JPH10268768A - Adhesive label for thermosensitive recording - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive label which does not require a release paper and has stable and small peeling strength and excellent adhesion characteristics and recording characteristics. SOLUTION: This adhesive label is produced by forming a thermosensitive recording layer containing a basic dye and a color developer and a release agent layer on the surface of a supporting body. and forming an adhesive layer on the back surface. The release agent layer is formed by using one or more kinds of polysiloxane selected from polysiloxane, polyslloxane having 1- propenylether groups and polysiloxane having vinylether groups, and polymerizing and hardening by irradiation of rays. The adhesive layer consists of a hot- melt or emulsion-type adhesive essentially comprising one or more kinds of rubber adhesives selected from natural rubber, polyisoprene rubber, styrene- butadiene rubber, polyisobutylene rubber, butyl rubber, styrene-isoprene block copolymer, styrene-butadiene copolymer, add styrene-ethylenebutylene copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive recording pressure-sensitive adhesive label utilizing a color-forming reaction between a colorless or light-colored basic dye and a color former, and more particularly to a heat-sensitive recording pressure-sensitive adhesive label which does not require a release paper. And the peeling force is stable and light,
The present invention relates to an adhesive label having excellent adhesive properties and excellent recording properties as heat-sensitive recording paper.

[0002]

2. Description of the Related Art Adhesive labels have been used as labels, stickers, stickers, patches and the like for a wide range of applications such as commercial use, office use, and home use. This adhesive label is generally formed by laminating a surface substrate, an adhesive layer, and a release paper. As the release paper, one obtained by applying a release agent such as a silicone compound or a fluorine compound to a base paper for release paper such as high-density paper such as glassine paper, clay-coated paper, or polyethylene laminated paper is used. For the pressure-sensitive adhesive layer, a solvent-type pressure-sensitive adhesive, an emulsion-type pressure-sensitive adhesive, a hot-melt-type pressure-sensitive adhesive, or the like is used. In addition, surface base materials include paper base materials such as high-quality paper, kraft paper, art paper, coated paper, cast coated paper, thermal recording paper, ink jet recording paper, thermal transfer image receiving paper, film, synthetic paper, metal foil, and the like. And the like.

On the other hand, the heat-sensitive recording paper used as the surface base material utilizes a color-forming reaction between a colorless or light-colored basic dye and an organic or inorganic coloring agent, and heat-melts the coloring material to bring the recorded image into contact. Recording papers in which a recording layer containing both of them is provided on a support so as to obtain the following are well known. This heat-sensitive recording paper is relatively inexpensive, has a compact recording device, and is easy to maintain, so that it is used not only as a recording medium for facsimile machines and various computing devices but also in a wide range of fields. For example, as one of the fields of application, POS (point-to-
f sales) With the expansion of systemization, the cases used as barcode adhesive labels are increasing.

[0004] The heat-sensitive recording pressure-sensitive adhesive label is generally provided with a pressure-sensitive adhesive layer on the back surface of the heat-sensitive recording paper and then provided with a release sheet, but after recording with a label printer and attaching the label to an adherend, A large amount of release sheet was discharged. This release sheet not only disturbs the labeling work, but also cannot be recycled and pulped in a normal waste paper recovery facility, and is currently incinerated or landfilled. In addition, the thermal recording paper, adhesive and release sheet are laminated when used, and the paper thickness is increased, so the winding length of the thermal recording adhesive label that can be built into the label printer is limited, and the label printer must be enlarged or There is also a problem that the roll of the thermosensitive recording adhesive label must be frequently replaced.

[0005] In view of the problem of discarding the release sheet, it is conceivable to remove the release sheet from the thermosensitive recording label for thermal recording. Finishing method (Tokuhei 4-
No. 15110). Regarding the method for producing the above-mentioned heat-sensitive recording pressure-sensitive adhesive label, a UV-curable, EB-curable, solvent-free or emulsion-type release agent, which can be cured at room temperature, is applied to the recording surface of general thermal recording paper. To form a release agent layer by curing, and then directly apply an adhesive on the upper surface of the release agent layer, or the back surface of the support, or using a process paper, after applying the adhesive, on the back surface of the support It is manufactured by forming an adhesive layer by transfer and finishing it into a tape shape.

However, in the case of a general heat-sensitive recording pressure-sensitive adhesive label, when stored in a roll, a release sheet, a pressure-sensitive adhesive layer, a support, a heat-sensitive recording layer, then a release sheet, a pressure-sensitive adhesive layer , The support, the heat-sensitive recording layer,..., The support and the release sheet exist between the pressure-sensitive adhesive layer and the heat-sensitive recording layer, and the influence of the pressure-sensitive adhesive on the heat-sensitive recording layer is slight. .

However, in the case of the above thermosensitive recording pressure-sensitive adhesive label, when stored in a roll, the pressure-sensitive adhesive layer, the support, the heat-sensitive recording layer, the release agent, the pressure-sensitive adhesive layer,
Support, thermal recording layer, release agent layer ... overlap,
Between the pressure-sensitive adhesive layer and the heat-sensitive recording layer, one is a support,
The other is a release agent layer. This release agent layer is usually formed by applying 0.1 to 5.0 g / m ² in view of the performance and price of the release agent, and is a very thin film.
The effect of the pressure-sensitive adhesive on the heat-sensitive recording layer is great. In particular, when a polyacrylate copolymer-based pressure-sensitive adhesive is used, there is a problem that the components in the pressure-sensitive adhesive penetrate into the heat-sensitive recording layer, thereby significantly lowering the sensitivity of the heat-sensitive recording layer.

In order to solve the above-mentioned problems, when an adhesive other than an acrylic resin-based adhesive is used as the adhesive used for the adhesive layer, the release force increases depending on the type of the selected release agent. In some cases, the support may be torn without peeling, or the heat-sensitive recording layer of the inner label may be peeled. When a release agent layer is formed using a polysiloxane containing a mercapto group, a vinyl group, or an acrylic group, heavy release occurs when an adhesive other than an acrylic resin-based adhesive is used.

The heat-sensitive recording adhesive label according to the present invention comprises:
Since printing is performed while the roll-shaped label is peeled off by the printer, if the peeling force becomes heavy, a running trouble in the printer occurs, resulting in printing trouble and running failure.

In the pressure-sensitive adhesive label for thermal recording according to the present invention, the release agent layer not only has a function as a release agent, but also has the same functions as general thermal recording paper, such as running property to a thermal printer and sticking. You have to balance them. In particular, when the release agent layer is formed, the curability of the release agent and the adhesion to the thermosensitive recording paper may be deteriorated depending on the release agent selected.

[0011] Glassine paper and polyethylene laminated paper, which are general base papers for release paper, hardly inhibit the curing of the release agent, but heat-sensitive recording paper may contain components that inhibit the curing of the release agent. is there. The pressure-sensitive adhesive label for heat-sensitive recording according to the present invention, since the release agent layer is in direct contact with the heating element of the thermal printer to perform printing, when the curability of the release agent is poor, the peeling force of the pressure-sensitive label is increased. In addition, the release agent peels off and accumulates as residue in the heating element, causing printing defects such as tailing.

[0012]

DISCLOSURE OF THE INVENTION The present invention is directed to a heat-sensitive recording adhesive label which eliminates the above-mentioned problems and does not require a release paper, and has a stable and light release force and excellent adhesive properties. Another object of the present invention is to provide an adhesive label having excellent recording characteristics as heat-sensitive recording paper.

[0013]

As a result of intensive studies in view of the present situation, the present inventors have found that a heat-sensitive recording layer containing a basic dye and a colorant is provided on the surface of a support, and then a release agent layer is provided. A heat-sensitive recording pressure-sensitive adhesive label having a pressure-sensitive adhesive layer provided on the back side thereof, wherein the release agent layer has an epoxy group-containing polysiloxane, a 1-propenyl ether group-containing polysiloxane, and a vinyl ether group-containing polysiloxane. A release agent layer obtained by polymerizing and curing at least one kind of polysiloxane selected from siloxane by irradiation with radiation, and the pressure-sensitive adhesive layer is formed of natural rubber, polyisoprene rubber, styrene-butadiene rubber, polyisobutylene; Rubber, butyl rubber, styrene-isoprene block copolymer, styrene-butadiene copolymer, styrene-ethylene-butylene copolymer Found that the above problems can be solved all by the adhesive layer containing as a main component at least one or more of the rubber adhesive is selected from the coalesced, thereby completing the present invention.

In the formation of the pressure-sensitive adhesive layer, when a solvent-type pressure-sensitive adhesive is applied and dried, the solvent in the pressure-sensitive adhesive may penetrate into the heat-sensitive recording layer, and the heat-sensitive recording layer may develop color. Even if it is formed, the solvent remaining in the pressure-sensitive adhesive layer may penetrate into the heat-sensitive recording layer to form a color. On this occasion,
By using a hot-melt adhesive or an emulsion-type adhesive and providing an adhesive layer on the back surface of the heat-sensitive recording paper, it was found that an excellent heat-sensitive recording adhesive label free from coloring by a solvent can be obtained.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION As described above, the present invention relates to a release agent constituting a pressure-sensitive adhesive label for thermal recording, wherein a polysiloxane containing an epoxy group, a polysiloxane containing a 1-propenyl ether group, and a vinyl ether group are contained. A specific effect can be obtained by using at least one kind of polysiloxane selected from the following polysiloxanes and polymerizing by radiation irradiation or the like to form a cured release agent layer.

The above-mentioned epoxy group, 1-propenyl ether group and vinyl ether group contained in the polysiloxane are functional groups, and a radical polymerization reaction is caused by radicals generated by irradiating ultraviolet rays or electron beams to cure. Alternatively, the resin is cured by causing a cationic polymerization reaction by a strong acid generated by ultraviolet light, heat, or the like.

The polysiloxane containing an epoxy group has an organopolysiloxane as a basic skeleton and is not particularly limited as long as it is a compound containing an epoxy group. The polysiloxane having a 1-propenyl ether group has an organopolysiloxane as a basic skeleton, and is not particularly limited as long as it is a compound having a 1-propenyl ether group. The polysiloxane containing a vinyl ether group has an organopolysiloxane as a basic skeleton and is not particularly limited as long as it is a compound containing a vinyl ether group.

From the viewpoint of suppressing coloring of the heat-sensitive recording layer due to heating, curling of the support, and the like, it is desirable not to involve a drying step, and a solvent-free one is preferred for the present invention. The viscosity of the resin is 10 to 1000 in consideration of the impregnation of the resin into the heat-sensitive recording layer and the uniformity of the coated surface.
About 0 cps is preferable. In addition, the release agent contains various radiation-curable resins, photopolymerization initiators, dyes, pigments, wetting agents, defoamers, dispersants, antistatic agents, leveling agents, lubricants, etc., if necessary. The agent can be appropriately added within a range that does not inhibit the desired effect.

The method of applying the release agent is not particularly limited, and ordinary application means such as a bar coater, a multi-stage roll coater, an air knife coater, a gravure coater, and an offset gravure coater are appropriately used. The application amount of the release agent is appropriately adjusted in the range of 0.1 to 5.0 g / m ² .

The radiation used to cure the release agent in the present invention includes ultraviolet rays, electron beams, and the like. Examples of the ultraviolet irradiation device include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and the like. There is also an ozone-less type with little ozone. Generally, a plurality of lamps having an output of 30 W / cm or more are often used in parallel.

As the electron beam irradiator, an electron beam accelerator having an acceleration voltage of 100 to 1000 kV, preferably 100 to 300 kV is used in terms of permeability and curability. It is desirable to adjust within the range of about 5 to 20 Mrad. If it is less than 0.5 Mrad, a sufficient irradiation effect cannot be obtained, and irradiation exceeding 20 Mrad is not preferable because it may deteriorate the base material. As an electron beam irradiation method, for example, a scanning method, a curtain beam method, a broad beam method, or the like is employed. In the electron beam irradiation step, the release agent layer can be cured while the shape of the synthetic resin film, metal foil, metal drum, or the like is adhered to the protective layer and the shape is transferred.

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

According to the present invention, as described above, in the pressure-sensitive adhesive layer constituting the heat-sensitive recording pressure-sensitive adhesive label, the pressure-sensitive adhesive is made of natural rubber, polyisoprene rubber, styrene-butadiene rubber,
It is necessary to use at least one or more rubber-based pressure-sensitive adhesives selected from polyisobutylene rubber, butyl rubber, styrene-isoprene block copolymer, styrene-butadiene copolymer, and styrene-ethylene-butylene copolymer. One type of these adhesives can be selected, or two or more types can be used in combination, depending on the use of the heat-sensitive recording adhesive label. Further, in consideration of the environment in which the pressure-sensitive adhesive label is used, it is desirable that the glass transition temperature of the pressure-sensitive adhesive be -20 ° C or lower.

The pressure-sensitive adhesive used in the present invention may contain, if necessary, a tackifier, a softener, a filler, a crosslinking agent, a thickener,
Various auxiliaries such as a wetting agent, a leveling agent, an antifoaming agent, a pigment, an antioxidant, and an ultraviolet absorber can be appropriately used as long as the desired effect is not impaired.

The form of the pressure-sensitive adhesive of the present invention may be any of a solvent type, a hot melt type and an emulsion type as long as the pressure-sensitive adhesive of the above-mentioned component is used. In the case of the solvent type, it is desirable that the viscosity be in the range of 100 to 15,000 cps from the problem of controlling the amount of application in various application apparatuses. In the case of a hot melt type, the composition is heated and melted, and the viscosity at the time of coating is desirably in the range of 100 to 15,000 cps from the viewpoint of easy control of the coating amount. In the case of emulsion type,
In terms of controlling the amount of coating in various coating devices,
The viscosity is preferably about 100 to 15,000 cps, and the solid content concentration is preferably 20 to 80%.

The coating amount of the pressure-sensitive adhesive of the present invention is 5% by dry weight.
~50g / m ² is preferred. More preferably, 10 to 30
g / m ² . Incidentally, if the coating amount is less than 5 g / m ² , sufficient adhesiveness cannot be obtained when used as a label, while if it exceeds 50 g / m ² , there is a problem that the adhesiveness is saturated and the economic efficiency is poor.

The method of applying the pressure-sensitive adhesive of the present invention to a support includes brush coating, spray coating, screen printing, gravure printing, offset printing, letterpress printing, Meyer bar coater, kiss roll coater, lip coater, and direct roll coater. This is performed by various coating apparatuses such as an offset roll coater, a gravure roll coater, a reverse roll coater, a rod coater, a blade coater, an air knife coater, and a slit die coater. If drying is necessary, it can be performed by a conventional method combined with the above-described apparatus for performing coating. In the drying, the drying is performed by appropriately adjusting the drying temperature so that the heat-sensitive recording layer provided on the support does not develop color. Also,
When curing by radiation is required, a radiation irradiation device similar to the ultraviolet irradiation device and the electron beam irradiation device used for curing the release agent can be appropriately used.

The thermal recording paper of the present invention is not particularly limited, and is generally used as a base paper for thermal recording paper.
On a support such as high-quality paper (acid paper, neutral paper), synthetic paper, film, coated paper, etc., a heat-sensitive recording layer and, if necessary, on the support, or on the heat-sensitive recording layer, or intermediate on the back of the support Thermal recording paper provided with a layer is used.

As the heat-sensitive recording layer, a recording layer utilizing a color reaction between a basic dye and a colorant generally used for heat-sensitive recording paper can be used. In addition, the intermediate layer, for the purpose of improving the storage stability of the record, imparting printability in the case of performing printing immediately before providing the release agent layer, improving the adhesiveness and film formability of the release agent layer, One or two or more intermediate layers can be provided. Further, for the purpose of improving image quality and image density, a super calender process may be performed.

In the present invention, a release agent layer is provided on the recording surface of the heat-sensitive recording paper by the above-described method, and then an adhesive layer is formed on the back surface, which prevents migration of adhesive components and the like into the support, An undercoat layer can be provided if necessary to provide a sufficient adhesive effect.

The heat-sensitive recording pressure-sensitive adhesive label of the present invention obtained as described above is a heat-sensitive recording pressure-sensitive adhesive label which does not require a release paper, and has a stable and light release force, excellent adhesive properties, and This is an adhesive label for thermal recording that has excellent recording characteristics as thermal recording paper.

[0032]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which, of course, are not intended to limit the scope of the present invention.
In the examples, parts and% are unless otherwise specified.
"Parts by weight" and "% by weight" are shown.

Example 1 "Manufacture of support" Softwood bleached kraft pulp (C.S.
F. Talc was added to a pulp slurry containing 25 parts of 550 ml) and 75 parts of hardwood bleached kraft pulp (CSF 560 ml) so that the paper ash content was 5.0%. Was added to 1.5% of absolutely dry pulp and 2.0% of aluminum sulfate to obtain a stock. This stock was paper-made by a fourdrinier multi-cylinder cylinder drier paper machine and processed by a 4-stage super calender to obtain a support of 58 g / m ² . The size of the 20% aqueous ethyl alcohol solution of the support was 10 seconds.

"Preparation of heat-sensitive recording paper" Preparation of solution A 10 parts of 3- (N-ethyl-N-isoamyl) amino-6-methyl-7-phenylaminofluoran 5 parts of a 5% methylcellulose aqueous solution and 40 parts of water Was pulverized with a sand mill until the average particle diameter became 3 μm. Solution B Preparation A composition comprising 30 parts of 4-hydroxy-4'-isopropyloxydiphenylsulfone, 5 parts of a 5% aqueous solution of methylcellulose, and 80 parts of water was pulverized with a sand mill until the average particle diameter became 3 µm. Solution C preparation 1,2-di (3-methylphenoxy) ethane 20 parts, 5
A composition comprising 5 parts of an aqueous methylcellulose solution and 55 parts of water was pulverized by a sand mill until the average particle diameter became 3 μm. Solution D Preparation of 10% acetoacetyl group-modified polyvinyl alcohol aqueous solution 200 parts, kaolin (trade name: UW-90, manufactured by EMC) 100 parts, 30% zinc stearate dispersion liquid 30 parts,
And 100 parts of water were mixed and stirred to obtain a coating liquid for a protective layer.

On the surface of the obtained support, 55 parts of solution A, B
A coating liquid obtained by mixing and stirring 115 parts of the liquid, 80 parts of the liquid C, 80 parts of a 10% aqueous solution of polyvinyl alcohol, and 35 parts of calcium carbonate is applied and dried so that the coating amount after drying is 6 g / m ^2. Thus, a recording layer was formed. On the recording layer, solution D was applied and dried so that the applied amount after drying was 5 g / m ^2, and after forming a protective layer, a super calender treatment was performed to produce a thermosensitive recording paper.

"Formation of release agent layer" An ultraviolet-curable silicone resin containing an epoxy group (trade name: using an offset gravure coater) on the protective layer of the thermal recording paper.
1.5 g of UV-9300, manufactured by Toshiba Silicone Co., Ltd.)
/ M ² and an ultraviolet irradiation device (trade name:
Using Rapid Cure, manufactured by Ushio Electric Co., Ltd., the composition was cured by irradiating ultraviolet rays at an irradiation dose of 200 mj / cm ² to obtain a thermosensitive recording paper having a release agent layer.

"Production of adhesive label" 100 parts by weight of a styrene-butadiene block copolymer (trade name: TR2601, manufactured by Nippon Synthetic Rubber Co., Ltd.), and an aromatic modified terpene resin (trade name: YS Resin TR105) as a tackifier 130 parts by weight, manufactured by Yashara Chemical Co., Ltd., and a naphthenic oil (trade name: Shellflex 371J) as a softening agent
Y, manufactured by Shell Japan Co., Ltd .; 20 parts by weight of an antioxidant (trade name: Nocrack NS-5, manufactured by Ouchi Shinko Chemical Co., Ltd.); Then, it was coated on a release paper for the process with a reverse roll coater so as to have a dry weight of 25 g / m ² and dried. Then, after the pressure-sensitive adhesive layer is transferred by bonding the pressure-sensitive adhesive layer and the back surface of the heat-sensitive recording paper having the release agent layer, the release paper for the process is peeled off, and the release agent layer has the pressure-sensitive adhesive layer. The heat-sensitive recording paper was finished in a roll shape to produce the heat-sensitive recording adhesive label of the present invention.

Example 2 A roll-shaped pressure-sensitive adhesive label for heat-sensitive recording was produced in the same manner as in Example 1 except that in Example 1 "Production of pressure-sensitive adhesive label", the production was carried out by the following method. "Production of adhesive label" Styrene-isoprene block copolymer (trade name: SIS5000, Japan Synthetic Rubber Co., Ltd.)
100 parts by weight, aliphatic petroleum resin as a tackifier (trade name: Escolets 1310, Exxon Chemical Co., Ltd.)
100 parts by weight, a softener (trade name: Diana Process NM280, manufactured by Idemitsu Kosan Co., Ltd.) 40 parts by weight, an antioxidant (trade name: Nocrack NS-5, manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) 1 The parts by weight were mixed to obtain a pressure-sensitive adhesive composition. The pressure-sensitive adhesive composition is heated and melted, and has a release agent layer used in Example 1 using a die coater (trade name: Park Coater C-400, manufactured by Yuri Roll Machine Co., Ltd.) so as to have a concentration of 25 g / m ^2. Apply to the back of thermal recording paper to form an adhesive layer,
Finished in a roll, an adhesive label for thermal recording was manufactured.

Example 3 A roll-shaped heat-sensitive recording adhesive label was prepared in the same manner as in Example 1 except that the pressure-sensitive adhesive composition used in "Production of pressure-sensitive adhesive label" in Example 1 was changed to the following composition. Was manufactured.
50 parts by weight of natural rubber, 50 parts by weight of styrene-butadiene copolymer resin (styrene: butadiene = 70: 30),
80 parts by weight of a rosin ester-based resin (trade name: Superester A-100, manufactured by Arakawa Chemical Co., Ltd.) as a tackifier, 20 parts by weight of a softener (trade name: Shellflex 371JY, manufactured by Shell Japan Co., Ltd.) Anti-aging agent (trade name: Nocrack NS-5, manufactured by Ouchi Shinko Chemical Co., Ltd.)
One part by weight was mixed to obtain a pressure-sensitive adhesive composition.

Example 4 A roll-shaped heat-sensitive recording adhesive label was prepared in the same manner as in Example 1 except that the pressure-sensitive adhesive composition used in "Production of pressure-sensitive adhesive label" in Example 1 was changed to the following composition. Was manufactured.
Polyisobutylene (trade name: Vistanex MML-1)
00, Exxon Chemical Co., Ltd.), 100 parts by weight, rosin ester-based resin as a tackifier (trade name: Super Ester A-100, Arakawa Chemical Co., Ltd.), 10 parts by weight, antioxidant (trade name: Nocrack) NS-5, 1 part by weight of Ouchi Shinko Chemical Industry Co., Ltd.) was mixed to obtain a pressure-sensitive adhesive composition.

Example 5 A roll-shaped pressure-sensitive adhesive label for heat-sensitive recording was produced in the same manner as in Example 1 except that the method of producing a pressure-sensitive adhesive label in Example 1 was repeated. "Production of adhesive label" styrene-butadiene copolymer latex (styrene: butadiene = 55: 45) 100
10 parts by weight of a rosin ester-based resin emulsion (trade name: Superester 710, manufactured by Arakawa Chemical Co., Ltd.) as a tackifier, and a reverse roll coater so that the dry weight is 25 g / m ^2. Then, the heat-sensitive recording paper having the release agent layer used in Example 1 was applied and dried on the back surface to form an adhesive layer, thereby producing a roll-shaped heat-sensitive recording adhesive label.

Example 6 In the "Formation of a release agent layer" in Example 1, an electron beam irradiator (trade name: Electron Curtain CB-15) was used instead of curing using an ultraviolet irradiator.
0, manufactured by ESI) under the conditions of an acceleration voltage of 175 kV and an irradiation current of 20 mA.
A roll-shaped heat-sensitive recording adhesive label was produced in the same manner as in Example 1 except that the curing was performed.

Example 7 In Example 1, "Formation of a release agent layer", a polysiloxane containing a vinyl ether group synthesized by the following method was used, and bis (dodecylphenyl) was used as a photopolymerization initiator.
A roll-shaped pressure-sensitive adhesive label for heat-sensitive recording was produced in the same manner as in Example 1 except that iodonium hexafluoroantimonate was added.

"Synthesis of polysiloxane" In a nitrogen atmosphere, potassium acetate and a platinum catalyst were added to 1,4-butanediol divinyl ether, and a polysiloxane represented by the following general formula (Chemical Formula 1) was added dropwise with stirring. Then, by heating and reacting, a polysiloxane containing a vinyl ether group represented by the following general structural formula (Formula 2) was synthesized.

[0045]

Embedded image m = 28

[0046]

Embedded image m = 28

Example 8 In Example 1, "Formation of release agent layer", a polysiloxane having a propenyl ether group synthesized by the following method was used, and bis (dodecylphenyl) iodonium hexafluoroantimonate was used as a photopolymerization initiator. A roll-shaped pressure-sensitive adhesive label for thermal recording was produced in the same manner as in Example 1 except that was added.

"Synthesis of polysiloxane" Under a nitrogen atmosphere, potassium acetate and a platinum catalyst were added to 1,4-butanediol di (1-propenyl ether), and the compound of the above general structural formula (Chemical Formula 1) was added with stirring. Was added dropwise, and the mixture was heated and reacted to synthesize a polysiloxane containing a 1-propenyl ether group.

Example 9 In Example 1, synthetic paper (trade name: FP) was used as a support.
Except for using H-80, manufactured by Oji Yuka Synthetic Paper Co., Ltd., an adhesive label for heat-sensitive recording was produced in the same manner as in Example 1.

Comparative Example 1 A roll-shaped pressure-sensitive adhesive label for heat-sensitive recording was produced in the same manner as in Example 1 except that the method of producing a pressure-sensitive adhesive label in Example 1 was repeated. "Production of pressure-sensitive adhesive label" An acrylic emulsion pressure-sensitive adhesive (trade name: L-145, manufactured by Nippon Carbide Industry Co., Ltd.) was used as a pressure-sensitive adhesive on the back surface of the heat-sensitive recording paper having a release agent layer used in Example 1. Coating and drying were performed with a reverse roll coater so that the dry weight was 25 g / m ² , to form an adhesive layer.

Comparative Example 2 A roll-shaped heat-sensitive recording pressure-sensitive adhesive label was produced in the same manner as in Example 1 except that the method of producing a pressure-sensitive adhesive label in Example 1 was repeated. "Manufacture of pressure-sensitive adhesive label" An acrylic solvent-type pressure-sensitive adhesive (trade name: Olivine BPS-5160, manufactured by Toyo Ink Co., Ltd.) was used as a pressure-sensitive adhesive, and the dry weight was 25 g / m ² for a process using a reverse roll coater. After coating and drying on a release paper, the pressure-sensitive adhesive layer and the back surface of the thermosensitive recording paper having the release agent layer used in Example 1 were bonded to transfer the pressure-sensitive adhesive layer. The heat-sensitive recording paper having the peeling-off layer and the pressure-sensitive adhesive layer was finished in a roll shape to produce the heat-sensitive recording pressure-sensitive adhesive label of the present invention.

Comparative Example 3 A roll-shaped adhesive label for heat-sensitive recording was produced in the same manner as in Example 1 except that the method of producing an adhesive label in Example 1 was repeated. "Manufacture of pressure-sensitive adhesive labels" Acrylic hot-melt type pressure-sensitive adhesive (trade name: Acronal DS3429, Nippon Shokubai Co., Ltd.)
Heat-melted, and heat-melted with a die coater (trade name: Park Coater C-400, manufactured by Yuri Roll Machine Co., Ltd.) having a release agent layer used in Example 1 so as to be 25 g / m ^2. The composition was applied to the back surface of the paper, cured by irradiating ultraviolet rays to form an adhesive layer, and finished in a roll shape to produce an adhesive label for thermal recording.

Comparative Example 4 In Example 1, “Formation of a release agent layer”, an ultraviolet-curable silicone containing a mercapto group (trade name:
BY-24-551A, 75 parts by Dow Corning Toray Silicone Co., Ltd.) and a UV-curable silicone containing a vinyl group (trade name: BY-24-551B,
A roll-shaped heat-sensitive recording adhesive label was produced in the same manner as in Example 1 except that a mixture of 25 parts of Toray Dow Corning Silicone Co., Ltd.) was used.

Comparative Example 5 A roll-shaped adhesive label for heat-sensitive recording was produced in the same manner as in Example 1 except that the release agent layer was formed by the following method in "Formation of release agent layer" in Example 1. "Formation of Release Agent Layer" Radiation-curable silicone containing an acrylic group (trade name: X-62-72) on the protective layer of the thermal recording paper using an offset gravure coater.
13. Shin-Etsu Chemical Co., Ltd.) was applied at a concentration of 1.5 g / m ^2, and an electron beam irradiation apparatus (trade name:
Using an Electron Curtain CB-150 (manufactured by ESI), irradiation was performed with an electron beam of 4 Mrad under the conditions of an acceleration voltage of 175 kV and an irradiation current of 20 mA to cure, thereby obtaining a thermosensitive recording paper having a release agent layer.

The following evaluations were performed on the 14 types of heat-sensitive recording adhesive labels thus obtained, and the results are shown in Tables 1 and 2. In addition, the evaluation method of each evaluation item is as follows.

[Peeling Force] The roll-shaped pressure-sensitive adhesive label for heat-sensitive recording was peeled at a peeling speed of 0.3 m / min and 10 m / mi.
Under the test conditions of n, the peeling force (g / 5 cm) when the pressure-sensitive adhesive label for thermal recording was peeled was measured.

[Whiteness] Measured according to JIS P 8123 standard. [Adhesiveness] The adhesive label for thermosensitive recording was adhered to a stainless steel plate, and after 2 hours, the adhesive force was measured at an angle of 180 ° at a speed of 0.3 m / min, and judged according to the following criteria. ◎: Adhesive strength is 1500 g / 25 mm or more, the substrate is completely broken at the time of measuring the adhesive strength, and the adhesive strength is particularly excellent. ：: Adhesive strength is 1000 g / 25 mm or more, and the substrate partially breaks when measuring the adhesive strength. Δ: Adhesive force of 600 g / 25 mm or more, which has no practical problem x: Adhesive force of 200 g / 25 mm or more, but easily peelable. XX: Adhesive force of less than 200 g / 25 mm and hardly adhered.

[Recording Density] A pressure-sensitive adhesive label for heat-sensitive recording was prepared using a commercially available printer (trade name: Prodigy Plus L).
(Inerless, manufactured by DATAMAX), and the maximum color density of the obtained recorded image was measured by a Macbeth densitometer (trade name: RD-914, Filter Visual / Macbeth).

[Roll Preservation Recording Density] A roll-shaped pressure-sensitive adhesive label for heat-sensitive recording was applied at 60 ° C. and 40 ° C. 90% RH.
After processing for 7 days under the conditions, recording was performed with the above printer, and the maximum color density of the obtained recorded image was measured with a Macbeth densitometer (trade name: RD-914, Filter Visual / Macbeth).

[Continuous printing property]
Printing was performed continuously for 100 m with the above-mentioned printer, and the state of the residue adhering to the thermal head and the printing length until a printing failure occurred were evaluated according to the following criteria. ：: No residue adhered to the thermal head at all, and there was no printing trouble. ：: The residue is slightly adhered to the thermal head, but there is no printing trouble. Δ: A large amount of residue adhered to the thermal head, but there was no printing failure. ×: Very large amount of lees adhered to the thermal head, 50 m to 10 m
Printing trouble occurs between 0 m. XX: Very large amount of residue adheres to the heat-sensitive head, and printing trouble occurs at less than 50 m.

[0061]

[Table 1]

[0062]

[Table 2]

From Tables 1 and 2, Examples 1 to 9 are shown.
In the above, polysiloxane containing an epoxy group, 1-
Polysiloxane containing a propenyl ether group, using at least one or more polysiloxanes selected from polysiloxanes having a vinyl ether group, are polymerized by irradiation and cured to form a release agent layer, and the pressure-sensitive adhesive layer has At least one rubber selected from natural rubber, polyisoprene rubber, styrene-butadiene rubber, polyisobutylene rubber, butyl rubber, styrene-isoprene block copolymer, styrene-butadiene copolymer, styrene-ethylene-butylene copolymer A heat-sensitive adhesive label using a pressure-sensitive adhesive mainly composed of a system-based pressure-sensitive adhesive had low peeling power, excellent adhesive properties, and excellent recording properties as a heat-sensitive recording paper.

On the other hand, in Comparative Examples 1 to 3 using an acrylic resin-based pressure-sensitive adhesive, the recording density of the rolls was significantly reduced. Further, in Comparative Examples 4 and 5, the release agent layer cured by irradiation with radiation using a polysiloxane containing a mercapto group, a polysiloxane containing a vinyl group, and a polysiloxane containing an acrylic group showed a peeling. The power became extremely heavy, making it unpractical. Further, Example 2 and Example 5
It can be seen that the whiteness was higher when a hot-melt adhesive or an emulsion adhesive was used.

[0065]

As described above, the heat-sensitive recording pressure-sensitive adhesive label obtained by the present invention is a heat-sensitive recording pressure-sensitive adhesive label which does not require a release paper, and has a stable and light peeling force and excellent adhesive properties. Further, it is an adhesive label having excellent recording characteristics as a heat-sensitive recording paper.

Claims (2)

[Claims] 1. A heat-sensitive recording pressure-sensitive adhesive label comprising: a heat-sensitive recording layer containing a basic dye and a colorant on the surface of a support; a release agent layer; and a pressure-sensitive adhesive layer on the back side.
The release agent layer is a polysiloxane containing an epoxy group,
A polysiloxane containing 1-propenyl ether groups,
A release agent layer which is polymerized by irradiation with at least one kind of polysiloxane selected from polysiloxanes containing a vinyl ether group and is cured, and the pressure-sensitive adhesive layer is made of natural rubber, polyisoprene rubber, styrene -Mainly contains at least one or more rubber-based adhesives selected from butadiene rubber, polyisobutylene rubber, butyl rubber, styrene-isoprene block copolymer, styrene-butadiene copolymer, and styrene-ethylene-butylene copolymer. An adhesive label for heat-sensitive recording, which is an adhesive layer. 2. The heat-sensitive recording pressure-sensitive adhesive label according to claim 1, wherein said pressure-sensitive adhesive is a hot-melt type pressure-sensitive adhesive or an emulsion type pressure-sensitive adhesive.