JPH0412530Y2 - - Google Patents

Description

[Detailed explanation of the idea]

(Industrial Application Field) This invention relates to a heat-sensitive coloring label, and particularly to a heat-sensitive coloring label that develops color by heating. (Prior Art) FIG. 4 is a sectional view showing an example of a conventional heat-sensitive coloring label. This thermosensitive coloring label 1 includes a sheet-like label base material 2, and a thermosensitive coloring layer 3 that develops color by heating is formed on the surface of this label base material 2. This heat-sensitive coloring label 1 is, for example,
It is sometimes used by being attached to the surface of packaging materials for products such as fresh foods. In this case, depending on the price of the product to which the heat-sensitive coloring label 1 is attached, the heat-sensitive coloring label with a glossy surface may be
May be required. For example, if the product to which heat-sensitive coloring labels are attached is expensive,
In accordance with this, there are cases where it is desired to give gloss to the surface of the heat-sensitive coloring label. (Problems to be Solved by the Invention) However, in the conventional heat-sensitive coloring label, since the heat-sensitive coloring layer is exposed on the surface, the surface is matte and does not have gloss. Therefore, in order to make the surface of a heat-sensitive coloring label glossy, an ultraviolet curable resin is applied flatly to the surface of the heat-sensitive coloring layer of the heat-sensitive coloring label, and the UV-curable resin is irradiated with ultraviolet rays. It is possible to form a glossy layer by curing the . However, if a glossy layer is formed on the surface of the heat-sensitive coloring layer in this way, the surface becomes glossy, but since the ultraviolet curing resin that is the material of the glossy layer is easily charged, the charged gloss Due to the electrostatic force of the layer, paper powder, dust, dust, etc., for example, are attracted to the surface of the heat-sensitive coloring label (glossy layer). Therefore, when coloring the heat-sensitive coloring layer of such a heat-sensitive coloring label, paper dust adsorbed on the surface of the heat-sensitive coloring label may adhere to the thermal head of a thermal printer, causing the heat-sensitive coloring of the heat-sensitive coloring label to become colored. It may not be possible to color the layer accurately. Therefore, the main purpose of this invention is to provide a heat-sensitive coloring label that has a glossy surface and is less likely to attract paper dust or the like to its surface. (Means for solving the problem) This invention consists of a label base material, a heat-sensitive coloring layer formed on the surface of the label base material that develops color when heated, and a heat-sensitive coloring layer formed on the surface of the heat-sensitive coloring layer. This is a heat-sensitive coloring label that includes a glossy layer mainly composed of an ultraviolet curable resin, and this glossy layer is blended with an ultraviolet crosslinkable resin that has antistatic ability. (Function) The glossy layer has gloss on its surface. The glossy layer is antistatic due to the ultraviolet cross-linked resin having antistatic ability. (Effect of the invention) According to this invention, since the glossy layer has gloss, a heat-sensitive coloring label having gloss on its surface can be obtained. Moreover, since the glossy layer is antistatic, a heat-sensitive coloring label is obtained in which, for example, paper powder and the like are not easily adsorbed on its surface. The above objects, other objects, features and advantages of the present invention will become more apparent from the following detailed description of embodiments with reference to the drawings. (Example) FIGS. 1 to 3 each show a continuous label body as an example of this invention, FIG. 1 is a perspective view thereof, and FIG. 2 is a sectional view thereof,
FIG. 3 is a plan view of the main part. The label continuum in this example consists of a number of labels 1
0,10,... and these labels 10,1
0... is an adhesive layer 12 made of an adhesive, for example.
As a result, they are temporarily attached to the surface of the release mount 14 at intervals in the longitudinal direction thereof. That is, the release mount 14 includes, for example, a belt-shaped sheet base material, and a release agent layer is formed on the surface of the sheet base material by applying a release agent such as silicone. Then, the label 10 is temporarily attached to the surface of the release agent layer of the release mount 14 by the adhesive layer 12. The label 10 includes a sheet-shaped label base material 16, as shown in FIG. This label base material 16
is made of a paper material such as high-quality paper. A printing layer 18 is formed on the surface of the label base material 16 at the center portion and the lower left portion in the vertical direction.
This printing layer 18 is printed with a predetermined ink using a printing device such as a gravure printing device.
It is formed by printing fixed information based on the retailer's address, characters, patterns, data, etc. Note that this printed layer 18 may not be formed. Further, a thermosensitive coloring layer 20 is formed on the surface of the label base material 16 at the upper center portion and the lower right portion thereof. This thermosensitive coloring layer 20 is formed by printing and applying a thermosensitive coloring agent, which will be described later, using a printing device such as a gravure printing device. Note that, on the surface of the label base material 16, a portion where the printing layer 18 and the thermosensitive coloring layer 20 are not formed is a blank portion 22. Further, a barrier layer 2 is provided on the surface of the thermosensitive coloring layer 20.
4 is formed. This barrier layer 24 is made of a water-soluble resin mainly composed of a water-soluble polymer, etc.
It is formed by applying it to the surface of. This barrier layer 24 is made of, for example, an ultraviolet curable resin that is a material of a glossy layer 26 to be described later, and a solvent that causes color reduction or color development of the heat-sensitive coloring layer 20.
This is to prevent the solvent, plasticizer, etc. from seeping into the thermosensitive coloring layer 20 when the solvent, plasticizer, etc. are included. Therefore, the barrier layer 24
is not formed of a solvent-based material that inhibits the heat-sensitive coloring layer 20, but is formed of a water-soluble resin mainly composed of a water-soluble polymer. Examples of the water-soluble polymer for forming this barrier layer 24 include polyvinyl alcohol,
Water-soluble resins such as carboxymethylcellulose, methylcellulose, ethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, polyacrylamide, polyvinyl, pyrrolidone, polyvinyl acetate, isobutylene-maleic anhydride copolymer,
Examples include alginate alkali metal salts such as sodium alginate, and natural products such as starch, gelatin, and casein. In addition, the ultraviolet curing resin that becomes the glossy layer 26 includes
If the thermosensitive color forming layer 20 does not contain a solvent, a plasticizer, etc. that causes color reduction or color development, the barrier layer 24 may not be formed. Label base material 18 including the surface of this barrier layer 24
A glossy layer 26 is formed on the surface. This glossy layer 26 is formed by, for example, printing and coating a resin in which an ultraviolet cross-linked resin having antistatic ability is mixed in an ultraviolet curable resin on the surface of the barrier layer 24, and irradiating the resin with ultraviolet rays. It is formed by curing the resin. Examples of the components of the ultraviolet curable resin forming the glossy layer 26 are as follows. The ultraviolet curable resin includes, for example, a prepolymer that is a photopolymerizable oligomer and provides the basic physical properties of the cured product, a photopolymerizable monomer, a photoinitiator, a sensitizer, a light stabilizer, a heat stabilizer, a plasticizer, etc. Consists of auxiliary agents, etc. In this case, polyester acrylate, polyester urethane acrylate, epoxy acrylate, polyol acrylate, etc. can be used as the prepolymer. Furthermore, monomers include monofunctional acrylates such as 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, and 2-hydroxypropyl acrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, and 1,6- Hexanediol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, polyethylene glycol 400 diacrylate, hydroxy bivalic acid ester neobentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate,
Monofunctional acrylates such as dipentaerythol hexaacrylate can be mentioned. In addition, the UV cross-linked resin having antistatic ability that is a component of the glossy layer 26 has the following general formula: Examples include phosphoric acid ester-based acrylate oligomers such as the compound represented by. In addition, as a compound represented by the above general formula,
For example, New Frontier A229E (trade name) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. can be used. Further, if the viscosity of the resin for forming the glossy layer 26 is set to 300 cps or less, the printed and applied resin can be quickly flattened, so that the manufacturing time can be shortened. The resin that becomes the glossy layer 26 is applied to a thickness of, for example, 20 microns or less, preferably 3 to 10 microns, and is coated with ultraviolet light using a UV lamp (high-pressure mercury lamp) for 1 to 2 seconds. The gloss layer 26 is then cured and formed as a glossy layer 26. This label 10 has a glossy surface because its surface is covered with a glossy layer 26. Furthermore, in the glossy layer 26 of this label 10,
Since the glossy layer 26 contains an ultraviolet cross-linked resin having antistatic properties, it is difficult to be charged. Therefore, paper dust, for example, is difficult to adhere to the surface of the label 10. And this label 10
For example, when coloring with a thermal printer,
For example, paper dust does not adhere to the thermal head of a thermal printer, and color development can be performed satisfactorily. Moreover, since the surface of this label 10 is covered with the glossy layer 26 made of a resin material, the surface has good water resistance and moisture resistance. In addition, in the above-mentioned embodiment, paper material such as high-quality paper was used as the label base material 16, but the label base material 16
As the material, other paper materials or synthetic resin sheet materials such as polypropylene or polyvinyl chloride can be used. Further, in the above-described embodiment, the printed layer 18 and the blank portion 22 are formed, but the printed layer 18 and the blank portion 22 may not be formed. That is, the thermosensitive coloring layer 20 and the gloss layer 26 may be formed in this order over the entire surface of the label base material 16. Note that the printed layer 18 may be formed on the surface of the barrier layer 24 or on the surface of the glossy layer 26. Experimental Example First, substances having the following composition were mixed to produce a mixture. - 35 parts by weight of crystal violet lactone (CVL) as a colorless dye - 10% polyvinyl alcohol (PVA) as a binder
10 parts by weight/150 parts by weight of water Next, substances having the following composition were mixed to prepare a mixture. - 35 parts by weight of bisphenol A as a color-forming acidic substance - 10% polyvinyl alcohol (PVA) as a binder
150 parts by weight/65 parts by weight of water Next, the above-mentioned mixtures were mixed in the following proportions to obtain a heat-sensitive coloring agent.・ Mixture 33 parts by weight ・ Mixture 67 parts by weight Then, use this heat-sensitive coloring agent as a sample.
, and a comparative example, , for example, 40 to 110 g/m ² as eight label base materials 16.
A heat-sensitive coloring layer 20 was formed on each of the surfaces of eight pieces of high-quality paper, for example, using a printing or coating device at a dry adhesion rate of 6 g/m ² . In this coating method, first, each label base material 1
A printing layer 18 is formed by printing lines such as predetermined characters by an existing printing method (gravure printing, etc.) on the part of the surface of 6 that is not coated with a heat-sensitive coloring agent, and then, A method was adopted in which a heat-sensitive coloring agent was applied to a portion of the surface of the label base material 16 other than the portion where the printing layer 18 was formed using a printing device such as a gravure printing device or a printing device such as a coating device. . Next, a water-soluble substance having the following composition is printed and coated on the surface of each heat-sensitive coloring layer 20 using a printing device such as a gravure printing device or a coating device such as a coating device, thereby forming a barrier. Layer 24 was formed. - 10 parts by weight of polyvinyl alcohol (PVA) - 5 parts by weight of other additives (water resistant agent, filler, wax) - 80 parts by weight of water In addition, ultraviolet curable resins having the components shown in Table 1 were prepared.

[Table] In Table 1, DPHA is KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd., and R-551 is KAYARAD R-551 manufactured by Nippon Kayaku Co., Ltd.
MANDA is KAYARAD manufactured by Nippon Kayaku Co., Ltd.
MANDA, D-310 is KAYARAD D-310 manufactured by Nippon Kayaku Co., Ltd., and TMPTA is KAYARAD TMPTA manufactured by Nippon Kayaku Co., Ltd.
NPGDA is KAYARAD manufactured by Nippon Kayaku Co., Ltd.
NPGDA, R-604 is KAYARAD R-604 manufactured by Nippon Kayaku Co., Ltd., and BF medium is BF medium manufactured by Toka Shiki Kagaku Kogyo Co., Ltd. Furthermore, a phosphoric acid ester-based acrylic oligomer was prepared as an ultraviolet cross-linked resin having antistatic ability. As this phosphate ester-based acrylic oligomer, for example, New Frontier A229E (trade name) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. can be used. Then, the above-mentioned ultraviolet cross-linked resin having antistatic ability was mixed into a portion of the above-mentioned ultraviolet curable resin, , and, respectively, in the proportions shown in Table 2 to prepare resins, , and.

[Table] Then, these resins are applied to four label base materials including the barrier layer 24 and the like using a printing and coating device such as a gravure printing device or a reverse roll coating device. 16 at a rate of 5 g/m ² , and the resin is irradiated with ultraviolet rays for 1 to 2 seconds using a UV lamp (high-pressure mercury lamp) to harden the resin, thereby forming the glossy layer 26. was formed. The four labels thus obtained were each coated with resin,...
Corresponding to this, we set the sample as . On the other hand, on the surfaces of the remaining four label base materials 16 including the barrier layer 24 etc., the above-mentioned ultraviolet curable resin, . . . is applied in the same amount as the above-mentioned resin, . A glossy layer 26 was formed by irradiating ultraviolet rays in the same manner as described above. Each of the four labels obtained in this way is
UV-curable resin applied to its surface,
, corresponding to the comparison example. Looking at these samples, , and comparative examples, their surfaces had gloss. Then, the samples, , and comparative examples, were colored using a thermal printer. As a result, good color development was achieved for the samples, but for the comparative examples,
, paper dust and the like adhering to the surface of the printer adhered to the thermal head of the thermal printer, resulting in poor color development. In addition, after measuring the surface resistivity of sample , , and comparative example , , for sample , ,
3.09×10 ¹² (Ω), 2.18×10 ¹² (Ω), 6.37, respectively.
×10 ¹² (Ω), 5.26 × 10 ¹² (Ω), comparative example,
,, respectively, 8.01×10 ¹⁵
(Ω), 1.39×10 ¹⁵ (Ω), 4.58×10 ¹⁵ (Ω), 3.76×
It was 10 ¹⁵ (Ω). From this, the sample,
It can be seen that the surface resistivity of , , is three orders of magnitude smaller than that of comparative example , , , and is less likely to be charged. in this way,
From the point of view of surface resistivity, the sample...
It can be seen that , is less likely to be charged than the comparative example, , . Note that the heat-sensitive coloring agent is not limited to the above-mentioned examples. For example, colorless dyes include crystal violet lactone (CVL), dyes such as malachide green lactone, rhodamine-B-lactam, and dye intermediates thereof, and color-forming acidic substances include bisphenol A.
In addition, P-phenylphenol, resorcinol, and organic acids such as oxalic acid or maleic acid are listed, and as binders, in addition to polyvinyl alcohol (PVA), binders that are water-soluble polymers such as carboxymethyl cellulose and methyl cellulose are listed. It will be done. Furthermore, colorless dyes other than crystal violet lactone (CVL) may be used as the colorless dye, color-forming acidic substances other than bisphenol A may be used as the color-forming acidic substance, and colors other than polyvinyl alcohol (PVA) may be used as the binder. In addition, in the coloring agent, the mixing ratio of colorless dye, coloring acidic substance, binder, etc. may be changed as appropriate.As other auxiliary agents, paraffin wax, higher fatty acids, etc. may be used. A lubricant, clays such as kaolin and calcium carbonate, antifoaming agents such as octyl alcohol, cycloxanol, and span, and waterproofing agents may be appropriately mixed.

[Brief explanation of the drawing]

FIG. 1 is a perspective view of a continuous label body as an embodiment of this invention. FIG. 2 is a sectional view of the embodiment of FIG. 1. FIG. 3 is a plan view of the embodiment shown in FIG. FIG. 4 is a sectional view showing an example of a conventional heat-sensitive coloring label. In the figure, 10 is a label, 12 is an adhesive layer,
14 is a release mount, 16 is a label base material, 18 is a printing layer, 20 is a heat-sensitive coloring layer, 22 is a blank area, 24 is a barrier layer, and 26 is a glossy layer.

Claims (1)

[Claims for Utility Model Registration] 1. A label base material, a heat-sensitive coloring layer formed on the surface of the label base material that develops color when heated, and a thermosensitive coloring layer formed on the surface of the heat-sensitive coloring layer mainly consisting of an ultraviolet curable resin. A heat-sensitive coloring label, comprising: a glossy layer, the glossy layer containing an ultraviolet cross-linked resin having antistatic ability. 2. The heat-sensitive coloring label according to claim 1, wherein the ultraviolet cross-linked resin includes a phosphate ester-based acrylic oligomer. 3. The ultraviolet crosslinking resin is blended in an amount of 10 parts by weight in 100 parts by weight of the ultraviolet curable resin.
A heat-sensitive coloring label according to claim 1 or 2 of the utility model registration claim. 4. A barrier layer formed between the heat-sensitive coloring layer and the glossy layer and containing a water-soluble polymer as a main ingredient;
A heat-sensitive coloring label according to any one of claims 1 to 3 of the utility model registration claims. 5. The heat-sensitive coloring label according to claim 4, wherein the water-soluble polymer includes a water-soluble resin containing polyvinyl alcohol.