophthalide, 3,3-bis (2-phenylindol-3-yl) -5-dimethylaminophthalide Triarylmethane dyes such as.

4,4'-Bis-dimethylaminophenylbenzhydrylbenzyl ether, 4,4'-bis-dimethylaminobenzhydrylbenzyl ether, N-halophenylleukoauramine, N-2,4. Diphenylmethane dyes such as 5-trichlorophenyl leuco auramine.

Thiazine-based dyes such as benzoyl leuco methylene blue and p-nitrobenzoyl leuco methylene blue.

3-methyl-spiro-dinaphthopyran, 3
-Ethyl-spiro-dinaphthopyran, 3,3'-dichlorospirodinaphthopyran, 3-phenyl-spiro-dinaphthopyran, 3-benzyl-spiro-dinaphthopyran,
3-propyl spirobenzopyran, 3-methylnaphtho-
Spiro dyes such as (3-methoxybenzo) spiropyran, 3-methyl-naphtho (6'-methoxybenzo) spiropyran, and 3-propyl-spiro-dibenzopyran.

Rhodamin-B-anilinolactam, ro-
Lactam dyes such as damine (p-nitroanilino) lactam and rhodamine (o-chloroanilino) lactam.

Rhodamine B anilinolactam, Rhodamine B p-chloroanilinolactam, 3-diethylamino-7-dibenzylaminofluorane, 3-dimethylamino-7-dibenzylaminofluorane, 3-diethylamino-7- Octylaminofluorane, 3-diethylamino-7-phenylfluorane, 3-dimethylamino-7-methoxyfluorane, 3-diethylamino-7-
N-diethylaminofluorane, 3-diethylamino-
7-Methoxyfluorane, 3-diethylamino-6-methoxyfluorane, 3-diethylamino-6-methyl-
7-chlorofluorane, 3-diethylamino-7-chlorofluorane, 3-diethylamino-6-chloro-7-
Methylfluorane, 3-diethylamino-7- (3,4
-Dichloroanilino) fluorane, 3-diethylamino-7- (2-chloroanilino) fluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-
Diethylamino-6-methyl-7-phenylaminofluorane, 3-diethylamino-6,7-dimethylfluorane, 3- (N-ethyl-N-tolyl) amino-6-methyl-7-anilinofluorane, 3 -Piperidino-6-
Methyl-7-anilinofluorane, 3- (N-ethyl-
N-tolyl) amino-6-methyl-7-phenethylfluorane, 3-diethylamino-7- (4-nitroanilino) fluorane, 3-dibutylamino-6-methyl-7.
-Anilinofluorane, 3- (N-methyl-N-propyl) amino-6-methyl-7-anilinofluorane, 3
-(N-ethyl-p-toluidino) -7-methylfluorane, 3- (N-ethyl-p-toluidino) -6-methyl-7-phenylaminofluorane, 3- (N-ethyl-p-toluidino) ) -6-Methyl-7- (p-toluidino) fluorane, 3-diethylamino-7- (2-carbomethoxy-phenylamino) fluorane, 3-diethylamino-7-N-acetyl-N-methylaminofluorane, 3 -(N-ethyl-N-isoamyl) amino-6
-Methyl-7-anilinofluorane, 3-diethylamino-7-N-chloroethyl-N-methylaminofluorane, 3-diethylamino-7-methyl-N-benzylaminofluorane, 3-diethylamino-7-N- Methylaminofluorane, 3- (N-methyl-N-cyclohexyl) amino-6-methyl-7-anilinofluorane,
3- (N-ethyl-N-iso-amylamino) -6-methyl-7-phenylaminofluorane, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-phenylaminofluorane, 3 -(N-Ethyl-N-tetrahydrofuryl) amino-6-methyl-7-anilinofluorane, 3-piperidino-6-methyl-7-phenylaminofluorane, 3-pyrrolidino-6-methyl-7-
Phenylaminofluoran, 3-diethylamino-6-
Methyl-7-xylidinofluorane, 3-diethylamino-7- (o-chlorophenylamino) fluorane, 3
-Dibutylamino-7- (o-chlorophenylamino)
Examples thereof include fluoran dyes such as fluoran and 3-pyrrolidino-6-methyl-7-p-butylphenylaminofluorane.

As the oil for dissolving the color-developing agent for pressure-sensitive recording in the pressure-sensitive recording layer, aromatic synthetic oils such as diarylalkane type, alkylnaphthalene type, alkylated biphenyl, hydrogenated terphenyl, kerosene, naphtha and paraffin oil are used. Aliphatic synthetic oils such as chlorinated paraffin, cottonseed oil, coconut oil, soybean oil, and vegetable oils such as linseed oil can be used.

As the protective agent for the microcapsules, cellulose powder, starch particles, talc, calcined kaolin, calcium carbonate and the like can be used.

As the color-developing agent for pressure-sensitive recording, clays (for example, activated clay, acid clay, attapulgite, bentonite, colloidal silica, aluminum silicate, etc.),
Organic acids (eg, aromatic carboxy compounds such as salicylic acid or metal salts thereof), mixtures of organic acids and metal compounds, acidic polymers (eg, phenol / formaldehyde resin, salicylic acid resin or zinc, magnesium, Aluminum, calcium, titanium, manganese, tin, nickel, etc.).

In addition, zinc stearate as an auxiliary agent,
Higher fatty acid metal salts such as calcium stearate, waxes such as paraffin, paraffin oxide, polyethylene, polyethylene oxide, stearic acid amide, castor wax, and dispersants such as sodium dioctyl sulfosuccinate, and sulfonic acid-modified polyvinyl alcohol; UV absorbers such as benzotriazoles, as well as surfactants, fluorescent dyes, antistatic agents, thickeners, preservatives, antioxidants, defoamers, release agents, lubricants, anti-blocking agents, and adhesives The imparting agent is a support,
It is added to the self-coloring pressure-sensitive recording layer, thermoplastic resin layer, heat-sensitive recording layer, and transparent paper as needed.

Further, as the constitution of the present invention, in order to obtain high color density, between the support and the self-coloring pressure-sensitive recording layer,
Calcium carbonate, talc, silica, clay, barium sulfate, magnesium carbonate, magnesium silicate, lead sulfate,
Lead white, zinc white, zinc sulfide, satin white, titanium oxide, antimony oxide, mica, bentonite, calcium silicate,
An anchor layer containing inorganic pigments such as gypsum and aluminum hydroxide, or finely divided organic pigments such as polystyrene, polyvinyl toluene, styrene / divinylbenzene copolymer, polymethyl methacrylate, urea / formaldehyde polymer, polyethylene, etc. Dispersion in the color-forming pressure-sensitive recording layer does not matter at all.

As the developer for heat-sensitive recording used in the present invention, an electron-accepting substance generally used in heat-sensitive sheets is used. Particularly, a phenol derivative, an aromatic carboxylic acid derivative or a metal compound thereof, N. , N'-diarylthiourea derivatives, mixtures of organic acids and metal compounds, acidic polymers (for example phenol / formaldehyde resins, salicylic acid resins or their zinc, magnesium, aluminum, calcium, titanium, manganese, tin, nickel And the like), especially phenol derivatives, aromatic carboxylic acid derivatives or metal compounds thereof, N, N'-diarylthiourea derivatives and the like.

Of these, particularly preferable are phenol derivatives, aromatic carboxylic acids and phenolic compounds thereof, specifically, 1,1-bis (p-hydroxyphenyl) propane and 2,2. -Bis (p-hydroxyphenyl) propane, 2,2-bis (p-hydroxyphenyl) butane, 2,2-bis (p-hydroxyphenyl)
Hexane, bisphenol sulfone, bis (3-allyl-4-hydroxyphenyl) sulfone, 4-hydroxy-4'-isopropyloxydiphenyl sulfone, 3,4-dihydroxy-4'-methyldiphenyl sulfone, diphenol ether, Benzyl p-hydroxybenzoate, propyl p-hydroxybenzoate, p-
Butyl hydroxybenzoate, p-tert-butylbenzoic acid, trichlorobenzoic acid, octyl 4-hydroxybenzoate, benzoic acid, terephthalic acid, 3-sec-butyl-4
-Hydroxybenzoic acid, 3-cyclohexyl-4-hydroxybenzoic acid, 3,5-dimethyl-4-hydroxybenzoic acid, salicylic acid, 3-isopropylsalicylic acid, 3
-Tert-butylsalicylic acid, 3-benzylsalicylic acid,
3- (α-methylbenzyl) salicylic acid, 3-chloro-
5- (α-methylbenzyl), 3,5-di-α-methylbenzylsalicylic acid, 3,5-di-tert-butylsalicylic acid, 3-phenyl-5- (α, α-dimethylbenzyl) salicylic acid, 4- tert-butylphenol, 4-hydroxydiphenoxide, α-naphthol, β-naphthol, 4-hydroxyacetophenol, 4-tert-catechol, 2,2′-dihydroxydiphenol , 2,
2'-methylenebis (4-methyl-6-tert-isobutylphenol, 4,4'-isopropylidenebis (2-
(tert-butylphenol), 4,4'-sec-butylidene diphenol, 4-phenylphenol, 4,4'-
Isopropylidene diphenol, 2,2'-methylenebis (4-chlorophenol), hydroquinone, 4,4 '
-Cyclohexylidene diphenol, dimethyl 4-hydroxyphthalate, hydroquinone monobenzyl ether,
Examples thereof include phenolic compounds such as novolac type phenolic resins and phenolic polymers.

In the present invention, the binder used for forming the self-coloring pressure-sensitive recording layer or the heat-sensitive recording layer includes starches, cellulose derivatives such as hydroxyethyl cellulose, methyl cellulose, ethyl cellulose and carboxymethyl cellulose, proteins such as casein and gelatin. , Aqueous natural polymer such as saccharose such as oxidized starch, ester compound starch, polyvinyl alcohol, modified polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, sodium polyacrylate, acrylic acid amide / acrylic acid ester copolymer, acrylic acid Amide / acrylic acid ester / methacrylic acid terpolymer, alkali salt of styrene / maleic anhydride copolymer, latex, polyacrylamide, styrene / maleic anhydride Water-soluble synthetic polymer compounds such as copolymers, latexes, water-soluble adhesive resins such as alkali salts of ethylene / maleic anhydride copolymers, polyvinyl acetate, polyurethane, polyacrylates, styrene / butadiene copolymer Examples thereof include polymer, acrylonitrile / butadiene copolymer, methyl acrylate / butadiene copolymer, acrylonitrile / butadiene / acrylic acid copolymer, and latex such as ethylene / vinyl acetate copolymer.

In order to further improve the sensitivity of the heat-sensitive recording layer, waxes such as N-hydroxymethylstearic acid amide, stearic acid amide and palmitic acid amide, and naphthols such as 2-benzyloxynaphthalene are used as sensitizers. Derivative, p-benzylbiphenyl, 4-
Biphenyl derivatives such as allyloxybiphenyl, 1,
2-bis (3-methylphenoxy) ethane, 2,2'-
Polyether compounds such as bis (4-methoxyphenoxy) diethyl ether and bis (4-methoxyphenyl) ether. Carbonic acid or oxalic acid diester derivatives such as diphenyl carbonate, dibenzyl oxalate, and di (p-chlorobenzyl) oxalate can be added.

Pigments used in the heat-sensitive recording layer or the self-coloring pressure-sensitive recording layer include diatomaceous earth, talc, kaolin, calcined kaolin, calcium carbonate, magnesium carbonate, titanium oxide, zinc oxide, silicon oxide, aluminum hydroxide, Examples include urea-formalin resin.

An undercoat layer is provided below the heat-sensitive recording layer, that is, on transparent paper to improve heat-sensitive color development and prevent dust from being printed, or color-development stains or water resistance on the heat-sensitive recording layer. There is no problem in providing an overcoat layer for the purpose of imparting.

The adhesive layer of the recording sheet of the present invention is provided with an adhesive on the release agent coated surface of the release paper, and the adhesive surface and the self-coloring pressure-sensitive recording layer of the support of the recording sheet are not provided. A method of stacking the surfaces and press-bonding them with a press roll or the like is generally performed, but an adhesive may be first applied to the recording sheet and then bonded to a release paper. As the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer, a rubber-based or acrylic resin-based pressure-sensitive adhesive can be used. The main rubber-based raw material is natural rubber or styrene-butadiene rubber. In natural rubber, a rosin-based resin and a plasticizer are added, and normally hexane is used as a solvent for coating. When styrene-butadiene rubber is used as the main raw material, it is melted before coating. The acrylic resin system is produced by polymerizing acrylic monomers such as 2-ethylhexyl acrylate, butyl acrylate, ethyl acrylate, acrylic acid and β-hydroxyethyl acrylate. Depending on the method of polymerization, an organic solvent such as ethyl acetate or toluene may be used, or an emulsion type polymerized while emulsifying in water with a surfactant may be used.

In order to improve the physical properties such as heat resistance and solvent resistance of the pressure-sensitive adhesive, a crosslinking reaction may be carried out by using a crosslinking agent such as an isocyanate type, a melamine type or a metal chelate type in the above raw material, or silica. , Kaolin, clay, calcium carbonate, aluminum hydroxide, zinc oxide, titanium oxide,
Add pigments such as melamine resin particles and starch particles,
Water-soluble polymer, petroleum resin, various paraffin wax,
Fatty acids or their derivatives, higher alcohols, metal soaps, silicones, as well as antistatic agents, thickeners, dispersants, preservatives, antioxidants, defoamers and the like may be added. These pressure-sensitive adhesives may be selected according to the use of the anti-counterfeit recording sheet.

The release layer used in the recording sheet of the present invention is preferably provided with a release agent containing a silicone resin as a main component. The silicone resin constituting the release layer is a functional group selected from acryloyl group, methacryloyl group, vinyl group, vinylamide group, hydrosilyl group, silanol group, diazo group, acetylene group and thiol group at the molecular end or side chain. It is a silicone resin having a group (mainly dialkyl polysiloxane). When curing the dialkylpolysiloxane, a silicone resin such as methylhydrogenpolysiloxane or methylmethoxypolysiloxane may be added and used depending on the reaction form. Examples of the form of these silicone resin compositions include a solvent type diluted with a solvent, an emulsion type dispersed and emulsified in water using an emulsifier, and a no-use agent type that does not use a solvent at all, but are limited in the present invention. Not something. The curing mechanism of the silicone resin is a polymerization reaction by heating, and a condensation type, addition type, crosslinking type, ring-opening polymerization type reaction or the like is possible.

As a matter of course, the self-coloring pressure-sensitive recording layer of the recording sheet according to the present invention should not have such a structure that it is affected by such a solvent, chemicals or heating.

These silicone resins may be used alone or
Two or more can be mixed and used. Further, a composition other than the silicone resin may be mixed and used. When mixing a composition other than the silicone resin, it is necessary to use a composition that does not impair the releasability of the silicone resin, such as a fluorine-containing resin, an alkyd resin, an acrylic resin, a polyolefin resin, or a polyvinyl alcohol resin. A resin composition having peelability is preferably used. Further, additives such as other binder components, colorants, and antioxidants can be mixed within the range that does not impair the releasability of the silicone resin composition. Furthermore, in the curing reaction by heating, it is preferable to proceed the reaction in the presence of a catalyst. Examples of the catalyst to be used include organotin-based catalysts and platinum-based catalysts, which can be selected and used depending on the type of silicone resin used. Moreover, at the time of curing, an appropriate reaction initiator or reaction control agent may be added. It should be noted that the resin composition must be colorless or as transparent as possible from the viewpoint of not impairing the permeability of the recording sheet even if these mixtures are added.

Among the solventless silicone resins, it is also possible to use radiation curable silicone resins which can be cured without applying heat. The radiation-curable silicone resin is mainly composed of a dialkyl polysiloxane having a functional group selected from acryloyl group, methacryloyl group, vinyl group, epoxy group, vinylamide group and diazo group at the molecular end or side chain. Is something
It can be cured by irradiation with an electron beam or ultraviolet rays. In the present invention, electron beams and ultraviolet rays are collectively called radiation. When using a radiation-curable silicone resin, a reaction initiator, a photoreaction initiator,
A sensitizer can be added and used.

When an electron beam curing type silicone resin is used, it is necessary to use an electron beam accelerator to cure the resin coating layer, and a curtain system, a scanning system or a double scanning system can be adopted. The curtain method is preferable because it is inexpensive and can easily obtain a large output. The acceleration voltage of the electron beam is 100 to 1000 kV, preferably 150 to 3
It is 00 kV, and the irradiation dose is 0.5-
10 Mrad. If the accelerating voltage is less than 100 kV, the amount of energy transmitted is insufficient, and if it exceeds 1000 kV, the energy efficiency is reduced, which is not economical. If the irradiation dose is less than this range, the curing reaction becomes insufficient and a tough layer cannot be obtained. When the irradiation dose is more than this range, not only the energy efficiency is lowered, but also unfavorable effects on quality such as deterioration of transparent paper, decomposition of resin and additives, strength reduction and coloring appear, which is not preferable.

When the silicone resin composition is cured by irradiation with ultraviolet rays, it is preferable to irradiate with ultraviolet rays from the coating side of the resin composition layer. Examples of the ultraviolet irradiation device used include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, and there is also an ozoneless type that generates less ozone. Generally output 80w / cm
A plurality of the above lamps are used in parallel.

Curing by irradiation with ultraviolet rays or electron beams is a radical reaction and depends on the oxygen concentration in the atmosphere. Therefore, replacement with an inert gas such as nitrogen, helium or carbon dioxide is carried out, and the oxygen concentration is 600 ppm or less, preferably 400 ppm. Irradiation is preferably performed in an atmosphere suppressed below.

In the recording sheet of the present invention, the release layer may be directly provided on the transparent paper to be used as a release paper having anti-counterfeit property, or the release layer may be provided on the heat-sensitive recording layer provided on the transparent paper. It is also possible to use a label heat-sensitive sheet having anti-counterfeiting properties. When a release layer is provided on the heat-sensitive recording layer, a barrier layer made of an aqueous polymer may be provided on the heat-sensitive recording layer and the release layer may be provided thereon, or a radiation-curable silicone may be provided on the heat-sensitive recording layer. The release layer can be provided using a resin without a heating step.

When the release layer is formed in the present invention, it can be provided by directly coating it on transparent paper. The transparent paper may be subjected to a surface treatment such as corona treatment in order to improve the adhesiveness to the transparent paper as the base material. Further, depending on the air permeability of the transparent paper, an anchor layer may be provided on the transparent paper, and a release layer may be further provided thereon.

The coating amount of the release layer varies depending mainly on the type of transparent paper, but is 0.3 to 10 g / m ² , more preferably 0.5.
~ 5 g / m ² . If the amount of release layer is less than this range,
It is difficult to cover the transparent paper evenly with the release layer, and pinholes are likely to occur, resulting in poor release properties. If the coating amount of the release layer resin is increased beyond this range, the characteristics will not change, and only the cost will increase, and the handleability may deteriorate from the viewpoints of transparency and rigidity.

In the present invention, the method of applying the self-coloring pressure-sensitive recording layer, the heat-sensitive recording layer, the peeling layer, the adhesive layer, etc. may be a gravure coater, a gravure offset coater,
Bar coater, roll coater, air knife coater,
U comma coater, AKKU coater, smoothing coater, microgravure coater, reverse roll coater, 4 or 5 (multistage) roll coater, curtain coater, blade coater, dip coater, drop curtain coater, slide coater, lip coater, die coater Various devices such as a squeeze coater, a short dwell coater, a size press, and a spray can be used on-machine or off-machine. After coating or impregnation of each layer, finishing may be performed using a calendar such as a machine calendar, a gloss calendar, a TG calendar, a super calendar, a soft calendar, or brushing. In addition, a printing method such as offset or silk screen is also used in some cases.

The method of printing or recording on the recording sheet of the present invention includes: writing / printing with pencil or ink, impact printer, electrophotography, thermal transfer, ink ribbon, heat sensitive, pressure sensitive,
There is no limitation by the method such as ink jet, flexographic printing, offset printing, gravure printing, letterpress printing, intaglio printing, laser printing, and label sticking. However, recording on the self-coloring pressure-sensitive recording layer after being integrated with the transparent paper is limited to a recording method involving color development by pressure. As a matter of course, recording on the heat-sensitive recording layer is performed by a heat-sensitive method using a thermal head. When recording on the self-coloring pressure-sensitive recording layer,
It is also possible to use an impact printer, and when it is necessary to record a large amount of the same information, it is also possible to record by letterpress printing. Also, a ballpoint pen,
It is also possible to record with an iron brush. General printing may be performed on the release layer, the heat-sensitive recording layer, the self-coloring pressure-sensitive recording layer, the thermoplastic resin layer, the transparent paper or the back surface of the support. Also, there is no problem in performing opacity by tint block printing.

Further, the recording sheet of the present invention can be used as a series of copying sheets in combination with other pressure sensitive recording sheets, back carbon copying sheets, adhesive sheets, printing sheets, transparent films and the like. Part of the pressure-bonded sheet of the present invention, or processing such as die cut to the whole, separation of a part of the support,
Processing of perforations, feed holes for printers, etc. does not matter at all.

[0070]

In the recording sheet of the present invention, not only recording such as heat-sensitive recording can be performed, but also by pressure printing, it is possible to color the self-coloring pressure-sensitive recording layer. It is possible to read through an upper recording layer such as a layer and transparent paper. In the recording sheet of the present invention, since the self-coloring pressure-sensitive recording layer is protected from the inside of the transparent paper, coloring stains due to careless rubbing during general handling, particularly during recording with other recording methods. Not only does it have high resistance to abrasion, but also has excellent weather resistance, water resistance, oil resistance, etc. for recording, excellent printability and handleability, and does not cause double feed due to the electrostatic charge peculiar to laminated paper, making it easy to handle. . In the recording sheet of the present invention, a single recording sheet enables both pressure-sensitive and heat-sensitive recording methods, so that the coloring method mainly used is for information recording and the recording method not mainly used is used. It can be used complementarily to prevent forgery. Further, as one of means for preventing forgery, by obtaining a release sheet having a pressure-sensitive self-coloring property, the label itself can be provided with anti-counterfeit property, and the release paper can be used as a copy sheet for copying the print contents. . Furthermore, by providing a peelable concealment layer on the self-coloring pressure-sensitive recording layer, after the concealment layer is provided on speed lottery paper, the lottery contents such as winnings, rankings, product names, and expiration dates are recorded. It is possible to provide a concealable pressure-sensitive color-developing recording sheet.

[0071]

Next, the present invention will be described in more detail by way of examples. All parts and% shown below are based on weight. Further, the value indicating the coating amount is the coating amount after drying unless otherwise specified.

Preparation Example 1 (Preparation of Self-Coloring Pressure-Sensitive Coating Solution) Microcapsules containing a color-forming agent used for pressure-sensitive recording were prepared as follows. First, 13 parts of crystal violet lactone was heated and dissolved in 90 parts of Hisol SAS N-296 (manufactured by Nippon Petrochemical) to obtain an internal phase oil. 10 parts of melamine and 25 parts of 37% formalin were heated together with 100 parts of water to obtain a melamine-formalin initial polycondensate. Next, the internal phase oil was emulsified in 150 parts of a 6% aqueous solution of styrene / maleic anhydride copolymer, and the above-mentioned melamine-formalin polycondensate was added to this emulsion, and the liquid temperature was raised to 70 ° C. for 3 hours. By holding, a microcapsule dispersion liquid containing a coloring agent having a melamine-formalin resin film was obtained. The average particle size of the obtained microcapsules was about 6 μm.

The coating material for the self-coloring pressure-sensitive recording layer was prepared by the following formulation. Microcapsule containing pressure-sensitive recording color former 130 parts Pressure-sensitive recording developer (Sumitomo Durez; PR26298) 70 parts Starch particles 280 parts Kaolin clay 100 parts Oxidized starch 100 parts Calcium carbonate 120 parts

Preparation Example 2 (Preparation of heat-sensitive coating liquid) The heat-sensitive coating liquid constituting the heat-sensitive recording layer was prepared as follows. The mixture having the following composition was pulverized and dispersed by a sand mill until the average particle size became about 1 μm, thereby preparing <Solution A> and <Solution B>.

<Solution A> 3- (N-methyl-N-cyclohexyl) amino-6-methyl-7-anilinofluorane 40 parts 10% aqueous solution of polyvinyl alcohol 20 parts Water 40 parts <solution B> Bisphenol A 50 parts 2-benzyloxynaphthalene 50 parts 10% aqueous polyvinyl alcohol solution 50 parts water 100 parts

Next, a heat-sensitive coating liquid was prepared by using the prepared <A solution> and <B solution> with the following formulation. <Solution A> 50 parts <Solution B> 250 parts Zinc stearate (40% dispersion) 25 parts 10% aqueous solution of polyvinyl alcohol 216 parts Calcium carbonate 50 parts Water 417 parts

Example 1 As transparent paper or semi-transparent paper having a self-coloring pressure-sensitive recording layer, (A) impregnated tracing paper having a basis weight of 15 g / m ² (transparency 84%), (B) basis weight 35 g / m ² diazo copy paper (transparency 50%), (C) grammage 45g / m ² quality paper (transparency 30%), (D) basis weight 50g / m ² quality paper (transparency 26%), respectively. A self-coloring pressure-sensitive recording layer having the composition described in Preparation Example 1 was applied so that the coating amount was 7 g / m ² , to obtain a self-coloring transparent paper. After the corona treatment on the self-coloring pressure-sensitive recording surface, low-density polyethylene (NUC8000, made by Nippon Unicar) was extruded from the melt extrusion die, and self-coloring transparent paper and commercially available high-quality paper (made by Mitsubishi Paper Mill, Diamond foam (70 kg) was laminated and integrated to obtain a scratch-resistant self-coloring pressure-sensitive recording sheet having a transparent paper layer. The coating amount of polyethylene resin is 12g /
It was m ² .

The self-coloring pressure-sensitive recording sheets using the respective transparent papers are referred to as pressure-sensitive paper (A), pressure-sensitive paper (B), pressure-sensitive paper (C) and pressure-sensitive paper (D). Pressure sensitive paper (A)
The heat-sensitive coating solution prepared in Preparation Example 2 was applied to the transparent paper surface of (D) so that the dry weight was 6 g / m ^2, and the heat-sensitive recording layer was provided by drying to provide the desired heat-sensitive / pressure-sensitive color forming recording. Got the sheet.

Example 2 In Example 1, 3- (N-methyl-N-) of Preparation Example 2 was used.
A target heat-sensitive / pressure-sensitive color forming recording sheet was obtained in the same manner as in Example 1 except that 40 parts of cyclohexyl) amino-6-methyl-7-anilinofluorane was changed to 40 parts of crystal violet.

Example 3 An adhesive layer (Ricabond AP-37 manufactured by Chuo Rika Kogyo Co., Ltd.) was formed on the back surface of the pressure-sensitive paper (A) obtained in Example 1 with a heat-sensitive recording layer on the support side of a heat-sensitive / pressure-sensitive color forming recording sheet. ) 20
The heat-sensitive / pressure-sensitive color-developing label was prepared by setting it to be g / m ² and covering the adhesive layer with a commercially available release paper.

Comparative Example 1 As a support having a self-coloring pressure-sensitive recording layer, a self-coloring pressure-sensitive recording layer having the composition described in Preparation Example 1 was coated on a commercially available high-quality paper (Diaform 70K, manufactured by Mitsubishi Paper Mills). Is 7
The self-coloring pressure-sensitive recording sheet coated to give g / m ² was used as it was.

Comparative Example 2 After subjecting the self-coloring pressure-sensitive recording sheet of Comparative Example 1 to corona treatment, a low-density polyethylene (manufactured by Nippon Unicar, NUC8008) was applied through a melt extrusion die so that the coating amount was 15 g / m ^2. It was extruded and provided with a coating layer of thermoplastic resin.

Comparative Example 3 As a support having a heat-sensitive recording layer, a commercially available high-quality paper (manufactured by Mitsubishi Paper Mills, Diafoam 70K) was coated with a heat-sensitive coating solution having the composition described in Preparation Example 2 to give a dry weight of 6 g / m ^2. To apply,
A thermosensitive recording layer was provided by drying to obtain a thermosensitive recording sheet.

Comparative Example 4 As a recording sheet having both a heat-sensitive recording layer and a self-coloring pressure-sensitive recording layer, the composition described in Preparation Example 2 was prepared on the recording sheet having the self-coloring pressure-sensitive recording layer obtained in Comparative Example 1. A heat-sensitive coating liquid was applied to a dry weight of 6 g / m ² and dried to provide a heat-sensitive recording layer, and a heat-sensitive / pressure-sensitive color-developing recording sheet having a heat-sensitive recording layer and a self-coloring pressure-sensitive recording layer was obtained. . The recording sheet obtained by this method was colored essentially by a paper feed roll of a thermal printer or was rubbed by a thermal head, and essentially was not capable of thermal recording.

Comparative Example 5 An adhesive layer (Ricabond AP-37, manufactured by Chuo Rika Kogyo) was provided on the back surface of the heat-sensitive recording sheet obtained in Comparative Example 3 so as to be 20 g / m ^2, and the adhesive layer was a commercially available release paper. The label was covered with a thermosensitive coloring label.

The recording sheets obtained in Examples 1 to 3 and Comparative Examples 1 to 5 were evaluated by the following methods.

<Pressure Sensitivity 1> Solid printing was performed on the recording sheets obtained in Examples and Comparative Examples by using a dot impact printer without an ink ribbon. After printing, the optical density was measured using a Macbeth densitometer. In practical use, the optical density at which even small characters can be sufficiently read is 0.50 or more, and if the optical density is below 0.40, accurate reading is difficult. When the optical density is less than 0.15, it is difficult to understand the presence or absence of color development.

<Heat-sensitive color development> Solid printing was performed using a commercially available heat-sensitive word processor. After printing, the optical density was measured using a Macbeth densitometer. When used practically, the optical density at which even small letters can be sufficiently read is 0.50 or more, and the thermosensitive coloring property was excellent. If the optical density is less than 0.40, accurate reading is difficult and the thermosensitive coloring property is poor. The thermosensitive color development was judged to be normal between the two. However, if you do not develop color at all when printing with a thermal word processor, and if unnecessary parts other than thermal printing print due to rubbing of the paper feed roll or thermal head, it is not suitable for thermal printer, The thermosensitive coloring property was judged as bad.

<Adhesive Strength> Thermal printing was performed on the labels obtained in Example 3 and Comparative Example 5 using a commercially available label printing device. The label release paper was peeled off and adhered to a stainless steel plate, and the adhesive strength was measured by peeling at 90 ° with a tensilon. Adhesive strength required for labels is usually 100g
f / 25 mm.

<Counterfeiting prevention property 1> Printing was performed on a recording sheet on which heat-sensitive recording was performed using a commercially available heat-sensitive word processor, using a dot impact printer not equipped with an ink ribbon. The anti-counterfeiting property is excellent when the pressure-sensitive color development can be read even if the heat-sensitive color development and the pressure-sensitive color development overlap.If the heat-sensitive color development and the pressure-sensitive color development overlap, the pressure-sensitive color development cannot be read, but the heat-sensitive color development does not occur. Good anti-counterfeiting property is when the pressure-sensitive color is readable in the non-colored part, and anti-counterfeiting property and pressure-sensitive coloration when the pressure-sensitive color is not readable even in the part without heat-sensitive color development The case where there was no heat-sensitive color development and the case where only heat-sensitive color development occurred were judged as poor anti-counterfeiting property.

<Counterfeiting Prevention Property 2> Thermal recording was performed with a printer having a thermal head on a recording sheet which was printed using a dot impact printer without an ink ribbon. Anti-counterfeiting is good even if the heat-sensitive color development and the pressure-sensitive color development overlap, but when the heat-sensitive color development and the pressure-sensitive color development overlap, the heat-sensitive color cannot be read, but there is no pressure-sensitive color development. If the heat-sensitive color development is readable, the anti-counterfeiting property is good.If the heat-sensitive color development cannot be read even in the part without pressure-sensitive color development, it can be confirmed that the heat-sensitive color is developed. The case where only the color was developed was judged as poor anti-counterfeiting property.

The recording sheets obtained in Examples 1 to 3 and Comparative Examples 1 to 5 were tested by the above evaluation method, and the results are shown in Table 1. In addition, the samples obtained from the pressure sensitive papers (A) to (D) in the examples are respectively used in Example 1.
A to Example 1D.

[0093]

[Table 1]

Example 4 Pressure-sensitive paper (A) and pressure-sensitive paper (B) obtained in Example 1
A releasable resin composition 1 having the following composition was applied to each of the transparent paper surfaces by a gravure coater so that the dry weight was 1 g / m ² . <Releasable resin composition 1> Silicone resin KS883 (manufactured by Shin-Etsu Chemical Co., Ltd.) 100 parts Diluent solvent Toluene 100 parts Catalyst CAT PS-80 2.5 parts Cured by placing in a dryer set at 150 ° C for 1 minute. A pressure-sensitive coloring release sheet was obtained.

Comparative Example 6 As a support having a self-coloring pressure-sensitive recording layer, a commercially available high-quality paper (manufactured by Mitsubishi Paper Mills, Diafoam 70K) was coated with the self-coloring pressure-sensitive recording layer having the composition described in Preparation Example 1. Is 7
Using the self-coloring pressure-sensitive recording sheet coated so as to be g / m ² , the releasable resin composition 1 similar to that in Example 3 was applied by the same application method as in Example 3, and set at 150 ° C. The sample was cured by placing it in a dryer for 1 minute to obtain a sample.

Comparative Example 7 As a support having no self-coloring pressure-sensitive recording layer, a commercially available high-quality paper (manufactured by Mitsubishi Paper Mills, Diafoam 70K) was coated with a peelable resin composition 1 similar to that used in Example 3. Apply by the same method as 3 and 1 in a dryer set at 150 ° C.
Curing was carried out by applying for a minute to obtain a sample.

The recording sheets or samples obtained in Example 4 and Comparative Examples 6 and 7 were evaluated by the following methods.

<Pressure Sensitive Coloring Property 2> An adhesive label having an adhesive layer was attached to the release layer of the recording sheet or sample obtained in Example 4 and Comparative Examples 6 and 7 to prepare a sample. Solid printing was performed on the label using a commercially available dot impact printer. The optical density of the color of the release sheet when the adhesive label was removed from the release layer was measured using a Macbeth densitometer. In practical use, the optical density at which even small characters can be sufficiently read is 0.50 or more, and if the optical density is below 0.40, accurate reading is difficult. When the optical density is less than 0.15, it is difficult to understand the presence or absence of color development.

<Label releasability> An adhesive label having an adhesive layer was attached on the release layer of the recording sheet or the sample obtained in Example 4 and Comparative Examples 6 and 7 to obtain a sample. The peeling feeling when the pressure-sensitive adhesive label was peeled from the release sheet was evaluated. If the adhesive label can be smoothly peeled off and the adhesive label does not deteriorate the performance as a label, the label releasability is excellent, the adhesive label cannot be smoothly peeled off, or the adhesive label also deteriorates the label performance ( Label peelability was judged to be poor in cases where the adhesive strength was reduced).

<Counterfeit Prevention 3> A pressure-sensitive adhesive label having a pressure-sensitive adhesive layer was attached on the release layer of the recording sheet or sample obtained in Example 4 and Comparative Examples 6 and 7 to obtain a sample. Printing was performed on the label using a commercially available dot impact printer. When peeling the adhesive label from the release layer, if the release sheet develops the same color as on the label and the correspondence between the label and the release sheet can be taken, it is not possible to duplicate the label by color copy etc. When the property 3 was excellent, the release sheet did not develop color, and the same label could not be discriminated by copying the same label by color copying or the like, the anti-counterfeit property 3 was judged as poor.

<Copyability> A pressure-sensitive adhesive label having a pressure-sensitive adhesive layer was attached to the release layer of the recording sheet or sample obtained in Example 4 and Comparative Examples 6 and 7 to obtain a sample. Printing was performed on the label using a commercially available dot impact printer. When the adhesive label is peeled from the release layer, the release sheet develops the same color as on the label and the correspondence between the label and the release sheet can be taken, and the release sheet can be used as a copy slip of the label. When the release sheet did not develop color and a new copy had to be made to save the label, the copyability was judged to be poor.

The release sheets obtained in Example 4 and Comparative Examples 6 and 7 were tested by the above evaluation method, and the results are shown in Table 2. The samples obtained with the pressure-sensitive paper (A) and the pressure-sensitive paper (B) in the examples are represented as Example 3A and Example 3B, respectively.

[0103]

[Table 2]

Example 5 Pressure-sensitive paper (A) and pressure-sensitive paper (B) obtained in Example 1
Each of the above-mentioned transparent paper surfaces was coated with a peelable concealing layer having the following composition so that the dry weight was 20 g / m ^2, and the final solid content was 50%.
It adjusted so that it might become, and it applied with the gravure coater.

<Releasable concealment layer> Aluminum metal powder 50 parts Rubber latex 100 parts Silica gel 40 parts Drying by placing in a dryer set at 150 ° C for 1 minute to provide a concealable concealment type pressure-sensitive cover. A color forming recording sheet was obtained.

Comparative Example 8 As a support having a self-coloring pressure-sensitive recording layer, a commercially available high-quality paper (manufactured by Mitsubishi Paper Mills, Diafoam 70K) was coated with the self-coloring pressure-sensitive recording layer having the composition described in Preparation Example 1. Is 7
Using the self-coloring pressure-sensitive recording sheet coated so as to have g / m ² , the same peelable concealing layer as in Example 4 was coated by the same coating method as in Example 4, and was placed in a dryer set at 150 ° C. The sample was cured by placing it for 1 minute into a sample.

Comparative Example 9 As a support having no self-coloring pressure-sensitive recording layer, a commercially available high-quality paper (manufactured by Mitsubishi Paper Mills, Diafoam 70K) was provided with a peelable concealing layer similar to that in Example 4 as in Example 4. Application was carried out by the same application method, and curing was carried out by placing in a dryer set at 150 ° C. for 1 minute to obtain a sample.

The recording sheets or samples obtained in Example 5 and Comparative Examples 8 and 9 were evaluated by the following methods.

<Pressure Sensitivity 3> Solid printing was performed using a commercially available dot impact printer from the peelable concealment layer of the recording sheets or samples obtained in Example 5 and Comparative Examples 8 and 9. The optical density was measured using a Macbeth densitometer for the color development of the hidden sheet when the hiding layer was scraped off. In practical use, the optical density at which even small characters can be sufficiently read is 0.50 or more, and if the optical density is below 0.40, accurate reading is difficult. When the optical density is less than 0.15, it is difficult to understand the presence or absence of color development.

<Color Confirmation> Example 5 and Comparative Example 8,
Printing was carried out from the side of the peelable concealing layer of the recording sheet or sample obtained in No. 9 by using the crusher printing method with resin letterpress. The hiding layer was scraped off so that the internal print could be read, and the color development of the sheet was confirmed. When scraping off the peelable hiding layer, the hiding layer can be peeled off without causing unnecessary color development inside, and when the internal print can be read, color confirmation is excellent, and the pressure is enough to scrape off the peelable hiding layer. When the color was developed and the print was difficult to read, the color confirmation property was poor, and when the hiding layer was scraped off, there was no color internally, the color confirmation property was bad.

<Post-Coloring Property> Example 5 and Comparative Examples 8 and 9
Printing was performed using a commercially available dot impact printer from the peelable concealment layer side of the recording sheet or sample obtained in 1. After scraping off the hiding layer, the color development of the sheet was confirmed. It was judged that the post-coloring property was excellent when it was possible to record on the concealed sheet portion even when printed from above the peelable hiding layer, and when it was not possible, the post-coloring property was poor.

<Counterfeiting Prevention Property 4> Printing was performed on the label from the peelable concealment layer of the recording sheet or sample obtained in Example 5 and Comparative Examples 8 and 9 using a commercially available dot impact printer. After the hiding layer was rubbed off, pressure was applied to areas other than the printed area to confirm the color developability of the sheet. If the peelable hiding layer can be colored on the hidden sheet after peeling off, a copy cannot be made by color copying or the like, so anti-counterfeiting property 4 is excellent, and the hidden sheet after peeling off the peelable hiding layer. In the case where the portion of No. 4 did not develop color and it could not be discriminated even if a similar sheet was duplicated by color copying or the like, the anti-counterfeiting property 4 was judged as poor.

The recording sheets or samples obtained in Example 5 and Comparative Examples 8 and 9 were tested by the above evaluation method, and the results are shown in Table 3. The recording sheets obtained with the pressure-sensitive paper (A) and the pressure-sensitive paper (B) in the examples are represented as Example 4A and Example 4B, respectively.

[0114]

[Table 3]

Evaluation: Heat sensitivity / obtained by Examples 1 to 3
The pressure-sensitive color-developing recording sheet or its label has heat-sensitive color development and pressure-sensitive color development on the same surface, and it is possible to develop two colors by using both recording methods. By enabling both the pressure-sensitive recording method, the color-developing method mainly used is for information recording (for example, heat-sensitive recording in anti-counterfeit property 1), and the recording method not mainly used (for anti-counterfeit property 1). It can be used for anti-counterfeiting purposes, etc. by using pressure-sensitive recording) as a complement. In particular,
The amount of money, the date, the seat number, etc. are entered by thermal recording on the recording sheet of the present invention printed for a ticket. When the ticket is used, the pressure-sensitive layer is colored by pressing a part of the ticket, and it can be confirmed that the ticket is genuine. If a mere heat-sensitive sheet is used for a ticket as in Comparative Example 3, such authenticity determination cannot be performed. The same thing can be said for a simple pressure-sensitive sheet, and it is not possible to judge authenticity by itself. Therefore, the recording sheet of the present invention has an authenticity judgment property, that is, a forgery prevention property.

The heat-sensitive / pressure-sensitive color-developing label in Example 3 is an application of the heat-sensitive / pressure-sensitive color-developing recording sheet of the present invention to an adhesive label, and has anti-counterfeiting properties not found in general heat-sensitive labels. Therefore, it has a function of preventing the counterfeiting of the label and the counterfeiting of the product to which the label is attached. However, in the case of heat-sensitive color development and pressure-sensitive color development, if the colors are the same, it is extremely difficult to determine which color is the other, so when using it for counterfeit prevention, it is better to change the color of heat-sensitive color development and pressure-sensitive color development. good.

The recording sheet of the present invention has excellent recording property and handling property while keeping the texture of paper. The transparent paper and the thermoplastic resin do not peel off during handling, and the abrasion resistance is excellent because the self-coloring pressure-sensitive recording layer is protected by transparent paper or the like.

On the other hand, the self-coloring pressure-sensitive recording sheet of Comparative Example 1 having only the self-coloring pressure-sensitive recording layer does not have sufficient abrasion resistance and the self-coloring pressure-sensitive recording sheet laminated with a thermoplastic resin is It has abrasion resistance but no anti-counterfeiting property. The sample of Comparative Example 3 having only the heat-sensitive recording layer also does not have the function of preventing forgery.

The pressure-sensitive color-developing release sheet obtained in Example 4 was prepared by sticking an adhesive label having an adhesive layer on the release layer to form a label and printing on the label using a dot impact printer. Similar printing appears on the release sheet after the label is peeled off, so that the label itself can be prevented from forgery. Further, when the pressure-sensitive adhesive label is peeled off from the release layer, the release sheet develops the same color as on the label, so that the release sheet can be used as a label slip.

When a peeling layer is provided as it is on the self-coloring pressure-sensitive recording layer as in Comparative Example 6, the self-coloring pressure-sensitive recording layer causes fog coloration to be unusable, or desensitized to form a color. There are problems such as not doing. The reason why a release sheet that does not have a self-coloring pressure-sensitive recording layer is neither forgery prevention nor a copy slip.
It is obvious.

In the recording sheet having a peelable concealing layer obtained in Example 5, the self-coloring pressure-sensitive recording layer can be printed after providing the concealing layer, and the content can be freely changed for printing. . Further, since the peelable concealing layer can be colored by pressure after being peeled off, a copy cannot be made by a color copy or the like, so that it has anti-counterfeiting property.

Only by providing the peelable hiding layer on the self-coloring pressure-sensitive recording layer, the abrasion resistance is insufficient, and when the peelable hiding layer is peeled off, the self-coloring pressure-sensitive recording layer develops color, which is unusable. . It is self-evident that even if a peelable concealment layer is provided on a support having no self-coloring pressure-sensitive recording layer, it has neither post-coloring property nor anti-counterfeiting property.

[0123]

EFFECTS OF THE INVENTION In the heat-sensitive / pressure-sensitive color-sensitive recording sheet of the present invention, not only heat-sensitive recording but also pressure-sensitive printing can be performed to color the self-coloring pressure-sensitive recording layer. The color development can be confirmed through the thermosensitive recording layer and transparent paper. Heat sensitivity of the present invention /
The pressure-sensitive color-developing recording sheet can be used as anti-counterfeit paper because it is possible to use two recording methods together, and can also be used as anti-counterfeit paper, and thus also for counterfeit prevention of products used with anti-counterfeit paper (for example, as a label). It plays a part. Even if a document or ticket using the heat-sensitive / pressure-sensitive color-developing recording sheet of the present invention is forged, for example, pressure-sensitive color development is performed after heat-sensitive recording, or conversely, heat-sensitive color development is performed after pressure-sensitive recording. Makes it easier to detect forgery. Since the self-coloring pressure-sensitive recording layer is protected inside the transparent paper, there is no worry of color stains due to careless rubbing and not only high abrasion resistance, but also a peeling layer and a peeling hiding layer on the transparent paper. If provided, it can be used as a pressure-sensitive color-developing release sheet or a concealment type pressure-sensitive color-sensitive recording sheet. Further, the series of recording sheets of the present invention have good weather resistance for recording, water resistance, oil resistance, etc., and since the surface is a transparent paper made of cellulose fiber, it has good affinity with the heat-sensitive recording layer and is easy to handle. It does not cause double feed due to electrostatic charge peculiar to laminated paper, and can be used not only for anti-counterfeit recording sheets but also for many forms such as continuous slips, pasting slips, labels, recording, dust-free recording paper, etc. , Of great industrial significance.

[Brief description of drawings]

FIG. 1 is a sectional view of a heat-sensitive / pressure-sensitive color forming recording sheet of the present invention.

FIG. 2 is a cross-sectional view of a heat-sensitive / pressure-sensitive color developing label of the present invention.

FIG. 3 is a cross-sectional view of a pressure-sensitive color-developing release sheet of the present invention.

FIG. 4 is a sectional view of a concealment type pressure-sensitive color-developing recording sheet of the present invention.

[Explanation of symbols]

 1 Support 2 Thermoplastic Resin Layer 3 Self-Coloring Pressure Sensitive Recording Layer 4 Transparent or Semi-Transparent Paper 5 Thermosensitive Recording Layer 6 Thermosensitive / Pressure Sensitive Colored Recording Sheet 7 Adhesive Layer 8 Thermosensitive / Pressure Sensitive Colored Label 9 Release Layer 10 Sensitive Pressure-sensitive color-developing release sheet 11 Releasable hiding layer 12 Hidden-type pressure-sensitive color-developing recording sheet

Claims (9)

[Claims] 1. At least one of a support, a thermoplastic resin layer, a color-developing agent for pressure-sensitive recording or a color-developing agent for pressure-sensitive recording is microencapsulated, and each is independently laminated or mixed to form a single layer of self-coloring. A pressure-sensitive recording layer (hereinafter referred to simply as a self-coloring pressure-sensitive recording layer), transparent or semi-transparent paper, a color-forming agent for heat-sensitive recording and a color-developing agent for heat-sensitive recording which develops color by contacting with the color-forming agent for heat-sensitive recording. Thermal recording layer (hereinafter,
A heat-sensitive / pressure-sensitive color-developing recording sheet in which heat-sensitive recording layers are simply laminated in order. 2. The heat-sensitive / pressure-sensitive color-sensitive recording sheet according to claim 1, wherein the color development of the self-coloring pressure-sensitive recording layer and the color development of the heat-sensitive recording layer are different from each other. 3. A forgery prevention or forgery detection can be performed by using at least both a heat-sensitive color development and a pressure-sensitive color development method using the heat-sensitive / pressure-sensitive color development recording sheet according to claim 1. Anti-counterfeit paper. 4. The method according to claim 1, wherein at least thermosensitive coloring is performed.
The heat-sensitive / pressure-sensitive color-developing recording sheet is subjected to pressure-sensitive color development to determine the difference from the heat-sensitive recording sheet having only the heat-sensitive color development. 5. The method according to claim 1, wherein at least pressure-sensitive color development is performed.
The heat-sensitive / pressure-sensitive color-developing recording sheet is partly heated to develop a heat-sensitive color, whereby a difference from a pressure-sensitive recording sheet having only pressure-sensitive color development is determined. 6. A support, a thermoplastic resin layer, a self-coloring pressure-sensitive recording layer, transparent or semi-transparent paper, and a heat-sensitive recording layer are sequentially laminated, and an adhesive layer is provided on the surface opposite to the support. Characteristic heat / pressure sensitive color development label. 7. A pressure-sensitive color-developing release sheet comprising a support, a thermoplastic resin layer, a self-color-developing pressure-sensitive recording layer, transparent or translucent paper, and a release layer, which are sequentially laminated. 8. A concealment type pressure-sensitive color-developing recording sheet comprising a support, a thermoplastic resin layer, a self-coloring pressure-sensitive recording layer, transparent or semi-transparent paper, and a peelable concealing layer, which are successively laminated. 9. The recording sheet according to claim 1, wherein the transparent or translucent paper has a transparency of at least 30% or more.