JP3489699B2 - Record sheet - Google Patents

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 color development. For example, an inkjet / pressure-sensitive color-developing recording sheet having anti-counterfeiting property according to the present invention means that ink-jet printing can be easily performed using an ink-jet printer, and pressure-sensitive color development can be easily performed using an impact printer or simple pressurization. The present invention relates to a possible ink jet recording and pressure sensitive color recording sheet. In addition, the magnetic recording / pressure-sensitive color-developing recording sheet not only prevents forgery by combining both the pressure-sensitive color development and the magnetic recording, but also confirms the identity of both recordings. You can determine the authenticity. Further, the present invention relates to a pressure-sensitive color-developing label, which can print a label while making a copy (reservation) just by using it together with a high-quality paper, and can provide a label capable of confirming forgery prevention even after the label is attached to an adherend. , And transparent pressure-sensitive color-developing label, the label can be printed while making a copy (copy) just by printing from the back side of the release paper, and it can be directly attached to a transparent adherend such as glass or plastic sheet, It is intended to provide a label which can read a printed record through an adherend, an adhesive layer and transparent paper and which is difficult to forge or modify. Such a series of recording sheets include slips, forms, recording papers, toys, communications,
It is a recording sheet with anti-counterfeit property that can be used for securities, cash vouchers, tickets, tickets, tickets, documents, stickers, lottery, labels and the like, and can easily discriminate the authenticity.

[0002]

2. Description of the Related Art In recent years, inkjet recording for printing by an inkjet method has been used in a wide range of fields such as printers and recorders for various measuring instruments, printers for labels, printers for POS, and vending machines for tickets and entrance tickets. It has come to be used. Inkjet recording is conveniently used in business offices, shops, and homes because it can record both monochrome and color. However, since the same printing can be easily performed in the ink jet recording due to the development of personal computers, printers, printing fonts, etc., there is a problem that it is easy to forge when handling it as a cash voucher such as a ticket. For the purpose of anti-counterfeiting, such a so-called cash voucher recording paper is printed with a tint block for anti-counterfeiting, or is printed with anti-counterfeiting by micro characters, but with the development of color copying in recent years, With regard to printing, even amateurs can easily make duplicates. In this situation, not only a cash voucher, but also a price tag, a label on which product details are entered, a speed lottery, or the like is easy to duplicate.

Due to the development of forgery methods in social life (particularly due to color copying), not only tickets and ticket vouchers but also labels, price tags, documents, etc. are targeted. No exception. That is,
In addition to ticket vouchers, tickets, stamps, stamps, bills, checks, certificates, etc., labels and manuals for books, CDs, game software, etc. that are available in the world, product price tags themselves, all kinds of lottery and voting. Currently, it is easy to make tickets (betting tickets, etc.), company stationery, etc. by making color copies.

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. . Its structure is a step of providing a support with microcapsules containing a colorless dye (hereinafter, referred to as a color former), and further, an electron-accepting substance such as acidic clay, a phenol resin, an organic acidic substance or the like on the coating layer. , A developer) by a two-layer coating consisting of two steps (including a reverse coating order), or at least one of the above two components is microencapsulated, Manufacturing method by uniformly mixing and coating one layer (Japanese Patent Publication No. 47-1609).
No. 6) is known.

As a matter of course, in the self-coloring pressure-sensitive recording sheet, both the color former and the color developer are present in close proximity to the surface of the support, and the color is developed by a little friction or pressure. is necessary. 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, there is a dilemma that, for example, when the ink is passed through an ink jet printer or the like, the traces of the paper feed roll are colored and become unusable.

In ink jet 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 the ink jet recording head and the impact head has been desired. One of the reasons for this is that since only one type of recording method such as ink jet recording or pressure sensitive recording can be easily forged as described above, it is possible to use a multifunctional recording sheet in which at least two or more recording methods can be used together. Development was desired.

Further, even in the case of the self-coloring pressure-sensitive recording sheet, the same printing can be easily performed due to the recent development of personal computers, printers, printing fonts, etc., like the ink jet recording body. Had a problem that it was easy to forge. The point that the copy-forgery-inhibited pattern printing for preventing forgery can be duplicated by color copying is also the same as in the case of inkjet.

As such a recording sheet, a double-sided recording sheet in which a pressure-sensitive recording layer and an inkjet recording layer are coated on both sides of a support is devised, and such a recording sheet is a printer for performing inkjet recording. However, there is a problem that the self-coloring pressure-sensitive recording layer develops color by the paper feed roll of the printer.

A magnetic recording method is often used as a means for preventing forgery or a means for mechanizing information processing. The magnetic recording method is rarely used as a single magnetic recording, and is usually used in combination with magnetic recording and ink jet recording, magnetic recording and printing (or anti-counterfeit printing), magnetic recording and thermal transfer recording. Generally, it is used in many fields such as magnetic tickets, magnetic admission tickets, betting tickets such as betting tickets, prepaid cards, credit cards, magnetic coupons, etc. Since it is basically readable, it was possible to forge by making magnetic recording paper with exactly the same magnetic characteristics. This can be seen from the large number of counterfeit telephone cards, which are one type of magnetic recording sheet. A ticket or the like uses magnetic information and heat-sensitive recording information, or magnetic information and fusion thermal transfer recording information in combination. Generally, since decoding is based only on magnetic information, if the magnetic information is decoded, the forgery prevention property is extremely low. Decoding is based only on magnetic information because it is not suitable for extremely short-time processing such as automatic ticket gates because the thermal recording or the melting thermal transfer recording is character information.

Further, generally used labels are often subjected to a recording method such as a fusion heat transfer method or a heat sensitive method. However, in these labels, information is written from the adhesive side of the label and the information is transferred to the adhesive side. You can't take the way you read from. In other words, even if the label is considered to be affected by rain or water, the information surface and the adhesive surface are on the opposite side, so the information surface must be exposed to the outside (that is, the side affected by rain or water). I didn't get it. Especially for transparent adherends such as glass and plastic film, it is useless to put the label on the outside without using its transparency and protection function, and thus it is possible to read and write information from the adhesive side. Is required as a method of displaying information on the glass surface (used for displaying parking hours, displaying vehicle inspection periods, displaying regular inspections, or documents for crossing vehicle borders, etc.). There was no technology to respond.

[0011]

A 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 ink jet recording. is there. Therefore, the present invention is not only capable of recording on a recording sheet itself, but also the pressure-sensitive recording layer (self-coloring pressure-sensitive recording layer) has sufficient abrasion resistance and is applicable to a recording method used for inkjet recording. An inkjet / pressure-sensitive color-developing recording sheet having sufficient properties such as printer suitability, solvent resistance, and roll resistance. By enabling both pressure-sensitive recording and inkjet 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 forgery prevention. It is to develop an anti-counterfeit recording sheet that can be used for.

The second problem to be solved by the present invention is
Another object of the present invention is to provide a pressure-sensitive color-developing recording sheet having a surface coated with a pigment coating layer for printing. By providing a pigment coating layer for printing, it is possible to achieve a wide range of forgery prevention by combining forgery prevention means by advanced printing such as micro-character printing and a simple forgery detection method called pressure-sensitive color development. it can.

A third problem to be solved by the present invention is to obtain a magnetic recording sheet having a pressure-sensitive self-coloring property as one of means for preventing forgery. In such a magnetic recording / pressure-sensitive color forming recording sheet, it is possible not only to prevent forgery in each of the magnetic recording, the pressure-sensitive color forming recording and the printing portion, but also to identify the coloring information and the magnetic information. By performing the magnetic recording, it is possible to judge the authenticity of the recording sheet.
An object is to provide a pressure-sensitive color forming recording sheet.

As a fourth problem to be solved by the present invention, a pressure-sensitive color-developing surface is provided on the premise that a pressure-sensitive label having copyability is provided and an object on which pressure-sensitive color-developed information is labeled is seen through. Another object of the present invention is to provide a transparent pressure-sensitive color-developing label having an adhesive surface on the same surface.

[0015]

The inventors of the present invention have found the following recording sheets as a result of earnest research for solving the above-mentioned problems.

At least one of the support, the color-developing agent and the color-developing agent is microencapsulated, and they are laminated or mixed individually to form a single layer of a self-coloring pressure-sensitive recording layer (hereinafter, simply self-coloring pressure-sensitive recording layer). An inkjet / pressure-sensitive color-developing recording sheet obtained by sequentially laminating a polyolefin resin layer, transparent or translucent paper, and an ink-receiving layer for ink-jet recording (hereinafter, simply ink-receiving layer).

A printing / pressure-sensitive color recording sheet comprising a support, a self-coloring pressure-sensitive recording layer, a polyolefin resin layer, transparent or semi-transparent paper, and a pigment coating layer for printing, which are successively laminated.

A magnetic recording comprising a support, a self-coloring pressure-sensitive recording layer, a polyolefin resin layer, transparent or semi-transparent paper, which are sequentially laminated, and a magnetic recording layer is provided on the surface opposite to the support. / Pressure-sensitive color forming recording sheet.

A copy property is characterized in that a support, a self-coloring pressure-sensitive recording layer, a polyolefin resin layer and transparent or semi-transparent paper are sequentially laminated, and an adhesive layer is provided on the surface opposite to the support. A pressure-sensitive color-developing label having.

A transparent type pressure-sensitive color-developing label having a copying property, which comprises a support, a self-color-developing pressure-sensitive recording layer, a polyolefin resin layer, transparent or semi-transparent paper, and an adhesive layer, which are successively laminated.

An anti-counterfeit paper comprising one of the above-mentioned recording sheets and capable of preventing forgery or detecting forgery based on the pressure-sensitive coloring property.

[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, glassine paper, cast paper and coated paper can be used, and wood pulp, synthetic pulp, filler and sizing agent can be used. Raw materials commonly used in papermaking, such as ultraviolet absorbers, antioxidants, pigments, paper strength enhancers, and dyes, can be used as necessary. In addition, polyethylene, polypropylene, polyethylene terephthalate, polyamide, polyvinyl chloride, polyvinylidene chloride, plastic sheet such as polymethylpentene, and synthetic paper or nonwoven fabric made of these synthetic fibers, or one side of these synthetic resins on paper, or You may use the laminated paper laminated on both sides. The material made of these synthetic resins may be white or colored.

In the present invention, a paper having a transparency of 26% 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. 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. For the transparent paper or semi-transparent paper of the present invention, raw materials usually used in papermaking such as wood pulp, synthetic pulp, fillers, sizing agents, UV inhibitors, antioxidants, paper strengthening agents, dyes, etc. may be used as necessary. It is possible to use.

The basis weight of transparent or translucent paper is 10 g / m ²
If it is smaller, the dimensional stability is poor and wrinkles are likely to occur during bonding, and it may break during writing, which is not preferable. On the other hand, if the basis weight is more than 85 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 or semi-transparent paper having a transparency of 26% or more is suitable for confirming the color development of the self-coloring pressure-sensitive recording layer through another recording layer such as an ink jet layer, and the transparency Is less than 26%, 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 26.
% Or more, glassine paper, resin-impregnated paper, typewriter paper, condenser paper, tracing paper, copy paper, impregnated tracing paper, Japanese paper, thin high-quality paper, etc. are not particularly limited,
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. The tracing paper referred to in the present invention is a transparent paper which is also called a natural trepe or a natural trepe for the purpose of distinguishing it from an impregnating type tracing paper.

In order to obtain the recording sheet of the present invention, typically, on one surface of a support, a color-forming agent or a color-developing agent, at least one of which is microencapsulated, is individually laminated or mixed to form a single layer. A step of providing a self-coloring pressure-sensitive recording layer, a step of integrating the self-coloring pressure-sensitive recording paper and a transparent paper with a polyolefin resin layer, a step of coating a recording layer of another recording system such as an inkjet recording layer on the transparent paper,
It can be manufactured by combining the above steps, but the details of these steps and the order of combination are not particularly limited. It is also possible to provide a magnetic recording layer or an adhesive layer on one side of the support on which no visible recording layer is provided, or to provide a release layer on the transparent paper.

As the polyolefin resin used in the recording sheet of the present invention, generally, any polyolefin resin used for polyolefin resin coating or polyolefin resin laminate can be used without limitation. For example, polyethylene (low density, medium density, high density, General-purpose melt-extruded resins such as linear low-density polyethylene), polypropylene, polytrimethylpentene, and polybutene can be used alone or in combination. As long as it is a transparent resin that has thermoplasticity and can be melt extruded or heat-sealed, it can be used in place of the polyolefin resin such as vinyl chloride, EVA, or high-milan, even if it is not a polyolefin resin. Since it comes into contact with the recording layer, it must be used in consideration of the effects of the plasticizer, dispersant, antioxidant, etc. in the resin.

To integrate the transparent paper and the support having the self-coloring pressure-sensitive recording layer with the polyolefin resin layer, a general melt extrusion die, a T die, or a multi-layer 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, a back coat layer such as an anti-curl, anti-static, pigment coat layer or water resistant layer can be provided, and the back coat layer comprises an antistatic agent, a hydrophilic binder and a latex. , A hardener, a pigment, a surfactant, an adhesive and the like can be appropriately combined and contained.

The coating amount (laminating amount) of the polyolefin resin is preferably in a certain range because it affects the color developing property of the self-coloring pressure-sensitive recording layer and the adhesive property with transparent paper. From the purpose of sufficiently maintaining the adhesive strength between the transparent paper and the support, a coating amount of 8 to 25 g / m ² is preferable, and in order to ensure sufficient color development of the self-coloring pressure-sensitive recording layer, at most 30
It is necessary to keep the coating amount below g / m ² . If the basis weight of the transparent paper or the coating amount of the polyolefin resin layer exceeds a certain range, the coloring property sufficient for reading or confirming the coloring is impaired. Further, if the polyolefin 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 the transparent paper 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, a wall material of the microcapsule, a color former, an oil dissolving the color former, a color developer, an adhesive resin, a microcapsule protective agent, or the like.

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

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

The color former and developer used in the present invention are not particularly limited as long as they are generally used in pressure-sensitive recording materials. For example, as a color former for pressure-sensitive recording, triallylmethane compounds, diarylmethane compounds, xanthene compounds, thiazine compounds, spiropyran compounds, diphenylmethane dyes, spiro dyes, lactam dyes, fluorane dyes. Dye etc. can be used.

Specifically, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (crystal violet lactone) and 3,3-bis (p-
Dimethylaminophenyl) phthalide, 3- (p-dimethylaminophenyl) -3- (1,2-dimethylindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-methylindo-) (Ru-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-methylpyrrol-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-dimethylamino Triallylmethane dyes such as phthalide.

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.

Lactam dyes such as rhodamine-B-anilinolactam, rhodamine (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-
Phenylaminofluorane, 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 former in the pressure-sensitive recording layer, aromatic synthetic oils such as diarylalkane type, alkylnaphthalene type, alkylated biphenyl, hydrogenated terphenyl, kerosene, naphtha, paraffin oil and chlorinated paraffin are used. Aliphatic synthetic oils such as, 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 silka, aluminum silicate, etc.),
Organic acid (for example, aromatic carboxy compound such as salicylic acid or metal salt thereof), mixture of organic acid and metal compound, acidic polymer (for example, phenol / formaldehyde resin, salicylic acid resin or zinc thereof,
Polyvalent metal salts such as magnesium, aluminum, calcium, titanium, manganese, tin, nickel) and the like can be used.

In addition, zinc stearate as an auxiliary agent,
Waxes such as higher fatty acid metal salts such as calcium stearate, paraffin, oxidized paraffin, polyethylene, oxidized polyethylene, stearamide, castor wax, etc., dispersants such as sodium dioctylsulfosuccinate and sulfonic acid modified polyvinyl alcohol, benzophenone type, UV absorbers such as benzotriazoles, surfactants, fluorescent dyes, antistatic agents, thickeners, preservatives, antioxidants, defoamers, release agents, lubricants, antiblocking agents, tackifiers Is a support,
It is added to the self-coloring pressure-sensitive recording layer, the polyolefin resin layer, the ink jet recording layer, and the transparent paper as needed.

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

Further, as the constitution of the present invention, in order to obtain a 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,
Anchor layer containing inorganic pigments such as gypsum and aluminum hydroxide, or fine powder organic pigments such as polystyrene, polyvinyltoluene, styrene / divinylbenzene copolymer, polymethylmethacrylate, urea / formaldehyde polymer, polyethylene, etc. There is no problem in dispersing in the color forming pressure-sensitive recording layer.

The ink receiving layer for ink jet in the present invention (hereinafter, simply referred to as ink receiving layer) is composed of a coating composition containing a pigment and a binder as main components, to which a dye fixing agent and a pigment dispersion are added. Agents, thickeners, fluidity improvers, defoamers, foam suppressors, release agents, foaming agents, penetrants, colored dyes, colored pigments, optical brighteners, ultraviolet absorbers, antioxidants, preservatives It is also possible to appropriately add a anti-fungal agent, a water resistance agent, a wet paper strength enhancer, a dry paper strength enhancer and the like.

The pigment used in the ink receiving layer includes
One or more known white pigments can be used. For example, light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, calcium silicate,
White inorganic pigments such as magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudo-boehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrohaloysite, magnesium carbonate, magnesium hydroxide, styrene plastic pigment, acrylic Organic pigments such as plastic pigments, polyethylene, microcapsules, urea resins and melamine resins can be used.

As the binder used in the ink receiving layer, polyvinyl alcohol, vinyl acetate, oxidized starch, etherified starch, carboxymethyl cellulose,
Cellulose derivatives such as hydroxyethyl cellulose,
Casein, gelatin, soybean protein, silyl-modified polyvinyl alcohol, etc .; maleic anhydride resin, conjugated diene-based copolymer latex such as styrene-butadiene copolymer, methyl methacrylate-butadiene copolymer; acrylic acid ester and methacrylic acid ester Acrylic polymer latex such as polymer or copolymer, acrylic acid and methacrylic acid polymer or copolymer; vinyl polymer latex such as ethylene vinyl acetate copolymer; or carboxyl group of these various polymers Functional group-modified polymer latex with functional group-containing monomer such as; Water-based adhesive such as thermosetting synthetic resin system such as melamine resin and urea resin; Polymethylmethacrylate, polyurethane resin, unsaturated polyester resin, vinyl chloride-acetic acid Vinyl copolymer, Polyvinyl butyral, it includes synthetic resin adhesive such as an alkyd resin, are used in one or more.

The aqueous ink used for ink jet recording in the present invention is a recording liquid containing a colorant, a liquid medium, and other additives. Examples of the colorant include water-soluble dyes such as direct dyes, acid dyes, basic dyes, reactive dyes and food dyes.

As the solvent for the aqueous ink, water and various water-soluble organic solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, C1-C4 alkyl alcohols such as isobutyl alcohol; amides such as dimethylformamide and dimethylacetamide;
Ketones or ketone alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2, 6-hexanetriol, thiodiglycol, hexylene glycol, diethylene glycol and other alkylene groups have 2 to 6
Alkylene glycols; lower alkyl ethers of polyhydric alcohols such as glycerin, ethylene glycol methyl ether, diethylene glycol methyl (or ethyl) ether, and triethylene glycol monomethyl ether. Among these many water-soluble organic solvents, polyhydric alcohols such as diethylene glycol, triethylene glycol monomethyl ether,
Lower alkyl ethers of polyhydric alcohols such as triethylene glycol monoethyl ether are preferred. Other additives include, for example, pH adjusters, sequestering agents,
Examples thereof include antifungal agents, viscosity modifiers, surface tension modifiers, wetting agents, surfactants, and rust preventives.

That is, the ink receiving layer in the present invention needs to have resistance to such solvents and chemicals,
In addition, the self-coloring pressure-sensitive recording layer of the recording sheet must not have a structure that is susceptible to such solvents and chemicals.

Below the ink jet recording layer, that is,
An undercoat layer is provided on transparent paper to improve inkjet color development and prevent printing blurring, or an overcoat layer is provided on the inkjet recording layer for the purpose of imparting abrasion resistance and water resistance. There is no problem in providing it.

In the present invention, the pigment coating layer for printing means
It is a coating layer for improving printability corresponding to ordinary offset printing, flexographic printing, gravure printing, etc.
As a matter of course, it can be used for printing such as a typewriter or a water-based or oil-based pen, and includes so-called slightly coated paper. The coating solution for the pigment coating layer for printing is a solution in which the pigment, binder, and other additives are dissolved or dispersed in water, and the concentration of the pigment, binder, and other additives is 10 to 70% by weight. To tell. The mixing ratio of the pigment and the binder is generally 5 parts by weight or more, and preferably 10 to 7 parts by weight with respect to 100 parts by weight of the pigment.
It is preferably 0 parts by weight.

The pigment used in the pigment coating layer for printing used in the present invention includes kaolin, clay, calcium carbonate, satin white, titanium oxide, aluminum hydroxide, zinc oxide, barium sulfate, calcium sulfate, silica, activated clay, Examples include rakes and plastic pigments.

In the present invention, the coating amount of the pigment coating layer for printing is 1 g / m ² or more, preferably 3 to 3 on a dry weight basis.
0 g / m ² is suitable. If the coating amount of the printing pigment coating layer is less than this, good printability is not exhibited and it is meaningless to provide the printing pigment coating layer, and if it is more than this, it does not contribute to the improvement of printability, Color development It is difficult to confirm the color development of the pressure-sensitive recording layer, and the anti-counterfeit property is deteriorated.

In the magnetic recording layer of the present invention, magnetic powder is used as polyester resin, vinyl chloride resin, polyurethane resin, vinyl chloride / vinyl acetate copolymer resin, styrene / butadiene copolymer resin, polyacrylic ester resin, epoxy resin. Dispersed uniformly in a binder such as, plasticizer, rubber, dispersant, antistatic agent, pigment, etc. are added according to the purpose,
It is formed by applying or printing the obtained coating material on a substrate. As magnetic powder, γ-Fe ₂ O ₃ , Fe ₃ O ₄ ,
γ-Fe ₂ O ₃ and Fe ₂ O ₄ mixed crystal, Co-containing Fe
₂ O ₄ , Ba ferrite, Sr ferrite and the like can be mentioned. In order to prevent the trouble that the magnetically recorded information is erased by the normal permanent magnet, the coercive force is 1500
˜5000 oersted Ba ferrite, Sr ferrite and the like are preferable.

It is also possible to provide a protective layer on the magnetic recording layer. Examples of the protective resin include cereal starch, pregelatinized starch, oxidized starch, etherified starch, gelatin, casein, collagen, proteins such as viscose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, and other celluloses. , Agar, polysaccharides such as sodium alginate, gum arabic, polyvinyl alcohol, polyvinylpyridone, polyacrylic acid, polyacrylamide, water-soluble binder of maleic acid copolymer, styrene butadiene type, acrylonitrile butadiene type methyl methacrylate butadiene type , Acrylic ester,
Vinyl acetate-based latex emulsion binders and their carboxy-modified products are mentioned.

It is possible to disperse a pigment in the protective layer to form a hiding layer. The pigment for the concealing layer is known, and examples thereof include carbonates, oxides, hydroxides, sulfates and natural silica of aluminum, zinc, magnesium, barium, calcium, titanium and the like, clay, zeolite, kaolin, calcined kaolin. Inorganic white pigments containing clays such as, synthetic silica, styrene resin, melamine resin,
One or more organic white pigments containing a copolymer such as an acrylic resin or a urea resin are used.

The protective layer or hiding layer coating solution is mixed with a dispersant, an antiseptic agent, an antifoaming agent and a dusting inhibitor, if desired, and applied by a method such as air knife coating, curtain coating, roll coating or blade coating. .
An anchor layer may be provided between the magnetic recording layer and the protective layer to improve adhesion.

A lubricant, an abrasive, a rust preventive, a dispersant, a thickener and the like may be added to the magnetic material composition of the present invention. In particular, lubricants include saturated and unsaturated higher fatty acids,
Fatty acid ester, higher fatty acid amide, higher alcohol,
There are silicon oil, mineral oil, fluorine compound, etc., which may be added during the preparation of the magnetic composition, or may be applied or sprayed on the surface of the magnetic layer.

The magnetic layer coated on the support can be optionally subjected to a treatment for orienting the magnetic substance in the layer.
The orientation treatment is performed at a right angle to the traveling direction of the support or at an angle of about 500 to 3 in the traveling direction.
It can be carried out under an AC or DC magnetic field condition of about 000 Oersted.

In the present invention, a self-coloring pressure-sensitive recording layer,
Binders used for forming the inkjet recording layer, the pigment coating layer for printing, and the magnetic recording layer include starches,
Cellulose derivatives such as hydroxyethyl cellulose, methyl cellulose, ethyl cellulose and carboxymethyl cellulose, proteins such as casein and gelatin,
Oxidized starch, ester compound starch, etherified starch, enzyme-modified starch and cold water-soluble starch obtained by flash-drying them, casein, natural polymer compounds such as soybean protein, polyvinyl alcohol, modified polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic Acid, polyacrylic acid soda, 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 Water-soluble synthetic polymer compounds and latexes such as styrene / maleic anhydride copolymer, vinyl acetate / acrylic, vinyl acetate / butyl acrylate copolymer, isobutene / maleic anhydride copolymer, ethylene / maleic anhydride Alkali of acid copolymer Water-soluble adhesive resin such as salt, polyvinyl acetate, polyurethane, polyacrylic ester, styrene / butadiene copolymer, acrylonitrile / butadiene copolymer, methyl acrylate / butadiene copolymer, acrylonitrile / butadiene / acrylic acid copolymer Examples include coalesce and latex such as ethylene / vinyl acetate copolymer. Further, if necessary, various auxiliaries such as a thickener, a water retention agent, a water resistance agent, and a colorant, which are mixed with a usual pigment for coated paper, can be appropriately used.

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 the pressure-sensitive color developing label of the present invention, the surface on which the adhesive layer can be provided can be used firstly on the surface opposite to the self-coloring pressure-sensitive recording layer, that is, on the support side.
In this case, the surface on which the adhesive layer is not provided, that is, the transparent paper side can be used as it is, or a heat-sensitive recording layer, an ink jet recording layer, a pigment coating layer for printing and the like can be provided. Secondly, an adhesive layer can be provided on the same surface as the self-coloring pressure-sensitive recording layer, that is, on the transparent paper side. In this case, the color-developed information of the self-coloring pressure-sensitive recording layer is read through the polyolefin resin layer, transparent paper and adhesive layer. In both the first case and the second case, the adhesive layer can be used together with a release paper having a release layer. In the first case,
In the second case as well, the pressure-sensitive color-developing label and the plain paper are overlapped and impact-printed, whereby information can be simultaneously obtained on the plain paper and the pressure-sensitive color-developing label. In the second case, the release paper can be used as a copy slip by using the non-release surface of the release paper located above the self-coloring pressure-sensitive recording layer as the recording surface.

In the present invention, a self-coloring pressure-sensitive recording layer,
Examples of the method for applying the ink receiving layer, the pigment coating layer for printing, the magnetic recording layer, the adhesive layer, etc. include a gravure coater, a gravure offset coater, a bar coater, a roll coater, an air knife coater, a U comma coater, and AKKU.
Coater, smoothing coater, micro gravure coater, reverse roll coater, 4 or 5 (multistage) roll coater, curtain coater, blade coater, dip coater, falling curtain coater,
Various devices such as a slide coater, a lip coater, a die coater, a squeeze coater, a short dwell coater, a size press, and a spray can be used on-machine or off-machine. After coating or impregnating each layer, calendering such as machine calender, gloss calender, TG calender, super calender, soft calender or brushing may be used for finishing. 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 a pencil or ink, impact printer, electrophotography, thermal transfer, ink ribbon, ink jet, pressure sensitive, ink jet, flexographic printing, offset printing, gravure. There is no limitation according to the method such as 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 formation by pressure. As a matter of course, the recording on the ink receiving layer is performed by an inkjet method using an inkjet recording head. When recording on the self-coloring pressure-sensitive recording layer, it is 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. It is also possible to record with a ballpoint pen, iron brush, etc. General printing may be performed on the peeling layer, the ink receiving layer, the self-coloring pressure-sensitive recording layer, the polyolefin resin layer, the transparent paper or the back surface of the support. Further, there is no problem in making the opaque by the 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 or all of the pressure-sensitive adhesive sheet of the present invention, such as die cutting, separation of part of the support,
There is no problem with processing perforations and feed holes for printers.

[0070]

In the recording sheet of the present invention, not only recording such as ink jet recording can be performed, but also pressure printing can be performed to color the self-coloring pressure-sensitive recording layer. It is possible to read through an upper recording layer or printing layer such as a layer, a polyolefin resin 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,
By enabling both pressure-sensitive and ink-jet recording methods with a single recording sheet, the ink-jet recording method can be used for information recording, and the pressure-sensitive color recording method can be used complementarily to prevent forgery. it can. Further, as one of the means for preventing forgery, it is possible not only to prevent forgery in each of magnetic recording, pressure-sensitive color recording, and printing portion by using a magnetic recording sheet having pressure-sensitive self-coloring property. It is possible to identify the coloring information and the magnetic information, and to judge the authenticity of the recording sheet. Furthermore, the provision of a pressure-sensitive label with copyability,
Also, we provide a transparent pressure-sensitive color-developing label that has a pressure-sensitive color-developing surface and an adhesive surface on the same surface, assuming that you can see through an object labeled with pressure-sensitive color-developed information while having copyability. can do. In such a transparent type pressure-sensitive color-developing label, the release paper is used as a slip and the pressure-sensitive color-developing surface is covered with the adhesive layer, so that the anti-counterfeiting property is high.

[0071]

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

<Preparation Example 1: Self-coloring pressure-sensitive coating liquid> Microcapsules containing a color-forming agent used for pressure-sensitive recording were prepared as follows. First, crystal violet lactone 1
3 parts by heating was dissolved in 90 parts of Hisol SAS N-296 (manufactured by Nippon Petrochemical Co., Ltd.) 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 into 150 parts of a 6% aqueous styrene / maleic anhydride copolymer solution, and the above melamine-formalin polycondensate was added to this emulsion to adjust the liquid temperature to 70 ° C.
It was kept for 3 hours to obtain a microcapsule dispersion liquid containing a color former having a melamine-formalin resin film. 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. Microcapsules containing color former 130 parts Developer (PR26298 manufactured by Sumitomo Durez Co., Ltd.) 70 parts Starch particles 280 parts Kaolin clay 100 parts Oxidized starch 100 parts Calcium carbonate 120 parts

Example 1 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
The pressure-sensitive recording sheet was coated so as to be g / m ² to obtain a self-coloring pressure-sensitive recording sheet. Self-coloring pressure-sensitive recording surface is subjected to corona treatment, low-density polyethylene (NUC8000, made by Nippon Unicar) is extruded from the melt extrusion die, and the self-coloring pressure-sensitive recording sheet and transparent paper are laminated together to form a transparent paper layer. A scratch-resistant self-coloring pressure-sensitive recording sheet having As transparent or semi-transparent paper (A) Tracing paper with 15 g / m ² basis weight (transparency 84%), (B) 35 g / m ² basis weight
Copy paper for diazo (transparency 50%), (C) Basis weight 4
5g / m ² high-quality paper (transparency 30%), (D) basis weight 50g / m ²
Using each of the high-quality paper (transparency 26%), a scratch-resistant self-coloring pressure-sensitive recording sheet having a transparent paper layer was obtained. The coating amount of polyethylene resin was 12 g / m ² .

The self-coloring pressure-sensitive recording sheets having respective transparent paper layers are referred to as pressure-sensitive paper (A), pressure-sensitive paper (B), pressure-sensitive paper (C) and pressure-sensitive paper (D). Using the ink-receiving layer coating liquid shown in Preparation Example 2 below as an ink-receiving layer composition, a dry coating amount of 5 was obtained using an air knife coater.
It was coated on the transparent paper side surface of the pressure sensitive papers (A) to (D) so as to be g / m ² to obtain the intended inkjet / pressure sensitive color forming recording sheet.

[0076] <Adjustment example 2: Ink receiving layer coating liquid formulation> 100 parts of synthetic amorphous silica (Fanseal X37B: manufactured by Tokuyama Soda Co., Ltd.) Polyvinyl alcohol (PVA117: Kuraray Co., Ltd.) 30 parts 20 parts of cationic dye fixing agent (Sumires Resin 1001: manufactured by Sumitomo Chemical Co., Ltd.) The above was adjusted to a solid concentration of 13%.

Comparative Example 1 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
The self-coloring pressure-sensitive recording sheet coated so as to have 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, 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 to provide a coating layer of polyolefin resin.

Comparative Example 3 As a support having an ink receiving layer, a commercially available high-quality paper (manufactured by Mitsubishi Paper Mills, Diafoam 70K) was coated with an inkjet coating solution having the composition described in Preparation Example 2 to give a dry weight of 5 g / m ^2. Thus, the ink-receiving layer was provided by coating and drying, and an inkjet recording sheet was obtained.

Examples 1 (A)-(D) and Comparative Examples 1-
The recording sheet obtained in No. 3 was evaluated by the following methods, and the results are shown in Table 1.

<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.

<Inkjet Suitability> Printing was performed using a commercially available inkjet printer (Epson MJ-700V2C). Immediately after printing, the printed surface was rubbed with a cloth to observe stains on the printed surface. 5 when the print is not dirty at all, 4 when the flow can be seen in a very small part of the print but cannot be understood without attention, 3 when the print flows but there is almost no effect on decoding, and most of the print flows and decode The ink jet aptitude was represented by 2 when it was not possible and 1 when the printing was not fixed at all.

However, in the case of printing using an inkjet printer, if the unnecessary portion other than the inkjet printing is colored due to the rubbing of the paper feed roll or the paper feed gear, it means that the inkjet printer is not suitable, The sex was judged as 0.

<Counterfeiting Prevention Property 1> Printing was performed on a recording sheet on which ink jet recording was performed using a commercially available ink jet printer, using a dot impact printer not equipped with an ink ribbon. If the ink-jet recording and the pressure-sensitive coloring overlap, the pressure-sensitive coloring can be read.The anti-counterfeiting property is excellent.If the ink-jet recording and the pressure-sensitive coloring overlap, the pressure-sensitive coloring cannot be read, but the ink-jet recording Good anti-counterfeiting properties when pressure-sensitive coloring is readable in areas where there is no ink-jet printing, and anti-counterfeiting when printing can be confirmed even when pressure-sensitive coloring is not readable even in areas without inkjet recording. Then, the case where only the pressure-sensitive color development was possible because of stains on the upper feed roll and the like and the case where only ink jet recording was possible were judged as poor anti-counterfeit property.

[0085]

[Table 1]

Example 2 On the transparent paper side of the pressure-sensitive papers (A) to (D) obtained in Example 1, a blade coater was used to adjust the absolute dry coating amount to 15 g / m ^2, and the following adjustment example was used. The solid content of the composition of 3 is 53
% Of the coating solution was applied as a pigment coating layer for printing and dried to obtain an intended printing / pressure-sensitive color recording sheet.

[0087] <Adjustment Example 3: Pigment coating liquid for printing> Commercially available heavy calcium carbonate (Carbital 90) 10 parts 30 parts of commercially available first-class kaolin (Ultra White 90) 20 parts of commercially available second-class kaolin (caobrite) Commercial cubic light calcium carbonate (Brilliant 15) 10 parts 30 parts of commercially available aragonite type calcium carbonate (HGA) Commercially available polyacrylic acid-based dispersant 0.2 parts Commercially available phosphorylated starch 2 parts Styrene / butadiene / latex 16 parts

Comparative Example 4 As a support having a pigment coating layer for printing, a commercially available high-quality paper (manufactured by Mitsubishi Paper Mills, Diafoam 70K) was used, and Preparation Example 3 was prepared.
A printing pigment coating liquid having the composition described above was applied so as to have a dry weight of 15 g / m ^2, and dried to provide a printing pigment coating layer, to obtain a printing paper.

The recording sheets obtained in Example 2 and Comparative Examples 1, 2, and 4 were evaluated by the following methods in addition to the above-described pressure-sensitive color development 1 test, and the results are shown in Table 2. .

<Printability> 4 using an offset printing machine
Color printing was performed. Immediately after printing, the printed surface was rubbed with a cloth to observe stains on the printed surface. 5 when the print is not dirty at all, 4 when the dirt is seen on a very small part of the print surface but cannot be seen without attention, 3 when the print surface is dirty but hardly affects the decoding, and most of the print is dirty The printability is represented by 2 when it cannot be decoded and 1 when it cannot be printed.

<Counterfeiting Prevention 2> Printing was performed on a recording sheet on which four-color printing was performed using an offset printing machine, using a dot impact printer not equipped with an ink ribbon. Anti-counterfeiting is good even if the pressure-sensitive color is printed even if it overlaps with the print.If the print and the pressure-sensitive color are overlapped, the pressure-sensitive color cannot be read, but in the part without printing Good anti-counterfeit property when pressure-sensitive color can be read,
When the pressure-sensitive color development could not be read even in a non-printed area but it was confirmed that the pressure-sensitive color development was observed, the anti-counterfeiting property was judged to be normal, and the case where only the pressure-sensitive color development was possible and only the printing was possible were judged to be poor anti-counterfeit property.

[0092]

[Table 2]

Example 3 30 g of the magnetic recording layer coating liquid prepared in Preparation Example 4 below was applied to the back surface (the surface opposite to the transparent paper) of the pressure sensitive papers (A) to (D) in Embodiment 1 using a gravure coater. Apply at a rate of / m ² ,
After magnetic field orientation, it was dried and lightly supercalendered to provide a magnetic recording layer to obtain a target magnetic recording / pressure-sensitive color forming recording sheet. This magnetic recording / pressure-sensitive color-sensitive recording sheet is not only used for printing on the self-coloring pressure-sensitive recording layer with a normal impact head, but is also pressure-sensitively colored on the self-coloring pressure-sensitive recording layer using a magnetized impact head. At the same time, magnetic recording was possible on the magnetic recording layer on the back surface.

<Preparation Example 4: Magnetic Recording Layer Coating Liquid> A mixture having the following composition was dispersed in a ball mill to prepare a magnetic recording layer coating liquid. Ba-ferrite (coercive force 2700 oersted) 100 parts Styrene-butadiene latex (manufactured by Japan Synthetic Rubber Co., Ltd.) 30 parts Water 200 parts

Comparative Example 5 As a support having a magnetic recording layer, a commercially available high-quality paper (manufactured by Mitsubishi Paper Mills, Diafoam 70K) was coated with a coating solution for the magnetic recording layer having the composition described in Preparation Example 4 at a dry weight of 30 g / m ^2. At a ratio of, magnetic field oriented, dried, super calendar finished,
A magnetic recording layer was provided to obtain a magnetic recording sheet.

Comparative Example 6 The self-coloring pressure-sensitive recording sheet obtained in Comparative Example 1 was coated with the magnetic recording layer coating solution having the composition described in Preparation Example 4 at a dry weight of 30 g / m ^2.
The magnetic recording sheet was obtained by applying the magnetic recording layer at a ratio of 1, 2, magnetic field orientation, drying and super calendering.

Example 3 and Example 1 (A), 2
The recording sheets obtained in (A) and Comparative Examples 1, 2, 5, and 6 were evaluated by the following method in addition to the above-described pressure-sensitive color development 1 test,
The results are shown in Table 3.

<Squareness Ratio> As a test of magnetic recording characteristics, the samples obtained in Examples and Comparative Examples were cut into 5 mm squares, and the maximum magnetization (Mm) and the residual magnetization (Mr) were measured using a vibrating magnetometer. The square ratio (Rs) of the sample was obtained by measurement and the following formula 1. The closer the squareness ratio is to 1, the more ideal the pressure-sensitive magnetic recording sheet.

[0099]

## EQU1 ## Rs = Mr / Mm

<Repeatability 1> As a test of magnetic recording characteristics, the samples obtained in Examples and Comparative Examples were passed through a commercially available reader / writer apparatus 100 times and the maximum magnetization ( The first value of Mm) and 1
The repeating characteristic was evaluated by the ratio (percentage) of the 00th value.

<Repeatability 2> In the examples, printing was carried out by an impact printer having no ink ribbon. Regarding Comparative Example 5, the same printing was performed by an impact printer having an ink ribbon. After printing, the paper was passed through a commercially available reader / writer device 100 times to check for stains on the portion contacted by the paper feed roll. Characteristic 2 is excellent when the print on the paper feed roll portion is readable, and print is not readable on the paper feed roll portion, but when the print is readable on other portions, the characteristic 2 is repeated and the print is not readable at all The case was repeated and the characteristic 2 was judged to be poor.

<Counterfeiting Prevention Property 3> In the examples, printing was carried out by an impact printer having no ink ribbon. Regarding Comparative Example 5, the same printing was performed by an impact printer having an ink ribbon. After printing, magnetic information is written by a commercially available reader / writer, and it is possible to retain both magnetic information and information of the pressure-sensitive color development part, and it is possible to have a high degree of forgery prevention. Those that can be produced, or those that can retain only the pressure-sensitive color development information, were judged to have poor anti-counterfeiting property 3.

[0103]

[Table 3]

Example 4 An adhesive layer (Ricabond AP-37 manufactured by Chuo Rika Kogyo Co., Ltd.) was dried on the back surface (support side) of the pressure sensitive papers (A) to (D) obtained in Example 1 to a dry weight of 20 g / m ^2. Then, the pressure-sensitive color-developing label was prepared by covering the adhesive layer with a commercially available release paper.

Comparative Example 7 As a support having an adhesive layer, a commercially available high-quality paper (made by Mitsubishi Paper Mills, Diafoam 70K) was coated with an adhesive layer (made by Chuo Rika Kogyo, Ricabond AP-37) at a dry weight of 20 g / m ² . And the adhesive layer was covered with a commercially available release paper to give a label.

Comparative Example 8 On the non-coloring surface side of the self-coloring pressure-sensitive recording sheet obtained in Comparative Example 1, an adhesive layer (Ricabond AP-3 manufactured by Chuo Rika Kogyo) was used.
7) was provided so as to have a dry weight of 20 g / m ^2, and the pressure-sensitive color-developing label was prepared by covering the adhesive layer with a commercially available release paper.

The labels obtained in Example 4 and Comparative Examples 7 and 8 were tested by the following evaluation methods in addition to the above pressure-sensitive color development test, and the results are shown in Table 4.

<Pressure-Sensitive Coloring Property 2> One sheet of high-quality paper is sandwiched between the pressure-sensitive coloring labels obtained in Examples and Comparative Examples or the surface (non-release paper side) of the label, and a commercially available dot impact printer is placed on the label. Was used for printing. The color density of the recording sheet was measured by using a Macbeth densitometer. In practical use, the optical density is 0.50 or more, which is sufficient to read even small characters, and the optical density is 0.40.
If it is below the level, 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.

<Adhesive Strength> The pressure-sensitive color-developing label or the release paper of the label obtained in Examples and Comparative Examples was peeled off and adhered to a stainless steel plate, and the adhesive strength was measured by Tensilon by 90 ° peeling. The adhesive strength required for the label is usually 100 gf / 25 mm.

<Counterfeiting Prevention 5> One piece of high-quality paper was sandwiched between the pressure-sensitive color-developing labels obtained in Examples and Comparative Examples or the surface of the label (non-release paper side) to obtain a sample. Printing was performed on the label using a commercially available dot impact printer. After peeling off the release paper and pasting it on the object to be adhered, if the label develops color with a light pressure, it is not possible to make a duplicate of the label by color copying, etc. Therefore, the anti-counterfeit property 5 is excellent, and the case where the label does not develop color and the same label cannot be discriminated by copying the same label by color copying or the like is judged as poor anti-counterfeit property 5.

<Copyability> One sheet of high-quality paper is sandwiched between the pressure-sensitive color-developing labels obtained in Examples and Comparative Examples or the surface (non-release paper surface side) of the label, and a commercially available dot impact printer is used thereon. Printing was performed. When the high-quality paper is peeled off, the label develops the same color as the printing on the high-quality paper, and when the high-quality paper can be used as a copy slip of the label, the copyability is excellent, the label does not develop color, When the other copying method had to be newly used, the copying property was judged to be poor.

[0112]

[Table 4]

Example 5 An adhesive layer (Ricabond A, manufactured by Chuo Rika Kogyo Co., Ltd.) was formed on the surfaces (transparent paper side) of the pressure sensitive papers (A) to (D) obtained in Example 1.
P-37) was provided so as to have a dry weight of 20 g / m ^2, and the pressure-sensitive adhesive layer was covered with a commercially available release paper (the non-release surface was fine paper) to give a transparent pressure-sensitive color developing label.

Comparative Example 9 As a support having an adhesive layer, a commercially available high-quality paper (made by Mitsubishi Paper Mills, Diafoam 70K) was coated with an adhesive layer (made by Chuo Rika Kogyo, Ricabond AP-37) at a dry weight of 20 g / m ² . And the adhesive layer was covered with a commercially available release paper to give a label.

COMPARATIVE EXAMPLE 10 An adhesive layer (Ricabond AP-3, manufactured by Chuo Rika Kogyo Co., Ltd.) was formed on the coloring surface side of the self-coloring pressure-sensitive recording sheet obtained in Comparative Example 1.
7) was provided so as to have a dry weight of 20 g / m ^2, and the adhesive layer was covered with a commercially available release paper to give a transparent pressure-sensitive color developing label.

The labels obtained in Example 5 and Comparative Examples 9 and 10 were tested by the following evaluation methods in addition to the above pressure-sensitive color development test, and the results are shown in Table 5.

<Pressure-sensitive color forming property 3> Printing is performed by using a commercially available dot impact printer having a transparent pressure-sensitive color forming label obtained in Examples and Comparative Examples having an adhesive layer or an ink ribbon on the release paper side of the label. I went. The optical density of the color developed when the release paper was peeled off 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 Adhesion> The transparent pressure-sensitive color-developing label or the release paper of the label obtained in Examples and Comparative Examples was peeled off and adhered to a stainless steel plate, and the adhesive strength was measured by Tensilon by 90 ° peeling. . The adhesive strength required for the label is usually 100 gf / 25 mm.

<Transparent Confirmation> The pressure-sensitive color-developing labels obtained in Examples and Comparative Examples or the release paper side of the label was printed on the label using a commercially available dot impact printer. Peel off the release paper, attach the label to a transparent adherend such as glass or plastic sheet, and if the colored part of the label can be seen through the adherend and the adhesive layer even with small letters, the visibility is excellent. When the colored part of the label can be read normally through the adherend and the adhesive layer, but it is difficult to read with small letters, the transparency confirmation is normal, and when the colored part of the label is difficult to read through the adherend and the adhesive layer. In the case where the see-through confirmation property was poor and the colored portion of the label could not be read at all through the adherend and the adhesive layer, the see-through confirmation property was judged as bad.

<Counterfeit Prevention 6> Printing was performed using a commercially available dot impact printer from the transparent pressure-sensitive color-developing label obtained in Examples and Comparative Examples or from the release paper side of the label. When the release paper is peeled off, the label develops the same color as the printing on the release paper, and the release paper can be used as a copy of the label. When the label cannot be modified, the anti-counterfeiting property 6 is excellent and the label is colored. In other words, it is judged that the anti-counterfeiting property 6 is poor in the case where another copying method must be newly used to make a copy, or the printed content can be modified by simply coloring the label because a copy cannot be made. .

[0121]

[Table 5]

Evaluation: The ink jet / pressure-sensitive color forming recording sheets obtained in Examples 1 (A) to (D) have ink jet suitability and pressure-sensitive color forming on the same surface, and both recording methods are used. By doing so, two types of printing methods are possible. By enabling both inkjet and pressure sensitive recording methods with one recording sheet, the printing method mainly used is for information recording (for example, anti-counterfeiting property 1 Inkjet recording) is used, and the printing method that is not mainly used (forgery prevention 1
The pressure-sensitive recording in 1) can be used complementarily to prevent counterfeiting. Specifically, the amount of money, the date, the seat number, and the like are recorded by inkjet recording on the recording sheet of the present invention printed for tickets. 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. When a simple ink jet recording 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 the authenticity by itself, nor is it suitable for inkjet recording. Therefore, the recording sheet of the present invention, the authenticity determination,
That is, it has anti-counterfeiting properties.

Printing / printing obtained in Examples 2 (A) to (D)
A pressure-sensitive color-developing recording sheet has printability and pressure-sensitive color development on the same surface. By using both recording methods, two types of printing methods are possible. By enabling both recording methods, the printing method mainly used is for information recording (for example, printing in anti-counterfeit property 2), and the printing method not mainly used (pressure-sensitive recording in anti-counterfeit property 2). ) Can be used complementarily to prevent counterfeiting. Specifically, for the ticket, the business name,
In the recording sheet of the present invention on which the amount of money, the date, and anti-counterfeiting micro printing, direct printing, fluorescent printing, etc. are printed, when the ticket is used, a part of the ticket is pressed to develop the pressure sensitive layer. Then, you can confirm that the ticket is genuine. When a printing paper having a simple printing layer is used as in Comparative Example 4, such authenticity determination cannot be performed.

In the magnetic recording / pressure-sensitive color-developing recording sheet of Example 3, the pressure-sensitive recording layer does not need to be repeatedly used by a magnetic recording reader / writer even though it is a pressure-sensitive recording sheet having a self-coloring property. It can be used without any color development. Therefore, the authenticity of the recording sheet can be discriminated by using both the pressure-sensitive color recording and the magnetic recording (counterfeiting prevention property 3). Obviously, such forgery prevention cannot be achieved only by magnetic recording paper and pressure-sensitive coloring paper.

The pressure-sensitive color-developing label obtained in Example 4 can be printed while making a copy (reservation) just by using it together with a high-quality paper. After the label is attached to the adherend, the label develops color with light pressure intelligence, so it is not possible to make a duplicate of the label by color copying, etc., and it is possible to determine the authenticity of the label while it is attached to the adherend and prevent forgery. Highly reliable (anti-counterfeit property 5). It is not possible to confirm by this color development with a simple label, and with a self-coloring pressure-sensitive recording sheet alone, the color is developed with a slight pressure, which is not suitable for general label applications.

The transparent pressure-sensitive color-developing label obtained in Example 5 can be printed while making a copy (copy) only by printing from the back surface of the release paper. The resulting label has a surface having adhesiveness and a surface having color developability in the same direction, so that it is directly attached to a transparent adherend such as a glass or a plastic sheet, and the adherend, an adhesive layer,
Printed records can be read through transparent paper. Since the label color side of this shape is adhered to a non-adhesive, it is difficult to rewrite the color print content, and it is difficult to forge or modify because the release paper also serves as a reserve. A label that does not have a self-coloring pressure-sensitive recording layer cannot be used in such applications because the adhesive surface of the label does not develop color, and it cannot be used as it is on the self-coloring pressure-sensitive recording layer. If a layer is to be provided, there is a problem that the self-coloring pressure-sensitive recording layer causes fog coloration to make it useless, or desensitization does not cause coloration, and thus cannot be used as a color-forming label.

[0127]

INDUSTRIAL APPLICABILITY In the ink-jet / pressure-sensitive color forming recording sheet of the present invention, not only ink-jet recording is possible, but also pressure printing is carried out so that the self-coloring pressure-sensitive recording layer can be colored. The color development can be confirmed through the ink jet recording layer, the polyolefin resin layer and the transparent paper. The inkjet / pressure-sensitive color-developing recording sheet of the present invention is difficult to counterfeit because two recording methods can be used in combination, and can be used as a counterfeit-proof sheet, and thus is used together with the counterfeit-preventive sheet (for example, as a label). It also helps prevent counterfeiting of products. The inkjet of the present invention /
Even if a document or a ticket using the pressure-sensitive color-developing recording sheet is forged, the forgery can be easily detected, for example, by performing pressure-sensitive color development after inkjet recording. 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 an adhesive layer on the transparent paper or on the back of the support. It can be provided as a pressure-sensitive color-developing label.

Further, the series of recording sheets of the present invention have good weather resistance, water resistance, oil resistance, etc. of recording, and since the surface is a transparent paper made of cellulose fiber, it has good affinity with the ink jet recording layer. It is easy to handle, does not cause double feeding due to electrostatic charge peculiar to laminated paper, and is used not only for recording sheets for anti-counterfeiting but also for many applications such as continuous slips, pasting slips, labels, recordings, dust-free recording papers, etc. It has a great industrial significance.

[Brief description of drawings]

FIG. 1 is a sectional view of an inkjet / pressure-sensitive color-developing recording sheet of the present invention.

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

FIG. 3 is a sectional view of a magnetic recording / pressure-sensitive color forming recording sheet of the present invention.

FIG. 4 is a sectional view of the pressure-sensitive color-developing label of the present invention.

FIG. 5 is a cross-sectional view of the transparent pressure-sensitive color-developing label of the present invention.

[Explanation of symbols]

1 support 2 Self-coloring pressure-sensitive recording layer 3 Polyolefin resin layer 4 Transparent or translucent paper 5 Inkjet recording layer 6 Inkjet / pressure-sensitive color forming recording sheet 7 Pigment coating layer for printing 8 Printing / pressure sensitive color recording sheet 9 Magnetic recording layer 10 Magnetic recording / pressure-sensitive coloring sheet 11 Adhesive layer 12 Pressure-sensitive coloring label 13 Release paper 14 Peeling surface 15 Transparent type pressure-sensitive color-developing label

─────────────────────────────────────────────────── --Continued from the front page (56) Reference JP-A-6-155897 (JP, A) JP-A-6-171213 (JP, A) JP-A-6-171212 (JP, A) JP-A-4- 363289 (JP, A) JP 5-286229 (JP, A) JP 8-300810 (JP, A) JP 8-52938 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) B41M 5/00 B41M 5/124

Claims (6)

(57) [Claims] 1. A self-coloring pressure-sensitive recording layer (hereinafter referred to simply as "self-coloring pressure-sensitive recording") in which at least one of a support, a color-developer and a color-developing agent is microencapsulated, and each is laminated or mixed individually. Layer), a polyolefin resin layer, transparent or translucent paper with a transparency of 26% or more,
An inkjet / pressure-sensitive color-developing recording sheet obtained by sequentially stacking an ink-receiving layer for ink-jet recording (hereinafter, simply ink-receiving layer). 2. A support, a self-coloring pressure-sensitive recording layer,
A printing / pressure-sensitive color recording sheet comprising a polyolefin resin layer, transparent or semi-transparent paper having a transparency of 26% or more, and a pigment coating layer for printing, which are sequentially laminated. 3. A support, a self-coloring pressure-sensitive recording layer,
A magnetic recording / pressure-sensitive color-developing recording sheet comprising a polyolefin resin layer and a transparent or semi-transparent paper having a transparency of 26% or more laminated in this order, and a magnetic recording layer provided on the surface opposite to the support. . 4. A support, a self-coloring pressure-sensitive recording layer,
A pressure-sensitive color-developing label having copyability, comprising a polyolefin resin layer and a transparent or translucent paper having a transparency of 26% or more, which are sequentially laminated, and an adhesive layer provided on the surface opposite to the support. 5. A support, a self-coloring pressure-sensitive recording layer,
A transparent pressure-sensitive color-developing label having a copying property, which is formed by sequentially laminating a polyolefin resin layer, transparent or semi-transparent paper having a transparency of 26% or more, and an adhesive layer. 6. An anti-counterfeit paper comprising the recording sheet according to any one of claims 1 to 5 and capable of performing forgery prevention or forgery detection by pressure-sensitive color development.