JP2009058961A - No-separator type thermosensitive recording label, label continuum and method for producing the same - Google Patents

Abstract

The present invention relates to a no-separator type thermal recording label that does not cause a phenomenon of adhering to a thermal head even when printing is performed by a printer, and a release layer is peeled off from a pressure-sensitive adhesive layer to which it is bonded without a release paper. A no-separator type thermal recording label continuum that has the property and does not generate a phenomenon of being attached to a thermal head even when printing is performed by a printer, and a method for manufacturing the same.
In a no-separator type thermal recording label in which a thermosensitive coloring layer and a release layer are laminated on one side of a substrate and an adhesive layer is provided on the other side of the substrate, the release layer is an emulsion type silicone resin. Heat-curing a coating layer containing an emulsion-type silicone resin in which an additive-dispersed thermosensitive recording label and label continuum, and a non-separator type thermal recording label formed from And a release layer is formed. The method for producing the label or the like.
[Selection] Figure 1

Description

  TECHNICAL FIELD The present invention relates to a no-separator type thermal recording label and a label continuum that do not require a release paper, and a method for producing the same. The present invention relates to a no-separator thermosensitive recording label, a label continuum, and a method for producing the same, which can prevent the formation of the surface layer of the recording label.

  For the no-separator type thermal recording label without release paper, it is possible to use the no-separator type thermal recording label in a wound state by forming a layer having releasability on the surface of the no-separator type thermal recording label. Thus, it becomes possible to obtain a roll-shaped no-separator type thermal recording label.

In order to perform printing on the thermosensitive coloring layer uniformly, the surface of the release layer is required to be smooth, but if the surface of the release layer is too smooth, the interface between the thermal head and the release layer interface Due to the interaction, the phenomenon that the surface layer of the no-separator type thermal recording label becomes easy to stick to the thermal head is recognized, and when printing is performed with a printer, a releasable substance adheres to the thermal head. May occur.
Silicone resins exist as substances having releasability, and silicone resins are roughly classified into emulsion systems that are aqueous dispersions, solvent systems that are dispersed in solvents such as organic solvents, and solventless systems that do not use solvents.
When this solvent-based silicone resin or solvent-less silicone resin is used as a release agent matrix, the additive consisting of an aqueous dispersion cannot be used as it is, but it will be used after removing moisture by drying, etc. When the additives are dried, the well dispersed additives aggregate, so there is a problem that even if these are added to solvent-based or solvent-less silicone resins, their original effects cannot be exhibited. is there.
In addition, when solvent-based silicone resin is used, it is necessary to volatilize the solvent, and the silicone resin is easily charged with static electricity, so it is necessary to consider the danger of explosion, and to volatilize harmful substances such as toluene. There may be a problem of having to.
On the other hand, when solventless silicone resin is used, there is a merit that it is not necessary to volatilize the solvent, but it is designed so that the solvent does not need to be used. Small and may cause insufficient cure bonding.

  Therefore, the main object of the present invention is to eliminate the sticking between the no-separator type thermal recording label and the thermal head, and to prevent the substance that forms the release layer from adhering to the thermal head even when printing is performed with a thermal printer. No-separator type thermal recording label that prevents and prevents sticking, and a substance that can be peeled off from the adhesive layer on the back without a release paper, and forms a release layer even when printing is performed with a printer It is an object to provide a no-separator type thermal recording label continuous body that prevents the phenomenon of sticking to a thermal head and prevents sticking, and a method for manufacturing the same.

The present inventor adds pigments, lubricants, powder particles, etc. to the silicone resin that is the release agent matrix of the release agent layer, and such additives are well dispersed in an aqueous dispersion such as an emulsion. In the case of using many solvent-based or solvent-less silicone resins as the release agent matrix, it is impossible to use an aqueous dispersion additive such as an emulsion, and the emulsion silicone resin is used as the release agent matrix. In addition, even when an additive composed of an aqueous dispersion is used, it is not necessary to dry the aqueous dispersion and it can be used as it is. Has reached
In the no-separator type thermosensitive recording label and the label continuous body according to claim 1 of the present invention, a thermosensitive coloring layer and a release layer are laminated on one side of a substrate, and an adhesive layer is provided on the other side of the substrate. In the no-separator type thermal recording label, the release layer is dispersed in a release agent matrix made of an emulsion type silicone resin so that sticking is prevented, and the release agent matrix is heated in the presence of a curing catalyst. A no-separator thermosensitive recording label and a label continuum characterized by being cured.
The no-separator thermosensitive recording label and the continuous label according to claim 2 of the present invention are characterized in that the emulsion type silicone resin is a condensation type silicone resin and / or an addition type silicone resin. It is a no-separator type thermal recording label and label continuum of description.
According to a third aspect of the present invention, there is provided a method for producing a no-separator thermosensitive recording label and a label continuum, wherein a thermosensitive coloring layer and a release layer are laminated on one side of a substrate, and an adhesive layer is formed on the other side of the substrate. A no-separator type thermosensitive recording label and a continuous label production method, wherein the coating layer containing the emulsion type silicone resin in which the additive is dispersed is heated and cured in the presence of a curing catalyst, A method for producing a no-separator thermosensitive recording label and a label continuum, wherein a release layer is formed.
According to a fourth aspect of the present invention, there is provided the method for producing a no-separator type thermal recording label and a continuous label body, wherein the emulsion type silicone resin is a condensation type silicone resin and / or an addition type silicone resin. Item 4. A method for producing a no-separator thermal recording label and a label continuum according to Item 3.

According to this invention, even if there is no release paper, the release layer has a peelability with respect to the pressure-sensitive adhesive layer to which it is bonded, and the phenomenon that it adheres to the thermal head even when printing is performed with a printer. It is possible to provide a no-separator type thermal recording label, a no-separator type thermal recording label continuous body that does not occur and has excellent head matching characteristics, and a method for producing the same.
The above object, other objects, features, and advantages of the present invention will become more apparent from the following detailed description of embodiments of the present invention with reference to the drawings.

FIG. 1 is a perspective view of a continuous body of a no-separator type thermal recording label according to an embodiment of the present invention, and FIG. 2 is a cross section of the continuous body of a no-separator type thermal recording label according to an embodiment of the present invention. FIG.
This no-separator type thermal recording label continuum 10 is a long one in which a plurality of no-separator type thermal recording labels 12 are continuously formed, and is formed at the boundary of each no-separator type thermal recording label 12. Each perforation 14 is cut into each and used as one thermal recording label.
In this no-separator type thermal recording label continuous body 10, a pressure-sensitive adhesive layer 18 made of a pressure-sensitive adhesive is formed on the back surface of a long substrate 16, and a release layer 20 is formed on the front surface side. .
Further, a thermosensitive coloring layer 22 is formed on the surface of the base material 16 below the release layer 20, and a protective layer 24 for protecting the thermosensitive coloring layer 22 is usually formed on the surface of the thermosensitive coloring layer 22. ing.
Further, usually, a printing layer 26 is formed on a part of the lower layer of the release layer 20 on the surface of the protective layer 24 and is covered with the release layer 20.
Furthermore, an undercoat layer may be formed between the base material 16 and the pressure-sensitive adhesive layer 18 and / or between the base material 16 and the thermosensitive coloring layer 22.

And, as shown in FIG. 1, the no-separator type thermal recording label continuum 10 is separated from each other and used as the no-separator type thermal recording label 12 before the release layer 20 side and the pressure-sensitive adhesive layer. The core 18 is wound in a roll shape so that 18 is bonded and temporarily attached. When the no-separator thermal recording label continuous body 10 is used, it is rewound by the action of the release layer 20. The pressure-sensitive adhesive layer 18 can be used by being separated into each no-separator type thermal recording label 12 and adhered to the other.
Further, in this no-separator type thermal recording label continuous body 10, a perforation 14 is formed. Each perforation 14 is formed at the boundary of each no-separator type thermosensitive recording label 12 constituting the no-separator type thermosensitive recording label continuum 10, and when each no-separator type thermosensitive recording label 12 is separated and used, Each no-separator type thermal recording label 12 is easily separated.

The long base material 16 can be cut by a machine or instrument such as paper, synthetic paper, cellophane, polystyrene, polyethylene terephthalate, or a plastic film or sheet, or aluminum foil. The material is desirable.
The pressure-sensitive adhesive layer 18 formed on the back surface of the base material 16 is for giving each no-separator type thermal recording label an adhesive force for adhering to other materials. For example, acrylic copolymer resin, rubber A known pressure-sensitive adhesive such as a system adhesive is used.

The thermosensitive coloring layer 22 formed on the surface of the substrate 16 is formed, for example, by applying and drying a thermosensitive coloring composition containing a mixture of a leuco dye, an acidic substance and a binder.
In this case, examples of the leuco dye include crystal violet lactone, 3-indolino-3-P-dimethylaminophenyl-6-dimethylaminophthalide, 3-diethylamino-7-chlorofluorane, 2-diethylamino-7-cyclohexyl. Aminofluorane, 3-diethylamino-5-methyl-7-t-butylfluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-p-butylanilino Examples include fluoran.

  Examples of acidic substances include 2,2-bis (4′-oxyphenyl) propane, 4-phenylphenol, 4-hydroxyacetophenone, 2,2′-dihydroxydiphenyl, 2,2′-methylenebis (4- Methyl-6-tert-butylphenol), 4,4′-isopropylidenediphenol, 4,4′-isopropylidenebis (2-chlorophenol), 4,4′-isopropylidenebis (2-methylphenol), 4 4,4′-ethylenebis- (2-methylphenol), 4,4′-thiobis (6-tert-butyl-3-methylphenol), and the like.

Furthermore, examples of the binder include polyvinyl alcohol, methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, polyacrylamide, polyacrylic acid, starch, gelatin, polystyrene, vinyl chloride-vinyl acetate copolymer, and the like.
The thermosensitive coloring layer 22 can be colored by heating it with a thermal head of a printer or the like.

  When the protective layer 24 is formed to protect the thermosensitive coloring layer 22, for example, it contains a resin such as polyvinyl alcohol or acrylic resin, and the thermosensitive coloring layer 22 has excellent chemical resistance, plasticizer resistance, etc. To be formed.

  When the printing layer 26 is formed, the printing layer 26 is formed by printing using a general printing ink by a known printing method such as flat plate, letterpress or offset printing. In particular, an ultraviolet curable ink or the like may be used in consideration of the influence on the thermosensitive coloring layer 22, for example, an adverse effect such as a so-called fog phenomenon.

The undercoat layer is formed in order to effectively use the heat of the thermal head, to prevent background fogging or fading of the heat-sensitive color developing layer 22.
This undercoat layer includes, for example, a latex such as SBR and NBR, a resin such as an aqueous resin such as polyvinyl alcohol and an acrylic resin, and can further include a particulate material such as calcium carbonate and silica, an elastic material, and the like.

The release layer 20 is usually formed by applying a dispersion of an additive to a release agent matrix 20a containing an emulsion type silicone resin as a main component, followed by heat curing in the presence of a curing catalyst.
For example, an additive composed of an emulsion-based aqueous dispersion is preferably used.
In the release layer of the present invention, the additive is well dispersed in the release layer matrix, and the release agent matrix is firmly bonded. As a result, when printing with a thermal head, sticking of the thermal head is prevented and high quality printing is obtained. It is done.

As the silicone resin used as the release agent matrix 20a of the present invention, an emulsion silicone resin is used.
When an emulsion silicone resin is used, water must be volatilized, but even if the additive is an aqueous dispersion, the aqueous dispersion can be used as it is without being dried, and the emulsion system is in a state where the additive is well dispersed. Due to the synergistic effect with the silicone resin mixed with the silicone resin, the original effect of the additive can be expressed well, and a release layer excellent in head matching characteristics with the thermal head can be formed.
As an emulsion-based silicone resin, a silicone resin containing polydimethylsiloxane containing a silanol group or the like as a base polymer and polymethylhydrogensiloxane or the like as a crosslinking agent is heated in the presence of a catalyst such as organotin to perform a condensation reaction. Condensation type silicone resin to be cured and silicone resin containing polydimethylsiloxane containing vinyl group as a base polymer and polymethylhydrogensiloxane etc. as a crosslinking agent are cured by addition reaction in the presence of a catalyst such as platinum. An addition type silicone resin or the like is used.

If the release agent matrix 20a of the release layer 20 that forms the outermost layer of the no-separator type thermal recording label 12 is, for example, a silicone resin that reacts and cures, it can be sufficiently cured by adding a catalyst. When the thermal recording label continuous body 10 is wound, even if the adhesive layer 18 formed on the back surface of the substrate 16 and the release layer 20 are joined, the release layer 20 has sufficient peelability and is rewound. It becomes possible.
The catalyst is not particularly limited as long as it can cure a thermosetting silicone resin, and for example, an organic tin, a platinum catalyst, or the like is used.
In addition, the thickness of the release layer 26 is generally 1 μm to 2 μm.

Various materials can be included in the emulsion type silicone resin as the release agent matrix 20a. For example, a lubricant such as fatty acid and metal soap is added to the release layer 20 to add lubricity, and powder particles such as colloidal silica and alumina are added to the release layer 20 to strengthen the release layer 20. . For example, the following various additives can be used.
_{PbO, Fe 3 O 4, Mn} 3 O 4, GeO 2, TeO 2, CuO, ZnO, BaTiO 3, SrTiO 3, BaZrO 3, Ba (Ti 1-x Zr x) O 3, Sr (Ti 1-x Zr _{x) O 3, (Ba 1} -x Sr x) TiO 3, MnFe 2 O 4, CoFe 2 O 4, NiFe 2 O 4, ZnFe 2 O 4, (Mn 1-x Zn x) Fe 2 O 4, Al _{2 O 3, MgO, In 2} O 3, BeO, Gd 2 O 3, Eu 2 O 3, Sm 2 O 3, Nd 2 O 3, La 2 O 3, Cr 2 O 3, BaSnO 3, SrSnO 3, CaSnO ₃ , MgSnO ₃ , SrGeO ₃ , SrTeO ₃ , ZrO ₂ , TiO ₂ , Nb ₂ O ₅ , Ta ₂ O ₅ , CaO, Ga ₂ O ₃ , SiO ₂ , Y ₂ O ₃ , Fe ₂ O ₃ , FeOOH, AlOOH, CaCO ₃ , Ba (SO ₄ ) ₂ , Al (OH) ₃ , kaolin, montmorillonite, hydroxyapatite, bitumen, ultramarine, talc, clay, diatomaceous earth, organic bentonite, polytetrafluoroethylene, sodium Terephthalate, polyurea, calcium soap, lithium soap, molybdenum disulfide, tungsten disulfide, graphite, boron nitride, gold, silver, cobalt, iron, nickel, platinum, palladium, rhodium, polyethylene, polypropylene, nylon, polyimide, polycarbonate, polyacetal , Molybdenum trisulfide, graphite fluoride, calcium fluoride, zinc stearate, cobalt stearate, stearic acid, potassium palmitate, sodium palmitate, palmitic acid, olein Zinc, potassium oleate, sodium oleate.

When an emulsion type silicone resin is used as the release agent matrix 20a and, for example, an additive which is a well-dispersed aqueous dispersion such as an emulsion type is added to the silicone resin, a product in which the additive is well dispersed in the emulsion type silicone resin is obtained. As an additive for this purpose, for example, an aqueous dispersion such as zinc stearate emulsion, colloidal silica, alumina colloidal dispersion, zirconia monodispersion, titania monodispersion is preferably used.
The aqueous dispersion is produced, for example, using techniques such as a sol-gel method, a colloid chemistry method, a metal alkoxide method, a precipitation method, an inorganic hydrolysis method, a chelate method, a microemulsion method, an emulsion polymerization method, and a seed polymerization method.

  The content of the additive 20b mixed in the release layer 20 is preferably 10 parts by weight or more and 75 parts by weight or less per 100 parts by weight of the release agent matrix 20a. If it is 10 parts by weight or less, the printer printing quality may be deteriorated. If it is 75 parts by weight or more, it is difficult to peel off from the pressure-sensitive adhesive layer 18 when wound as the no-separator type thermal recording label continuous body 10. This is because it may cause

  Hereinafter, although an example explains the present invention still in detail, the present invention is not limited to this example.

A 130 LHB thermal paper manufactured by Ricoh Co., Ltd., on which the thermosensitive coloring layer 22 was formed, was used as the substrate 16, and an acrylate-based adhesive was used as the pressure-sensitive adhesive 18.
A protective layer forming coating solution made of polyvinyl alcohol is applied to the surface of the substrate 16 on which the thermosensitive coloring layer 22 is formed, so that the coating amount after drying is 1 g / m ² , thereby forming the protective layer 24. did.
Thereafter, the release layer 20 was provided on the protective layer 24 as follows.
[Example 1]
The release layer 20 consists of 100 parts by weight of a thermosetting silicone resin (Shin-Etsu Chemical X-52-195 (emulsion system)), 6 parts by weight of a curing catalyst (Shin-Etsu Chemical CAT-PM-10), and zinc stearate as an additive. (Chukyo oil hydrin Z-7-30 (emulsion type)) 15 parts by weight of a release layer forming coating solution was applied so that the coating amount after drying was 1 g / m ^2, and then with a heat curing device By heating, the release agent matrix 20a was cured and the release layer 20 was formed.
An acrylic ester-based pressure-sensitive adhesive, which is a pressure-sensitive adhesive, is applied to the surface of the substrate 16 opposite to the surface on which the release layer 20 is formed so that the coating amount after drying is 20 g / m ^2. Then, a pressure-sensitive adhesive layer 18 was formed.
[Example 2]
The release layer 20 consists of 100 parts by weight of a thermosetting silicone resin (Shin-Etsu Chemical KS774 (solvent type)), 2.5 parts by weight of a curing catalyst (Shin-Etsu Chemical CAT-PL-3), zinc stearate as an additive (Japan) By applying a release layer-forming coating liquid consisting of 15 parts by weight of oil and fat zinc stearate (powder type) so that the coating amount after drying is 1 g / m ^2, and then heating with a heat curing device, The release agent matrix 20a was cured to form the release layer 20.
An acrylic ester-based pressure-sensitive adhesive, which is a pressure-sensitive adhesive, is applied to the surface of the substrate 16 opposite to the surface on which the release layer 20 is formed so that the coating amount after drying is 20 g / m ^2. Then, a pressure-sensitive adhesive layer 18 was formed.
[Example 3]
The release layer 20 is 100 parts by weight of a thermosetting silicone resin (Toray Dow Corning BY24-468C (solventless type)), 10 parts by weight of a curing catalyst (BY24-453 of Toray Dow Corning), stearic acid as an additive Applying a peeling layer forming coating solution consisting of 15 parts by weight of zinc (Chukyo Oil Hydrin Z-7-30 (used after drying the emulsion type)) so that the coating amount after drying is 1 g / m ² , Thereafter, the release agent matrix 20a was cured by heating with a heat curing apparatus, and the release layer 20 was formed.
An acrylic ester-based pressure-sensitive adhesive, which is a pressure-sensitive adhesive, is applied to the surface of the substrate 16 opposite to the surface on which the release layer 20 is formed so that the coating amount after drying is 20 g / m ^2. Then, a pressure-sensitive adhesive layer 18 was formed.
In addition, about the quantity of the curing catalyst of Examples 1-3, the quantity considered to be optimal was employ | adopted as the quantity of each system.

  For Examples 1 to 3, the sample was printed with a direct thermal printer DP-360 (manufactured by Teraoka Seiko) under the conditions of a printing speed of 80 mm / sec and a duty of 49%, and the printer printing quality and sticking properties were examined. The results shown in Table 1 were obtained.

The test items were evaluated as follows.
(1) Printer print quality As the evaluation, a three-step evaluation of ◯, Δ, and × was performed.
“◯” as an evaluation represents a state where printing is performed satisfactorily.
“△” as an evaluation shows a slight blur of printing.
“X” as an evaluation is faint in printing and missing.

(2) Sticking property As evaluation, three-step evaluation of (circle), (triangle | delta), and x was performed.
“◯” as an evaluation indicates that no stick is recognized.
“Δ” as an evaluation indicates that the stick is slightly recognized.
“X” as an evaluation indicates that the stick is remarkable.

  As can be seen from Table 1, Example 1 using an emulsion-based silicone resin is effective in preventing sticking and improves printing quality.

In addition, this invention is not limited to the said illustration, A various change is possible.
For example, as shown in the no-separator type thermal recording label continuum 10 shown in FIG. 3, the pressure-sensitive adhesive layer 18 is formed on the entire back surface of each no-separator type thermal recording label 12. Alternatively, a band-shaped blank portion in which the pressure-sensitive adhesive layer 18 does not exist may be provided at a certain width around the periphery of each no-separator type thermal recording label.
Further, a desensitizing agent that weakens the adhesive force of the pressure-sensitive adhesive layer 18, for example, a desensitizing agent containing powder such as titanium white, has a certain width from the periphery of each no-separator thermosensitive recording label 12. The strip-shaped desensitizer layer may be formed over the periphery of each no-separator type thermal recording label 12.

By using an emulsion type silicone resin as the release agent matrix 20a of the release layer 20, the additive is well dispersed in the release agent matrix 20a and the bond of the emulsion type silicone resin becomes stronger. The contact with the surface becomes smooth, the thermal head moves smoothly, and the matching property of the release layer 20 to the thermal head is improved.
This is considered to contribute to prevention of sticking.

  As described above, the no-separator type thermal recording label, the label continuum, and the production method thereof of the present invention have been described. The configuration can be changed.

  The no-separator type thermal recording label of the present invention, the label continuum, and the method for producing the same have the thermal recording label characteristics that do not cause the phenomenon of adhering to the thermal head even when printing is performed with a printer. It can be suitably used for the use of a type thermosensitive recording label or a label continuum.

It is a perspective view of the no-separator type thermal recording label continuous body which is one embodiment of this invention. BRIEF DESCRIPTION OF THE DRAWINGS FIG. It is an illustration figure which shows an example of another label of the example shown in FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 No-separator type thermosensitive recording label continuous body 12 No-separator type thermosensitive recording label 14 Perforation 16 Base material 18 Pressure sensitive adhesive layer 20 Peeling layer 20a Peeling agent matrix 20b Additive 22 Thermosensitive coloring layer 24 Protective layer 26 Print layer 28 Core tube

Claims (4)

  In a no-separator type thermal recording label in which a thermosensitive coloring layer and a release layer are laminated on one side of the substrate and an adhesive layer is provided on the other side of the substrate, the release layer is an emulsion so as to prevent sticking. A no-separator thermosensitive recording label and a continuous label, wherein an additive is dispersed in a release agent matrix made of a silicone resin and the release agent matrix is heat-cured in the presence of a curing catalyst.   The no-separator thermosensitive recording label and label continuum according to claim 1, wherein the emulsion type silicone resin is a condensation type silicone resin and / or an addition type silicone resin.   A method for producing a no-separator type thermosensitive recording label and a label continuum in which a thermosensitive coloring layer and a release layer are laminated on one side of a base material, and an adhesive layer is provided on the other side of the base material. A method for producing a no-separator type heat-sensitive recording label and a label continuum, wherein a release layer is formed by heat-curing a coating layer containing an emulsion-type silicone resin in which is dispersed in the presence of a curing catalyst.   The method for producing a no-separator type thermosensitive recording label and label continuum according to claim 3, wherein the emulsion type silicone resin is a condensation type silicone resin and / or an addition type silicone resin.

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