JPH10268772A - Sheet and adhesive label for prevention against forgery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the sheet and adhesive label for forgery prevention which disables illegal acts by forming a single layer, containing both self-coloring type pressure-sensitive coloring compositions of leuco-based heat-sensitive recording dye and a developer, and at least one of a coloring agent and the developer in microcapsules, on one surface of a base. SOLUTION: On one surface of the base 6, the heat-sensitive and pressure- sensitive mixed coloring layer 1 (i.e., organic solvent coloring layer 4) is laminated to obtain the forgery preventive sheet 9 and on the reverse surface (the other surface of the base 6) of the forgery preventive sheet 9, an adhesive layer 7 and a peeling sheet 8 are laminate din order to obtain the adhesive label 10 for forgery prevention. This constitution makes the organic solvent coloring layer colors when the label tries to be peeled by using an organic solvent such as a lalbel peeler, and then a print layer is dissolved with the organic solvent to flow out and leaves traces of the use of the organic solvent, so the peeling of the label or the removal of a seal impression can distinctively be detected.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anti-counterfeit sheet and an anti-counterfeit pressure-sensitive adhesive label, and more particularly to the prevention of improper reuse of a label.

[0002]

2. Description of the Related Art In recent years, an adhesive label for sealing has often been used for the purpose of certifying goods, sealing, and the like. However, there has been a large number of unfair acts of removing the sealing label once, modifying the contents, or replacing the contents, and then sealing again with the same label. In stamps and tickets, a means (so-called postmark or check mark) indicating that the stamp ink is in use or has been used by stamping the date with a stamp is used. Forgery, which is illegally reused after the removal, has become a problem. In order to prevent such unjust label re-attachment and reuse, between the transparent film material and the transparent adhesive layer, by interposing a transparent in-layer release resin layer,
If the label is intentionally peeled off, the peelable resin layer in the layer remains on the adherend as a hidden character, and even if the label is reattached, the hidden character remaining on the adherend and the missing character on the label side exactly overlap. In addition, a method (Japanese Patent Application Laid-Open No. 62-135879) has been disclosed in which it is possible to confirm that an act of peeling has been performed. However, by impregnating the pressure-sensitive adhesive layer of the label with a specific organic solvent and floating the entire pressure-sensitive adhesive layer from the adherend, without revealing hidden characters in the label, peeling off the label and attaching the label again As a result, there has been a problem that the label is re-attached without the third party realizing the history of peeling off the label.

[0003] As another method, a lower layer label having a film substrate and an adhesive and having a cut line, and an upper layer label having an adhesive on a fragile film substrate are laminated in two layers, and the label is peeled off. In this case, a method (Japanese Patent Laid-Open No. 1-2277) discloses that a label is destroyed by fragility. However, also in this method, if the adhesive layer is carefully impregnated with a specific organic solvent and peeled off, it is possible to peel off the label without breaking it, and the manufacturing process is complicated or difficult to handle, It has drawbacks such as the label may be unnecessarily destroyed during handling.

As means for preventing label forgery, various means have been proposed, such as a method of performing hidden printing, a method of using a hologram, a method of using ultraviolet light-emitting ink, and a method of using magnetic recording. However, it cannot cope with the act of once peeling off and re-attaching the label.

[0005]

SUMMARY OF THE INVENTION In view of such circumstances, the present invention provides a method for removing a stamp ink using an organic solvent or removing a label using an organic solvent. An object of the present invention is to provide an anti-counterfeiting sheet and an adhesive label using the same, which make it impossible to use the same label again because an imprint remains.

Also, in order to prevent the same label from being re-attached to another counterfeit label, an anti-counterfeit sheet which can be easily authenticated and an adhesive sheet using the same are provided. It is intended to provide labels.

[0007] Solvents used for peeling labels on the market include a wide range from hydrocarbon non-polar solvents such as mineral spirits to polar solvents such as esters and alcohols. Further, the label can be peeled off with a solvent such as benzene or alcohol without using a commercially available seal peeling. When peeling off the label, the pressure-sensitive adhesive layer may be softened by auxiliary heating with a drier or the like.

[0008]

Means for Solving the Problems The present inventors usually try to remove the stamp ink stamped on the label surface with an organic solvent, which is usually colorless or pale, or remove the label with a commercially available label peeling or organic solvent. We thought that it would be sufficient to provide a layer that developed color when label peeling (organic solvent) was applied in order to peel it, and the use history of the organic solvent became clear.

The layer which is usually colorless or light-colored when an organic solvent is applied is generally composed of a leuco-based thermosensitive recording dye and a component used as a developer, ie, a colorless or light-colored basic dye as a color former. A layer containing an inorganic or organic acidic substance as a color developer is preferable, and when an attempt is made to heat the pressure-sensitive adhesive layer as an auxiliary means, heat-sensitive coloring also occurs. We thought that we could confirm clearly.

However, a problem here is that, in the case of a combination of a leuco-based thermosensitive coloring dye and a developer, coloring may not occur with a certain non-polar organic solvent. Therefore, the leuco-based heat-sensitive recording dye and developer are used in combination with a self-coloring type pressure-sensitive coloring composition in which at least one of the color former or the developer is microencapsulated (mixed to form a single layer, (Or separately laminated), surprisingly, for no apparent reason, it has been found that even a nonpolar solvent which does not originally form a color produces a trace of coloring.

Further, by further laminating a printing layer made of an ink containing a dye soluble in an organic solvent, the ink dissolves and flows out of the printing layer when an organic solvent is applied.
We thought that the traces of trying to remove the label would be clear.

On the other hand, in order to easily determine the authenticity of the forgery-preventing sheet or the forgery-preventing pressure-sensitive adhesive label, the self-coloring pressure-sensitive coloring composition using the self-coloring type pressure-sensitive coloring composition is particularly effective.
It was thought that it was possible to easily determine the authenticity by using this (a counterfeit if no coloring occurred). As a result of intensive studies from such a viewpoint, the following inventions have been completed.

A self-coloring type pressure-sensitive coloring composition comprising: A) a leuco dye for thermal recording and a color developer, and B) at least one of a color former or a color developer on one side of the support. A forgery prevention sheet comprising a single layer containing both of the above.

At least one of a leuco-based thermosensitive recording dye / color developer layer, a color former or a color developer is microencapsulated on one side of the support, and each layer is independently laminated or mixed to form a single layer of self-coloring. An anti-counterfeit sheet formed by sequentially laminating a type pressure-sensitive coloring layer.

At least one of a color former and a developer is microencapsulated on one side of the support, and each of them is laminated or mixed alone to form a single-layer self-coloring type pressure-sensitive coloring layer, a leuco-based thermosensitive recording dye. / Color developing agent layer in order.

A self-coloring type pressure-sensitive coloring composition comprising microencapsulated A) a leuco dye for thermal recording and a color developer on one side of a support; and B) a color former or a color developer. Are laminated in a single layer or separately laminated, and further provided with a printing layer of an ink composition containing an organic solvent-soluble dye.

An anti-counterfeit pressure-sensitive adhesive label comprising a pressure-sensitive adhesive layer and a release sheet sequentially laminated on another side of the support of the anti-counterfeit sheet.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The anti-counterfeit sheet of the present invention is obtained by microencapsulating a leuco-based thermosensitive recording dye and a developer and at least one of a color former and a developer on one surface of a support. A self-coloring type pressure-sensitive coloring composition can be obtained by mixing and forming a single layer or separately laminating. Further, by providing a printing layer of an ink containing an organic solvent-soluble dye on the coating layer side of the anti-counterfeit sheet obtained in this manner, a anti-counterfeit sheet with further improved anti-counterfeit performance can be obtained. Hereinafter, for convenience, a leuco-based heat-sensitive recording dye and a developer, and a self-coloring pressure-sensitive coloring composition in which at least one of the color former or the developer is microencapsulated, are provided as a mixture. The layer is a heat-sensitive and pressure-sensitive mixed color-forming layer, and the leuco-based heat-sensitive recording layer when separately laminated The dye / developer layer is microencapsulated with at least one of a leuco-based thermosensitive color-forming layer, a color former or a color developer, respectively. A single layer of the self-coloring type pressure-sensitive coloring layer, which is laminated or mixed alone, is referred to as a self-coloring type pressure-sensitive coloring layer. Also, a heat-sensitive pressure-sensitive mixed coloring layer,
The organic solvent coloring layer is a generic term for the laminated leuco-based thermosensitive coloring layer and the self-coloring type pressure-sensitive coloring layer (in any order of lamination).

The configuration of the present invention will be described with reference to the drawings.
FIG. 1 shows a self-coloring type pressure-sensitive coloring composition in which A) a leuco-based thermosensitive recording dye and a color developer, and B) at least one of a color former and a color developer are microencapsulated on one surface of a support. And a forgery prevention sheet in which a layer containing both (thermosensitive and pressure-sensitive mixed coloring layer) is provided as a single layer, and an anti-counterfeiting sheet in which an adhesive layer and a release sheet are sequentially laminated on another side of the support. It is sectional drawing of an adhesive label. The heat-sensitive and pressure-sensitive mixed color-forming layer 1 (that is, the organic solvent color-forming layer 4) is laminated on one side of the support 6 to obtain a forgery prevention sheet 9, and the back surface of the forgery prevention sheet 9 (another side of the support 6) 2), the pressure-sensitive adhesive layer 7 and the release sheet 8 are sequentially laminated to obtain the forgery prevention pressure-sensitive adhesive label 10.

FIG. 2 shows that at least one of a leuco-based thermosensitive recording dye / developer layer (leuco-based thermosensitive coloring layer), a color former or a developer is microencapsulated on one surface of the support, and each of them is used alone. An anti-counterfeit sheet formed by sequentially laminating or mixing a single layer of a self-coloring type pressure-sensitive coloring layer (self-coloring type pressure-sensitive coloring layer), and an adhesive layer on another surface of the support. It is sectional drawing of the forgery prevention adhesive label which laminates a peeling sheet sequentially. On one surface of the support 6, the leuco-based heat-sensitive coloring layer 3 and the self-coloring type pressure-sensitive coloring layer 2 are sequentially laminated (that is, the organic solvent coloring layer 4) to obtain a forgery prevention sheet 9. The pressure-sensitive adhesive layer 7 and the release sheet 8 are sequentially laminated on the back surface (another surface of the support 6) to obtain the anti-counterfeit pressure-sensitive adhesive label 10.

FIG. 3 shows that at least one of a color former and a developer is microencapsulated on one side of a support, and each of them is laminated or mixed alone to form a single layer of a self-coloring type pressure-sensitive coloring layer (self-coloring layer). Pressure-sensitive coloring layer), a leuco-based thermosensitive coloring dye / a color developer layer (leuco-based thermosensitive coloring layer), a forgery prevention sheet, and an adhesive layer on another side of the support. It is sectional drawing of the forgery prevention adhesive label which laminates a sheet sequentially. On one surface of the support 6, the self-coloring type pressure-sensitive coloring layer 2 and the leuco-based thermosensitive coloring layer 3 are sequentially laminated (that is, the organic solvent coloring layer 4) to obtain a forgery prevention sheet 9; The pressure-sensitive adhesive layer 7 and the release sheet 8 are sequentially laminated on the back surface (another surface of the support 6) to obtain the anti-counterfeit pressure-sensitive adhesive label 10.

FIG. 4 shows a self-coloring type pressure-sensitive type in which at least one of A) a leuco dye for thermal recording and a color developer, and B) a color former or a color developer is microencapsulated on one surface of the support. An anti-counterfeit sheet in which a layer containing both a color-forming composition (a heat-sensitive and pressure-sensitive mixed color-forming layer) is further provided with a printing layer of an ink composition containing an organic solvent-soluble dye, and another side of the support FIG. 3 is a sectional view of a forgery-preventive pressure-sensitive adhesive label formed by sequentially laminating a pressure-sensitive adhesive layer and a release sheet. On one surface of the support 6, a heat-sensitive and pressure-sensitive mixed color-forming layer 1 (that is, an organic solvent color-forming layer 4) is laminated, and a printing layer 5 made of an ink composition containing an organic solvent-soluble dye is further laminated thereon to forge. The anti-counterfeit sheet 9 is obtained, and the anti-counterfeit pressure-sensitive adhesive label 10 is obtained by sequentially laminating the pressure-sensitive adhesive layer 7 and the release sheet 8 on the back surface of the anti-counterfeit sheet 9 (another side of the support 6).

FIG. 5 shows that at least one of a leuco-based thermosensitive recording dye / developer layer (leuco-based thermosensitive color-developing layer), a color former or a developer is microencapsulated on one surface of the support, and each of them is used alone. A single layer of self-coloring type pressure-sensitive coloring layer (self-coloring type pressure-sensitive coloring layer) by laminating or mixing in order, and further providing a printing layer of an ink composition containing an organic solvent-soluble dye. FIG. 3 is a cross-sectional view of an anti-counterfeit pressure-sensitive adhesive label formed by sequentially laminating an adhesive sheet and a release sheet on another side of the support sheet and the support. A leuco-based heat-sensitive coloring layer 3 and a self-coloring type pressure-sensitive coloring layer 2 are provided on one side of a support 6.
Are sequentially laminated (that is, an organic solvent coloring layer 4), and a printing layer 5 made of an ink composition containing an organic solvent-soluble dye is formed thereon.
Is further laminated to obtain a forgery prevention sheet 9, and an adhesive layer 7 is provided on the back surface of the forgery prevention sheet 9 (another side of the support 6).
And release sheet 8 are sequentially laminated to prevent forgery-preventive adhesive label 10
Is obtained.

FIG. 6 shows that at least one of a color former and a developer is microencapsulated on one side of the support, and each of them is laminated or mixed alone to form a single layer of a self-coloring type pressure-sensitive coloring layer (self-coloring layer). Type pressure-sensitive coloring layer), a leuco-based thermosensitive coloring dye / a color developer layer (leuco-based thermosensitive coloring layer), and a printing layer of an ink composition containing a dye dissolved in an organic solvent is provided. FIG. 4 is a cross-sectional view of a forgery prevention pressure-sensitive adhesive label in which a pressure-sensitive adhesive layer and a release sheet are sequentially laminated on a sheet and another surface of the support. A self-coloring type pressure-sensitive coloring layer 2 and a leuco-based thermosensitive coloring layer 3 are sequentially laminated on one surface of a support 6 (that is, an organic solvent coloring layer 4), and an ink composition containing an organic solvent-soluble dye is formed thereon. The forgery prevention sheet 9 is obtained by further laminating the printing layer 5, and the pressure-sensitive adhesive layer 7 and the release sheet 8 are sequentially laminated on the back surface of the forgery prevention sheet 9 (another surface of the support 6) to thereby prevent the forgery prevention adhesive. The label 10 is obtained.

The support in the present invention is not particularly limited as long as it is generally used as a printing paper or a printing sheet. Examples of the support include glassine paper, woodfree paper,
Paper such as art paper, coated paper, cast paper, tracing paper, mica paper, glass paper, etc. can be used, and wood pulp, synthetic pulp, fillers, sizing agents, paper strength agents, dyes, etc. The raw materials used can be used as needed. Also, polyethylene terephthalate, polybutylene terephthalate,
Polyester such as polyethylene naphthalate, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyethylene, polypropylene, polyvinyl alcohol, ethylene and vinyl alcohol copolymer, ethylene and vinyl acetate copolymer, aliphatic or aromatic polyamide (nylon and aramid) ), Polyimide, polycarbonate, polyurethane, fluororesin, polyacrylonitrile, TP
X, polybutene, polyarylate, polyetheretherketone, polysulfone, polyethersulfone,
Polyetherimide, polyphenylene sulfide, polyphenylene ether, polyacetal, cellophane,
Ionomer, or synthetic resin film obtained by compounding them by copolymerization, coextrusion, coating, blending, etc., or nonwoven fabric, woven fabric, synthetic paper, synthetic resin made of synthetic fiber, natural fiber, pulp fiber, glass fiber, etc. Can be arbitrarily used according to the purpose, a laminated paper obtained by laminating on one side or both sides on paper, a metal foil, or a composite sheet obtained by combining these. Synthetic resins can be made opaque with inorganic or organic pigments.

In the present invention, the leuco-based heat-sensitive recording dye and the color developer are a combination of a colorless or light-colored basic dye as a color former and an inorganic or organic acidic substance as a color developer. Used for thermal recording media such as thermal paper,
It is usually colorless and develops color when an organic solvent is applied or when heated. As described above, the heat-sensitive and pressure-sensitive mixed coloring layer may be used, or the self-coloring and pressure-sensitive coloring layer may be separately laminated.

Here, examples of the colorless or pale-colored basic dye serving as a color former include the following, but are not particularly limited thereto.

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-methylindol-3-yl) phthalide, 3,3
-Bis (1,2-dimethylindol-3-yl) -5
-Dimethylaminophthalide, 3,3-bis (9-ethylcarbazol-3-yl) -6-dimethylaminophthalide, 3,3-bis (2-phenylindol-3-yl) -6 Dimethylaminophthalide, 3-p-dimethylaminophenyl-3- (1-methylpyrrol-3-yl) -6-dimethylaminophthalide, 3-p-dimethylaminophenyl-3- (1-methylpyrrole- 2-yl) -6-dimethylaminophthalide, 3- (p-dimethylaminophenyl) -3- (2-methylindole-3
-Yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-phenylindol-3-yl) phthalide, 3,3-bis (1,2-dimethylindole-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)-
Triallylmethane dyes such as 5-dimethylaminophthalide.

4,4'-bis-dimethylaminophenylbenzhydryl benzyl ether, 4,4'-bis-dimethylaminobenzhydrylbenzyl ether, N-halophenylleuco auramine, N-2,4, Diphenylmethane dyes such as 5-trichlorophenylleuco auramine.

Thiazine dyes such as benzoyl leucomethylene blue and p-nitrobenzoyl leucomethylene blue;

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

Rhodamine B-anilinolactam, rhodamine B (p-nitroanilino) lactam, rhodamine B
(O-chloroanilino) lactam, rhodamine B (p-
Lactam dyes such as chloroanilino) lactam.

3-diethylamino-7-dibenzylaminofluoran, 3-dimethylamino-7-dibenzylaminofluoran, 3-diethylamino-7-octylaminofluoran, 3-diethylamino-7-phenylfluoran, 3 -Dimethylamino-7-methoxyfluorane, 3-diethylamino-7-N-diethylaminofluoran, 3-diethylamino-7-methoxyfluoran, 3-diethylamino-6-methoxyfluoran, 3
-Diethylamino-6-methyl-7-chlorofluoran, 3-diethylamino-7-chlorofluoran, 3-
Diethylamino-6-chloro-7-methylfluoran,
3-diethylamino-7- (3,4-dichloroanilino) fluoran, 3-diethylamino-7- (2-chloroanilino) fluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3-diethylamino-
6-methyl-7-phenylaminofluoran, 3-diethylamino-6,7-dimethylfluoran, 3- (N-
Ethyl-N-tolyl) amino-6-methyl-7-anilinofluoran, 3-piperidino-6-methyl-7-anilinofluoran, 3- (N-ethyl-N-tolyl) amino-6-methyl -7-phenethylfluoran, 3-diethylamino-7- (4-nitroanilino) fluoran,
3-dibutylamino-6-methyl-7-anilinofluoran, 3- (N-methyl-N-propyl) amino-6
Methyl-7-anilinofluoran, 3- (N-ethyl-
p-Toluidino) -7-methylfluoran, 3- (N-
Ethyl-p-toluidino) -6-methyl-7-phenylaminofluoran, 3- (N-ethyl-p-toluidino) -6-methyl-7- (p-toluidino) fluoran, 3-diethylamino-7- ( 2-carbomethoxy-
Phenylamino) fluoran, 3-diethylamino-7
-N-acetyl-N-methylaminofluoran, 3-
(N-ethyl-N-isoamyl) amino-6-methyl-
7-anilinofluoran, 3-diethylamino-7-N
-Chloroethyl-N-methylaminofluoran, 3-diethylamino-7-methyl-N-benzylaminofluoran, 3-diethylamino-7-N-methylaminofluoran, 3- (N-methyl-N-cyclohexyl) amino -6-methyl-7-anilinofluoran, 3- (N-
Ethyl-N-iso-amylamino) -6-methyl-7-
Phenylaminofluoran, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-phenylaminofluoran, 3- (N-ethyl-N-tetrahydrofuryl) amino-6-methyl-7-ani Linofluoran,
3-piperidino-6-methyl-7-phenylaminofluoran, 3-pyrrolidino-6-methyl-7-phenylaminofluoran, 3-diethylamino-6-methyl-7
-Xylidinofluoran, 3-diethylamino-7-
Fluorane dyes such as (o-chlorophenylamino) fluoran, 3-dibutylamino-7- (o-chlorophenylamino) fluoran, and 3-pyrrolidino-6-methyl-7-p-butylphenylamino fluoran;

These can be used alone or as a mixture.

As the inorganic or organic acidic substance (developing agent), an electron-accepting substance generally used for a thermosensitive recording medium is used. In particular, a phenol derivative, an aromatic carboxylic acid derivative or its metal compound, N, N'-diarylthiourea derivatives, mixtures of organic acids and metal compounds, acidic polymers (e.g., phenol and formaldehyde resins, salicylic acid resins or their zinc, magnesium, aluminum, calcium, titanium, manganese, tin, nickel, etc.) And phenol derivatives, aromatic carboxylic acid derivatives or metal compounds thereof, and N, N'-diarylthiourea derivatives.

Among them, particularly preferred are phenol derivatives, aromatic carboxylic acids and phenolic compounds thereof, and specifically, 1,1-bis (p-hydroxyphenyl) propane and 2,2-bis (p -Hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,
5-dichlorophenyl) propane, 2,2-bis (p-
(Hydroxyphenyl) butane, 1,1-bis (p-hydroxyphenyl) hexane, 2,2-bis (p-hydroxyphenyl) hexane, 1,1-bis (p-hydroxyphenyl) -2-ethyl-hexane, bisphenol Sulfone, bis (3-allyl-4-hydroxyphenyl) sulfone, 4-hydroxy-4'-isopropyloxydiphenylsulfone, 2,4'-dihydroxydiphenylsulfone, 3,4-dihydroxy-4'-
Methyl diphenyl sulfone, diphenol ether,
p-hydroxybenzoic acid, ethyl p-hydroxybenzoate, propyl p-hydroxybenzoate, butyl p-hydroxybenzoate, octyl p-hydroxybenzoate, p
Benzyl hydroxybenzoate, p-tert-butylbenzoic acid, trichlorobenzoic acid, 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-butylidenediphenol, 4-phenylphenol, 4-octylphenol, 4,4'-isopropylidenediphenol, 2,2'-methylenebis (4-chlorophenol), hydroquinone, 4,4'-
Examples include phenolic compounds such as cyclohexylidene diphenol, dimethyl 4-hydroxyphthalate, hydroquinone monobenzyl ether, novolak type phenol resin, and phenol polymer. These can be used alone or as a mixture.

The ratio of the color former to the developer is 0.25 to 15 parts by weight, especially 0.5 to 15 parts by weight, per 1 part by weight of the color former.
It is preferable to use 10 parts by weight.

Further, in order to improve the sensitivity of the leuco-based thermosensitive coloring layer, as sensitizers, waxes such as N-hydroxymethylstearic amide, stearic amide, palmitic amide, and 2-benzyloxynaphthalene. Naphthol derivative, p-benzylbiphenyl, 4
Biphenyl derivatives such as allyloxybiphenyl,
1,2-bis (3-methylphenoxy) ethane, 2,
Polyether compounds such as 2'-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.

The self-coloring type pressure-sensitive coloring composition of the present invention is a component that is usually colorless and develops a color when pressurized, such as is generally used for a self-coloring type pressure-sensitive recording medium such as a self-coloring type pressure-sensitive recording paper. It is. The color former or developer in which at least one of the main components is microencapsulated may be laminated alone or mixed to form a single layer.

The technique relating to the color former and the developer for pressure-sensitive recording is not particularly limited, and conventionally known techniques can be used. For example, a method of microencapsulation, a wall material for microcapsules, a dye for pressure-sensitive recording or an oil dissolving the dye, or a developer for pressure-sensitive recording, a polymer binder (binder), a protective agent for microcapsules, etc. is there.

Examples of the microencapsulation method include a coacervation method (US Pat. No. 2,800,458), an interfacial polymerization method (Japanese Patent Publication No. 47-1763, etc.), and an in-situ polymerization method (JP-A-51-9079). Gazettes) can be used.

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

The color former and the developer used in the self-coloring type pressure-sensitive coloring layer (composition) used in the present invention are not particularly limited as long as they are generally used in pressure-sensitive recording materials. For example, as the coloring agent, the same dyes as described in the description of the leuco-based thermal recording dye, that is, triallylmethane-based dye, diphenylmethane-based dye, thiazine-based dye, spiro-based dye, lactam-based dye, and fluoran-based dye can be used. One or more dyes can be used.

In the self-coloring type pressure-sensitive coloring composition, oils which dissolve a color former or a developer and become an internal phase oil of the microcapsules include diarylalkanes, alkylnaphthalenes, alkylated biphenyls, hydrogenated Aromatic synthetic oils such as terphenyl, aliphatic synthetic oils such as kerosene, naphtha, paraffin oil and chlorinated paraffin, vegetable oils such as cottonseed oil, coconut oil, soybean oil, and linseed oil can be used.

Examples of the color developing agent in the self-coloring type pressure-sensitive coloring composition include clays (for example, activated clay, acid clay, attapulgite, bentonite, colloidal silica, aluminum silicate, etc.), novolak-type phenol resins and polyvalent thereof. Metal salts, salicylic acid derivatives or polyvalent metal salts thereof, salicylic acid resins or polyvalent metal salts thereof, mixtures of organic acids and metal compounds, formaldehyde resins or polyvalent metal salts thereof, and the like can be used. The difference from the developer used for the leuco-based heat-sensitive coloring layer is mainly that it is generally of a higher molecular weight than the heat-sensitive developer, and has higher solubility in oils forming the microcapsule inner layer oil. Or that the oils have a high reactivity with a color former in a system using the solvent as a solvent or a dispersion medium.

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

Calcium oxide, calcium hydroxide, calcium carbonate, calcium silicate, talc, silica, clay, barium sulfate are used for the purpose of increasing the pressure-sensitive coloring density and absorbing the inner layer oil when the microcapsules are broken (color developing). ,
Magnesium carbonate, magnesium silicate, magnesium hydroxide, lead sulfate, lead white, zinc white, zinc sulfide, titanium oxide, satin white, antimony oxide, mica, bentonite,
Plaster, aluminum hydroxide, inorganic pigments such as aluminum silicate, or polystyrene, polyvinyl toluene,
Finely divided organic pigments such as styrene and divinylbenzene copolymer, polymethyl methacrylate, urea / formalin resin, melamine / formalin resin, benzoguanamine, polyethylene, etc. are put in the self-coloring type pressure-sensitive coloring layer or the heat-sensitive pressure-sensitive mixed coloring layer. There is no problem with dispersion.

As the polymer binder (binder) used for forming the organic solvent coloring layer of the present invention, a known water-based adhesive polymer (that is, a water-soluble or emulsion or latex form) can be used. For example, the following can be used alone or in combination, but are not limited thereto.

Starches such as starch, oxidized starch, esterified starch, hydroxyethylated starch, acetylated starch, cationized starch, dextrin, cellulose derivatives such as methylcellulose, ethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, casein, gelatin, etc. Protein, agar, xanthan gum, pullulan, chitosan, star gum, guar gum, gum arabic, tragacanth gum, natural polymer polysaccharides such as alginic acid derivatives, polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, polyacrylic acid,
Polyacrylates such as sodium polyacrylate, polyacrylates, polyacrylamide, acrylamide / acrylate copolymer, acrylamide / acrylate / methacrylic acid terpolymer, isobutylene / maleic anhydride copolymer Copolymer, styrene / maleic anhydride copolymer and its alkali salt, ethylene / maleic anhydride copolymer alkali salt, styrene / acrylic acid copolymer, polyvinyl acetate, polyurethane, styrene / butadiene copolymer, acrylonitrile / Butadiene copolymer, methyl acrylate / butadiene copolymer,
Vinyl acetate / acrylic acid (ester) copolymer, acrylonitrile / butadiene / acrylic acid copolymer, ethylene / vinyl acetate copolymer, vinylidene chloride, polychloroprene, organopolysiloxane, polyethylene, etc.

In the organic solvent coloring layer of the present invention, if necessary, pigments, water-proofing agents, defoamers, surfactants, waxes, metal soaps, dispersants, fluorescent dyes, ultraviolet absorbers, antioxidants An agent, a background antifoggant, an antistatic agent, a thickener, a preservative, a release agent, a lubricant, an anti-blocking agent, or the like may be appropriately added as an auxiliary.

In order to obtain a high color density, a single layer or a plurality of undercoat layers made of a pigment or a resin may be provided between the support of the present invention and the organic solvent color layer. In order to protect the layer, an overcoat layer may be provided as long as it does not hinder the color development when applying an organic solvent.

The coating amount of the heat-sensitive and pressure-sensitive mixed color-forming layer is suitably from ² to 30 g / m ^{2 in} solid content. Leuco-based thermosensitive coloring layer,
And the coating amount of the self-coloring type pressure-sensitive coloring layer is 1 to 2 in solid content.
0 g / m ² is appropriate. The solid weight ratio of the heat-sensitive coloring component to the pressure-sensitive coloring component in the heat-sensitive and pressure-sensitive mixed coloring layer, and the coating dry weight ratio of the leuco-based heat-sensitive coloring layer and the self-coloring type pressure-sensitive coloring layer when separately laminated are 20. / 80 to 80/20 is appropriate.

In the present invention, the method of applying the organic solvent coloring layer includes a gravure coater, a gravure offset coater, a bar coater, a roll coater, an air knife coater, a U comma coater, an AKKU coater, a smoothing coater, a microgravure coater, and a reverse coater. Roll coater, 4 or 5 rolls (multistage) roll coater, curtain coater, blade coater, dip coater, drop curtain coater, slide coater, lip coater, die coater, squeeze coater, short dwell coater, size press, spray, etc. The device can be used on-machine or off-machine.

The ink composition of the present invention to be printed on the organic solvent coloring layer coated on one side of the support contains at least an organic solvent-soluble dye, and other components include:
Components similar to those used in ordinary printing inks (ie,
Vehicles, pigments, auxiliaries, etc.).

As the organic solvent-soluble dye, for example, “12996 Chemical Product” published by Chemical Daily Co., Ltd.
The organic solvent-soluble dyes described in (1) are used. These dyes are water-insoluble and are soluble in mineral oils, essential oils, fats, fatty acids, waxes, and many other organic solvents, and are used for coloring gasoline identification, candles, soap, shoe polish, and plastics. .

Specifically, most of them belong to azo dyes having an amino group and a hydroxyl group which do not contain a hydrophilic group because of their chemical structure, and fatty acid salts of anthraquinone dyes and basic dyes are also oil-soluble. Belongs to this. C. I. Solvent Yellow5, Solvent
Yellow6, Solvent Yellow3
3, Solvent Yellow44, Solven
t Yellow93, Solvent Yellow
114, Solvent Yellow 116, Sol
vent Blue35, Solvent Blue6
3, Solvent Blue83, Solvent
Blue105, Solvent Red23, Sol
vent Red111, Solvent Red13
5, Solvent Red146, Solvent
Red179, Solvent Red180, Sol
vent Orange2, Solvent Orange
ge7, Solvent Orange80, Solv
ent Orange 87, Solvent Viol
et13, Solvent Violet36, Sol
vent Green 3, and the like, but are not limited to these compounds.

The oils constituting the vehicle include, for example, mineral oil (volatile oil, kerosene, light oil, machine oil, etc.), vegetable oil (linseed oil, tung oil, soybean oil, etc.), synthetic dry oil (dehydrated castor oil, Maleated oil, styrenated oil, vinyltoluene oil, etc.).

Examples of the solvent constituting the vehicle include high boiling petroleum solvents having a temperature of 200 ° C. or higher, higher fatty acid esters, higher alcohols, and glycol solvents.
In the case of non-evaporation drying type ink such as osmotic drying or oxidative polymerization, or methanol, ethanol, n-propyl alcohol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, methyl acetate, ethyl acetate, butyl acetate, methyl isobutyl ketone, cyclohexane , Toluene, xylene, hexane, ligroin, etc.
(In the case of evaporative drying type ink).

As a binder such as a resin constituting the vehicle, for example, rosin, polymerized rosin, cured rosin,
Rosin ester, maleic acid resin, modified maleic acid resin, phenolic resin, modified phenolic resin, alkyd resin, modified alkyd resin, petroleum resin, hydrogenated petroleum resin, polyamide resin, vinyl resin, acrylic resin, nitrocellulose, ethyl cellulose, Modified amino resin, shellac, rubber derivative, drying oil varnish, and the like.

When an ultraviolet / electron beam curable ink is used, (meth) acrylate-based, vinyl-based, unsaturated polyester / styrene-based monomers may be used as vehicle components.
Oligomers and prepolymers are used. For example, the following compounds may be mentioned.

(1) Poly (meth) acrylate of aliphatic, alicyclic, aromatic, araliphatic polyhydric alcohol and polyalkylene glycol (2) Aliphatic, alicyclic, aromatic, araliphatic Poly (meth) acrylate of polyhydric alcohol obtained by adding alkylene oxide to polyhydric alcohol (3) Polyester poly (meth) acrylate (4) Polyurethane poly (meth) acrylate (5) Epoxy poly (meth) acrylate (6) Polyamide Poly (meth) acrylate (7) poly (meth) acryloyloxyalkyl phosphate ester (8) vinyl- or diene-based compound having (meth) acryloyloxy group at the side chain or terminal (9) monofunctional (meth) acrylate , (Meth) acryloyl compound (10) rosin ester (meth) acrylate ( 11) Cyano compounds having an ethylenically unsaturated bond (12) Mono- or polycarboxylic acids having an ethylenically unsaturated bond and their alkali metal salts, ammonium salts, amine salts, etc. (13) Ethylenically unsaturated (meth) Acrylamide or alkyl-substituted (meth) acrylamide and its multimer (14) Vinyl lactam and polyvinyl lactam compound (15) Polyether having an ethylenically unsaturated bond and its ester (16) Ester of an alcohol having an ethylenically unsaturated bond ( 17) Polyalcohol having an ethylenically unsaturated bond and its ester (18) Aromatic compound having one or more ethylenically unsaturated bonds such as styrene and divinylbenzene (19) Side chain of (meth) acryloyloxy group or Pos at the end Organosiloxane-based compound (20) Silicone compound having an ethylenically unsaturated bond (21) Vinylpyrrolidone, vinyl ether-based monomer or oligomer (22) Multimer or oligoester (meth) of the compound described in (1) to (20) above Acrylate modified

In addition to the above, it is also possible to use an epoxy / Lewis acid resin or a polyene / thiol resin.

These resins can be used alone or as a mixture with other resins. Further, it can be used without a solvent or can be used after being dissolved in an organic solvent. Also, an appropriate amount of a polymerization inhibitor can be added.

In the case of using an ultraviolet curable ink, it is necessary to add a photoinitiator at the stage of mixing. Examples of typical photoinitiators include acetophenones, benzophenone,
Michler's ketone, benzyl, benzoin and derivatives thereof, benzoin alkyl ethers, benzyl ketals, tetramethylthiuram monosulfide, xanthones, thioxanthones, azo compounds, anthraquinones, oximes, (radical polymerization system), onium salts (cations) Polymerization type). The amount of the photoinitiator to be used is usually in the range of 0.1 to 10% by weight based on the ultraviolet curable resin.

A photosensitizer may be used together with a photoinitiator. For example, amines (aliphatic amines, amines containing aromatic groups, nitrogen heterocyclic compounds such as piperidine), urea (allylic, o-tolylthiourea, etc.), sulfur compounds (sodium diethyldithiophosphate, aromatic sulfinic acid) Soluble salts, etc.), nitriles (N, N-disubstituted-p-
Aminobenzonitrile compounds, etc.), phosphorus compounds (tri-n-butylphosphine, sodium diethylthiophosphate, etc.), other nitrogen-containing compounds (Michler's ketone, N-nitrosohydroxylamine derivatives, oxazoline compounds, etc.), chlorine compounds (tetrachloride) Carbon, hexachloroethane, etc.).

In some cases, a storage stabilizer is used in combination with the photoinitiator. For example, quaternary ammonium chloride, diethylhydroxyamine, cyclic amide, nitrile compound, substituted urea, benzothiazole, hydroquinone, hydroquinone monomethyl ether, organic acids such as lactic acid, oxalic acid, and benzoic acid, copper naphthenate, and the like.

The ratio of the organic solvent-soluble dye to the vehicle in the ink composition is such that when the organic solvent is applied to the printed portion using the ink composition, the appearance of the organic solvent-soluble dye flowing out can be clearly confirmed. If it is, it is not particularly limited, but vehicle / organic solvent soluble dye = 99.9 / 0.
It is preferably in the range of 1 to 70/30 (weight ratio). If the ratio of the organic solvent-soluble dye is smaller than this range, the effect when the organic solvent is applied is poor. On the other hand, if it is larger than this range, the dye dissolved in the organic solvent drops off due to the rubbing of the printing surface, causing stains and causing an economical cost increase.

In order to control the hue, the ink viscosity, and the curability of the ink in the case of an ultraviolet curable ink, the pigment may be added to the ink composition at all. Examples of the pigment include titanium oxide, zinc white, lithopone, calcium carbonate, magnesium carbonate, aluminum hydroxide, alumina white, barium sulfate, zinc oxide, kaolin, activated clay, silica (white carbon), lamp black, carbon black, Chrome yellow, chrome green, cadmium yellow, cadmium red, molybdenum red, navy blue, ultramarine, azo pigments, phthalocyanine pigments, lake pigments, toners, and the like.

Compounds (compounds, non-crystal compounds, gel compounds, and the like) may be used as auxiliaries for the purpose of improving printability, accelerating drying, and preventing set-off.
Heat set compounds, etc.), dryers (resin acid salts such as lead, manganese, cobalt, etc., fatty acid salts, other organic acid salts, inorganic acid salts, etc.), silicone, starch, metal soaps, ultraviolet absorbers, antioxidants, fluorescence Dyes, starch, dextrin and the like may be appropriately added to the ink composition.

The ink composition can be of any type of a drying mechanism, such as a penetration drying type, an oxidative polymerization type, an evaporation drying type, an ultraviolet curing type, an electron beam curing type, and a cooling solidification type. However, (1) it is easy to control the degree of curing of the ink, and therefore it is easy to control the outflow of the dye dissolved in the organic solvent.
(2) fast drying time, (3) solvent-free, (4) no set-off or blocking,
(5) Excellent in on-machine stability, halftone dot reproducibility, gloss, film strength, etc. (6) Non-spray printing is possible, (7) No fear of rubbing stains by guide rolls, etc., (8) Low temperature curing For this reason, it is preferable to use an ultraviolet ray or an electron beam curing type because it can be applied to a support having poor heat resistance. The thermosetting ink is not preferable because the heat-sensitive pressure-sensitive mixed color-forming layer or the leuco-based heat-sensitive color-forming layer causes color fog due to heat at the time of curing. Further, the heat-sensitive and pressure-sensitive mixed color-forming layer or the leuco-based heat-sensitive color-forming layer often causes color fog due to a solvent component in the ink. Therefore, it is necessary to use a solventless or nonpolar solvent-based ink.

The method of kneading the ink is selected from known methods such as a three-roll mill method, a kneader method, a flash method, a method using a media type disperser (sand mill, ball mill, attritor, etc.), a chip method and the like. .

Inks include gravure, letterpress (letterpress, flexo), lithographic (offset), intaglio, stencil (screen)
Printing is performed by various printing methods such as. The amount of ink applied to the support by printing varies considerably depending on the plate type, but is 0.5 to 40 g / m ² in terms of dry weight.

When an ultraviolet or electron beam curable ink is used, the support on which the ink has been printed is guided to an ultraviolet or electron beam irradiation device, and the ink is cured by irradiation.

In the ultraviolet irradiation device, ultraviolet lamps of the required length and number are arranged in a plane or three-dimensionally. Examples of the ultraviolet lamp include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, an ozone-less lamp that generates less ozone, a xenon lamp, a tungsten lamp, and an electroless lamp. Generally, a plurality of lamps having an output of 30 w / cm or more are used in parallel.

For the electron beam irradiation, it is preferable to use an electron beam accelerator having an acceleration voltage of 100 to 300 kV from the viewpoints of transmission power and curing power so that the absorbed dose in one pass is 0.5 to 20 Mrad. If the acceleration voltage or the amount of electron beam irradiation is lower than this range, the penetrating power of the electron beam is too low to perform sufficient curing, and if it is higher than this range, not only does the energy efficiency deteriorate, but also the ink Disassembly,
An unfavorable effect on quality such as a decrease in the strength of the base paper appears.

The electron beam irradiation system may be, for example, any of a curtain beam system, a scanning system, a double scanning system, a broad beam system, and an ion plasma system.

At the time of electron beam irradiation, if the oxygen concentration is high, the curing of the electron beam curable resin is hindered. Therefore, replacement with an inert gas such as nitrogen, helium, carbon dioxide or the like is performed to reduce the oxygen concentration to 600 ppm or less, preferably 400 ppm. The irradiation is preferably performed in an atmosphere controlled as follows.

The anti-counterfeit pressure-sensitive adhesive label is obtained by sequentially laminating a known pressure-sensitive adhesive layer and a release sheet on the non-coating layer surface of the anti-counterfeit sheet of the present invention (that is, the side on which the organic solvent coloring layer and the printing layer are not provided). Is manufactured. Lamination may be integrated with the release surface of the release sheet and the pressure-sensitive adhesive layer facing each other after providing the pressure-sensitive adhesive layer on the non-printing surface of the forgery prevention sheet, or provided with the pressure-sensitive adhesive layer on the release surface of the release sheet. The non-printing surface of the anti-counterfeit sheet and the pressure-sensitive adhesive layer may be integrated later.

Adhesives used in the present invention include acrylic resins, natural and synthetic rubbers, styrene / butadiene copolymers, polyvinyl acetate, vinyl acetate / ethylene copolymers,
Starch, silicone-based compounds, glue, casein, polyvinyl alcohol, known resins for adhesives such as polyurethane, petroleum resin, terpene resin, rosin resin, coumarone indene resin, tackifiers such as phenolic resin, if necessary, Known additives such as plasticizers, various stabilizers, and fillers are added.

The pressure-sensitive adhesive is used in any one of a solvent system, an aqueous system (as an aqueous solution or an emulsion), a solventless system, and a hot melt system. The method of setting the adhesive may be any method such as heat drying, air drying, hot melt, solvent-free two-part curing, ultraviolet ray and electron beam curing.

A known release sheet can be used. That is, a film having releasability itself such as a polyolefin resin film or a fluororesin film, or a paper or film coated or impregnated with a release component such as silicone, a fluorine compound or a long-chain alkyl compound.

In the anti-counterfeit sheet or anti-counterfeit adhesive label of the present invention, if an organic solvent (label stripping agent) is used to peel the label, color formation will surely occur in the organic solvent coloring layer. Can be determined. On the organic solvent coloring layer, by further laminating a printing layer of an ink composition containing an organic solvent-soluble dye, because the organic solvent-soluble dye dissolves and flows out when the organic solvent is applied, the organic solvent as a clearer trace. The application history can be determined.

Here, the organic solvent coloring layer has a very good color development with respect to the polar solvent, but the coloring with respect to the non-polar organic solvent is a little thin although it is at a practical level. on the other hand,
The printing layer made of an ink composition containing an organic solvent coloring dye has a very good solubility of the ink in a non-polar solvent.
The ink may flow out, but the dissolution and outflow properties of the ink in some polar solvents may be slightly inferior. Therefore, by providing both the organic solvent coloring layer and the printing layer made of the ink composition containing the organic solvent coloring dye, the response at the time of applying the organic solvent acts complementarily, so that a more preferable effect is exhibited.

The heat-sensitive and pressure-sensitive mixed color-forming layer or the self-coloring type pressure-sensitive color-forming layer can be easily judged to be authentic by performing color development under pressure. Use of the technology of the present invention in combination with other known forgery prevention technology or re-pasting (replacement) prevention technology is not a problem.

[0085]

EXAMPLES The present invention will be described below with reference to examples of the present invention, but the present invention is not limited to these examples. Further, “parts” and “%” shown in the examples indicate parts by weight or% by weight.

Preparation Example 1 (Preparation of Coating Solution for Leuco-Based Thermosensitive Coloring Layer) A coating solution constituting the leuco-based thermosensitive coloring layer was prepared as follows. Each mixture having the following composition was pulverized and dispersed by a sand mill until the average particle size became about 1 μm, and then <A liquid>
And <solution B> were prepared.

<A Liquid> 3- (N-methyl-N-cyclohexyl) amino-6-methyl-7-anilinofluoran (25% dispersion) 40 parts Polyvinyl alcohol (10% aqueous solution) 10 parts Water 5 parts <B Liquid> bisphenol A 15 parts 2-benzyloxynaphthalene 10 parts polyvinyl alcohol (10% aqueous solution) 20 parts water 90 parts

Next, using the prepared <Solution A> and <Solution B>, a leuco-based thermosensitive coloring solution was prepared according to the following formulation. <Solution A> 55 parts <Solution B> 135 parts Zinc stearate (40% dispersion) 25 parts Polyvinyl alcohol (10% aqueous solution) 40 parts Calcium carbonate 30 parts Water 125 parts

Preparation Example 2 (Preparation of Coating Solution for Self-Coloring Type Pressure-Sensitive Coloring Layer) A microcapsule containing a color-forming agent used for pressure-sensitive recording was 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 solution for the self-coloring type pressure-sensitive recording layer was prepared according to the following formulation. Microcapsules 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 Solids concentration 20%

Preparation Example 3 (Preparation of Coating Solution for Heat-Sensitive Pressure-Sensitive Mixed Coloring Layer) The coating solution for the heat-sensitive pressure-sensitive mixed coloring layer was the coating solution for the leuco-based heat-sensitive coloring layer of Preparation Example 1 / the self-coloring type of Preparation Example 2. It was prepared by mixing the pressure-sensitive coloring layer coating solution in 1/1.

Preparation Example 3A (Preparation of Ink Composition Containing Dye Dissolved in Organic Solvent) An ink was prepared by previously mixing according to the following formulation and then kneading with a three-roll mill. However, 2, 2
-Dimethoxy-2-phenylacetophenone was added at the time of milling. Pentaerythritol triacrylate 58 parts Ethylene oxide-modified bisphenol A diacrylate 29 parts Nippon Kayaku Kayaset Blue N (organic solvent-soluble dye) 8 parts 2,2-dimethoxy-2-phenylacetophenone 5 parts

Preparation Example 3B (Preparation of Ink Composition Containing No Organic Solvent-Dissolving Dye) An ink was prepared by previously mixing according to the following formulation and then kneading with a three-roll mill. However, 2, 2
-Dimethoxy-2-phenylacetophenone was added at the time of milling. Pentaerythritol triacrylate 50 parts Ethylene oxide-modified bisphenol A diacrylate 25 parts Ultramarine (insoluble organic pigment) 20 parts 2,2-Dimethoxy-2-phenylacetophenone 5 parts

Preparation Example 4A (Preparation of Ink Composition Containing Dye Dissolved in Organic Solvent) An ink was prepared by previously mixing according to the following formulation and then kneading with a three-roll mill. Toagosei Aronix M-6200 (polyester acrylate) 72 parts Tripropylene glycol diacrylate 9 parts Nippon Kayaku Kayaset Flavin FG (organic solvent soluble dye) 19 parts

Preparation Example 4B (Preparation of Ink Composition Containing No Organic Solvent-Dissolving Dye) An ink was prepared by previously mixing according to the following formulation and then kneading with a three-roll mill. Toagosei Aronix M-6200 (polyester acrylate) 64 parts Tripropylene glycol diacrylate 8 parts Phthalocyanine blue (organic solvent insoluble pigment) 28 parts

Preparation Example 5A (Preparation of Ink Composition Containing Dye Dissolved in Organic Solvent) An ink was prepared by previously mixing according to the following formulation and then kneading with a three-roll mill. Nippon Kayaku Kayaset Red B (organic solvent soluble dye) 15 parts Alkyd resin varnish 55 parts Linseed oil varnish 18 parts Compound 4 parts Petroleum solvent 4 parts Cobalt dryer 4 parts

Preparation Example 5B (Preparation of Ink Composition Containing No Organic Solvent-Dissolving Dye) An ink was prepared by previously mixing according to the following formulation and then kneading with a three-roll mill. Phthalocyanine blue (organic solvent insoluble pigment) 20 parts Carbon black 3 parts Alkaline blue toner 2 parts Alkyd resin varnish 50 parts Linseed oil varnish 16 parts Compound 3 parts Petroleum solvent 3 parts Cobalt dryer 3 parts

Example 1 As a support, commercially available high-quality paper (manufactured by Mitsubishi Paper Mills, diamond form 70 kg) was coated with the coating solution described in Preparation Example 3 so that the coating amount was 9 g / m ^2. A heat-sensitive and pressure-sensitive mixed color-forming layer was provided to obtain a target forgery prevention sheet. Further, an acrylic ester copolymer-based pressure-sensitive adhesive layer and a silicone-based release paper were laminated on another side of the support to obtain a desired anti-counterfeiting pressure-sensitive adhesive label.

Example 2 As a support, commercially available high-quality paper (manufactured by Mitsubishi Paper Mills, diamond form 70 kg) was coated with the coating solution described in Preparation Example 1 so that the coating amount was 4 g / m ^2. A leuco-based thermosensitive coloring layer was provided, and the coating amount described in Preparation Example 2 was further applied thereon in an amount of 4 g.
/ M ² to provide a self-coloring type pressure-sensitive coloring layer to obtain a target forgery prevention sheet. Furthermore,
An acrylic ester copolymer-based pressure-sensitive adhesive layer and a silicone-based release paper were laminated on another side of the support to obtain a desired anti-counterfeit pressure-sensitive adhesive label.

Example 3 As a support, commercially available high-quality paper (manufactured by Mitsubishi Paper Mills, diamond form 70 kg) was coated with the coating solution described in Preparation Example 2 in an amount of 4%.
g / m ² to form a self-coloring type pressure-sensitive coloring layer, and further apply the coating liquid described in Preparation Example 1 thereon to a coating amount of 4 g / m ^2.
g / m ² to provide a leuco-based thermosensitive coloring layer, thereby obtaining a target forgery prevention sheet. Furthermore,
An acrylic ester copolymer-based pressure-sensitive adhesive layer and a silicone-based release paper were laminated on another side of the support to obtain a desired anti-counterfeit pressure-sensitive adhesive label.

Example 4 The ink of Preparation Example 3A was printed (gravure) on the heat-sensitive and pressure-sensitive mixed coloring layer of the anti-counterfeit sheet obtained in Example 1, and the printed surface was irradiated with ultraviolet rays (high-pressure mercury lamp, 120 W / cm, 60m
/ Min) to obtain the desired forgery prevention sheet. Further, an acrylic ester copolymer-based pressure-sensitive adhesive layer and a silicone-based release paper were laminated on the non-printing surface of the support to obtain a target anti-counterfeiting pressure-sensitive adhesive label.

Example 5 The ink of Preparation Example 4A was printed (flexo) on the heat-sensitive and pressure-sensitive mixed coloring layer of the anti-counterfeit sheet obtained in Example 1, and the printed surface was irradiated with an electron beam (acceleration voltage 175 kV, irradiation dose). 2Mr
ad, 50 m / min) to obtain a target forgery prevention sheet. Further, an acrylic ester copolymer-based pressure-sensitive adhesive layer and a silicone-based release paper were laminated on the non-printing surface of the support to obtain a target anti-counterfeiting pressure-sensitive adhesive label.

Example 6 The ink of Preparation Example 5A was printed (letterpress) on the heat-sensitive and pressure-sensitive mixed coloring layer of the anti-counterfeit sheet obtained in Example 1 to obtain a target anti-counterfeit sheet. Further, an acrylic ester copolymer-based pressure-sensitive adhesive layer and a silicone-based release paper were laminated on the non-printing surface of the support to obtain a target anti-counterfeiting pressure-sensitive adhesive label.

Example 7 The ink of Preparation Example 3A was printed (gravure) on the self-coloring type pressure-sensitive coloring layer of the anti-counterfeit sheet obtained in Example 2, and the printed surface was irradiated with ultraviolet rays (high-pressure mercury lamp, 120 W / cm). , 60
m / min) to obtain the desired forgery prevention sheet. Furthermore,
An acrylic ester copolymer-based pressure-sensitive adhesive layer and a silicone-based release paper were laminated on the non-printed surface of the support to obtain a desired anti-counterfeiting pressure-sensitive adhesive label.

Example 8 The ink of Preparation Example 4A was printed (flexo) on the self-coloring type pressure-sensitive coloring layer of the anti-counterfeit sheet obtained in Example 2, and the printed surface was irradiated with an electron beam (acceleration voltage 175 kV, irradiation). Dose 2M
rad, 50 m / min) to obtain a target forgery prevention sheet. Further, an acrylic ester copolymer-based pressure-sensitive adhesive layer and a silicone-based release paper were laminated on the non-printing surface of the support to obtain a target anti-counterfeiting pressure-sensitive adhesive label.

Example 9 The ink of Preparation Example 5A was printed (letterpress) on the self-coloring pressure-sensitive coloring layer of the anti-counterfeit sheet obtained in Example 2 to obtain the desired anti-counterfeit sheet. Further, an acrylic ester copolymer-based pressure-sensitive adhesive layer and a silicone-based release paper were laminated on the non-printing surface of the support to obtain a target anti-counterfeiting pressure-sensitive adhesive label.

Example 10 The ink of Preparation Example 3A was printed (gravure) on the leuco-based thermosensitive coloring layer of the anti-counterfeit sheet obtained in Example 3, and the printed surface was irradiated with ultraviolet rays (high-pressure mercury lamp, 120 W / cm, 60 m).
/ Min) to obtain the desired forgery prevention sheet. Further, an acrylic ester copolymer-based pressure-sensitive adhesive layer and a silicone-based release paper were laminated on the non-printing surface of the support to obtain a target anti-counterfeiting pressure-sensitive adhesive label.

Example 11 The ink of Preparation Example 4A was printed (flexo) on the leuco-based thermosensitive coloring layer of the anti-counterfeit sheet obtained in Example 3, and the printed surface was irradiated with an electron beam (acceleration voltage: 175 kV, irradiation dose: 2 Mr).
ad, 50 m / min) to obtain a target forgery prevention sheet. Further, an acrylic ester copolymer-based pressure-sensitive adhesive layer and a silicone-based release paper were laminated on the non-printing surface of the support to obtain a target anti-counterfeiting pressure-sensitive adhesive label.

Example 12 The ink of Preparation Example 5A was printed (letterpress) on the leuco-based thermosensitive coloring layer of the anti-counterfeit sheet obtained in Example 3 to obtain the desired anti-counterfeit sheet. Further, an acrylic ester copolymer-based pressure-sensitive adhesive layer and a silicone-based release paper were laminated on the non-printing surface of the support to obtain a target anti-counterfeiting pressure-sensitive adhesive label.

Example 13 The intended anti-counterfeit sheet and anti-counterfeit adhesive label were obtained in the same manner as in Example 4, except that the support was changed to a polyester (PET) film of 75 μm.

Example 14 A target anti-counterfeit sheet and anti-counterfeit adhesive label were obtained in the same manner as in Example 8, except that the support was changed to a polyester (PET) film of 75 μm.

Example 15 The intended anti-counterfeit sheet and anti-counterfeit adhesive label were obtained in the same manner as in Example 12, except that the support was changed to a polyester (PET) film of 75 μm.

Example 16 Except that the ink was changed from Preparation Example 3A to Preparation Example 3B,
In the same manner as in Example 4, a forgery prevention sheet and a forgery prevention adhesive label were obtained.

Example 17 Except that the ink was changed from Preparation Example 4A to Preparation Example 4B,
In the same manner as in Example 8, a forgery prevention sheet and a forgery prevention adhesive label were obtained.

Example 18 Except that the ink was changed from Preparation Example 5A to Preparation Example 5B,
In the same manner as in Example 12, a forgery prevention sheet and a forgery prevention adhesive label were obtained.

Comparative Example 1 Commercially available high quality paper (Diaform 70K, manufactured by Mitsubishi Paper Mills)
g) was used as a sheet as it was. Further, an acrylic ester copolymer pressure-sensitive adhesive layer and a silicone release paper were laminated on one surface of the support to obtain a pressure-sensitive adhesive label.

Comparative Example 2 A commercially available high-quality paper (manufactured by Mitsubishi Paper Mills, Diamond Foam 70 kg) was used as a support, and the coating solution described in Preparation Example 1 was coated in an amount of 4%.
g / m ² to obtain a sheet provided with a leuco-based thermosensitive coloring layer. A self-coloring type pressure-sensitive coloring layer and a printing layer made of an ink containing an organic solvent-soluble dye were not provided. An acrylic ester copolymer pressure-sensitive adhesive layer and a silicone release paper were laminated on another side of the support to obtain a pressure-sensitive adhesive label.

Comparative Example 3 A commercially available high-quality paper (manufactured by Mitsubishi Paper Mills, diamond form 70 kg) was used as a support, and the coating liquid described in Preparation Example 2 was applied in an amount of 4%.
g / m ² to obtain a sheet provided with a self-coloring type pressure-sensitive coloring layer. A leuco-based thermosensitive coloring layer and a printing layer using an ink containing a dye dissolved in an organic solvent were not provided. Also, by laminating an acrylic ester copolymer pressure-sensitive adhesive layer and silicone-based release paper on the non-printing surface of the support,
An adhesive label was obtained.

Comparative Example 4 The ink of Preparation Example 3B was printed (gravure) on commercially available high-quality paper (manufactured by Mitsubishi Paper Mills, diamond form 70 kg) as a support, and the printed surface was irradiated with ultraviolet light (high-pressure mercury lamp, 120 W /
cm, 60 m / min) to obtain a sheet having a printing layer containing no organic solvent-soluble dye. Also, an acrylic ester copolymer-based pressure-sensitive adhesive layer and a silicone-based release paper were laminated on the non-printing surface of the support to obtain a pressure-sensitive adhesive label.

Comparative Example 5 The ink of Preparation Example 4B was printed (flexo) on commercially available high-quality paper (manufactured by Mitsubishi Paper Mills, diamond form 70 kg) as a support, and the printed surface was irradiated with an electron beam (acceleration voltage 175 kV, irradiation dose 2 Mrad). , 50 m / min) to obtain a sheet having a printing layer containing no organic solvent-soluble dye. Also, an acrylic ester copolymer-based pressure-sensitive adhesive layer and a silicone-based release paper were laminated on the non-printing surface of the support to obtain a pressure-sensitive adhesive label.

Comparative Example 6 The ink of Preparation Example 5B was printed on a commercially available high-quality paper (manufactured by Mitsubishi Paper Mills, Diamond Foam 70 kg) as a support (letterpress).
Thus, a sheet having a printing layer containing no organic solvent-soluble dye was obtained. Also, by laminating an acrylic ester copolymer pressure-sensitive adhesive layer and silicone-based release paper on the non-printing surface of the support,
An adhesive label was obtained.

Incidentally, for the sake of evaluation, all of the printed patterns in Examples 4 to 18 and Comparative Examples 4 to 6 were 1 mm diameter dots (11 dots / inch).

Tests: Printability, discriminability of using an organic solvent, authenticity judgment, and attachment to various substrates were tested as shown below.

Test 1: Printability The sheets obtained in Examples 4 to 18 and Comparative Examples 4 to 6 were used for printing an ink containing an organic solvent-soluble dye (or optionally containing no organic solvent-soluble dye). Scratch, ground stain, paper peeling (only when the support is paper-based),
The printed portion was evaluated for peeling and set-off when rubbed after printing. Blurring: The percentage of dots with blurring is measured in a printing area of a fixed area taken out at random and measured in 5 steps (5; blurring rate of less than 5%, 4; 5 to 10%, 3; 10 to 10%).
30%, 2; 30 to 50%, 1; 50% or more). Background stain: The presence or absence of unnecessary ink transfer to a non-printed portion (background portion) is visually determined. Five levels (5; no transfer, 4; slight transfer observed, but little noticeable but practically no problem) No; 3; some transition was observed and it was somewhat difficult to put to practical use. 2; transition was conspicuous and the practicality was clearly lacking. 1; transition was severe and there was no practicality. Paper peeling: The presence or absence of paper peeling was determined only when the support was paper. Peeling: In a printing area of a fixed area taken out at random, the percentage of dots where peeling occurred after strongly rubbing with a paper wipe was measured, and 5 levels (5; peeling rate less than 5%, 4; 5)
-10%, 3; 10-30%, 2; 30-50%, 1;
50% or more). Set-off: The presence or absence of ink set-off to the non-printing surface which overlaps with the printing surface is visually determined, and 5 levels (5; no set-off,
4: slight set-off is observed but hardly noticeable and there is no problem in practical use. 3; slight set-off is recognized and slightly difficult to be put to practical use. 2; set-off is noticeable and practically lacks practicality. , 1; the set-off is so bad that there is no practical use)
Was evaluated.

Test 2: Discriminability of use of organic solvent A For the sheets obtained in Examples 1 to 18 and Comparative Examples 1 to 6, fixed amounts of various organic solvents were dropped on the printing surface (or the organic solvent coloring layer surface). The discriminability of using an organic solvent was determined as follows. ◎: Both coloring of the coloring layer and ink outflow from the printing layer occurred, and the discrimination was made very well. ○: Ink outflow from the printing layer occurred and discriminated well. △: At least the printed portion to which the organic solvent was applied was blurred, or the color-forming layer was thinly colored, and it was determined that the organic solvent was applied. × △: The printed portion to which the organic solvent was applied slightly blurred. Alternatively, the coloring layer appears to be very thin, but it was difficult to recognize that the organic solvent was applied. ×: No change occurred. Organic solvent A: Peeling off a commercially available label (peeling off a seal made by Maruzen,
Polar solvent type, ester type) Organic solvent B: Commercial label peeling (peeling off the seal made by Wrec, non-polar solvent type, mineral spirit + L
PG) Organic solvent C: Toluene Organic solvent D: o-xylene Organic solvent E: Methyl ethyl ketone Organic solvent F: Isopropanol Organic solvent G: Ethanol Organic solvent H: Cyclohexane Organic solvent I: LPG Organic solvent J: Naphtha

Test 3: Discriminability B Using Organic Solvent The sheets obtained in Examples 1 to 18 and Comparative Examples 1 to 6 were stamped on the printing surface (or the organic solvent coloring layer surface) using a commercially available stamp stand. After that, the following various organic solvents were sprayed in a sufficient amount, and the discriminability of the use of the organic solvent when rubbed with a paper wipe to such an extent that the stamped portion was removed was evaluated as “Test 2: Discrimination A of the use of the organic solvent A”. Judgment was made according to the criteria in Organic solvent C: toluene Organic solvent E: methyl ethyl ketone Organic solvent G: ethanol Organic solvent K: ethyl acetate Organic solvent L: acetone Organic solvent M: N-N'-dimethylformamide

Test 4: Judgment of Authenticity With respect to the sheets obtained in Examples 1 to 18 and Comparative Examples 1 to 6, the printed surface (or the organic solvent coloring layer surface) was rubbed with the tip of a nail, so that the authenticity could be easily judged. It was determined whether or not. ：: Scratched part developed strong color and could be distinguished very well. ：: Scratched part developed and distinguished well. Δ: Scratched part developed color, but color was light or slow. ×: Difficult to determine ×: No change was recognized in the scratched part, and no determination was possible

Test 5: Stickiness to Various Substrates The pressure-sensitive adhesive labels obtained in Examples 1 to 18 and Comparative Examples 1 to 6 were applied in accordance with the method described in JIS Z0237 (Testing method for pressure-sensitive adhesive tapes and sheets). The label was pressed against the substrate in one round trip at 300 mm / min using a manual pressing device of 2,000 g and the temperature was 30 ° C. in an environment of 40 ° C. and 90% relative humidity.
After storage for 3 days, the label was peeled, turned up, and shifted in three stages (○: no peeling, turning up, no shift, Δ; no peeling, but a slight turn up or shift was observed, ×;
Peeling, large turning, and displacement are recognized). The label was attached to the following substrate. Base material 1: Stainless steel (SUS304) Base 2: Aluminum sheet Base 3: Polycarbonate Base 4: Polyethylene Base 5: Polypropylene Base 6: Acrylic plate Base 7: Fine paper Base 8: Cast coated paper Base 9: Glass

[0129]

[Table 1]

[0130]

[Table 2]

[0131]

[Table 3]

[0132]

[Table 4]

Evaluation: Example 1 was an example in which a heat-sensitive and pressure-sensitive mixed color-forming layer was provided as a single layer as an organic solvent color-forming layer on a support, and Example 2 was a leuco-based heat-sensitive layer formed as an organic solvent color-forming layer on a support. Example in which a color-forming layer and a self-coloring type pressure-sensitive coloring layer were laminated in this order, and Example 3 is an example in which a self-coloring type pressure-sensitive coloring layer and a leuco-based heat-sensitive coloring layer were laminated in this order as an organic solvent coloring layer on a support.
In any case, when an organic solvent (label peeling) is applied in accordance with the purpose of peeling the pressure-sensitive adhesive layer or the purpose of removing the stamp ink, the organic solvent coloring layer develops a color for any organic solvent. The use history could be determined. Examples 4 to 15 are examples in which a printing layer made of an ink containing an organic solvent-soluble dye was further provided on the organic solvent coloring layer corresponding to Examples 1 to 3, and the discriminability of the organic solvent use history was higher. It was further improved and could be clearly identified. Here, in Examples 12 to 15, the support was changed from high-quality paper to a polyester (PET) film, but the effects of the invention were completely the same. Examples 16 to 18 are examples in which a printing layer using an ink containing an organic solvent-insoluble pigment (not including an organic solvent-soluble dye) was provided on the organic solvent coloring layer. Although no dissolution or outflow of the ink from the printing layer occurred, coloring occurred in the organic solvent coloring layer, so that the usage history of the organic solvent could be determined.

Further, in Examples 1 to 18, by utilizing the pressure-sensitive coloring property of the self-coloring type pressure-sensitive coloring component, it is easy to apply pressure by using a sharp object such as a nail. The authenticity could be determined.

On the other hand, Comparative Example 1 is an example in which high-quality paper was used as it was, and did not have any discriminating property and authenticity discriminating property when using an organic solvent. Comparative Examples 2 and 3 are examples in which only the leuco-based heat-sensitive coloring layer or the self-coloring type pressure-sensitive coloring layer was provided on the support. Depending on the type of the organic solvent, the leuco-based thermosensitive coloring layer or the self-coloring layer was used. Since the pressure coloring layer does not develop color, there is a risk that the label may be peeled off without realizing it. Comparative Examples 4 to 6 are examples in which a printing layer made of an ink composition containing no organic solvent-soluble dye was provided on a support (high quality paper). Since there is no possibility of dissolving or flowing out, there is a great risk that the label will be re-applied without understanding and the stamp ink will be removed.
Regarding printability and label stickability when labeling,
There was no difference in the performance between the example and the comparative example, which was at a level that was not problematic in practical use. 4, 5, 7, 8, 10, 11, 13, 1
4, 16, and 17 and Comparative Examples 4 and 5) were particularly preferable.

[0136]

According to the present invention, when an attempt is made to peel a label using an organic solvent such as peeling off a label, or to remove a stamp by a stamp, the organic solvent coloring layer develops a color, and When a printing layer printed using an ink composition containing a soluble dye is provided, the printing layer dissolves and flows out with the organic solvent, leaving a trace of the use of the organic solvent. The removal attempt can be clearly detected. Further, by utilizing the pressure-sensitive coloring property of the self-coloring type pressure-sensitive coloring component, it is possible to easily determine the authenticity. Therefore, the anti-counterfeit sheet of the present invention, and the anti-counterfeit pressure-sensitive adhesive label using the anti-counterfeit sheet, while preventing improper acts such as re-labeling, also eliminates the risk of being replaced with a counterfeit label, utilization It is of great value.

Also, by controlling the ink composition to be of an ultraviolet or electron beam curable type and using an ultraviolet or electron beam curing method as a means for drying the ink, it is possible to control the degree of curing of the ink, that is, to control the outflow of the dye dissolved in the organic solvent. , The drying speed of the ink is high, and set-off after printing can be prevented.

[Brief description of the drawings]

FIG. 1 is a self-coloring type feeling obtained by microencapsulating at least one of A) a leuco-based thermosensitive recording dye / color developing agent, B) a color forming agent or a color developing agent on one surface of a support according to the present invention. A forgery-preventing sheet in which a layer (a heat-sensitive and pressure-sensitive mixed color-forming layer) containing both the pressure-sensitive coloring composition and a pressure-sensitive coloring composition is provided as a single layer, and an adhesive layer and a release sheet are sequentially laminated on another side of the support. FIG. 2 is a cross-sectional view of the anti-counterfeit adhesive label.

FIG. 2 shows at least one of a leuco-based thermosensitive recording dye / developer layer (leuco-based thermosensitive color-developing layer), a color former or a developer, which is microencapsulated on one surface of a support according to the present invention. An anti-counterfeit sheet formed by sequentially laminating or mixing a single layer of a self-coloring type pressure-sensitive coloring layer (self-coloring type pressure-sensitive coloring layer), and an adhesive layer on another side of the support. FIG. 2 is a cross-sectional view of a forgery-preventing pressure-sensitive adhesive label formed by sequentially laminating release sheets.

FIG. 3 is a diagram illustrating a single-layer self-coloring pressure-sensitive coloring layer (self-coloring layer) in which at least one of a coloring agent and a developing agent is microencapsulated on one surface of a support according to the present invention, and each of them is laminated or mixed alone. A color-forming pressure-sensitive coloring layer), a leuco-based thermosensitive coloring dye / a color developer layer (leuco-based thermosensitive coloring layer), and a forgery-preventing sheet, which is sequentially laminated, and on another side of the support,
Sectional drawing of the forgery prevention adhesive label which laminates an adhesive layer and a peeling sheet sequentially.

FIG. 4 is a self-coloring type impression obtained by microencapsulating at least one of A) a leuco-based thermosensitive recording dye / coloring agent, and B) a coloring agent or a coloring agent on one surface of a support according to the present invention. An anti-counterfeit sheet obtained by further laminating a printing layer of an ink composition containing an organic solvent-soluble dye on a layer containing both a pressure-sensitive coloring composition (a heat-sensitive and pressure-sensitive mixed coloring layer); FIG. 4 is a cross-sectional view of a forgery-preventive pressure-sensitive adhesive label obtained by sequentially laminating a pressure-sensitive adhesive layer and a release sheet on one surface of the label.

FIG. 5 shows at least one of a leuco-based thermosensitive recording dye / developer layer (leuco-based thermosensitive color-developing layer), a color former or a developer, which is microencapsulated on one surface of a support according to the present invention. A single layer of a self-coloring type pressure-sensitive coloring layer (self-coloring type pressure-sensitive coloring layer), which is laminated or mixed alone, is sequentially laminated, and a printing layer of an ink composition containing a dye dissolved in an organic solvent is further laminated. FIG. 2 is a cross-sectional view of an anti-counterfeiting sheet and an anti-counterfeiting pressure-sensitive label formed by sequentially laminating an adhesive layer and a release sheet on another side of the support.

FIG. 6 shows at least one of a color former and a color developer microencapsulated on one surface of a support of the present invention, and each of them is laminated or mixed alone to form a single-layer self-coloring type pressure-sensitive coloring layer (self-coloring layer). A color-forming type pressure-sensitive coloring layer), a leuco-based thermosensitive coloring dye / a color developer layer (leuco-based thermosensitive coloring layer) are sequentially laminated, and a printing layer of an ink composition containing an organic solvent-soluble dye is further laminated. FIG. 4 is a cross-sectional view of an anti-counterfeit sheet and an anti-counterfeit adhesive label formed by sequentially laminating an adhesive layer and a release sheet on another side of the support.

[Explanation of symbols]

1) A leuco-based thermosensitive recording dye / developing agent, B) at least one of a coloring agent or a developing agent is microencapsulated, and each of them is laminated or mixed alone to form a single-layer, self-coloring type pressure-sensitive coloring composition. (Thermosensitive pressure-sensitive mixed color-forming layer) 2 At least one of the color former and the developer is microencapsulated, and each of them is laminated or mixed alone to form a single-layer self-coloring type pressure-sensitive color. Layer (self-coloring type pressure-sensitive coloring layer) 3 Leuco-based thermosensitive recording dye / developer layer (leuco-based thermosensitive coloring layer) 4 Organic solvent coloring layer 5 Printing layer with ink composition containing organic solvent-soluble dye 6 Support Body 7 Adhesive layer 8 Release sheet 9 Anti-counterfeit sheet 10 Anti-counterfeit adhesive label

Claims (6)

[Claims] 1. A self-coloring type pressure-sensitive coloring composition in which at least one of A) a leuco dye for thermal recording and a color developer, and B) a color former or a color developer is microencapsulated on one surface of a support. Anti-counterfeit sheet comprising a single layer provided with a layer containing both of the above. 2. A layer of at least one of a leuco-based thermosensitive recording dye / developer layer, a color former or a developer on one side of a support.
The anti-counterfeit sheet is obtained by laminating a single layer of a self-coloring type pressure-sensitive coloring layer, which is microencapsulated and individually laminated or mixed. 3. A color forming agent or a color developing agent is microencapsulated on one side of a support, and each of them is individually laminated or mixed to form a single-layer self-coloring type pressure-sensitive coloring layer, a leuco-based thermosensitive coloring. An anti-counterfeit sheet formed by sequentially laminating a dye / a color developer layer. 4. A self-coloring type pressure-sensitive coloring composition in which at least one of A) a leuco dye for thermal recording and a color developer, and B) a color former or a color developer is microencapsulated on one surface of a support. Anti-counterfeit sheet comprising a single layer or a mixture of the above materials, and a printed layer of an ink composition containing a dye dissolved in an organic solvent, further provided thereon. 5. A forgery-preventing pressure-sensitive adhesive label comprising a pressure-sensitive adhesive layer and a release sheet sequentially laminated on another side of the support of the forgery-preventing sheet according to claim 1. 6. The forgery-preventing sheet or the forgery-preventive pressure-sensitive adhesive label according to claim 4, wherein the ink composition forming the printing layer is an ultraviolet-curable ink or an electron-beam-curable ink.