JP7188921B2 - print media - Google Patents

Description

The present invention relates to print media.

2. Description of the Related Art A glittering print layer containing a pearl pigment is provided on the surface of a printing medium using thermal paper, such as a ticket, for the purpose of preventing counterfeiting.

In Patent Document 1, a base material having a glossiness defined by JIS P 8142 of 15 to 30% is coated with a resin layer having a smoothness of 100 or more defined by JIS P8119. An anti-counterfeiting printed material is disclosed, characterized in that a pattern obtained with ink containing 1 to 50% by weight of is formed.

In Patent Document 2, for thermal paper, it contains a binder component that can be cured by irradiation with ionizing radiation, a pearl pigment, and, if necessary, a photopolymerization initiator, and has a viscosity of 2000 to 8000 cP. A pearl ink is disclosed.

In Patent Document 3, a heat-sensitive or pressure-sensitive coloring layer is laminated on one side of a base material layer, and a light interference reflecting layer mixed with a pearl pigment is formed on the heat-sensitive or pressure-sensitive coloring layer. A printed matter is disclosed.

Patent Document 4 discloses a heat-sensitive recording material having a support and a heat-sensitive layer, wherein the heat-sensitive layer contains a heat-sensitive coloring material and an aco complex.

Japanese Patent Application Laid-Open No. 2001-080252 JP-A-2003-147251 JP-A-9-169161 JP-A-54-118845

Conventionally, natural mica-based pearl pigments have been generally used as luster pigments (pearl pigments). However, in recent years, child labor associated with mineral mining has become an international problem, and due to safety issues, it is desired to use synthetic mica-based pearl pigments instead of natural mica-based pearl pigments. .

On the other hand, it is necessary to use a synthetic mica-based colored pearl pigment in order to give a colored luster like natural mica with synthetic mica.

In this regard, the natural mica-based pearl pigment had a colored luster, but when it was copied, the color did not remain. The present inventors have found that there is a problem that color remains on the surface.

Accordingly, the present invention provides a print medium that uses synthetic mica as a glitter pigment, has a colored gloss, and is difficult to reproduce in a color copy.

As a result of intensive studies, the present inventors have found that the above problems can be solved by the following means, and completed the present invention. That is, the present invention is as follows:
<Aspect 1> A thermal recording sheet and a colored glitter print layer on the thermal recording sheet,
The colored glitter print layer contains a synthetic mica-based pearl pigment and a binder resin,
The print medium, wherein the synthetic mica-based pearl pigment is composed of a synthetic mica-based uncolored pearl pigment and a synthetic mica-based colored pearl pigment.
<Aspect 2> The print medium according to Aspect 1, wherein the colored glitter print layer has a thickness of 2 μm or less.
<Aspect 3> The print medium according to Aspect 1 or 2, wherein the content of the synthetic mica-based pearl pigment is 40 to 58% by mass based on the total mass of the colored glitter print layer.
<Aspect 4> Aspects 1 to 3, wherein the content of the coloring pigment in the synthetic mica-based pearl pigment is 2 to 90% by mass based on the total mass of the pearl pigment. print media.
<Aspect 5> The print medium according to any one of Aspects 1 to 4, wherein the average particle size of the synthetic mica-based pearl pigment measured by a laser diffraction/scattering method is 10 to 40 μm.
<Aspect 6> The print medium according to any one of Aspects 1 to 5, wherein the colored glitter print layer further contains wax.
<Aspect 7> The print medium according to any one of aspects 1 to 6, wherein the binder resin is a polyester-based resin.
<Aspect 8> The print medium according to Aspect 7, wherein the binder resin is a urethane-modified polyester.
<Aspect 9> The thermosensitive recording sheet comprises a substrate layer, a thermosensitive recording layer, and a protective layer in this order, whereby the print medium comprises the substrate layer, the thermosensitive recording layer, and the protective layer. 9. The print medium according to any one of aspects 1 to 8, comprising a layer and the colored glitter print layer in this order.
<Aspect 10> The print medium according to any one of Aspects 1 to 9, further comprising another print layer between the heat-sensitive recording sheet and the colored glitter print layer.
<Aspect 11> The print medium according to any one of Aspects 1 to 10, further comprising a magnetic recording layer on the thermal recording sheet.

According to the present invention, it is possible to provide a print medium having a glitter print layer containing a synthetic mica-based pearl pigment, which solves the above problems.

FIG. 1 is a schematic diagram of the print medium of the present invention.

《Printed media》
As shown in FIG. 1, the print medium 100 of the present invention comprises a thermal recording sheet 20 and a colored glitter printing layer 10 on the thermal recording sheet 20,
The colored glitter print layer 10 contains a synthetic mica-based pearl pigment and a binder resin,
The synthetic mica-based pearl pigment is composed of a synthetic mica-based uncolored pearl pigment and a synthetic mica-based colored pearl pigment.

The present inventors have found that the above configuration can provide the same appearance and color copy non-reproducibility as when a natural mica-based pearl pigment is used.

More specifically, a conventional print medium having a colored glitter print layer using a natural mica-based pearl pigment has a colored gloss when viewed from a specific angle. In addition, this printing medium cannot reproduce this color when a color copy is made.

In contrast, when synthetic mica-based pearl pigments were simply used, the color of natural mica-based pearl pigments could not be reproduced. In addition, when synthetic mica-based colored pearl pigments that match the color of natural mica-based pearl pigments are used, although the above-mentioned colored luster is visible, there is a problem that this color can be reproduced by color copying. The inventors have found.

In contrast, the present inventors have found that the synthetic mica-based pearl pigment is composed of a synthetic mica-based uncolored pearl pigment and a synthetic mica-based colored pearl pigment, thereby reproducing the above-mentioned colored luster and making a color copy. We have found that it is possible to provide a print medium that is not reproduced by

The colored glitter print layer 10 may be present on the entire thermal recording sheet 20, or may be present partially on the thermal recording sheet 20 as shown in FIG. 1(a).

Also, as shown in FIG. 1(a), the thermal recording sheet 20 comprises a substrate layer 26, a thermal recording layer 24, and a protective layer 22 in this order, thereby forming the printing medium 100 of the present invention. However, the substrate layer 26, the heat-sensitive recording layer 24, the protective layer, and the colored glitter printing layer may be provided in this order.

Moreover, the print medium of the present invention may further comprise a magnetic recording layer on the heat-sensitive recording sheet. This magnetic recording layer may be present on the opposite side of the thermal recording sheet to the colored glitter printing layer. In particular, when the heat-sensitive recording sheet comprises a substrate layer, a heat-sensitive recording layer, and a protective layer in this order, the magnetic recording layer may be present on the opposite side of the substrate layer to the heat-sensitive recording layer.

Each component of the present invention will be described below.

<Thermal recording sheet>
A thermal recording sheet is a sheet having a thermal recording layer. The heat-sensitive recording sheet may comprise, for example, a substrate layer, a heat-sensitive recording layer, and a protective layer in this order.

(Base material layer)
The base layer is not particularly limited as long as it can support other layers of the thermal recording sheet, and may be, for example, a paper base layer.

(Heat-sensitive recording layer)
The thermosensitive recording layer is not particularly limited as long as visible information can be formed by heating. As the heat-sensitive recording layer, for example, a reaction between a leuco dye and an electron-accepting substance represented by a phenolic substance, a reaction between an imino compound and an isocyanate compound, and a long-chain fatty acid iron salt and a polyhydric phenol. can be used. Specific examples of these combinations are described in Patent Document 4, for example.

(protective layer)
The protective layer is not particularly limited as long as it is a layer capable of imparting functions such as anti-fading and water resistance to the thermosensitive recording layer. The protective layer may be, for example, a layer containing a curable resin such as a thermosetting resin or an ultraviolet curable resin.

<Colored glitter printing layer>
The colored glitter print layer contains a synthetic mica-based pearl pigment and a binder resin. The colored glitter printing layer further contains wax, from the viewpoint of imparting abrasion resistance to the colored glitter printing layer and suppressing adhesion of the colored glitter printing layer to the thermal head during thermal recording printing. It is preferable from the viewpoint of

The content of the synthetic mica-based pearl pigment is preferably 40% by mass or more, or 45% by mass or more, based on the total mass of the colored glitter print layer, from the viewpoint of facilitating the production of luster by the pearl pigment. A content of 60% by mass or less, 58% by mass or less, or 55% by mass or less is preferable from the viewpoint of promoting non-reproducibility of color copies.

The thickness of the colored glitter printing layer is preferably 2.5 μm or less, or 2.0 μm or less, from the viewpoint of promoting heat transfer to the thermal recording layer during thermal recording printing. This thickness may be 0.5 μm or more, or 1.0 μm or more.

When the colored glitter print layer contains wax, the mass ratio of wax to binder resin may be 0.01 or more, 0.02 or more, or 0.03 or more, and may be 0.10 or less, 0 It may be 0.09 or less, 0.07 or less, 0.05 or less, or 0.04 or less. When the colored glitter print layer is formed by applying or printing the composition for a colored glitter print layer shown below, the above mass ratio means the mass ratio of the solid content.

For the colored glitter printing layer, for example, the substances and solvent components shown below are mixed to prepare a composition for the colored glitter printing layer, which is coated or printed on a heat-sensitive recording sheet, and dried to remove the solvent component. It can be formed by removing. As the solvent component, for example, ethyl acetate, methyl ethyl ketone, toluene, isopropyl alcohol, ethanol, methanol, etc. can be used alone or in combination.

Application of the composition for the colored glitter printing layer can be performed using, for example, a bar coater.

Printing of the composition for a colored glitter printing layer can be performed by known printing means such as gravure printing, offset printing, flexographic printing, and silk screen printing. In this case, it is preferable that the composition for the colored glitter printing layer is printed by gravure printing.

(Synthetic mica-based pearl pigment)
The synthetic mica-based pearl pigment is composed of a synthetic mica-based uncolored pearl pigment and a synthetic mica-based colored pearl pigment.

The content of the synthetic mica-based colored pearl pigment in the synthetic mica-based pearl pigment is 2% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass, based on the mass of the entire synthetic mica-based pearl pigment. It is preferably at least 25% by mass, at least 25% by mass, at least 30% by mass, or at least 35% by mass from the viewpoint of favorably producing colored gloss, and is at most 90% by mass, at most 85% by mass, and at least 80% by mass. 75% by mass or less, 70% by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, or 50% by mass or less is preferable from the viewpoint of promoting non-reproducibility of color copies.

The average particle size of the synthetic mica-based pearl pigment is 10 μm or more, 13 μm or more, or 15 μm or more, and 40 μm or less, 25 μm or less, 22 μm or less, or 20 μm or less, so that the synthetic mica-based pearl pigment produces luster. It is preferable from the viewpoint of facilitating. The average particle size of the synthetic mica-based uncolored pearl pigment and the average particle size of the synthetic mica-based colored pearl pigment may be the same or different. Here, in the present specification, the average particle size means the median size (D50) calculated on a volume basis in the laser diffraction/scattering method.

The mica-based pearl pigment is obtained by coating the surface of mica with a high refractive index layer generally made of a high refractive index metal oxide such as titanium oxide. It is a pigment that provides a pearly luster due to the reflection caused by the difference in refractive index. Among such mica-based pearl pigments, those using natural mica as the core mica are natural mica-based pearl pigments, and those using synthetic mica as the core mica are synthetic mica-based pearl pigments. In general, natural mica has a dull color due to the presence of impurities, whereas synthetic mica is made from pure raw materials and does not have the dullness due to the presence of impurities like natural mica.

The synthetic mica-based colorless pearl pigment may be, for example, a synthetic mica-based pearl pigment in which titanium oxide is coated on synthetic mica as a core. The synthetic mica-based colored pearl pigment may be, for example, synthetic mica as a core, or a synthetic mica-based pearl pigment in which iron oxide is coated on the synthetic mica-based uncolored pearl pigment.

(binder resin)
Examples of binder resins that can be used include polyester resins, acrylic resins, polyvinyl butyral, and urethane-modified polyester resins.

A crystalline or amorphous polyester resin can be used as the polyester resin.

As the acrylic resin, for example, a polymer of an acrylic component and a copolymer of an acrylic component and ethylene can be used. Acrylic components include, for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, and 2-ethylhexyl (meth)acrylate and the like.

As the urethane-modified polyester-based resin, a urethane-modified copolyester having an aromatic polyester as a basic skeleton and a urethane component attached to the side chain is used, or a skeleton having a repeating unit of an ester and a repeating unit of a urethane is used. A urethane-modified copolyester or the like contained therein can be used. As such a urethane-modified polyester resin, for example, Vylon (trademark) UR series manufactured by Toyobo Co., Ltd. can be used.

(wax)
Examples of waxes include synthetic hydrocarbon waxes such as polyethylene wax and Fischer-Tropsch wax; petroleum waxes such as paraffin wax, microcrystalline wax and petrolatum; plant waxes such as candelilla wax, carnauba wax and rice wax; can be used.

<Other printed layers>
Another printed layer may be, for example, a pattern printed layer.

<Magnetic recording layer>
The magnetic recording layer is not particularly limited as long as it contains a magnetic compound. The magnetic recording layer may also contain other components such as dispersants, antistatic agents, waxes, carbon black and additives.

Examples of magnetic compounds include γ-ferrite, cobalt-containing ferrite, barium ferrite, chromium oxide, and strontium ferrite.

The magnetic recording layer can be obtained, for example, by coating the above components by a known method.

EXAMPLES The present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these.

《Preparation of print media》
<Example 1>
Urethane-modified polyester (Vylon UR-8200, Toyobo Co., Ltd., solid content 30% by mass) as a binder resin 66.7 parts by mass, polyethylene wax as a wax (Slip Aid SL-551, Elementis Japan KK, solid content 18.5 % by mass) 2.2 parts by mass, synthetic mica-based uncolored pearl pigment (TWINCLE PEARL YXB, Nihon Koken Kogyo Co., Ltd., average particle size of about 13 μm) 13.72 parts by mass, synthetic mica-based colored pearl pigment (TWINCLE PEARL RYXB , Nihon Koken Kogyo Co., Ltd., average particle size of about 13 μm) 0.28 parts by weight, 60 parts by weight of methyl ethyl ketone as a solvent, and 33.3 parts by weight of ethyl acetate as a solvent are mixed to obtain a composition for a colored glitter printing layer made things.

The prepared composition for colored glitter printing layer was coated on a red and black two-color thermal paper (Oji F-Tex Co., Ltd.) with a bar coater No. 1. 7 and dried in an oven at 70° C. for 1 minute to form a 2 μm-thick colored glitter print layer to prepare a print medium of Example 1. The mass ratio of the wax to the solid content of the binder resin was 0.02.

<Examples 2 to 18 and Comparative Examples 1 to 4>
Example 1, except that the average particle size and content of the synthetic mica-based uncolored pearl pigment and the synthetic mica-based colored pearl pigment were changed so that the colored glitter print layer having the configuration shown in Table 1 was obtained. Print media of Examples 2 to 18 and Comparative Examples 1 to 4 were produced in the same manner. The mass ratio of the wax to the solid content of the binder resin was 0.02.

TWINCLE PEARL YXD (Nihon Koken Kogyo Co., Ltd.) was used as a synthetic mica-based uncolored pearl pigment having an average particle size of about 21 μm. TWINCLE PEARL RYXD (Nihon Koken Kogyo Co., Ltd.) was used as a synthetic mica-based colored pearl pigment having an average particle size of about 21 μm. TWINCLE PEARL YXE (Nihon Koken Kogyo Co., Ltd.) was used as a synthetic mica-based uncolored pearl pigment having an average particle size of about 37 μm. TWINCLE PEARL RYXE (Nihon Koken Kogyo Co., Ltd.) was used as a synthetic mica-based colored pearl pigment having an average particle size of about 37 μm.

<Examples 19 to 23>
As the binder resin, 20 parts by mass of an amorphous polyester resin (Vylon 270, Toyobo Co., Ltd., solid content 100% by mass) was used, and the masses of methyl ethyl ketone and ethyl acetate were changed to 80 parts by mass and 60 parts by mass, respectively. Print media of Examples 19 to 23 were produced in the same manner as in Examples 9, 2, and 10 to 12, except that The mass ratio of the wax to the solid content of the binder resin was 0.02.

<Reference example>
Except that 14 parts by mass of natural mica-based pearl pigment (MY-100RF, Nihon Koken Kogyo Co., Ltd., average particle size 13 μm) was used instead of synthetic mica-based uncolored pearl pigment and synthetic mica-based colored pearl pigment. A print medium of a reference example was produced in the same manner as in Example 1. The mass ratio of the wax to the solid content of the binder resin was 0.02.

"evaluation"
〈Colored luster〉
The presence or absence of colored gloss on the produced print media was visually confirmed. Evaluation criteria were as follows:
〇: Colored gloss was visible △: Colored gloss was visible, but slightly thin ×: Colored gloss was not visible

<Color copy reproducibility>
Using DocuCentre-V C5576 (Fuji Xerox Co., Ltd.), the printed media produced were color-copied under the following settings, and the reproducibility of the colored glitter printed layer was visually confirmed.
Full Color Density: Normal Sharpness: Normal Saturation: Normal Background Erase: Enable Contrast: Normal Hue: Normal Image Quality: Text/Photo Color Balance: Standard Auto Image Quality Adjustment: Standard Quality

Evaluation criteria were as follows:
〇: The color of the colored glitter printing layer is not reproduced in a color copy △: The color of the colored glitter printing layer can be reproduced lightly in a color copy ×: The color of the colored glitter printing layer is equivalently dark in a color copy reproduced at

<Print sensitivity>
Using a thermal printer PX430 (Phoenix Co., Ltd.) with a printing energy of 8, a straight line with a thickness of 0.15 mm and 0.30 mm was drawn so as to straddle the area where the colored glitter printed layer was formed and the area where it was not formed. and printed. We compared the difference in printing sensitivity between the presence and absence of a coating film. Evaluation criteria are as follows.
〇: In the area where the colored glitter printing layer exists, a straight line with the same density can be printed △: In the area where the colored glitter printing layer exists, the printed straight line becomes slightly lighter ×: Colored glitter Printed straight lines are very faint in areas where the printed layer is present

Tables 1 and 2 show the configurations and evaluation results of Examples and Comparative Examples.

From Table 1, it can be seen that the printing media of Examples 1 to 8, which are provided with colored glitter printing layers containing synthetic mica-based uncolored pearl pigments and synthetic mica-based colored pearl pigments, use natural mica-based pearl pigments. It can be understood that, similarly to the printing medium of the reference example described above, while reproducing colored gloss, it is not reproduced by color copying.

On the other hand, the printing media of Comparative Examples 1 and 3, which do not have a colored glitter print layer, cannot reproduce the colored gloss, and Comparative Example 2, which does not contain a synthetic mica-based uncolored pearl pigment. It can be seen that the print media of and 4 are not good in color copy non-reproducibility.

Further, from Table 2, it is preferable that the content of the synthetic mica-based pearl pigment is 40% by mass or more based on the total mass of the colored glitter print layer, from the viewpoint of reproducing the colored gloss well. And the content of the synthetic mica-based pearl pigment is preferably 58% by mass or less based on the total mass of the colored glitter printing layer, from the viewpoint of improving color copy non-reproducibility and printability. Let's do it.

REFERENCE SIGNS LIST 10 colored glitter printing layer 20 thermosensitive recording sheet 22 protective layer 24 thermosensitive recording layer 26 base layer 100 printing medium

Claims (9)

A print medium comprising a thermal recording sheet and a colored glitter print layer on the thermal recording sheet,
The thermosensitive recording sheet comprises a substrate layer, a thermosensitive recording layer, and a protective layer in this order, whereby the print medium comprises the substrate layer, the thermosensitive recording layer, the protective layer, and the Equipped with colored glitter printed layers in this order,
The colored glitter print layer contains a synthetic mica-based pearl pigment and a binder resin,
The synthetic mica-based pearl pigment is composed of a synthetic mica-based uncolored pearl pigment and a synthetic mica-based colored pearl pigment, and the content of the synthetic mica-based colored pearl pigment in the synthetic mica-based pearl pigment is 2 to 90% by mass based on the total mass of the synthetic mica-based pearl pigment,
print media. 2. The print medium according to claim 1, wherein the colored glitter print layer has a thickness of 2 [mu]m or less. 3. The print medium according to claim 1, wherein the synthetic mica-based pearl pigment has a content of 40 to 58% by mass based on the total mass of the colored glitter print layer. The print medium according to any one of claims 1 to 3, wherein the average particle size of the synthetic mica-based pearl pigment measured by a laser diffraction/scattering method is 10 to 40 µm. The print medium according to any one of claims 1 to 4, wherein the colored glitter print layer further contains wax. The print medium according to any one of claims 1 to 5, wherein the binder resin is a polyester resin. 7. The print medium of claim 6, wherein the binder resin is urethane-modified polyester. 8. The print medium according to claim 1, further comprising another print layer between said thermal recording sheet and said colored glitter print layer. 9. The thermosensitive recording sheet further comprises a magnetic recording layer, and the magnetic recording layer is present on the opposite side of the base layer to the thermosensitive recording layer. The print medium according to item 1.

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