JPH056143Y2 - - Google Patents

Description

[Detailed explanation of the idea] 〔Technical field〕 The present invention relates to a heat-sensitive recording adhesive sheet.

[Prior art]

A thermosensitive recording material is a recording material having a structure in which a so-called thermosensitive coloring layer that develops color when heated is formed on a support such as paper, synthetic paper, or resin film, and a thermal head is used for heating to develop the color. A built-in thermal printer is used. Compared to other recording materials, such recording materials are capable of producing records in a relatively short period of time without complex processes such as phenomenon and fixing, do not generate noise, and are relatively inexpensive. Due to these advantages, it is useful not only for copying books, documents, etc., but also for recording materials for various information and measuring instruments such as electronic computers, facsimile machines, telex, medical measuring instruments, etc., as well as for station management system tickets, department stores, markets, etc. It is also widely used as a label for POS systems.

This kind of label is used by printing the product name, price, etc. and barcode in color using a printer with a thermal head, then peeling off the release paper and pasting it on the product. In addition to providing information such as price, the barcode recorded on the label is read by an automatic reader at the point of sale of the product, and the information recorded in the barcode is processed by a computer. It is used to manage sales, inventory, ordering, etc.

Furthermore, in addition to the above uses, this label can also be used for
It can also be used as a means of conveying other information intended by the seller to the product purchaser.

For example, when holding a discount sale or special sale, a label can be used to convey information that allows a purchaser to identify the target product from other products.

Conventionally, for such identification, a method has been used in which figures or characters are printed using colored printing ink on a white heat-sensitive coloring label, but in this case, the printing process is quite time-consuming, and thermal When recording with the head, the pattern formed by the printing ink comes into contact with the thermal head, so the head tends to get dirty, which has the disadvantage of causing residue to adhere to the head and staining of the thermal printing area.

Furthermore, since such heat-sensitive colored labels are attached to products, if they come into contact with food containing oil or plastic film containing plasticizer used to package food, the colored image may smudge. ,
Although it is required that the color does not fade, the current situation is that nothing satisfactory has been obtained yet.

〔the purpose〕

The object of the present invention is to provide a heat-sensitive recording type adhesive sheet which has a remarkable discrimination effect, does not cause a colored image to bleed or fade, and does not cause residue on a thermal head or dirt on a thermal printing part.

〔composition〕

According to the present invention, there is provided a heat-sensitive recording characterized in that a heat-sensitive coloring layer, a protective layer containing an organic fluorescent pigment and a binder as main components are sequentially provided on a support, and an adhesive layer is provided on the back surface of the support. A mold adhesive sheet is provided.

Next, the heat-sensitive recording adhesive sheet according to the present invention will be explained with reference to the accompanying drawings. In Figure 1, reference numeral 1 is a conventional support such as paper or film, on which a thermosensitive coloring layer and a protective layer mainly composed of an organic fluorescent pigment and a binder are sequentially provided, and on the back side there is an adhesive. There are layers.

FIG. 2 shows another embodiment of the present invention, in which the peelable mount 5 shown in FIG. 1 is provided. FIG. 3 shows yet another embodiment of the present invention, in which a release layer of silicone resin or the like is provided on the protective layer of FIG. 1.

As mentioned above, the heat-sensitive recording adhesive sheet of the present invention has a protective layer mainly composed of an organic fluorescent pigment and a binder on the top surface of the heat-sensitive coloring layer, so it has a remarkable identification effect and a colored image. It does not smear or fade, and it also does not cause residue on the thermal head or dirt on the thermal printing area, and is of extremely high practical value.

In the present invention, known organic fluorescent pigments are used to be contained in the protective layer, such as:
Powder of a fluorescent dye in a solid solution in a synthetic resin is used. This organic fluorescent pigment can be easily produced by dyeing or dissolving a fluorescent dye in the synthetic resin production process or after production, and pulverizing the resulting colored lumpy resin, emulsion polymerization method, or resin precipitation method. be able to.

Fluorescent dyes used in this invention include:
Examples include: The value in parentheses is the color index value.

Frilliansulfoflavine FF (CI56205) Basic yellow HG (CI46040) Eosine (CI45380) Rhodamine 6G (CI45160) Rhodamine B (CI45170) Thioflavine (CI49005) Fluoresein (CI35350) Synthetic resins to be dyed include acrylic resin and vinyl chloride resin. , alkyd resin, aromatic sulfonamide resin, urea resin, melamine resin,
Benzoguanamine resins, cocondensation polymers thereof, and the like are used.

In the present invention, the binders used in the protective layer include polyvinyl alcohol, carboxymethylcellulose, methylcellulose, ethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, polyacrylamide, starch, gelatin,
Water-soluble polymers such as casein and polyvinylpyrrolidone, or water-dispersible resins such as polystyrene emulsion can be used. Further, in order to make the water-soluble polymer water resistant, a water resistant agent such as formaldehyde, glyoxal, chromium alum, melamine, melamine-formaldehyde resin, polyamide resin, polyamide-epichlorohydrin resin, etc. can be added. Furthermore, organic or inorganic fillers or fillers may be added to the protective layer to improve head matching. The amount of organic fluorescent pigment added is 10 parts by weight when the weight of the protective layer is 100 parts by weight.
A suitable amount is 130 parts by weight, preferably 40 to 110 parts by weight. Further, as the adhesive layer on the back surface of the support in the present invention, an acrylic adhesive, a starch adhesive, a styrene/butadiene latex, or a microcapsule of these can be used.

Various types of heat-sensitive coloring layers can be used for the present invention, and for example, the following thermocoloring systems can be employed.

(1) A thermochromic system consisting of a combination of long-chain aliphatic iron salts such as ferric stearic acid and ferric myristate and phenols such as tannic acid, gallic acid, and ammonium salicylate.

(2) A thermochromic system consisting of a combination of heavy metal sulfates, such as silver, lead, mercury, and thorium sulfates, and sulfur compounds, such as Na-tetrathionate, sodium thiosulfate, and thiourea.

(3) noble metal salts of organic acids such as silver behenate, silver stearate, protocatechuic acid, spiroindane,
A thermochromic system consisting of a combination with an aromatic organic reducing agent such as hydroquinone.

(4) Organic acid lead salts such as lead caproate, lead belargonate, and lead behenate and ethylenethiourea, N-
A thermochromic system consisting of a combination with a thiourea derivative such as dodecylthiourea.

(5) A thermochromic system consisting of a combination of a leuco dye and a color developer may be mentioned, but it is preferable to use the leuco dye of (5) in terms of color development sensitivity and clear color development.

Specific examples of color-forming substances used in the present invention include 3-{N-(p-tolylamino)}-7-
Anilinofluorane, 3-{N-(p-tolyl)-
N-methylamino}-7-anilinofluorane,
3-{N-(p-tolyl)-N-ethylamino}-7
-anilinofluorane, 3-{N-(p-tolyl)
-N-propylamino}-7-anilinofluorane, 3-{N-(p-tolyl)-N-butylamino}
-7-anilinofluorane, 3-dimethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-dipropylamino-6-methyl-7 −
Anilinofluorane, 3-dibutylamino-6-
Methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3-
Piperidino-6-methyl-7-anilinofluorane, 3-piperazino-6-methyl-7-anilinofluorane, 3-N-(N'-methylpiperazino)
-6-Methyl-7-anilinofluorane, 3-morpholino-6-methyl-7-anilinofluorane, 3-dibenzylamino-6-methyl-7-anilinofluorane, 3-(N-methyl -N-cyclohexyl)-6-methyl-7-anilinofluorane, 3-(N-cyclohexylamino)-6-methyl-7-anilinofluorane, and the like.

As a color developer that causes a color-forming substance to develop color when heated, 2,2'-methylenebis(4-ethyl-6-t
-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4,
4'-isopropylidene diphenol, 4,4'-isopropylidene bis(2-chlorophenol),
4,4'-isopropylidene bis(2,6-dibromophenol), 4,4'-isopropylidene bis(2,6-dichlorophenol), 4,4'-isopropylidene bis(2-methylphenol), 4 ，
4'-isopropylidene bis(2,6-dimethylphenol), 4,4'-isopropylidene bis(2
-t-butylphenol), 4,4'-sec-butylidene diphenol, 4,4'-sec-butylidene bis(2-methylphenol), 4,4'-cyclohexyldene diphenol, 4,4'-cyclohexyldene bis (2-methylphenol), 2,2'-
Thiobis(4,6-dichlorophenol), P,
Examples include, but are not limited to, P'-(1-methyl-n-hexylidene) diphenol.

Conventionally, a thermosensitive color forming layer usually contains a binder. Conventional binders include, for example, gelatin, starch, hydroxyethylcellulose, polyacrylic acid, carboxyethylcellulose, methoxycellulose, polyvinyl alcohol, polyvinylpyrrolidone, and the like.

Further, inorganic or organic fillers, sensitizers, etc. may be added to the heat-sensitive coloring layer in order to improve head matching properties.

〔effect〕

The heat-sensitive recording adhesive sheet of the present invention has the above-mentioned structure, has a remarkable discrimination effect, does not cause the colored image to smudge or fade, and is extremely free from adhering to the thermal head or staining the thermal printing area. It is highly practical and is widely used as a heat-sensitive coloring label.

〔Example〕

Next, the present invention will be explained with reference to examples.

A mixture consisting of the following formulation was mixed with a magnetic ball mill for 24 hours.
A coloring agent (liquid A) was prepared by time-pulverization and dispersion.

A-liquid formulation 3-(N-Ethyl-N-p-tolyl)6-methyl-7-anilinofluorane 150 parts 5% polyvinyl alcohol aqueous solution 150 parts Water 200 parts Next, a mixture consisting of the following formulation was heated in a magnetic ball mill for 24 hours. A color developer (liquid B) was prepared by time-pulverization and dispersion.

B liquid formulation Bisphenol A 120 parts Stearic acid amide 120 parts 5% polyvinyl alcohol aqueous solution 120 parts Water 200 parts 100 parts of liquid A and 400 parts of liquid B were mixed to prepare a thermosensitive coloring layer forming liquid.

Next, this liquid was applied and dried on a high-quality paper weighing 52 g/m ² to a dry weight of 5 g/m ² .

Liquid C Carboxy-modified polyvinyl alcohol 50 parts Thermosetting organic filler 10 parts Water resistance agent 5 parts Water 500 parts Next, add 10 parts (50 % dispersion) was mixed and applied onto the heat-sensitive layer at a dry weight of 7 g/m ²
After coating and drying, the surface was treated with a calender.

Next, an adhesive layer was provided on the lower surface of the support, and it was temporarily attached to a release mount having a coating of silicone resin or the like to obtain a heat-sensitive recording adhesive sheet of the present invention.

This heat-sensitive recording adhesive sheet exhibited an orange fluorescent color tone and had a remarkable distinguishing effect. Furthermore, when printed with a thermal head, a clear black image was obtained.

Comparative Example 1 A thermosensitive coloring layer forming liquid was applied and dried in the same manner as in Example 1, and then the following liquid D was added at a dry weight of 2.4 g/m ²
A heat-sensitive recording type adhesive sheet for comparison was prepared by coating and drying, providing a protective layer, and calendering.

D liquid formulation Carboxy-modified polyvinyl alcohol 50 parts Urea-formaldehyde resin filler 10 parts CI Basic yellow 90 0.8 parts Water 332.5 parts Comparing this comparative product and this example product, the skin of this example has stronger fluorescence It had a bright yellow color and was highly distinguishable.

[Brief explanation of the drawing]

1 to 3 are cross-sectional views of the heat-sensitive recording adhesive sheet of the present invention. In the figure, 1...Support, 2...Thermosensitive coloring layer, 3...Protective layer, 4...Adhesive layer, 5...
...Release mount, 6...Release layer.

Claims (1)

[Scope of Claim for Utility Model Registration] (1) A heat-sensitive coloring layer, a protective layer containing an organic fluorescent pigment and a binder as main components are sequentially provided on a support, and an adhesive layer is provided on the back side of the support. Features a heat-sensitive recording adhesive sheet. (2) A heat-sensitive recording adhesive sheet according to claim 1 of the utility model registration claim, wherein the adhesive layer is provided with a release mount. (3) A heat-sensitive recording adhesive sheet according to claim 1 of the utility model registration, which has a release layer on the protective layer. (4) The heat-sensitive recording adhesive sheet according to claims 1 to 3 of the utility model registration claim, wherein the adhesive is microencapsulated.