NZ620282B2

NZ620282B2 - Thermosensitive recording label

Info

Publication number: NZ620282B2
Application number: NZ620282A
Authority: NZ
Inventors: Toshiaki Ikeda; Yutaka Kuga; Tomoyuki Kugoh
Original assignee: Ricoh Company Ltd
Priority date: 2011-11-07
Filing date: 2012-10-30
Publication date: 2016-03-30

Abstract

Disclosed is a liner-less thermosensitive recording label, which contains a base substrate layer (e.g., paper) with, an under layer (e.g., styrene-butadiene copolymer), a thermosensitive colouring layer (e.g., leuco dye), a barrier layer (e.g., polyvinyl alcohol), and a release layer (e.g., silicone resin) on one side and an adhesive (e.g., acrylic adhesive) layer on the other. The label is rolled so as to contact the adhesive and the release layers so as to avoid the requirement of a liner on the adhesive layer. The release layer contains a cured product of a heat curing silicone resin, and the barrier layer contains a cured product of a water-soluble resin with a crosslinking agent, and an inorganic filler. resin) on one side and an adhesive (e.g., acrylic adhesive) layer on the other. The label is rolled so as to contact the adhesive and the release layers so as to avoid the requirement of a liner on the adhesive layer. The release layer contains a cured product of a heat curing silicone resin, and the barrier layer contains a cured product of a water-soluble resin with a crosslinking agent, and an inorganic filler.

Description

DESCRIPTION Title of ion THERMOSENSITIVE RECORDING LABEL Technical Field The present invention relates to a thermosensitive recording label without e paper (liner-less thermosensitive recording label) used with a printer equipped with a thermal heat, which colors a sensitive coloring layer with heat in the fields of printers for computer output or calculator, recorders for medical instrumentation, low-speed or high speed facsimiles, automatic ticket es, thermosensitive copying, handy terminals, and labels such as POS system. ound Art Use of an adhesive sheet for a label having a thermosensitive coloring layer has been increased in recent years as for labels for displaying prices, labels for displaying product information (barcode), labels for displaying quality of products, labels for displaying measurements, labels for advertizing (stickers), or the like. As for a recording method thereof, there are inkjet recording, thermosensitive recording, and pressure sensitive recording. Conventionally, a typical adhesive sheet for a label, which has a laminate ure where an adhesive layer and release paper are laminated on an opposite surface of the sheet to a thermosensitive coloring layer, can be used also in the rolled state, as the adhesive layer and the sensitive coloring layer are brought into a contact Via the release paper.

Moreover, the ve sheet for a label is widely used because it is easily adhered by peeling the release paper to expose the adhesive layer at the time of adhering.

However, this conventional adhesive sheet for a label requires peeling the release paper upon use. As it is ult to reuse the e paper as peeled, it is disposed in most cases, which leads to wasting of natural resources.

To solve the aforementioned problem, proposed is a rolled liner-less thermosensitive recording label, which has a release layer formed on a surface of the thermosensitive coloring layer, and having ing ty against the adhesive layer, and thus can used in the state of a roll without the release paper.

This liner-less thermosensitive recording label, however, has the release layer on the surface of the thermosensitive coloring layer, and therefore the release layer is adhered (stacked) on a thermal head as printed by means of a r equipped with the thermal head, causing a problem that printing cannot be med adequately. Therefore, there have been needs for a thermosensitive recording label, with which printing can be performed adequately, and in which the adhesive layer and the release layer can be appropriately released from each other.

In order to prevent adhesion between a thermosensitive recording label and a thermal head, and prevent deposition of a e layer forming material onto a thermal head, for example, proposed is heating a release layer forming material (e.g., an emulsion type silicone resin, zinc stearate emulsion, and colloidal silica) with a curing catalyst to sufficiently cure (see PTL 1). In this proposal, r, matching ability of a resulting label to a thermal head is not necessarily adequate. Moreover, as the release layer contains zinc stearate, it is difficult to cure the ne resin, causing reduction in release ability of the release layer.

Further, proposed is a thermosensitive recording label, in which a thermosensitive coloring layer, a protective layer, and a release layer are laminated, where the protective layer contain a powder having a particle diameter of 0.01 pm to 10 pm to form lar shapes on a surface of the release layer, to thereby prevent adhesion between a thermal head and the label (see PTL 2). In this proposal, however, a resin for forming the e layer is a UV curing ne resin, which causes volume shrinkage during UV curing, resulting in low binding ability between the e layer and the protective layer.

Moreover, proposed is to improve curing ability of a release layer formed by curing polysiloxane containing an epoxy group, polysiloxane containing a 1-propenyl ether group, and loxane containing a vinyl ether group by applying ctive rays, and to improve close contactness between a protective layer and the release layer, using the protective layer containing a water-soluble resin and colloidal silica as main components (see PTL 3). However, this proposal cannot t volume shrinkage during UV curing, which leads to a problem that anti-sticking property of the release layer is low.

Moreover, proposed is a thermosensitive recording ve label containing a release layer formed by curing a material ning a solventless radioactive ray curing organopolysiloxane compound and organohydrogen polysiloxane by application of radioactive rays (see PTL 4). In this proposal, however, the solventless silicone resin has a small molecular weight compared to that of a solvent silicone resin and tends to result icient curing bonds. A crosslink reaction proceeds quickly in radioactive ray curing to form a cured coating film within a few seconds. ore, ESiH groups tend to remain and crosslink density becomes low, which may cause sticking.

Proposed is release paper having a release layer formed by heat curing a solventless silicone resin (see PTL 5). This proposal, however, does not aim to prevent sticking, and to e binding ability with a barrier layer.

Further, proposed is a thermosensitive recording material, WO 69581 which contains a base, a thermosensitive ng layer containing a leuco dye and a developing agent, a first protective layer containing a water-soluble resin and a inking agent, and a second protective layer containing a water-soluble resin, a inking agent, and a pigment, Where the thermosensitive coloring layer, the first protective layer, and the second protective layer are ted on the base in this order, and the second protective layer contains diacetone'modified polyvinyl alcohol, and an acrylic resin or maleic copolymer (see PTL 6). In this proposal, however, the protective layer is the outer e layer, and it does not teach about compatibility with a release layer formed of a solventless silicone resin provided the outermost surface.

As mentioned above, the liner-less thermosensitive recording labels described in the conventional art have problems that a sufficient binding strength between the protective layer and the release layer cannot be obtained, and both anti-sticking property and sufficient release ability of the release layer to the adhesive layer cannot be obtained at the same time.

Citation List Patent Literature PTL 13 Japanese Patent (JP-B) No. 4409809 PTL 21 Japanese Patent Application Laid-Open (JP-A) No. 2003-34076 PTL 3: JP-A No. 11-116909 PTL 4: JP-A No. 2003-171630 PTL 5: JP-A No. 2008-231171 PTL 6: JP-A No. 2008-260275 Summary of Invention Technical m The present invention aims to provide a thermosensitive recording label, which is releasable without causing blocking between a release layer provided on a surface of the thermosensitive recording label and an adhesive layer provided on a back surface thereof, when it is mounted in a shape of a roll without release paper, which prevents sticking between the sensitive recording label and a thermal head, and prevents ng of a material for forming the release layer as printed by a thermal printer, and which does not lower its coloring ivity lowing of which is generally caused by providing a release layer.

It is an alternative object of the invention to at least provide the public with a useful choice.

Solution to Problem As a result of the diligent researches and studies conducted by the present inventors to solve the entioned ms, it has been found that a combination of a certain release layer and a certain r layer can solve the aforementioned problems. Specifically, a thermosensitive recording label containsi a base; an under layer; a thermosensitive coloring layer; a barrier layer; a release layer; and an adhesive layer, where the under layer, the thermosensitive coloring layer, the barrier layer, and the release layer are disposed on one surface of the base in this order, and the adhesive layer is disposed on the other e of the base, wherein the release layer contains a cured product of a heat curing silicone resin, and the barrier layer contains a cured product of a water-soluble resin with a inking agent, and inorganic filler. With such thermosensitive recording label, the following insights have been found. The high curing y is exhibited during formation of the release layer even when a heat value for heat curing the heat curing ne resin is reduced, and moreover the heat curing silicone resin has a small degree of volume shrinkage. Therefore, binding ability between the release layer and the barrier layer after heat curing the silicone resin improves, which lead to improvement in releasability between the release layer and the binder layer when the thermosensitive recording label is in a form of a roll. As a result of the improvement in the binding ability between the release layer and the barrier layer, moreover, the thermosensitive recording label improves ance properties in high temperature high humidity environments, and anti-sticking properties in low temperature low humidity environment, as printed with a l head.

The thermosensitive recording label of the t invention, which is the mean of the aforementioned problems, includes: a base; an under layer; a thermosensitive coloring layer; a barrier layer; a release layer; and an ve layer, where the under layer, the thermosensitive coloring layer, the barrier layer, and the release layer are disposed on one surface of the base in this order, and the adhesive layer is disposed on the other surface of the base, wherein the under layer contains an adhesive resin and filler, and wherein the release layer contains a cured product of a heat curing silicone resin, and the barrier layer ns a cured product of a water-soluble resin with a crosslinking agent, and inorganic filler.

Advantageous Effects of Invention The present ion can solve the aforementioned various problems in the conventional art, achieve the entioned object, and provide a thermosensitive recording label, which is releasable without causing blocking between a release layer provided on a surface of the sensitive recording label and an adhesive layer provided on a back surface thereof, when it is mounted in a shape of a roll without release paper, which prevents sticking between the thermosensitive recording label and a thermal head, and prevents sticking of a material for g the release layer as printed by a l printer, and which does not lower its coloring sensitivity lowing of which is generally caused by providing a release layer.

Unless the t clearly es otherwise, throughout the description and claims the terms “comprise”, “comprising” and the like are to be construed in an inclusive sense, as opposed to an exclusive or exhaustive sense. That is, in the sense of “including, but not limited to”.

Description of Embodiments (Thermosensitive Recording Label) The thermosensitive recording label of the present invention contains a base, an under layer, a thermosensitive coloring layer, a barrier layer, a release layer, and an adhesive layer, where the under layer, the thermosensitive coloring layer, the r layer, and the e layer are disposed in this order on one surface of the base, and the adhesive layer is ed on the other surface of the base. The thermosensitive recording label of the present invention may further contain other layers, if [Followed by page 9a] necessary. <Release Layer> The release layer contains a cured product of a heat curing silicone resin, and may r contain other components, if [Followed by page 10] [Followed by page 10] necessary.

'Cured Product of Heat Curing Silicone Resin- The cured product of the heat curing silicone resin can be appropriately selected without any limitation, but it preferably contains an addition reaction curable silicone resin and a crosslinking agent as by'products are not generated after curing.

"-Addition Reaction e Silicone '- The addition reaction curable silicone resin can be appropriately selected Without any limitation, but it is ably organosiloxane containing a Vinyl group, a mercapto group, an epoxy group, a methacryl group, a maleimide group, a methacryl amide group, a thioacryl group, or a hexenyl group at a side chain of a silicon bond (‘Si') of siloxane, in View of peel force, safety, hazard, and cost. More preferred is organopolysiloxane containing a hexenyl group at a side chain of a silicon bond (‘Si') of siloxane, in View of l bonding strength of the adhesive layer and the release layer.

---Crosslinking Agent"- The crosslinking agent can be appropriately selected without any limitation, but it is preferably organohydrogen ne in View of vity to the addition reaction curable silicone resin. Note that, the organohydrogen polysiloxane is a compound containing a reactive silicon (ESiH) at least either at a terminal of a principle chain or at a al of side chain-cf a molecule thereof.

Especially when the thermosensitive recording label is formed into a roll, a problem occurs such that bonding strength between the adhesive layer and the release layer increases over time.

The cause of the aforementioned problem includes bonding of a reactive silicon (ESiH) remained in the organohydrogen polysiloxane due to insufficient crosslink of the release layer, with a carboxyl group (-COOH) of polyacrylic acid or the like contained in the adhesive layer.

Use of organopolysiloxane having a hexenyl group, which hardly cause steric nce during a crosslink on enables to increase reactivity with the reactive silicone (ESiH) in organohydrogen polysiloxane, to thereby reduce the reactive silicone (ESiH) remained.

Typically, a crosslink reaction is induced by irradiation of radioactive rays, but the on reaction curable silicone resin can be ted to a crosslink reaction by heat applied during a drying process by adding a catalyst thereto.

Curing performed by UV radiation is difficult to affect evenly on a silicone resin. When curing is partially insufficient, initially performance of a ant may be excellent, but a resistance at the time of peeling may increase as time passes.

On the other hand, heat curing can be med evenly, and 2012/078556 , and therefore peel force is ent over time.

The release layer is appropriately selected depending on the intended e without any limitation, but it is preferably cured with heat at 90°C to 110°C in order to prevent coloring of a thermosensitive coloring layer, and it ably contains a catalyst to sufficiently perform crosslink curing in the aforementioned temperature range.

The catalyst is appropriately selected depending on the intended purpose without any limitation, and es thereof include organic acid metal salts, 1,3-diketone metal complex salt, metal alkoxide, and platinum.

Among them, platinum is preferable because it hardly inhibits a curing reaction.

The organic acid metal salt is appropriately selected depending on the intended purpose t any limitation, and examples thereof include dibutyl tin dilaurate, dibutyl tin maleate, zinc 2'ethylhexan0ate.

The 1,3'diketone metal complex salt is appropriately selected ing on the intended purpose without any limitation, and examples thereof e nickel acetylacetonate, and zinc acetylacetonate.

The metal alkoxide is appropriately selected depending on the intended purpose without any limitation, and examples thereof include titanium tetrabutoxide, and zirconium tetrabutoxide.

An amount of the catalyst is appropriately selected depending on the intended purpose Without any limitation, but it is preferably 2.5 parts by mass to 4 parts by mass, relative to 100 parts by mass of the resin component. When the amount thereof is smaller than 2.5 parts by mass, the resin may not be sufficiently cured. <Barrier Layer> The barrier layer contains a cured product of a soluble resin with a crosslinking agent, and inorganic , preferably further contains resin particles, and may r contain other components, if necessary.

The barrier layer has both a on of protecting an image, and a function of improving g strength with the release layer.

'Water'Soluble Resin- The water-soluble resin is appropriately selected depending on the intended e without any limitation, provided that it is a resin dissolved in an amount of 3 g or greater in 100 g of water of 25°C. Examples of the water-soluble resin include water-soluble polymers, such as polyvinyl l, starch and derivatives thereof, cellulose derivatives (e.g., methoxy cellulose, hydroxyethyl cellulose, and carboxymethyl cellulose), sodium polyacrylate, polyvinyl pyrrolidone, alkali salt of a styre'ne'maleic anhydride copolymer, alkali salt of an isobutylene-maleic anhydride copolymer, polyacryl amide, gelatine, and casein.

The weight average molecular weight of the water-soluble polymer is appropriately selected ing on the intended purpose without any limitation, ed that it is in the range of ,000 to 300,000, but it is preferably 10,000 to 200,000 in View of bonding strength.

Among them, the water-soluble resin is preferably a resin that is hardly dissolved or softened by heat, and has high heat resistance, in View of preventing the aforementioned problem associated with sticking. Specifically, preferred is polyvinyl alcohol containing a ve carbonyl group, more preferred are diacetone-modified nyl alcohol and itaconic acid-modified polyvinyl alcohol, and particularly red is itaconic acid-modified polyvinyl l.

An amount of the diacetone group in the diacetone-modified polyvinyl alcohol is appropriately selected depending on the intended purpose without any limitation, but it is ably 0.5 mol% to 20 mol% relative to the entire polymer, more preferably 2 mol% to 10 mol% in View of water resistance.

When the amount thereof is smaller than 0.5 mol%, water resistance may be insufficient for practical use. When the amount thereof is greater than 20 mol%, further improvement in WO 69581 water resistance may not be expected, and use in such amount is economically disadvantageous in View of its high cost.

The polymerization degree of the diacetone'modified polyvinyl l is appropriately selected depending on the intended purpose Without any limitation, but it is preferably 300 to 3,000, more preferably 500 to 2,200. er, the, saponification degree of the diacetone'modified polyvinyl alcohol is preferably 80% or more.

'Crosslinking Agent- The crosslinking agent is appropriately selected depending on the intended purpose Without any tion, and examples thereof include a lent amine compound, a polyvalent de compound, a dihydrazide compound, a water-soluble methylol compound, a polyfunctional epoxy compound, polyvalent metal salt, boric acid, and titanium lactate. These may be used in combination with any other conventional crosslinking agents.

The polyvalent amine compound is appropriately selected depending on the intended purpose without any tion, and examples thereof include ethylene diamine.

The polyvalent aldehyde compound is appropriately selected depending on the intended purpose without any limitation, and examples thereof include l, glutar aldehyde, and dialdehyde.

The dihydrazide compound is appropriately selected depending on the intended purpose without any limitation, and es thereof include adipic acid dihydrazide, and phthalic acid dihydrazide.‘ The water-soluble methylol compound is appropriately selected depending on the intended purpose Without any limitation, and examples thereof include urea, melamine, and phenoL es of a quantitative method of the cured product of the water-soluble resin with crosslinking agent include HS-GC/MS, and CP/MAS.

An amount of the cured product of the water-soluble resin with the crosslinking n the barrier layer can be appropriately selected without any limitation, but it is preferably % by mass to 20% by mass.

'Inorganic Filler- The nic filler is riately ed depending on the intended purpose without any limitation, and examples thereof e inorganic powder, such as aluminum hydroxide, calcium carbonate, silica, zinc oxide, titanium oxide, zinc hydroxide, barium sulfate, clay, talc, thermally surface treated calcium, thermally surface d silica, and thermally surface treated kaolin.

Among them, aluminum hydroxide is preferable because it contributes to provide preferable bonding strength between the barrier layer and the release layer, and to provide abrasion resistance to the thermosensitive recording label t a thermal head, when printing is performed over a long period, through there is no direct contact between the barrier layer and the thermal heat.

The average particle diameter of the inorganic filler is appropriately selected depending on the intended purpose without any limitation, but it is preferably 0.1 pm to 2 pm, in . view of sensitivity of a resulting thermosensitive recording label.

'Resin Particles- The resin particles are appropriately selected depending on the intended purpose without any limitation, but they are ably either silicone resin particles, or crosslinked thyl methacrylate particles.

Use of resin particles in combination with the inorganic filler leads to further ement in abrasion resistance, binding ability with the release layer, and releasability between the release layer and the ve layer.

. "Silicone Resin Particles-- Use of silicone resin particles leads to further improvement in abrasion ance, binding ability with release layer, and releasability between the e layer and the adhesive layer.

The silicone resin particles are particles formed by dispersing and curing a silicone resin into fine powder, and include those composed of spherical particles and those composed of irregularly-shaped particles, but the silicone resin particles are preferably spherical particles.

As a ne resin of the silicone resin particles, a r of a three-dimensional k structure, having a siloxane bond in its principle chain can be used. As well as those having a methyl group in its side chain, those having a phenyl group, a yl group, a vinyl group, a nitrile group, an alkoxy group, or de atom can be widely applied. The powder of the cured product using the polymer of the three dimensional network structure, which has a siloxane bond in its principle chain, is excellent in dispersibility, and heat resistance, and does not swell or dissolve with an organic solvent.

An amount of the ne resin particles in the barrier layer is appropriately selected depending on the intended purpose without any limitation, but it is preferably 10 parts by mass to 80 parts by mass, relative to 100 parts by mass of the soluble resin.

"Crosslinked Polymethyl Methacrylate Particles-- The crosslinked polymethyl methacrylate particles are typically particles formed by bonding a linear polymer of polymethyl methacrylate in the three-dimensional network WO 69581 structure as a result of a reaction between methyl methacrylate, a divinyl compound, and a l initiator to initiate radical rization. Such crosslink structure gives polymethyl methacrylate a high ing point.

An analysis method for the polymethyl methacrylate includes, for example, 1H-NMR, and 13C-NMR.

Examples of an analysis method for the crosslink structure include those methods used for the polymethyl methacrylate.

The crosslinked polymethyl methacrylate particles can increase bonding th between the barrier layer and the release layer, and prevent a problem that printing cannot be performed adequately because a releasing al in the release layer is deposited on a thermal head when printing is performed by means of a printer having the l head.

The structure of each crosslinked polymethyl rylate particle can be. appropriately selected depending on the intended purpose without any limitation, but it is preferably porous in View of g strength between the release layer and the barrier layer.

The porosity is appropriately selected-depending on the intended purpose without any limitation, but it is preferably bulk density of 0.45 g/mL to 1.00 g/mL.

A measurement method of the bulk density includes, for example, a method in which the crosslinked polymethyl rylate particles to be measured are added to a measuring cylinder to measure a volume and mass thereof, and (measured mass/ measured volume) is calculated to determine the bulk density.

The volume average particle diameter of the crosslinked polymethyl methacrylate particles is appropriately selected depending on the intended purpose without any tion, but it is preferably 1.0 pm to 8.0 pm. When the volume average particle diameter thereof is smaller than 1.0 pm, an effect of preventing sticking during printing using a printer having a thermal head is lowered. When the volume average particle diameter thereof is r than 8.0 um, the degree of close contact n the l head and the thermosensitive coloring layer is lowered to reduce coloring sensitivity.

Examples of the measurement method of the volume average particle diameter e a method using a laser scattering/diffraction particle sizer.

An amount of the crosslinked polymethyl methacrylate les in the barrier layer is appropriately selected depending _on the intended purpose without any. limitation, but it is preferably 25 parts by mass to 100 parts by mass relative to 100 parts by mass of the water-soluble resin. When the amount of the crosslinked polymethyl methacrylate particles is smaller than 25 parts by mass, an effect of the crOsslinked polymethyl methacrylate particles to inhibit sticking may be insufficient.

When the amount thereof is greater than 100 parts by mass, the barrier layer may conceal the thermosensitive coloring layer to thereby lower an effect of preventing reduction of image density. <Under Layer> The under layer is appropriately selected depending on the intended purpose t any tion, but contains an adhesive resin, and filler, and may further contain other ents, if necessary.

-Binder Resin- The binder resin is appropriately selected depending on the intended e without any tion, and examples thereof include: water-soluble polymers such as a styrene-butadiene copolymer, polyvinyl alcohol, various modified nyl alcohol, starch and derivatives thereof, cellulose derivatives (e.g., ymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, and ethyl cellulose), sodium polyacrylate, polyvinyl pyrrolidone, an acryl amide/acrylic acid ester copolymer, an acryl amide-acrylic acid ester-methacryl acid terpolymer, an alkali salt of a styrene-maleic anhydride copolymer, an alkali salt of an isobutylene-maleic anhydride copolymer, ryl amide, sodium alginate, gelatine, and casein; and emulsion such as polyvinyl acetate, polyurethane, polyacrylic acid, polyacrylate, a vinyl 2012/078556 de-vinyl acetate copolymer, polybutyl methacrylate, an ethylene-Vinyl acetate copolymer. These may be used independently or in combination.

-Filler- The filler is appropriately selected without any limitation, and examples f include inorganic , and organic .

"Inorganic Filler" The inorganic filler is appropriately selected Without any limitation, and examples thereof include those usable in the barrier layer.

"Organic Filler-- The organic filler is appropriately selected without any limitation, but it is preferably hollow thermoplastic resin particles in View of heat retentiveness.

---Hollow Thermoplastic Resin lesm The hollow thermoplastic resin particles are appropriately selected depending on the intended purpose without any limitation, but particles, each of which contains a shell of a plastic resin, and encapsulates a gas such as air, are preferable.

The term “hollow” typically means a structure where an article has a void inside, and is specifically a structure having at least either a space in which gas such as air can be encapsulated, or a hole through which gas such as air can be passed through all the time.

""Thermoplastic Resin-"- The thermoplastic resin is appropriately selected depending on the ed purpose without any tion, and examples thereof include a e-acryl resin, a yrene resin, an acrylic resin, a polyethylene resin, a polypropylene resin, a polyacetal resin, a chlorinated polyether resin, a polyvinyl chloride resin, a vinylidene chloride-acrylonitrile copolymer resin, a phenol-formaldehyde resin, a urea 'formaldehyde resin, a melamine-formaldehyde resin, a furan resin, an unsaturated polyester resin, and a crosslinked MMA resin. These may be used independently or in combination.

Among them, a styrene-acryl resin and a mer mainly composed of dene chloride and acrylonitrile are preferable because they can give a high void ratio, and less variation in the average particle diameter thereof, which are suitable for blade coating.

The volume average particle diameter (outer particle diameter) of the hollow thermoplastic resin particles is appropriately selected depending on the intended purpose without any limitation, but it is preferably 0.2 pm to 2-0 pm, more preferably 2 pm to 5 pm. When the volume average particle diameter is smaller than 0.2 pm, it is technically difficult to make particles hollow, and therefore the under layer may not exhibitits function sufficiently. When the volume average particle diameter thereofis greater than 20 um, smoothness of the surface after coating and drying may be degraded, and ore the sensitive coloring layer may not be coated evenly.

Accordingly, it is preferred that the hollow thermoplastic resin particles have uniform le distribution peak without variation, as well as having the volume average particle diameter in the aforementioned range.

A measurement method of the volume average le diameter includes, for examples, those methods used for measuring the volume average particle diameter of the crosslinked polymethyl methacrylate particles.

A void ratio of the hollow thermoplastic resin particles is appropriately selected depending on the intended purpose without any tion, but it is preferably 30% to 95%, more preferably 80% to 95%, in View of heat retentiveness. When the void ratio is less than 30%, the thermal ting properties of the under layer is insufficient, and therefore heat energy from a thermal head is released outside of a thermosensitive ing material through base. As a result, an effect of improving ivity of the thermosensitive recording material may be insufficient.

Examples of a measurement method of the void ratio include a method using a scanning electron microscope (SEM).

WO 69581 Note that, the void ratio is a ratio between the outer diameter and inner diameter (diameter of a void part) of the hollow thermoplastic. resin particle, and can be ented by the following on (1).

Void ratio = (inner diameter of hollow thermoplastic resin particle/ outer diameter of hollow thermoplastic resin particle) X 100 Equation (1) An amount of the hollow thermoplastic resin particles in the under layer is appropriately selected depending on the intended purpose without any limitation, but it is preferably 1.0 g/m2 to 3.0 g/m2 in order to in sensitivity and evenness in coating. When the amount of the hollow thermoplastic resin particles is less than 1.0 g/mz, sufficient sensitivity may not be attained. When the amount thereof is more than 3.0 g/mz, bonding strength of the under layer may be lowered. <<Bonding Strength>> The bonding strength between the release layer and the barrier layer is appropriately selected depending on the ed purpose without any tion, but it is preferably stronger than the g strength between the adhesive layer and the release layer.

Examples of a measuring method of the bonding strength include a method described in JIS P0001. <Thermosensitive Coloring Layer> The thermosensitive coloring layer is appropriately selected depending on the intended purpose t any limitation, but the thermosensitive coloring layer contains a leuco dye and a developing agent, and may further contain other components, if necessary.

'Leuco Dye- The leuco dye can be appropriately selected depending on the intended purpose Without any limitation, and examples thereof an electron-donating compound that is per se colorless or pale d and is a dye precursor, such as triphenylmethane phthalide nds, triallyl methane compounds, ﬂuoran compounds, phenothiazine compounds, oran compounds, xanthen compounds, indophthalyl compounds, spiropyran compounds, azaphthalide compounds, chromenopyrazole compounds, methine compounds, rhodamine aniline lactum compounds, rhodamine lactum compounds, quinazoline compounds, diazaxanthen compounds, and bislactone compounds.

These may be used ndently or in combination.

In View of coloring properties, and quality of an image, in terms of fading in an imaging part due to moisture, heat, and light, and background fogging in a background part, preferred as the leuco dye are 2-anilin0'3'methyl'6-diethylaminofluoran, inomethyl-6'(di-n-butylamin0)fluoran, 2- anilino- 3'methyl(di-n-pentylamino)fluoran, Z-anilinomethy1'6'(N-n'propyl'N'methylamin0)fluoran, 2-anilinomethy1'6'(N'isopropyl-N-methylamino)ﬂuoran, 2-anilinomethy1‘6'(N‘isobutyl-N-methylamin0)fluoran, 2-anilino-3'methyl-6'(N-n-amy1-N-methy1 amin0)ﬂu0ran, 2-anihno-3'methy1'6'(N'sec-butyl-N-ethyl amino)fluoran, 2-anilin0'3'methy1-6'(N-n'amy1-N-ethy1 amin0)flu0ran, 2'anilino'3-methy1-6‘(N'iso-amyI'N-ethyl amin0)ﬂuoran, Z'anilino-B-methy1-6'(N-cyclohexyl-N-methyl amino)ﬂu0ran, 2-ani1inomethy1-6'(N-ethyI-p-toluidin0)ﬂuoran, 2-anilin0'3'methy1-6'(N-methyl-p-toluidin0)flu0ran, 2'(m-trichloromethy1 0)-3'methy1diethy1 aminofluoran, 2'(m'trifluoromethy1 aniline)3-methy1diethy1 aminofluoran, 2-(m-trifluoromethy1 anilino)methy1'6-(N-cyclohexyl-N-methyl amino)ﬂuoran, 2'(2,4-dimethy1 anilino)methy1’6-diethyl aminoﬂuoran, 2-(N-ethyl-p-toluidino)methy1-6‘(N-ethyl anilino)flu0ran, 2'(N-methy1-p-toluidin0)'3'methyl'6'(N'propy1-p-toluidin0) , 2-aniline-6'(N'n-hexyl-N-ethyl amino)ﬂuoran, 2'(o-chloranilino)'6-diethyl aminoﬂuoran, 2‘(o-bromoanilino)'6'diethy1 aminofluoran, 2'(0'chloranilino)'6'dibutylaminoﬂuoran, uoroanilino)'6-dibuty1aminofluoran, rifluoromethy1 aniline)'6-diethy1aminoﬂuoran, 2‘ (p 'acetylanilino) ‘6‘ (N-n-amyl-N'n'butylamin0)ﬂuoran, 2-benzy1amino-6"(N-ethyl'p'toluidino)f1uoran, 2-benzy1amino(N-methyl '2,4-dimethy1 anilin0)fluoran, 2-benzy1amino(N-ethy1 '2,4-dimethy1 anilino)fluoran, 2'dibenzy1amino(N-methyl'p-toluidin0)fluoran, 2-dibenzylamino-6'(N'ethy1-p-toluidino)fluoran, 2'(di-p-methyl benzylamino)'6'(N'ethyl-p-t01uidino)f1uoran, 2'(u'phenylethy1 amino)'6'(N'ethyl'p-toluidino)fluoran, 2-methy1 amino(N'methy1 0)ﬂuoran, 2-methyl 6‘(N'ethy1 anilino)ﬂuoran, 2-methy1 amino-6'(N'propylanilino)ﬂuoran,I 2'ethy1 amino(N-methyl-p-toluidino)fluoran, 2-methy1 amino(N'methyl '2,4-dimethyl o)ﬂuoran, 2-ethyl amino-6'(N'methy1 ~2,4'dimethyl anilino)f1uoran, 2-dimethy1 amino(N-methy1 anilino)ﬂuoran, 2'dimethyl amino(N'ethyl anilino)fluoran, 2-diethy1 amino(N-methyl'p-toluidino)fluoran, ' benzo leuco methylene blue, 2-[3,6-bis (diethyl amin0)]'6"(o-chloranilin0)xanthy1 benzoic acid; lactam, 2-[3,6-bis(diethy1 amino”'9'(o-chloranilino)xanthy1 benzoic acid lactam, s(p-dimethy1 aminopheny1)phthalide, 3,3-bis(p'dimethyl aminopheny1)dimethy1 aminophthalide, 3,3-bis(p-dimethyl aminopheny1)diethyl aminophthalide, 3,3-bis(p'dimethy1 aminophenyl)'6-ch10rphthalide, 3, 3-bis(p ' laminopheny1)phthalide, 8‘(2'methoxy'4-dimethy1 aminophenyl) '3' r0xy'4, 5 'dichlorpheny1)phthalide, ydroxydimethyl aminophenyl)‘3'(2'methoxy'5-chlorpheny1)phthalide, 3'(2'hydroxydimethoxyaminophenyl)'3'(2'methoxy chlorphenyl)phthalide, ydroxydimethyl aminophenyl)'3'(2'methoxy'5-nitrophenyl)phthalide, 3-(2-hydroxy'4-diethyl aminophenyl)'3'(2-methoxy-5'methyl phenyl)phthalide, 3,6-bis(dimethyl amino)fluorenespiro(9,3’)'6’-dimethyl aminophthalide, 6’-chloro-8’-methoxy'benzoindolino-spiropyran, and 6"bromo-2’-methoxy-benzoindolino-spiropyran.

An amount of the leuco dye in the thermosensitive ng layer is appropriately selected depending on the intended purpose Without any limitation, but it is preferably 5% by mass to % by mass, more preferably 10% by mass to 15% by mass in View of coloring density -Developing Agent- The developing agent is appropriately selected depending on the intended purpose without any limitation. Since various electron-donating materials that react with the leuco dye upon application of heat to color, preferred are bisphenol A, tetrabromo bisphenol A, gallic acid, salicylic acid, 3-isopropyl salicylate, 3'cyclohexyl salicylate, 3,5'di-tert-butyl salicylate, 3,5'di'a'methylbenzyl salicylate, opropylidenediphenol, 1,1"isopropylidenebis(2-chl0rophenol), 4,4"isopropylidenebisCZ,6-di‘bromophenol), 4,4"isopr0pylidenebis(2,6-dichlorophenol), 4,4"isopropylidenebis(2'methyl ), 4,4’-isopropylidenebis(2,6-dimethy1 phenol), 4,4’-isopropylidenebis(2-tert-butylphenol), 4,4’-sec-butylidene diphenol, yclohexy1idene bisphenol, 4,4’-cyclohexylidene bis(2-methyl phenol), 4'tert-butylphenol, 4-pheny1phenol, 4*hydr0xy diphenoxide, o'naphthol, B'naphthol, 3,5-xylenol, thymol, methyl-4*hydrothenzoate, 4-hydroxyacetophenone, novolak phenol resin, hi0bis(4,6-dichlorophenol), catechol, resorcin, hydroquinone, pyrogallol, fluoroglycine, ﬂuoroglycine carboxylic acid, 4-tert-octylcatechol, 2,2’-methy1enebis(4'chlorophenol), 2,2"methylenebis(4-methyltert-butylphenol), 2,2"dihydroxydipheny1, ethyl oxy benzoate, propyl p-hydroxy benzoate, butyl p-hydroxy te, benzyl oxy benzoate, p'chlorobenzyl-p-hydroxy benzoate, O'chlorobenzyl'p'hydroxy benzoate, p'methyl benzy1~p'hydroxy benzoate, n‘octyl-p-hydroxy benzoate, benzoic acid, zinc salicylate, 1-hydroxynaphthoic acid, 2‘hydroxynaphthoic acid, zinc 2-hydroxynaphthoate, 4-hydroxydipheny1 sulfone, 4-hydroxy-4’-chlorodipheny1 sulfone, bis(4-hydroxyphenyl)sulfide, 2-hydroxy-p-toluic acid, zinc 3,5'di'tert-butylsalicylate, tin -tert-butylsalicylate, tartaric acid, oxalic acid, maleic acid, citric acid, succinic acid, stearic acid, oxyphthalic acid, ' boric acid, thiourea derivatives, 4-hydroxythiophen01 derivatives, bis(4-hydroxypheny1) acetic acid, ethyl hydroxypheny1) acetate, n'propyl-bis(4i'hydroxyphenyl) acetate, n'butyl-bis(4'hydroxypheny1) acetate, phenyl hydroxypheny1) acetate, benzyl bis(4'hydroxypheny1) acetate, phenethyl bis(4-hydroxyphenyl) acetate, methyl '4-hydroxypheny1) acetic acid, methyl bis(3'methy1 '4'hydroxypheny1) acetate, yl'bis(3'methy1 '4-hydroxyphenyl) acetate, 1,7-bis(4-hydr0xyphenylthio)'3,5'dioxaheptane, 1,5-bis(4-hydroxyphenylthio)'3'oxaheptane, dimethyl 4-hydroxy phthalate, 4-hydroxy'4"methoxydiphenyl sulfone, 4-hydroxy'4"ethoxydiphenyl sulfone, 4-hydroxy-4’-isopropxydiphenyl sulfone, 4'hydr0xy'4’”propxydiphenyl sulfone, 4-hydroxy-4"butoxydiphenyl sulfone, 4'hydr0xy'4"isopropxydiphenyl sulfone, 4-hydroxy-4"seC'butoxydipheny1 sulfone, 4-hydroxy-4’-tert-but0xydipheny1 sulfone, 4-hydr0xy'4"benzyloxydipheny1 sulfone, 4-hydroxy'4"phenoxydiphenyl sulfone, 4-hydr0xy'4"(m'methyl benzyloxy)dipheny1 sulfone, 4-hydroxy'4"(p'methyl benzyloxy)dipheny1 sulfone, 4*hydroxy-4“ (o-methyl 2012/078556 benzyloxy)diphenyl sulfone, 4-hydroxy'4"(p'chlorobenzyloxy)diphenyl sulfone, and 4-hydroxy-4"oxyally1diphenyl sulfone. These may be used independently or in combination.

A mixing ratio between the leuco dye and the developing agent in the thermosensitive coloring layer is appropriately selected depending on the intended purpose Without any limitation, but it is preferably 0.5 parts by mass to 10 parts by mass of the developing agent relative to 1 part of the leuco dye in View of ng y, more preferably 1 part by mass to 5 parts by mass of the developing agent relative to 1 part by mass of the leuco dye.

'Other Components- Other components are appropriately selected depending on the intended purpose without any limitation, and examples thereof include a binding agent, filler, a plastic material, a crosslinking agent, a pigment, a tant, a cent brightener, and a lubricant. These may be used independently or in combination.

"Binding Agent'- The binding agent is‘appropriately selected depending on the ed purpose Without any limitation, provided that it improves coating ability of a layer, and binding ability, and examples thereof include starches, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatine, casein, Arabian gum, nyl alcohol, a salt of a diisobutylene'maleic ' anhydride copolymer, a salt of a styrene'maleic anhydride copolymer, a salt of an ethylene-acrylic acid copolymer, a salt of a styrene'acryl copolymer, and emulsion of a salt of a styrene’butadiene mer.

"Filler" The filler is appropriately selected depending on the ed purpose without any limitation, and examples thereof include inorganic pigments (e.g., calcium carbonate, aluminum oxide, zinc oxide, titanium dioxide, silica, aluminum hydroxide, barium sulfate, talc, , alumina, and clay), and organic ts known in the art.

Among them, , alumina and kaolin, which are acid pigments, are preferable in View of their water resistance, and silica is more preferable in View of its coloring density.

"Thermoplastic Material-- The thermoplastic material is appropriately selected ing on the intended purpose without any limitation, provided that it is a material dissolved at ature of 80°C or higher,»and examples thereof include fatty acid, fatty acid amide, , N-substituted amide, bisfatty acid amide, hydroxyfatty acid amide, fatty acid metal salts, p'benzyl biphenyl, terphenyl, triphenyl methane, benzyl p'benzyloxy benzoate, B-benzyloxy naphthalene, phenyl B'naphthoate, phenyl 1-hydroxynaphthoate, methyl oxynaphthoate, diphenylcarbonate, benzyl thalate, 1,4’dimethoxynaphthalene, 1,4'diethoxynaphthalene, 1,4-dibenzyloxy naphthalene, 1,2-diphenoxy ethane, 1,2-bis(4'methyl phenoxyethane), 1,4-diphenoxy'2'butene, 1,2'bis(4-methoxyphenylthio)ethane, dibenzoylmethane, 1,4-diphenylthiobutane, pheny1thiobutene, s(2-vinyloxyethoxy)benzene, 1,4-bis(2'Vinyloxyethoxy)benzene, p'(2'Vinyloxyethoxy)biphenyl, p-aryloxybiphenyl, dibenzoyloxy methane, oyloxy propane, dibenzyl disulfide, 1,1-diphenylethanol, 1,1'dipheny1propanol, yloxybenzyl alcohol, 1,3-phenoxypropanol, N-octadecyl carbamoyl-p“methoxycarbonylbenzene, N'octadecyl carbamoyl benzene, 1,2'bis(4'methoxyphenoxy)propane, 1,5-bis(4'methoxyphenoxy)'3'0xapentane, dibenzyl oxalate, bis(4'methylbenzyl) oxalate, and bis(4-chlorobenzy1) e.

The fatty acid is appropriately selected depending on the intended purpose Without any limitation, and examples thereof include stearic acid, and behenic acid.

The fatty acid amide is appropriately selected depending on the intended purpose Without any limitation, and examples thereof include stearic amide, euracamide, palmitic amide, and behenic amide.

The N‘substituted amide is appropriately selected depending on the intended purpose without any tion, and examples thereof include N'lauryl lauric amide, N-stearyl stearic acid, and N-oleyl stearic amide.

The bisfatty acid amide is appropriately ed depending on the ed purpose without any limitation, and examples thereof include methylene bisstearic amide, ethylene aric amide, ethylene bislauric amide, ne biscapric amide, and ethylenebisbehenic amide.

The hydroxyl fatty acid amide is appropriately selected depending on the intended purpose without any limitation, and examples thereof include hydroxyl stearic amide, methylene bishydroxy stearic amide, ethylene bishydroxy stearic amide, and hexamethylene bishydroxy stearic amide.

The fatty acid metal salt is appropriately selected depending on the intended purpose without any limitation, and es thereof include zinc stearate, um stearate, calcium stearate, zinc palmitate, and zinc behenate.

"Crosslinking Agent-- The crosslinking agent is appropriately selected depending on the intended purpose without any limitation. In the case where the barrier layer contains the aforementioned polyvinyl l containing a ve carbonyl group, it is easy to induce a crosslink reaction when N-aminopolyacryl amide is contained as 2012/078556 a inking agent at least either in the barrier layer, or in the thermosensitive coloring layer, which is preferred because water resistance can be improved without adding other crosslinking agents that may inhibit coloring. nt-- The pigment is appropriately ed depending on the intended purpose without any limitation, but it is preferably a white pigment in order to improve contrast of an image.

"-White Pigment-'- The white pigment is appropriately selected depending on - the intended purpose without any limitation, and examples thereof include kaolin, clay, silica, ium carbonate, and calcium carbonate. These may be used independently or in combination.

"Fluorescent Brightener" The ﬂuorescent brightener is appropriately selected . ing on the intended purpose without any limitation, but it is preferably a diaminostilbene-based compound because such compound has an effect of improving back ground whiteness, and has stability with a coating liquid of a barrier layer.

A method for g the thermosensitive coloring layer is appropriately ed depending on the intended purpose without any limitation. For example, the thermosensitive coloring layer can be formed by preparing a thermosensitive coloring layer coating liquid in the following manner, and applying the thermosensitive coloring layer coating liquid onto the base. The thermosensitive coloring layer coating liquid is prepared by crushing and dispersing the leuco dye and the developing agent together with a g agent and/or other components by means of a disperser, such as a ball mill, attritor, and sand mill, to give dispersed particle diameters of 1 pm to 3 um, followed by mixing optionally with filler and thermoplastic material (a sensitizing agent) dispersion liquids in a n '10 a.

The average thickness of the thermosensitive coloring layer is riately selected depending on the intended purpose Without any limitation, but it is preferably 1 pm to 50 pm, more preferably 8 mm to 20 pm, in view of coloring density. <Base> The base is appropriately selected depending on the intended purpose without any limitation.

-Shape, etc., of Base- A shape of the base is appropriately ed depending on the intended purpose without any limitation, and examples thereof include shapes of a plate, a sheet, and a film.

A ure of the base is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a single layer ure, and a laminate structure.

A size of the base is appropriately selected depending on the intended purpose without any limitation, and for example, the size thereof is appropriately selected depending on a size of the thermosensitive coloring layer, or the like.

The average ess of the base is appropriately selected ing on the intended purpose t any limitation, but it is preferably 50 pm to 2,000 um, more preferably 100 pm to 1,000 pm, in View of convenience.

A material of the base is appropriately selected depending on the intended e without any limitation, and examples thereof e an inorganic material, and an organic material.

'Inorganic Material- The inorganic material is appropriately selected depending on the intended purpose without any limitation, and examples thereof include glass, quartz, n oxide, and aluminum oxide. ic Material- The organic material is appropriately selected depending on the intended purpose without any tion, and examples thereof include paper, and a resin.

"Paper" The paper is appropriately selected depending on the intended purpose without any limitation, and examples thereof include wood free paper, art paper, coat paper, and synthetic WO 69581 paper.

Among them, wood free paper and art paper are preferable in View of the cost.

"Resin-- The resin is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a cellulose derivative, polyester, polycarbonate, polystyrene, polymethyl methacrylate, polyethylene, and polypropylene. _ The cellulose derivative is appropriately selected depending on the intended purpose without any limitation, and examples thereof include cellulose triacetate.

The polyester is appropriately selected depending on the intended purpose without any tion, and examples thereof include polyethylene terephthalate (PET), and polybutylene thalate.

The base is preferably ted to a surface modification, , such as by corona discharging, oxidation on (chromic acid etc.), etching, a treatment for adhesion, and anti-static treatment, for the purpose of improving adhesion of a coating layer.

Moreover, the paper is preferably colored in white by adding o a white pigment, such as titanium oxide. <Adhesive Layer> An ve for use in the adhesive layer is appropriately WO 69581 selected depending on the intended purpose without any limitation, but it is preferably acryl-based emulsion in view of safety, quality, and cost. In the case of the acryl-based emulsion used as the adhesive, 3 thickener used for adjusting a fluid viscosity of the adhesive is preferably a similar type of polyacrylate that will not adversely affect the adhesion properties of the adhesive.

Since the rylic acid has a small molecular weight compared with that of the ve and tends to move, a carboxyl group (—COOH), which is a functional group of the polyacrylic acid, is likely to orientated to an ace of the adhesive layer, which increases bonding strength by g to the reactive silicon (ESiH), which is remained in the organohydrogen polysiloxane in the release layer due to insufficient inking.

Therefore, an amount of the polyacrylic acid contained is adjusted as small as possible. In View of coating ability, however, adjustment in viscosity of the adhesive is required. For this reason, use of an adhesive composed of acryl emulsion containing 1.0% by mass to 3.0% by mass of the polyacrylic acidis preferable, and the viscosity of the adhesive is adjusted by adjusting stirring time with the aforementioned range of the amount of the polyacrylic acid. Use of such ve realizes reduction in variation of the binding strength between the release layer and the adhesive layer over time.

The viscosity of the adhesive is appropriately selected depending on the intended purpose without any limitation, but it . is preferably 15,000 mPa-s :l: 5,000 mPa-s, more preferably 15,000 mPa-s i 3,000 mPa-s, in View of coatability. When the viscosity is lower than 10,000 mPa-s, air bubbles tend to be included during coating, which tends to leave. lines from g. When the Viscosity is greater than 20,000 mPa's, a coating surface becomes uneven, which may adversely affect on properties.

A coating method of the adhesive is appropriately selected depending on the intended purpose without any limitation, and examples thereof include bar coating, roll coating, comma coating, and gravure coating.

An amount of the adhesive in the ve layer is appropriately selected depending on the intended purpose without any tion, but it is preferably 10 g/m2 to 25 g/m2 because a resulting adhesive layer can stably exhibit adhesion regardless of a surface configuration of a t to which a resulting thermosensitive ing label is adhered, and ﬂoating of the label is prevented even when the label is d to a subject, such as a cardboard box. When the amount thereof is smaller than 10 g/m2, the adhesive cannot over a surface of a cardboard box when a subject has rough e such as the cardboard box, and therefore adhesion of the label is extremely low. When the amount thereof is greater than 25 g/m2, especially in the case where the label is in the form of a roll, the adhesive may bleed out, and a problem in terms of cost may occur. <Other Layers> Other layers are riately selected depending on the intended purpose without any limitation, and examples thereof include an image adjustment layer provided on an opposite surface (back surface) to a surface of the base where the thermosensitive ng layer is provided.

The image adjustment layer may contain other components, such as organic filler, and a lubricant.

'Image Adjustment Layer- The image adjustment layer has a on of protecting an image of the thermosensitive recording label, and a on of adjusting contrast of the image.

The image adjustment layer is appropriately selected depending on the intended purpose without any limitation, but the image adjustment layer preferably contains a pigment, and a cured product of a water-soluble resin with a inking agent.

"Pigment" The pigment is appropriately selected ing on the intended purpose without any limitation, but it is preferably a white pigment because of its ability of ing contrast of an image.

"-White Pigment-'- The white pigment is riately selected depending on the intended purpose Without any limitation, and examples thereof e those usable in the thermosensitive coloring layer.

"Water-Soluble Resin-- The water-soluble resin is appropriately selected depending on the ed purpose without any limitation, and examples thereof include polyvinyl alcohol, starch and derivatives thereof, a ose derivative (e.g., methoxy cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, and ethyl cellulose, sodium polyacrylate, polyvinyl pyrrolidone, an acryl acrylic acid ester copolymer, an acryl amide-acrylic acid ester-methacrylic acid terpolymer, an alkali salt of a styrene/maleic anhydride mer, an alkali salt of an isobutylene-maleic anhydride copolymer, polyacryl amide, sodium alginate, gelatine, and casein. These may be used independently or in combination. Among them, it is preferred that the water-soluble resin be used in the state of polymer emulsion in View of easiness in coating on the image adjustment layer.

"'Polymer Emulsion-~- The polymer emulsion is appropriately selected depending on the intended purpose without any limitation, and es thereof include latex of an c acid ester copolymer, a styrene-butadiene mer, or a styrene'butadiene-acryl'based copolymer, and emulsion of a vinyl acetate resin, a vinyl acetate-acrylic acid copolymer, a styrene-acrylic acid ester copolymer, an acrylic acid ester resin, or a polyurethane resin.

These may be used independently or in combination.

"Crosslinking Agent" The crosslinking agent is riately selected depending on the intended purpose without any limitation, and examples thereof include those usable in the barrier layer.

"Organic Filler-- The organic filler is appropriately selected depending on the intended purpose t any tion, and examples thereof include a silicone resin, a cellulose resin, an epoxy resin, a nylon resin, at phenol resin, a polyurethane resin, a urea resin, a melamine resin, a polyester resin, a polycarbonate resin, a styrene-based resin, an based resin, a polyethylene resin, a formaldehyde-based resin, and a polymethyl methacrylate resin.

These may be used independently or in combination.

A method for forming the image adjustment layer is appropriately selected depending on the intended purpose without any limitation, but it is ably a method in which a coating liquid of an image adjustment layer is applied onto a base by coating to form the image adjustment layer.

The g method of the image adjustment layer is appropriately selected depending on the intended purpose without any limitation, and examples thereof include spin coating, dip coating, kneader coating, curtain coating, and blade g.

The average thickness of the image adjustment layer is appropriately ed depending on the intended purpose without any limitation, but it is preferably 0.1 mm to 10 um, more preferably 0.5 pm to 5 pm, in View of ng sensitivity. <Structure of Thermosensitive Recording Label> A structure of the thermosensitive recording label can be riately selected without any limitation, and examples f e in the form of a roll, a sheet, and a film. Among them, a roll is particularly preferable in View of convenience.

Examples The present invention will be more specifically explained through Examples and Comparative Examples hereinafter, but these Examples shall not be construed as limiting the scope of the t invention. Moreover, “part(s)” and “%” described in each Example respectively represent “part(s) by mass” and “% by mass” unless otherwise stated.

(Example A1) <Production of Thermosensitive Recording Label > (1) Preparation of Under Layer Coating Liquid [Liquid Al ' Calcined kaolin 36 parts ' e-butadiene copolymer latex 10 parts (product namei SMARTEX PA'9159, manufactured by Nippon A & L Inc., solid tration: 47.5%) ° Water 54 parts (2) Preparation of Thermosensitive Coloring Layer, Coating Liquid [Liquid Bl ‘ 2-anilino-S'methyl'B'(di'n'butylamino)fluoran 20 parts ' 10% aqueous solution of itaconic acid-modified 20 parts polyvinyl alcohol (modification ratei 1 mol%) ° Water 60 parts [Liquid Cl ' 4-hydroxy-4"isopropxydiphenyl e 20 parts ' 10% aqueous solution of itaconic acid-modified 20 parts polyvinyl alcohol (modification rate1 1 mol%) ' Silica 10 parts ' Water 50 parts [Liquid Dl Liquid B and Liquid C each formed of the aforementioned formulation were each dispersed by means of a sand mill to have the average particle diameter of 1.0 um or smaller, to thereby prepare a dye dispersion liquid, Liquid B, and a developing agent dispersion liquid, Liquid C, respectively.

Subsequently, Liquid B and Liquid C were mixed a ratio (mass ratio) of 137, and the solid concentration of the mixture was adjusted to 25%, and was stirred, to thereby prepare a thermosensitive coloring layer coating liquid, Liquid D. (4) Preparation of Barrier Layer Coating Liquid [Liquid E-l] ' Calcined kaolin 20 parts ° 10% aqueous solution of itaconi‘c acid-modified 20 parts polyvinyl alcohol (K POLYMER , manufactured by Kuraray Co., Ltd., modification ratei 1 mol%) ' Water 60 parts The materials of the formulation above were dispersed for 24 hours by means of a sand mill, to thereby prepare Liquid E-l.

[Liquid F-l] ° Liquid E1 75 parts ° 10% aqueous solution of deacetone-modified 100 parts nyl alcohol (DM'17, manufactured by JAPAN VAM POVAL CO., LTD., modification rate2 4 mol%) ' 10% s on of adipic dihydrazide 10 parts - Water 90 parts The materials of the formulation above were mixed and d to thereby prepare a barrier layer coating liquid, Liquid (5) Preparation of Release Layer g Liquid [Liquid G] ° Vinyl group-containing heat curing silicone 100 parts resin (BY24-46SC, ctured by Dow Corning Toray Co., Ltd.) ° Curing catalyst (SRX212, manufactured by 3.0 parts Dow Corning Toray Co., Ltd.) ’ The materials of the formulation above were mixed to y prepare Liquid F.

Onto a surface of base paper (wood free paper having a basis weight of about 60 g/mz), the under layer coating liquid, Liquid A, was applied by blade coating to give a dry deposition amount of 3.0 g/m2, and then was dried, to thereby form an under layer.

Next, onto the under layer, the thermosensitive coloring layer coating liquid, Liquid D, and the barrier layer coating liquid, Liquid F-l were successively applied and laminated to give dry tion amounts of 5.0 g/mz, and 1.0 g/mz, respectively, followed by drying to thereby form a thermosensitive coloring layer, and a barrier layer. Thereafter, calendering was performed to give a surface with Oken-type smoothness of about 2,000 seconds.

WO 69581 Next, the release layer coating liquid, Liquid G, was applied onto the barrier layer by coating to give a dry mass of 1.0 g/mZ, followed by drying at temperature and time period by which the thermosensitive coloring layer would not color, by means of a dryer box (dryer EHT-6025, of ETAC), to thereby cure the release layer. As a result, a thermosensitive recording material provided with the release layer was obtained. The curing state of the release layer was determined as a non-liquid state when touching a e layer with s. (6) Formation of Adhesive Layer Next, an acrylic adhesive (manufactured by Henkel Japan Ltd., solid concentrationi 54%) was applied onto a surface of a base opposide to the surface thereof where the release layer of the sensitive recording material had been provided, to give a dry mass of 20 g/m2. After drying the applied acrylic ve, the resultant was wound into a roll in the manner that the e layer and the adhesive layer were bonded to each other, to thereby produce a thermosensitive recording label of Example A1.

, (Example A2) <Production of Thermosensitive Recording Label> A sensitive recording label of Example A2 was produced in the same manner as in Example A1, provided that calcined kaolin contained in Liquid A of the under layer» coating liquid was replaced with Vinylidene chloride-acrylonitrile copolymer particles (molar ratio of vinylidene de/acrylonitrile = 6/4), which had a solid content concentration of 27.5%, the average particle diameter of 3 pm, and a void ratio of 90%.

(Example A3) ction of Thermosensitive ing Label> A thermosensitive recording label of Example A3 was produced in the same manner as in Example A2, provided that the Vinyl group-containing heat curing silicone resin (BY24-468C, manufactured by Dow Corning Toray Co., Ltd.) contained in the release layer coating , Liquid G, was replaced with a hexenyl group-containing heat curing silicone resin (LT01056L, manufactured by Dow Corning Toray Co., Ltd).

(Example A4) 1 5‘ <Production of Thermosensitive Recording Label> . A thermosensitive recording label of Example A4 was produced in the same manner as in Example A3, provided that the barrier layer coating , Liquid E1, was replaced with Liquid F-2 described below. d F-2] ' Liquid E1 75 parts ‘ 10% aqueous solution of itaconic acid-modified 100 parts polyvinyl alcohol (modification rate: 1 mol%) ‘ 10% aqueous solution of adipic dihydrazide 10 parts ' Water » 90 parts The materials ted above were mixed and stirred to thereby prepare a barrier layer coating liquid, Liquid F-2.

(Example A5) <Production of Thermosensitive Recording Label> A thermosensitive recording label of e A5 was produced in the same manner as in Example A4, provided that Liquid E-l was replaced with Liquid E-2 described below.

[Liquid E-2l ' Aluminum hydroxide. 20 parts ' 10% aqueous solution of itaconic odified 20 parts polyvinyl alcohol (modification rate: 1 mol%) ' 10% s solution of 10 parts polyamide-epichlor0hydrin resin ' Water , 60 parts The materials of the formulation above were dispersed for 24 hours by means of a sand mill to thereby prepare Liquid E-2. le A6) <Production of Thermosensitive Recording Label> A thermosensitive recording label of Example A6 was produced in the same manner as in Example A5, provided that the barrier layer coating liquid, Liquid F-2, was replaced with Liquid F'3 presented below.

[Liquid H] ' cal ne resin particles (KMP-590, 30 parts ctured by Shin-Etsu Chemical Co., Ltd., volume average particle diameterl 2.0 um)' ' 10% aqueous solution of alkyl sulfosuccinate 10 parts ' Water 60 parts The materials of the formulation above were stirred with a stirrer for 1 hour, to thereby prepare Liquid H.

[Liquid F-3l ° Liquid E2 75 parts ‘ Liquid H 5 parts ' 10% aqueous solution of itaconic acid-modified 100 parts polyvinyl alcohol (modification rate: 1 mol%) ° 10% aqueous solution of 10 parts polyamide'epichlorohydrin resin ° Water 90 parts The materials of the formulation above were mixed and stirred to thereby prepare a r layer coating liquid, Liquid F-3.

(Comparative Example A1) <Production of Thermosensitive Recording Label> A thermosensitive recording label of Comparative Example Al was ed in the same manner as in Example A1, provided that the barrier layer c0ating liquid, Liquid F-l, was replaced with Liquid F-4 described below.

[Liquid F'4l ° Styrene-butadiene copolymer latex 21 parts (product name: SMARTEX PA-9159, manufactured by Nippon A & L Inc., solid concentration: 47.5%) ' Water 79 parts The materialsof the formulation above were mixed and stirred to y prepare a barrier layer coating , Liquid F-4.

(Comparative Example A2) <Production of Thermosensitive Recording Label> A thermosensitive recording label of Comparative Example A2 was produced in the same manner as in Example A1, provided that the barrier layer coating , Liquid F-l, was replaced with Liquid F-5 described below.

[Liquid F-5l ' 10% aqueous solution of itaconic acid-modified 50 parts polyvinyl alcohol (modification rate: 1 mol%) ' 10% aqueous solution of 5 parts polyamideepichlorohydrin resin ‘ Water 45 parts The materials of the formulation above were mixed and stirred, to thereby prepare a r layer coating liquid, Liquid (Comparative e A3) <Pr0ducti0n of Thermosensitive Recording Label> A thermosensitive recording label of Comparative Example A3 was produced in the same manner as in Example A2, provided that Liquid G was ed with Liquid G-2, and a release layer was provided by applying Liquid G'Z to give a dry mass of 1.0 g/mz, followed by applying ultraviolet rays twice by means of an ultraviolet ray irradiation device (device name: TOSURE 2000, model name3 KUV-20261‘1X, product of TOSHIBA DENZAI CO., LTD.) in the entire ng state (at 10 ampere to 12 ampere measured by an ammeter) and at an irradiation speed of 5 m/min, to thereby cure the release layer coating liquid.

[Liquid G'Zl ' UV curing silicone resin [a mixed composition 100 parts of 30 part of mercapto group-containing (1.5 mol%) organopolysiloxane and 70 parts of vinyl group-containing (1.5 mol%) organopolysiloxane] actured by Shin-Etsu Chemical CO., Ltd.) ' Curing catalyst (acetophenone) 3.0 parts Table A1 IRelease layer Barrier layer Water-soluble Inorganic Resin Filler resin ﬁller particles Ex. A1 calcined calcined kaolin kaolm. heat curing silicone polyvinyl alcohol resin Ex. A2 vinyl diacetone calcined group-containing -modiﬁed kaolin chloride- heat curing silicone polyvinyl alcohol acrylonitrile resin copolymer Ex. A3 hexenyl calcined vinylidne containing kaolin chlorideheat curing silicone polyvinyl alcohol acrylonitrile resin copolymer Ex. A4 hexenyl itaconic calcined vinylidne group-containing acid-modiﬁed kaolin chloride- heat curing silicone nyl alcohol acrylonitrile resin copolymer Ex. A5 hexenyl ‘ vinylidne group-containing chloride- acrylonitrile Ex. A6 hexenyl dne group-containing chloride- acrylonitrile copolymer Comp.

Ex. A1 Comp. itaconic Ex. A2 acid-modiﬁed resin UV curing silicone Diacetone resin 'modiﬁed chloride- polyvinyl alcohol acrylonitrile copolymer Various properties of thermosensitive ing labels ed in the aforementioned manner were each evaluated.

The results are presented in Table A2. <Peal Property> Two thermosensitive recording labels in the laminate state WO 69581 was cut into a size of 4 cm X 20 cm, and a pealing property was evaluated when the upper label and the lower label were pealed from each other by hand with a pealing angle of 90°.

The evaluation was performed just after the production of sample (initial stage) and after left to stand for 3 months (Over time).

[Evaluation Criteria] -A3 Pealed easily and without any problem Bz Pealed with some resistance, but without any problem '01 Pealed with some resistance D1 Peeled with significant ance <Binding Ability> The ing procedure was d out on each thermosensitive recording label. About one minute after coating and heat curing of a release layer before the formation of an adhesive layer thereon, a surface of the release layer was strongly rubbed with a finger ten times. A degree of the release layer peeled was evaluated. The evaluation criteria of the peel test of the release layer are as follows.

[Evaluation Criteria] A3 The release layer was not peeled at all.

B1 The glossiness of the area where was rubbed was slightly lowered.

CI Peeling was confirmed at a very small part in the area 2012/078556 Where was rubbed.

DZ Peeling occurred. <Evaluation on Sticking in Low ature Low Humidity Environment> Each thermosensitive recording label and a printer (L’esprit R-12, manufactured by Saton Inc.) was left to stand for 1 hour in the low temperature and low humidity nment of 5°C, %RH, to adjust the moisture, followed by ‘carried out printing.

Then, ng during the ng was evaluated; In the case Where anti-sticking property is excellent, a printing pattern is accurately printed. In the case Where anti-sticking property is not excellent, on the other hand, a printing pattern is not accurately printed because printing is performed and superimposed on the same area of the thermosensitive recording label. The printed image was ly observed, and the sticking was evaluated based on the following criteria. Note that, the sticking was evaluated in the low ature environment, because the sticking tends to occur in the low temperature environment compared to in the moderate to high temperature environment, due to a temperature difference between the label and a thermal head.

[Ranks of sticking by visual observation (5 standards)] A1 No sticking occurred.

B1 Sticking slightly occurred to the level which was not a WO 69581 problem in the quality of the image.

C3 Sticking occurred to the level which was a problem in the quality of the image.

D1 The level was not conveyed perfectly and sticking occurred.

E3 The level was not conveyed at all. <Sensitivity Scale Factor> Each thermosensitive recording label was printed by means of a thermosensitive print testing device having a thin film head, manufactured by Panasonic Electronic Device Inc., under the following conditions, which were a heat powder of 0.45 W/dot, l'line recording time of 20 msec/L, scanning density of 8 X 385 . The printing was performed with a pulse width of 0.2 msec to 1.2 msec per 0.1msec. The print density was ed by Macbeth Densitometer RD-914, and the pulse width with which the density was 1.0 was calculated.

Taking Comparative Example A1 as a standard, a sensitivity scale factor was calculated using the following equation. The greater the value is, more excellent the sensitivity (thermal se) is.

Sensitivity scale factor = (pulse Width of Comparative Example A1)/(pulse width of measured sample) Table A2 Evaluation results Peel force Release Low Sensitivity layer temperature scale factor l Over time g sticking ability Comp. Ex. A1 E Comp. Ex. A2 C Comp. Ex. A3 1.00 Examples A1 to A6, in each of which the water-soluble resin of the barrier layer was polyvinyl alcohol containing a reactive carbonyl group, unlikely had residues of uncured silicone resin in their release layer, and therefore they had excellent peel force. In contrary, as Comparative e A1 used the styrene-butadiene mer latex, curing of the silicone resin in the release layer was inhibited, leaving residues of the uncured silicone resin, which adhered to the ve. As a result, the peel force was not desirable.

(Example B1) <Production of Thermosensitive Recording Label> (1) Preparation of Under Layer Coating Liquid [Liquid A] ° Calcined kaolin (product name3 Ultra White 90, 36 parts manufactured by BASF Corporation) ' Styrene-butadiene copolymer latex ct 10 parts name: SMARTEX PA'9159, manufactured by Nippon A & L Inc., solid concentration: 47.5%)- ° Water 54 parts (2) Preparation of Thermosensitive Coloring Layer Coating Liquid d Bl ° 2-anilinomethyl'6'(di-n-butylamino)ﬂuoran 20 parts ° 10% aqueous solution of itaconic acid-modified 20 parts polyvinyl alcohol (modification ratei 1 mol%) (product name: Kuraray K Polymer KL-318, manufactured by Kuraray Co., Ltd.) ' Water 60 parts d C] ' 4-hydroxy-4"isopropxydiphenyl sulfone 20 parts ° -10% aqueous solution of itaconic odified 20 parts nyl alcohol (modification rate3 1 mol%) (product name: Kurary K Polymer KL'318, manufactured by Kuraray Co., Ltd.) - ° Silica (product namei MIZUKASIL P-603, 10 parts manufactured by MIZUSAWA INDUSTRIAL CHEMICALS, LTD)" ' Water 50 parts [Liquid D] Liquid B and Liquid C each formed of the respective formulation above were each dispersed by means ofa sand mill to give the average le diameter of 1.0 pm or smaller, to thereby prepare a dye dispersion liquid, Liquid B, and a developing agent dispersion liquid, Liquid C.

Subsequently, Liquid B and Liquid C were mixed at a ratio of 1 part/7 parts, and a solid content of the mixture was adjusted to 25%, followed by stirring, to thereby prepare a thermosensitive coloring layer coating liquid, Liquid D. (3) Preparation of r Layer Coating Liquid [Liquid E-ll ' Calcined kaolin (product name: Ultra White 90, 20 parts manufactured by BASF Corporation) ° 10% aqueous solution of itaconic acid-modified 20 parts polyvinyl alcohol (modification rate: 1 mol%) (product name3 Kuraray K Polymer KL'318, . manufactured by Kuraray Co., Ltd.) ' Water 60 parts The materials of the formulation above were dispersed for 24 hours by means of a sand mill, to thereby e Liquid E'l.

[Liquid F-ll ' Liquid El 75 parts ° Non-porous crosslinked polymethyl 5 parts 2012/078556 methacrylate les (product name: GM-0105, manufactured by GANZ CHEMICAL CO., LTD.) having the volume average particle diameter of 2.0 um, and the bulk density of 0.50 g/mL' ' 10% aqueous on of one-modified 100 parts polyvinyl alcohol (modification ratei 4 mol%) (product name: DM-17, manufactured by JAPAN VAM POVAL CO., LTD.) ' 10% aqueous solution of adipic dihydrazide 10 parts ' Water 85 parts The materials of the formulation above were mixed and stirred to prepare a barrier layer coating liquid, Liquid F-l.

Note that, the bulk density was determined by adding the non-porous crosslinked polymethyl rylate particles (product namei PM-OSO, manufactured by GANZ CHEMICAL CO., LTD.) having the volume average particle diameter of 0.3 um into a measuring cylinder (100 mL in volume) up to 10 mL, measuring the mass thereof, and calculating the value of the measured mass/the measured volume. (4) Preparation of Release Layer g Liquid [Liquid Gl ° Vinyl group-containing heat curing silicone 100 parts - resin (product namei BY24‘4680, manufactured by Dow Corning Toray Co., Ltd)” 2012/078556 ' Curing catalyst (product name3 SRX212, 3.0 parts manufactured by Dow Corning Toray Co., Ltd.) The materials of the formulation above were mixed to prepare Liquid G.

Onto a surface of base paper (wood free paper having a basis weight of about 60 g/mz), the under layer coating liquid, Liquid A, was applied by blade coating to give a dry tion amount of 3.0 g/m2, and then was dried, to thereby form an under layer.

Next, onto the under layer, the thermosensitive coloring layer coating liquid, Liquid D, and the barrier layer coating liquid, Liquid F-l were successively d and laminated to give dry deposition amounts of 5.0 g/mz, and 1.0 g/mZ, respectively, followed by drying to y form a thermosensitive coloring layer, and a barrier layer. Thereafter, calendering was performed to give a surface with Oken'type smoothness of about 2,000 seconds. The curing state of the water-soluble resin with the crosslinking agent was confirmed by HS-GC/MS.

Next, the release layer coating liquid, Liquid G, was applied onto the barrier layer by g to give a dry mass of 1.0 g/mz, followed by drying at temperature and time period by which the thermosensitive coloring layer would not color, by means of a dryer box (dryer EHT-6025, of ETAC), to thereby cure the release layer. As a result, a thermosensitive recording material ed with the release layer was obtained. The curing state of the release layer was determined as a quid state when touching a release layer with fingers. (5) Formation of Adhesive Layer Next, an acrylic adhesive (product name3 Olibin BPW6111A, manufactured by EM CO., LTD.) was applied onto a surface of the base opposite to the surface thereof where the release layer of the thermosensitive ing material had been provided, to give a dry mass of 20 g/m2. After drying the applied acrylic ve, the resultant was wound into a roll in the manner that the release layer and the adhesive layer were bonded to each other, to thereby produce a thermosensitive ing label of Example B1.

(Example B2) <Production of Thermosensitive Recording Label> A thermosensitive recording label of e B2 was produced in the same manner as in Example B1, provided that the crosslinked polymethyl methacrylate particles were replaced with porous crosslinked polymethyl methacrylate particles (product name: GM-0401S, manufactured by GANZ CHEMICAL CO., LTD.) having the volume average particle diameter of 2.0 pm, and the bulk density of 0.48 g/mL.

(Example B3) <Production of Thermosensitive Recording Label> A thermosensitive recording label of Example B3 was produced in the same manner as in Example B2, provided that the calcined kaolin (product name: Ultra White 90, manufactured by BASF Corporation) in Liquid A was replaced with Vinylidene de-acrylonitrile copolymer (molar ratio of vinylidene chloride/acrylonitrile = 6/4, solid concentrationi 27.5%, volume average particle erl 3 pm, void ratiol 90%). Note that, the void ratio was measured by means of a scanning electron microscope (product no.1 8-3700, manufactured by Hitachi, Ltd).

(Example B4) <Production of Thermosensitive Recording Label > A thermosensitive recording label of Example B4 was produced in the same manner as in e B3, ed that the vinyl group-containing heat curing ne resin (product namei 680, manufactured by Dow Corning Toray Co., Ltd.) in Liquid G was replaced with a heat curing ne resin(product namei LTClO56L, manufactured by Dow Corning Toray Co., Ltd.) containing hexenyl group-containing organopolysiloxane and organohydrogen polysiloxane.

(Example B5) <Production of Thermosensitive Recording Label> A thermosensitiVe recording label of Example B5 was produced in the same manner as in Example B4, provided that the barrier layer coating liquid, Liquid F-l, was replaced with Liquid F-2 bed below.

[Liquid F‘Z] ' Liquid El 75 parts ’ Porous crosslinked polymethyl methacrylate 5 parts particles (product namei GM'0105, manufactured by GANZ CHEMICAL 00., LTD.) having the bulk density of 0.50 g/mL, and the volume average particle diameter of 2.0 um ' 10% aqueous solution of itaconic acid-modified 100 parts polyvinyl alcohol (modification ratei 1 mol%) (product name1 Kuraray K Polymer , manufactured by Kuraray Co., Ltd.)- ’ 10% aqueous solution of adipic dihydrazide 10 parts ° Water 90 parts The materials of the formulation above were mixed and stirred to thereby prepare a barrier layer coatingliquid, Liquid F-2. le B6) ction of sensitive Recording Label> A thermosensitive recording label of Example B6 was produced in the same manner as in Example B5, provided that Liquid E-l was replaced with Liquid E-2 described below.

[Liquid E-2l 2012/078556 ° Aluminum hydroxide- 20 parts ' 10% aqueous solution of itaconic acid-modified 20 parts polyvinyl alcohol ication ratei 1 mol%) (product name: Kuraray K Polymer KL'318, Kuraray CO., Ltd.) ' 10% aqueous solution of 10 parts polyamide'epichlorohydrin resin (product name1 , manufactured by Japan PMC Corporation) ° Water 60 parts The materials of the formulation above were dispersed for 24 hours by means of a sand mill, to thereby prepare Liquid E-Z.

(Example B7) <Production of Thermosensitive Recording Label> A thermosensitive recording label of Example B7 was produced in the same manner as in Example B6, ed that the crosslinked polymethyl methacrylate particles were replaced with porous crosslinked polymethyl rylate particles(product namei GM-0405, manufactured by GANZ CHEMICAL CO., LTD.) having the volume average particle diameter of 5.0 um, and the bulk density of 0.50 g/mL.

(Comparative Example B1) <Production of Thermosensitive Recording Label> A thermosensitive recording label of Comparative Example B1 was produced in the same manner as in Example B2, provided that Liquid G was replaced with Liquid G-2 described below, and a release layer was formed by applying Liquid G2 to give a dry mass of 1.0 g/m2, followed by applying ultraviolet rays twice by means of an ultraviolet ray irradiation device (device namei TOSURE 2000, model namel KUV1X, product of A DENZAI (30., LTD.) in the entire lighting state (at 10 ampere to 12 ampere measured by an ammeter) and at an ation speed of 5 m/min, to thereby cure the release layer coating liquid. d G'Zl ° UV curing silicone resin [mixed composition of 100 parts parts of a mercapto group-containing (1.5 mol%) organopolysiloxane and 70 parts of a vinyl group-containing (1.5 mol%) organopolysiloxanel (manufactured by Shin-Etsu Chemical Co., Ltd.) ' Curing catalyst 3.0 parts Table B 1 Release layer Barrier layer Under layer Main nic Crosslinked component of ﬁller polymethyl water- methacrylate soluble resin les Particle Shape Filler Void size ratio ( m) E X. B 1 vinyl group one- calcined 2.0 non- calcined 0% containing modiﬁed kaolin porous kaolin heat curing polyvinyl silicone resin alcohol EX. B2 vinyl group diacetone' 2,0 porous calcined 0% containing modiﬁed kaolin heat curing polyvinyl ' ' silicone resin alcohol Ex. B 3 vinyl group calcined 2.0 porous vinylidene 90% containing kaolin chloride—acryl heat curing nitrile silicone resin copolymer Ex. B4 hexenyl group diace’oone-mo calcined 2.0 porous vinylidene 90% containing diﬁed kaolin chloride-acryl heat curing polyvinyl nitrile silicone resin alcohol copolymer Ex. B 5 hexenyl group itaconic calcined 2.0 porous vinylidene 90% containing acid-modiﬁed kaolin chloride-acryl heat curing polyvinyl nitrile silicone resin alcohol copolymer Ex. B6 hexenyl group ic Aluminum 2.0 porous vinylidene 90% containing acid-modiﬁed ide chloride-acryl heat curing polyvinyl nitrile silicone resin alcohol copolymer l group itaconic 5.0 porous vinylidene 90% containing acid-modiﬁed hydroxide chloride-acryl heat curing polyvinyl e silicone resin alcohol mer UV‘curing diacetone-mo calcined 2.0 porous calcined 0% silicone resin diﬁed kaolin kaolin polyvinyl alcohol The thermosensitive recording labels obtained in the aforementioned manner were evaluated in terms of the s properties f in the same evaluation manner to that for Examples Al to A6 and Comparative Examples A1 to A3. The results are presented in Table B2.

Table B2 Evaluation results Release Low ivity Initial Over layer temperature scale factor time binding sticking ability EX. Bl Ian The embodiments of the t invention are as followsi <1> A thermosensitive recording label, comprisingi a base; an under layer; a thermosensitive coloring layer; a barrier layer; a release layer; and an adhesive layer, where the under layer, the thermosensitive coloring layer, the barrier layer, and the release layer are disposed on one surface of the base in this order, and the ve layer is disposed on the other surface of the base, wherein the release layer contains a cured product of a heat curing silicone resin, and the barrier layer contains a cured product of a water-soluble resin with a inking agent, and inorganic filler. <2> The thermosensitive recording label according to <1>, WO 69581 wherein the heat curing silicone resin contains polysiloxane containing a hexenyl group, and organohydrogen polysiloxane. <3> The thermosensitive recording label according to any of <1> or <2>, wherein the water-soluble resin is itaconic acid-modified polyvinyl alcohol. <4> The thermosensitive recording label according to any one of <1> to <3>, wherein the inorganic filler is aluminum hydroxide. <5> The thermosensitive recording label according to any one of <1> to <4>, wherein the barrier layer r contains resin particles. <6> The thermosensitive recording label according to <5>, wherein the resin particles are silicone resin particles, crosslinked polymethyl rylate particles, or both thereof. <7> The thermosensitive recording label according to <6>, n the crosslinked polymethyl methacrylate particles have a volume average particle er of 1.0 um to 8.0 pm. <8> The thermosensitive recording label according any of <6> or <7>, wherein the crosslinked polymethyl methacrylate particles are porous. <9> The thermosensitive recording label according to any one of <1> to <8>, wherein the under layer further contains hollow plastic resin particles. <10> The thermosensitive recording label according to any one of <1> to <9>, wherein a g strength between the release layer and the barrier layer is stronger than a bonding strength between the adhesive layer and the release layer. <11> The thermosensitive recording label ing to any one of <1> to <10>, wherein the thermosensitive recording label in the form of a roll.

Claims

1. A thermosensitive recording label, comprising: a base; an under layer; 5 a thermosensitive coloring layer; a barrier layer; a release layer; and an ve layer, where the under layer, the thermosensitive coloring layer, 10 the r layer, and the e layer are disposed on one surface of the base in this order, and the adhesive layer is disposed on the other surface of the base, wherein the under layer contains an ve resin and filler, and 15 wherein the release layer contains a cured product of a heat curing silicone resin, and the barrier layer contains a cured product of a water-soluble resin with a inking agent, and inorganic filler.

2. The thermosensitive recording label according to claim 1, 20 wherein the heat curing silicone resin contains organopolysiloxane containing a hexenyl group, and organohydrogen polysiloxane.

3. The thermosensitive recording label according to any one of claim 1 or 2, wherein the water-soluble resin is itaconic acid-modified polyvinyl alcohol.

4. The thermosensitive recording label according to any one of claims 1 to 3, wherein the inorganic filler is aluminum hydroxide.

5 5. The thermosensitive recording label according to any one of claims 1 to 4, wherein the barrier layer further contains resin particles.

6. The thermosensitive recording label according to claim 5, wherein the resin particles are silicone resin particles, 10 crosslinked polymethyl methacrylate les, or both thereof.

7. The thermosensitive recording label ing to claim 6, wherein the crosslinked polymethyl methacrylate particles have a volume average particle diameter of 1.0 mm to 8.0 mm.

8. The thermosensitive recording label ing any one of 15 claim 6 or 7, wherein the inked thyl methacrylate particles are porous.

9. The thermosensitive recording label according to any one of claims 1 to 8, wherein the under layer further contains hollow thermoplastic resin particles. 20

10. The thermosensitive recording label according to any one of claims 1 to 9, wherein a bonding strength between the release layer and the barrier layer is stronger than a bonding strength between the adhesive layer and the release layer.

11. The thermosensitive recording label according to any one of claims 1 to 10, wherein the sensitive recording label in the form of a roll.

12. A thermosensitive recording label as claimed in claim 1, substantially as herein described with reference to any one of the 5 embodiments illustrated in the accompanying description.