JP5948800B2 - Reversible thermosensitive recording medium and reversible thermosensitive recording member - Google Patents

Description

  The present invention relates to a reversible thermosensitive recording medium and a reversible thermosensitive recording member having the reversible thermosensitive recording medium.

  Conventionally, a thermal recording medium using a color developing reaction between an electron donating color developing compound and an electron accepting compound is known. Thermal recording media are being used as output paper for facsimiles, word processors, scientific measuring instruments, etc. with the progress of OA, as well as transportation commuter pass, various prepaid cards, magnetic cards such as point cards, IC cards, etc. It is also used as an IC tag. In particular, recently, from the viewpoint of environmental problems, waste problems, etc., development of cards, tags, labels, etc. using reversible thermosensitive recording media has attracted attention.

  Patent Document 1 discloses a support, a reversible thermosensitive recording layer comprising a reversible thermosensitive composition containing an electron donating color-forming compound and an electron accepting compound, a polyvinyl alcohol polymer, and an ethylene-vinyl alcohol copolymer. A gas barrier layer containing a resin containing at least one selected from the group consisting of a coalescence, an organic metal compound containing at least one of an organic titanium compound and an organic zirconium compound, and an inorganic layered compound, and a protective layer for protecting the gas barrier layer A sequentially reversible thermosensitive recording medium is disclosed.

  However, it is desired to further improve the light resistance of the reversible thermosensitive recording medium.

  The present invention has been made in view of the above problems of the prior art, and an object thereof is to provide a reversible thermosensitive recording medium having excellent light resistance and a reversible thermosensitive recording member having the reversible thermosensitive recording medium.

In the reversible thermosensitive recording medium of the present invention, a reversible thermosensitive recording layer, a gas barrier layer and a protective layer are sequentially laminated on a support, and the reversible thermosensitive recording layer comprises an electron donating color-forming compound and an electron. The gas barrier layer includes a receptive compound, and the gas barrier layer includes three or more layers including a resin, an organometallic compound, and an inorganic layered compound, and the outermost layer of the three or more layers is the outermost layer. The metal content is larger than other layers, the resin is a polyvinyl alcohol resin and / or an ethylene-vinyl alcohol copolymer resin, and the organometallic compound is an organotitanium compound and / or an organozirconium. A compound.

  The reversible thermosensitive recording member of the present invention has an information storage unit and a reversible display unit, and the reversible display unit has the reversible thermosensitive recording medium of the present invention.

  According to the present invention, a reversible thermosensitive recording medium excellent in light resistance and a reversible thermosensitive recording member having the reversible thermosensitive recording medium can be provided.

1 is a partial cross-sectional view showing a first embodiment of a reversible thermosensitive recording medium of the present invention. It is a fragmentary sectional view which shows 2nd embodiment of the reversible thermosensitive recording medium of this invention. It is a fragmentary sectional view which shows 3rd embodiment of the reversible thermosensitive recording medium of this invention. It is a fragmentary sectional view which shows 4th embodiment of the reversible thermosensitive recording medium of this invention. It is a fragmentary sectional view which shows 5th embodiment of the reversible thermosensitive recording medium of this invention. It is a fragmentary sectional view which shows the method of forming an image on the reversible thermosensitive recording medium of FIG. FIG. 2 is a partial cross-sectional view showing a method for erasing an image formed on the reversible thermosensitive recording medium of FIG. 1.

  Next, the form for implementing this invention is demonstrated with drawing.

  FIG. 1 shows a first embodiment of a reversible thermosensitive recording medium of the present invention. In the reversible thermosensitive recording medium 10, a reversible thermosensitive recording layer 12, a gas barrier layer 13 and a protective layer 14 are sequentially laminated on a sheet-like support 11.

  The gas barrier layer 13 includes a resin, an organometallic compound, and an inorganic layered compound. For this reason, discoloration and discoloration of the reversible thermosensitive recording layer 12 due to oxygen entering the reversible thermosensitive recording layer 12 can be suppressed.

  At this time, in the gas barrier layer 13, a first layer 13a, a second layer 13b, and a third layer 13c containing a resin, an organometallic compound, and an inorganic layered compound are sequentially laminated. For this reason, gas barrier property can be improved. As a result, the light resistance of the reversible thermosensitive recording medium 10 is improved, and fading and discoloration of the reversible thermosensitive recording layer 12 can be suppressed for a long period of time.

  Instead of the gas barrier layer 13, a gas barrier layer in which two or more layers including a resin, an organometallic compound, and an inorganic layered compound are laminated may be formed.

  The thickness of the gas barrier layer 13 is usually 0.1 to 10 μm, and preferably 0.3 to 5 μm. If the thickness of the gas barrier layer 13 is less than 0.1 μm, the gas barrier property may be insufficient, and if it exceeds 10 μm, the thermal sensitivity of the reversible thermosensitive recording layer 12 may decrease.

  The resin is a polyvinyl alcohol resin and / or an ethylene-vinyl alcohol copolymer resin.

  Although it does not specifically limit as a polyvinyl alcohol-type resin, Polyvinyl alcohol, the derivative of polyvinyl alcohol, modified polyvinyl alcohol, etc. are mentioned, You may use 2 or more types together.

  Examples of the polyvinyl alcohol derivative include polyvinyl alcohol in which up to about 40 mol% of the hydroxyl group is acetalized.

  Examples of the modified polyvinyl alcohol include a copolymer with a vinyl monomer having a modifying group such as a carboxyl group or an amino group.

  The degree of polymerization of the polyvinyl alcohol-based resin is usually 100 to 5000, preferably 500 to 3000.

  The saponification degree of the polyvinyl alcohol-based resin is usually 60 mol% or more, and preferably 75 mol% or more.

  The ethylene-vinyl alcohol copolymer resin is not particularly limited, and examples thereof include an ethylene-vinyl alcohol copolymer, a resin obtained by saponifying a copolymer of ethylene, vinyl acetate, and other vinyl monomers, and the like. Two or more species may be used in combination.

  Content of the structural unit derived from ethylene of ethylene-vinyl alcohol copolymer system resin is 20-60 mol% normally. When the ethylene-vinyl alcohol copolymer-based resin has a content of ethylene-derived structural units of less than 20 mol%, the gas barrier property of the gas barrier layer 13 under high humidity may deteriorate. When the content exceeds 60 mol%, the gas barrier layer The gas barrier property of 13 may be lowered.

  The saponification degree of the ethylene-vinyl alcohol copolymer resin is usually 95 mol% or more. If the saponification degree of the ethylene-vinyl alcohol copolymer-based resin is less than 95 mol%, the gas barrier property of the gas barrier layer 13 may be lowered.

  As the ethylene-vinyl alcohol copolymer-based resin, a terminal-modified ethylene-vinyl alcohol copolymer that has been treated with a peroxide or the like to lower the molecular weight is preferable from the viewpoint of dissolution stability.

  The organometallic compound is an organotitanium compound and / or an organozirconium compound. Thereby, the water resistance and adhesion of the gas barrier layer 13 can be improved.

Although it does not specifically limit as an organic zirconium compound, General formula Zr (OR) _n (X) _4-n
(In the formula, R is an organic group, X is a ligand, and n is an integer of 0 to 3.)
Zirconium chelate represented by the general formula Zr (OR ¹ ) _n (OCOR ² ) _4-n
(R ¹ and R ² are each independently an organic group, and n is an integer of 0 to ^3. )
Zirconate acylate represented by the general formula Zr (OR) ₄
(In the formula, R is an organic group.)
And a zirconium alkoxide represented by

  Examples of the zirconium chelate include zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, zirconium butoxyacetylacetonate bis (ethylacetoacetate), zirconium dibutoxybis (ethylacetoacetate), zirconium tetraacetylacetonate and the like.

  Examples of the zirconium acylate include zirconium acetate and zirconium tributoxy systemate.

  Examples of the zirconium alkoxide include tetra-n-propoxyzirconium and tetra-n-butoxyzirconium.

Although it does not specifically limit as an organic titanium compound, General formula Ti (OR) _n (X) _4-n
(In the formula, R is an organic group, X is a ligand, and n is an integer of 0 to 3.)
Titanium chelate represented by the general formula Ti (OR ¹ ) _n (OCOR ² ) _4-n
(In the formula, R ¹ and R ² are organic groups, and n is an integer of 0 to ^3. )
Titanium acylate represented by the general formula Ti (OR) ₄
(In the formula, R is an organic group.)
The titanium alkoxide represented by these is mentioned.

  Examples of the titanium chelate include titanium acetyl acetate, triethanolamine titanate, titanium ammonium lactate, titanium lactate, titanium diisopropoxybis (triethanolaminate), and the like.

  Examples of titanium acylate include polyhydroxy titanium stearate, polyisopropoxy titanium stearate and the like.

  Examples of the titanium alkoxide include tetraisopropyl titanate, tetra-n-butyl titanate, tetra (2-ethylhexyl) titanate, and tetrastearyl titanate.

  The organometallic compound is preferably a chelate compound or an acylate compound in terms of water resistance and adhesion.

  The content of the metal contained in the organometallic compound in the layer other than the outermost layer of the gas barrier layer 13, that is, the second layer 13b is usually 0.10 to 10% by mass, and 0.20 to 8.0% by mass. % Is preferable, and 0.50 to 5.0 mass% is more preferable. When the content of the metal contained in the organometallic compound in the second layer 13b is less than 0.10% by mass, the adhesion between the layers of the first layer 13a, the second layer 13b, and the third layer 13c, that is, the gas barrier The adhesiveness of the layer 13 in the layer may be lowered, and if it exceeds 10% by mass, the gas barrier property of the gas barrier layer 13 may be lowered.

  In this case, the outermost layer of the gas barrier layer 13, that is, the first layer 13 a (third layer 13 c) has a metal content contained in the organometallic compound more than the layer other than the outermost layer, that is, the second layer 13 b. Larger is preferred. Thereby, the gas barrier property of the gas barrier layer 13 and the adhesion between the adjacent reversible thermosensitive recording layer 12 and the protective layer 14, that is, the adhesion between the layers can be improved.

  At this time, the ratio of the content of the metal contained in the organometallic compound in the first layer 13a (third layer 13c) to the content of the metal contained in the organometallic compound in the second layer 13b is usually 1. It is 5-5, and 2-3 are preferable. When the ratio of the content of the metal contained in the organometallic compound in the first layer 13a (third layer 13c) to the content of the metal contained in the organometallic compound in the second layer 13b is less than 1.5, The adhesion between the layers of the gas barrier layer 13 may be reduced, and if it exceeds 5, the gas barrier property of the gas barrier layer 13 may be reduced.

  The metal content can be measured using an energy dispersive X-ray analyzer.

  The inorganic layered compound is not particularly limited as long as it can be oriented in the gas barrier layer 13 to improve the gas barrier property, but belongs to the kaolinite group having a 1: 1 structure of phyllosilicate and a group of jamonites. Antigolite group, smectite group, hydrated silicate mineral vermiculite group, mica group and the like can be mentioned.

  Specific examples of inorganic layered compounds include kaolinite, nacrite, dickite, halloysite, hydrous halloysite, antigolite, chrysotile, pyrophyllite, montmorillonite, beidellite, saponite, hectorite, soconite, stevensite, tetrasilic mica, Synthetic products such as sodium teniolite, muscovite, margarite, talc, vermiculite, phlogopite, xanthophyllite, chlorite, scaly silica and other natural products, synthetic mica, and physical or chemical treated mica And two or more of them may be used in combination. Among these, montmorillonite or mica is preferable in terms of gas barrier properties of the gas barrier layer 13.

  The inorganic layered compound is preferably swollen and cleaved in the dispersion medium.

  The length and width of the inorganic layered compound are each usually 5 nm to 5 μm, preferably 10 nm to 3 μm. If the length or width of the inorganic layered compound is less than 5 nm, the gas barrier property of the gas barrier layer 13 may be deteriorated. If it exceeds 5 μm, uneven mixing may occur in the gas barrier layer 13.

  The ratio of the length to the thickness of the inorganic layered compound is usually 10 to 10,000, and preferably 50 to 5,000. When the ratio of the length to the thickness of the inorganic layered compound is less than 10, the gas barrier property of the gas barrier layer 13 may be deteriorated, and when it exceeds 10,000, uneven mixing may occur in the gas barrier layer 13.

  The mass ratio of the inorganic layered compound to the resin is usually 5/95 to 50/50, preferably 10/90 to 35/65. If the mass ratio of the inorganic layered compound to the resin is less than 5/95, the gas barrier property of the gas barrier layer 13 may be reduced, and if it exceeds 50/50, the adhesion between the layers of the gas barrier layer 13 may be reduced. is there.

  The gas barrier layer 13 may further contain an adhesion improver.

  Although it does not specifically limit as an adhesive improvement agent, A silane coupling agent, a titanium coupling agent, an isocyanate compound, an aziridine compound, a carbodiimide compound etc. are mentioned, You may use 2 or more types together.

  Examples of silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, vinyltriacetoxysilane, 3-propyltrimethoxy methacrylate. Alkoxy silane having a vinyl group such as silane; having an epoxy group such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Alkoxy silane; Alkoxy having amino group and / or imino group such as 3-aminopropyltriethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane Silane; Isocyanate alkoxysilane such as triethoxysilylpropyl isocyanate; Alkoxysilane having mercapto group such as γ-mercaptopropyltrimethoxysilane; Alkoxysilane having ureido group such as γ-ureidopropyltriethoxysilane. Among them, a trialkoxysilane compound having an amino group or a trialkoxysilane compound having a mercapto group is preferable in terms of a reaction rate with an organic residue in a layer adjacent to the gas barrier layer 13. From the viewpoint of reaction rate, trimethoxysilane is more preferable.

  Examples of the aziridine compound include trimethylolpropane tris (3-aziridinylpropionate), trimethylolpropane tris [3- (2-methylaziridinyl) propionate], trimethylolpropane tris (2-aziridinylbutyrate). ), Tris (1-aziridinyl) phosphine oxide, pentaerythritol tris-3- (1-aziridinylpropionate), pentaerythritol tetrakis-3- (1-aziridinylpropionate), 1,6-bis (1-aziridinocarbamoyl) hexamethylenediamine and the like.

  Examples of isocyanate compounds include hydrogenated toluene diisocyanate (hydrogenated TDI), hydrogenated xylylene diisocyanate (hydrogenated XDI), hydrogenated 4,4′-diisocyanate diphenylmethane (hydrogenated MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate. Aliphatic or alicyclic diisocyanates such as (IPDI) and xylylene diisocyanate (XDI); tri- or higher functional polyisocyanates such as burette type, isocyanurate type and adduct type which are derivatives thereof; various oligomers having an isocyanate group Aliphatic isocyanate compounds such as polymers; phenylene diisocyanate (PDI), toluene diisocyanate (TDI), naphthalene diisocyanate (NDI), 4,4′-diisocyanate dipheny Aromatic diisocyanates such as methane (MDI); tri- or higher functional polyisocyanates such as burette type, isocyanurate type and adduct type which are derivatives thereof; aromatic isocyanate compounds such as various oligomers and polymers having an isocyanate group, etc. Is mentioned. Among these, from the viewpoint of suppressing the reaction with water, a self-emulsifying polyisocyanate compound in which a hydrophilic group is introduced into the skeleton of the isocyanate compound is preferable, and a self-emulsifying polyisocyanate compound in which a hydrophobic group is further introduced is more preferable.

  As the carbodiimide compound, a self-emulsifying carbodiimide compound is preferable. Among these, from the viewpoint of balance between stability and thermosetting, a compound obtained by reacting a carbodiimide compound having an isocyanate group at the terminal with a polyol compound and then modifying the terminal with a hydrophilic oligomer is preferable.

  The first layer 13a, the second layer 13b, and the third layer 13c of the gas barrier layer 13 are obtained by dispersing or dissolving a composition containing a resin, an organometallic compound, and an inorganic layered compound on a reversible thermosensitive recording layer 12 in a solvent. It can form by apply | coating the coating liquid which is.

  The method for applying the coating solution is not particularly limited as long as the inorganic layered compound can be oriented. However, a roll coating method using a gravure cylinder, a doctor knife method, an air knife / nozzle coating method, a bar coating, and the like. Method, spray coating method, dip coating method and the like, and two or more of them may be used in combination.

Examples of the method for preparing the coating solution include the following methods.
(1) A method in which an inorganic layered compound is added to a solution in which a resin and an organometallic compound are dissolved in a solvent, and the inorganic layered compound is dispersed using a stirrer or a dispersing device (the inorganic layered compound is water or the like). It may be swollen and cleaved in advance using a dispersion medium).
(2) A solution in which a resin and an organometallic compound are dissolved in a solvent in which the inorganic layered compound is swollen and cleaved using a dispersion medium such as water and then dispersed using a stirrer or a dispersion device. How to add.

  In addition, when adding an adhesive improvement agent, you may add, after preparing dispersion | distribution of resin, an organometallic compound, and an inorganic layered compound.

  Further, when the inorganic layered compound is a natural product, an alkaline earth metal salt or alkali metal salt such as magnesium hydroxide or calcium hydroxide is used to suppress oxidative deterioration of the gas barrier layer 13 due to impurity inorganic metal ions. It is preferable to add.

  The solvent is not particularly limited as long as the resin and the organometallic compound can be dissolved, and examples thereof include water, a mixed solvent of water and an alcohol having 2 to 4 carbon atoms, and the like.

  Examples of the alcohol having 2 to 4 carbon atoms include ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, and tert-butyl alcohol. Also good. Among these, n-propyl alcohol or isopropyl alcohol is preferable.

  The stirrer or the dispersion device is not particularly limited as long as the inorganic layered compound can be dispersed, and examples thereof include a high-pressure disperser and an ultrasonic disperser.

  As high-pressure dispersers, Nanomizer (manufactured by Nanomizer), Microfluidizer (manufactured by Microflydex), Ultimizer (manufactured by Sugino Machine), DeBee (manufactured by Bee), Niro Soabi homogenizer (Niro Soabi) Manufactured) and the like.

  The pressure condition of the high-pressure disperser is usually 1 to 100 MPa. When the pressure condition of the high-pressure disperser is less than 1 MPa, the dispersion of the inorganic layered compound may be insufficient, and when it exceeds 100 MPa, the inorganic layered compound may be crushed.

  In the case of using an ethylene-vinyl alcohol copolymer resin, a terminal-modified ethylene-vinyl alcohol copolymer that has been treated with a peroxide or the like to lower its molecular weight is composed of water and an alcohol having 2 to 4 carbon atoms. It is preferable to prepare a coating solution by dissolving in a mixed solvent.

  In this case, the content of the alcohol having 2 to 4 carbon atoms in the mixed solvent is usually 15 to 50% by mass. When the content of the alcohol having 2 to 4 carbon atoms in the mixed solvent is less than 15% by mass, the solubility of the terminal-modified ethylene-vinyl alcohol copolymer may be lowered, and when the content exceeds 50% by mass. The cleavage of the inorganic layered compound may be insufficient.

  Although it does not specifically limit as the support body 11, Resin-made films, such as paper and a PET film, resin-made sheets, synthetic paper, metal foil, a glass plate, etc. are mentioned.

  In addition, the support body 11 may be a composite body in which a plurality of support bodies are bonded together.

  The thickness of the support 11 is usually about several μm to several mm. For example, the thickness of the PET film is usually 10 μm or more, preferably 30 μm or more, and more preferably 50 μm or more.

  The support 11 preferably has gas barrier properties. Here, when the gas barrier property of the support 11 is insufficient, the gas barrier layer 13 may be formed on the surface of the support 11 where the reversible thermosensitive recording layer 12 is not formed.

  The support 11 has a magnetic recording layer and an IC chip on the surface on the side where the reversible thermosensitive recording layer 12 is formed, the surface opposite to the side where the reversible thermosensitive recording layer 12 is formed, and the inside. You may have.

  When the reversible thermosensitive recording layer 12 is self-supporting, the reversible thermosensitive recording layer 12 also serves as the support 11.

  The reversible thermosensitive recording layer 12 contains a binder resin, an electron donating color developing compound, and an electron accepting compound, and the color development state changes depending on the heating temperature and / or the cooling rate after heating. At this time, the reversible thermosensitive recording medium 12 is reversible in coloring and decoloring.

  The reversible thermosensitive recording layer 12 develops or decolors the electron donating color developing compound and the electron accepting compound by melting or solidifying the binder resin.

  The electron-donating color-forming compound is not particularly limited, but it is a colorless or light-colored dye precursor, a fluoran compound, a triphenylmethane phthalide compound, an azaphthalide compound, a phenothiazine compound, a leucooramine compound, an indoline. Examples include nophthalide compounds.

  Examples of the fluorane compound include 2-anilino-3-methyl-6-diethylaminofluorane, 2-anilino-3-methyl-6-di-n-butylaminofluorane, 2-anilino-3-methyl-6- ( N-n-propyl-N-methylamino) fluorane, 2-anilino-3-methyl-6- (N-isopropyl-N-methylamino) fluorane, 2-anilino-3-methyl-6- (N-isobutyl- N-methylamino) fluorane, 2-anilino-3-methyl-6- (Nn-amyl-N-methylamino) fluorane, 2-anilino-3-methyl-6- (N-sec-butyl-N- Methylamino) fluorane, 2-anilino-3-methyl-6- (Nn-amyl-N-ethylamino) fluorane, 2-anilino-3-methyl-6- (N-isoami -N-ethylamino) fluorane, 2-anilino-3-methyl-6- (Nn-propyl-N-isopropylamino) fluorane, 2-anilino-3-methyl-6- (N-cyclohexyl-N-methyl) Amino) fluorane, 2-anilino-3-methyl-6- (N-ethyl-p-toluidino) fluorane, 2-anilino-3-methyl-6- (N-methyl-p-toluidino) fluorane, 2- (m -Trichloromethylanilino) -3-methyl-6-diethylaminofluorane, 2- (m-trifluoromethylanilino) -3-methyl-6-diethylaminofluorane, 2- (m-trichloromethylanilino)- 3-methyl-6- (N-cyclohexyl-N-methylamino) fluorane, 2- (2,4-dimethylanilino) -3-methyl-6-di Tylaminofluorane, 2- (N-ethyl-p-toluidino) -3-methyl-6- (N-ethylanilino) fluorane, 2- (N-ethyl-p-toluidino) -3-methyl-6- (N -Propyl-p-toluidino) fluorane, 2-anilino-6- (Nn-hexyl-N-ethylamino) fluorane, 2- (o-chloroanilino) -6-diethylaminofluorane, 2- (o-chloroanilino) -6-dibutylaminofluorane, 2- (m-trifluoromethylanilino) -6-diethylaminofluorane, 2,3-dimethyl-6-dimethylaminofluorane, 3-methyl-6- (N-ethyl- p-toluidino) fluorane, 2-chloro-6-diethylaminofluorane, 2-bromo-6-diethylaminofluorane, 2-chloro-6-dip Propylaminofluorane, 3-chloro-6-cyclohexylaminofluorane, 3-bromo-6-cyclohexylaminofluorane, 2-chloro-6- (N-ethyl-N-isoamylamino) fluorane, 2-chloro- 3-methyl-6-diethylaminofluorane, 2-anilino-3-chloro-6-diethylaminofluorane, 2- (o-chloroanilino) -3-chloro-6-cyclohexylaminofluorane, 2- (m-trifluoro) Methylanilino) -3-chloro-6-diethylaminofluorane, 2- (2,3-dichloroanilino) -3-chloro-6-diethylaminofluorane, 1,2-benzo-6-diethylaminofluorane, 3 -Diethylamino-6- (m-trifluoromethylanilino) fluorane and the like.

  Examples of azaphthalide compounds include 3- (1-ethyl-2-methylindol-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-methyl) Indol-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -7-azaphthalide, 3- (1-octyl-2-methylindol-3-yl) -3- (2-ethoxy-4-) Diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-methylindol-3-yl) -3- (2-methyl-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2) -Methylindol-3-yl) -3- (2-methyl-4-diethylaminophenyl) -7-azaphthalide, 3- (1-ethyl-2-methylindole) 3-yl) -3- (4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-methylindol-3-yl) -3- (4-Nn-amyl-N-methylamino) Phenyl) -4-azaphthalide, 3- (1-methyl-2-methylindol-3-yl) -3- (2-hexyloxy-4-diethylaminophenyl) -4-azaphthalide, 3,3-bis (2- And ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3,3-bis (2-ethoxy-4-diethylaminophenyl) -7-azaphthalide, and the like.

  Colorless or pale dye precursors include 2- (p-acetylanilino) -6- (Nn-amyl-Nn-butylamino) fluorane, 2-benzylamino-6- (N-ethyl- p-toluidino) fluorane, 2-benzylamino-6- (N-methyl-2,4-dimethylanilino) fluorane, 2-benzylamino-6- (N-ethyl-2,4-dimethylanilino) fluorane, 2-benzylamino-6- (N-methyl-p-toluidino) fluorane, 2-benzylamino-6- (N-ethyl-p-toluidino) fluorane, 2- (di-p-methylbenzylamino) -6 (N-ethyl-p-toluidino) fluorane, 2- (α-phenylethylamino) -6- (N-ethyl-p-toluidino) fluorane, 2-methylamino-6- (N-methyl) Anilino) fluorane, 2-methylamino-6- (N-ethylanilino) fluorane, 2-methylamino-6- (N-propylanilino) fluorane, 2-ethylamino-6- (N-methyl-p-toluidino) Fluorane, 2-methylamino-6- (N-methyl-2,4-dimethylanilino) fluorane, 2-ethylamino-6- (N-ethyl-2,4-dimethylanilino) fluorane, 2-dimethylamino -6- (N-methylanilino) fluorane, 2-dimethylamino-6- (N-ethylanilino) fluorane, 2-diethylamino-6- (N-methyl-p-toluidino) fluorane, 2-diethylamino-6- (N- Ethyl-p-toluidino) fluorane, 2-dipropylamino-6- (N-methylanilino) fluorane, 2-dipro Pyramino-6- (N-ethylanilino) fluorane, 2-amino-6- (N-methylanilino) fluorane, 2-amino-6- (N-ethylanilino) fluorane, 2-amino-6- (N-propylanilino) Fluorane, 2-amino-6- (N-methyl-p-toluidino) fluorane, 2-amino-6- (N-ethyl-p-toluidino) fluorane, 2-amino-6- (N-propyl-p-toluidino) ) Fluorane, 2-amino-6- (N-methyl-p-ethylanilino) fluorane, 2-amino-6- (N-ethyl-p-ethylanilino) fluorane, 2-amino-6- (N-propyl-p-) Ethylanilino) fluorane, 2-amino-6- (N-methyl-2,4-dimethylanilino) fluorane, 2-amino-6- (N-ethyl-2) 4-dimethylanilino) fluorane, 2-amino-6- (N-propyl-2,4-dimethylanilino) fluorane, 2-amino-6- (N-methyl-p-chloroanilino) fluorane, 2-amino- 6- (N-ethyl-p-chloroanilino) fluorane, 2-amino-6- (N-propyl-p-chloroanilino) fluorane, 1,2-benzo-6- (N-ethyl-N-isoamylamino) fluorane, 1,2-benzo-6-dibutylaminofluorane, 1,2-benzo-6- (N-methyl-N-cyclohexylamino) fluorane, 1,2-benzo-6- (N-ethyl-N-toluidino) A fluoran etc. are mentioned and it may use 2 or more types together.

  The average particle diameter of the electron donating color-forming compound is usually 0.05 to 0.7 μm, preferably 0.1 to 0.5 μm, and more preferably 0.1 to 0.3 μm. Thereby, the color developability of the reversible thermosensitive recording layer 12 can be improved.

  The average particle size of the electron donating color-forming compound can be measured using a laser analysis / scattering method.

  The electron donating color-forming compound can be dispersed by adding a dispersant and / or a surfactant as necessary.

  The addition amount of the dispersant and / or the surfactant is usually 5 to 20% by mass with respect to the electron donating color-forming compound.

  The dispersing device for dispersing the electron donating color developing compound is not particularly limited, and examples thereof include a ball mill, an attritor, a sand mill, and a high pressure jet mill. Among them, a method using a medium such as a ball is preferable, a method using a zirconia medium having a diameter of 0.5 mm or less, or a coarse pulverization using a zirconia medium having a diameter of 0.5 to 1.0 mm, and then the diameter is 0. A method using zirconia media of 5 mm or less is more preferable.

  The electron-accepting compound is not particularly limited as long as it can develop the color of the electron-donating color-forming compound. However, the organic phosphoric acid compound, the aliphatic carboxylic acid compound, the phenol compound, the metal salt of mercaptoacetic acid, phosphorus Acid ester etc. are mentioned.

  The electron-accepting compound has a general formula in terms of color density and erasing properties.

（式中、ｌは、０〜２の整数であり、ｍは、０又は１であり、ｎは、１〜３の整数であり、Ｘ及びＹは、それぞれ独立に、Ｎ又はＯを含む二価基であり、Ｒ_１は、置換基を有していてもよい炭素数が２以上のアルキレン基であり、Ｒ_２は、置換基を有していてもよい炭素数が１以上のアルキル基である。）
で表される化合物が好ましい。

(In the formula, l is an integer of 0 to 2, m is 0 or 1, n is an integer of 1 to 3, and X and Y are each independently two containing N or O. R ₁ is an alkylene group having 2 or more carbon atoms which may have a substituent, and R ₂ is an alkyl group having 1 or more carbon atoms which may have a substituent. .)
The compound represented by these is preferable.

In the general formula (1), the aliphatic hydrocarbon group in R ₁ and R ₂ may be either a straight chain or a branched chain, and may have an unsaturated bond.

  Examples of the substituent of the aliphatic hydrocarbon group include a hydroxyl group, a halogen atom, and an alkoxy group.

The sum of the carbon numbers of R ₁ and R ₂ is preferably 8 or more, and more preferably 11 or more. When the sum of the carbon numbers of R ₁ and R ₂ is 7 or less, the color development stability and decoloring property may be lowered.

Examples of the aliphatic hydrocarbon group for R ₁ include groups represented by the following general formula.

（式中、ｑ、ｑ'、ｑ''及びｑ'''は、それぞれ、脂肪族炭化水素基の炭素数を満たす整数である。）
中でも、一般式
−（ＣＨ_２）ｑ−
で表される基が好ましい。

(In the formula, q, q ′, q ″ and q ′ ″ are each an integer satisfying the carbon number of the aliphatic hydrocarbon group.)
Among them, the general formula — (CH ₂ ) q—
The group represented by these is preferable.

Examples of the aliphatic hydrocarbon group for R ₂ include groups represented by the following general formula.

（式中、ｑ、ｑ'及びｑ''は、それぞれ、脂肪族炭化水素基の炭素数を満たす整数である。）
中でも、一般式
−（ＣＨ_２）ｑ−ＣＨ_３
で表される基が好ましい。

(In the formula, q, q ′ and q ″ are each an integer satisfying the carbon number of the aliphatic hydrocarbon group.)
Among them, the formula _{- (CH 2) q-CH} 3
The group represented by these is preferable.

  X and Y preferably each independently have one or more groups represented by the following chemical formulas.

Ｘ及びＹの具体例としては、以下の化学式で表される基が挙げられる。

Specific examples of X and Y include groups represented by the following chemical formulas.

中でも、以下の化学式で表される基が好ましい。

Among these, a group represented by the following chemical formula is preferable.

一般式（１）で表される化合物としては、以下の一般式で表される化合物が挙げられる。

Examples of the compound represented by the general formula (1) include compounds represented by the following general formula.

（式中、ｒは、２以上の整数であり、ｓは、１以上の整数である。）
電子受容性化合物の平均粒子径は、通常、０．１〜２．５μｍであり、０．５〜２．０μｍが好ましい。これにより、可逆性感熱記録層１２の発色性を向上させることができる。

(In the formula, r is an integer of 2 or more, and s is an integer of 1 or more.)
The average particle size of the electron-accepting compound is usually 0.1 to 2.5 μm, preferably 0.5 to 2.0 μm. Thereby, the color developability of the reversible thermosensitive recording layer 12 can be improved.

  The average particle diameter of the electron accepting compound can be measured using a laser analysis / scattering method.

  The electron-accepting compound can be dispersed by adding a dispersant and / or a surfactant together with the electron-donating color-forming compound as necessary.

  The molar ratio of the electron-accepting compound to the electron-donating color-forming compound is usually from 0.1 to 20, and preferably from 0.2 to 10. When the molar ratio of the electron accepting compound to the electron donating color developing compound is less than 0.1 or more than 20, the color density of the reversible thermosensitive recording layer 12 may be lowered.

  The electron-donating color-forming compound and the electron-accepting compound can be used by being encapsulated in microcapsules.

  It is preferable that the molar ratio of the binder resin to the electron donating color developing compound and the electron accepting compound in the reversible thermosensitive recording layer 12 is 0.1 to 10. When the molar ratio of the binder resin to the electron donating color-forming compound and the electron-accepting compound in the reversible thermosensitive recording layer 12 is less than 0.1, the heat intensity of the reversible thermosensitive recording layer 12 may decrease. If it exceeds 10, the color density of the reversible thermosensitive recording layer 12 may decrease.

  The binder resin is not particularly limited as long as it can disperse the electron-donating color-forming compound and the electron-accepting compound, but polyvinyl chloride, polyvinyl acetate, vinyl chloride vinyl acetate copolymer, ethyl cellulose, Polystyrene, styrene copolymer, phenoxy resin, polyester, aromatic polyester, polyurethane, polycarbonate, polyacrylic acid ester, polymethacrylic acid ester, acrylic acid copolymer, maleic acid copolymer, polyvinyl alcohol, modified polyvinyl Examples include alcohol, hydroxyethyl cellulose, carboxymethyl cellulose, and starches. Among these, a thermosetting resin that is cured by a curing agent is preferable in terms of heat resistance.

  The thermosetting resin is not particularly limited, and examples thereof include acrylic polyol resin, polyester polyol, polyurethane polyol, phenoxy resin, polyvinyl butyral, cellulose acetate propionate, and cellulose acetate butyrate.

  As the monomer having a hydroxyl group constituting the acrylic polyol resin, hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA), 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl methacrylate (HPMA), 2-hydroxybutyl mono Examples include acrylate (2-HBA) and 1-hydroxybutyl monoacrylate (1-HBA). Among these, 2-hydroxyethyl methacrylate is preferable in terms of crack resistance and durability of the coating film.

  Although it does not specifically limit as a hardening | curing agent, Isocyanates etc. are mentioned.

  Examples of the isocyanates include urethane-modified products, allophanate-modified products, isocyanurate-modified products, burette-modified products, carbodiimide-modified products, and blocked isocyanates.

  Although it does not specifically limit as an isocyanate monomer which comprises a modified body, Tolylene diisocyanate (TDI), 4,4'- diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), naphthylene diisocyanate (NDI), p -Phenylene diisocyanate (PPDI), tetramethylxylylene diisocyanate (TMXDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI), lysine diisocyanate (LDI), isopropylidenebis (4-cyclohexylisocyanate) ) (IPC), cyclohexyl diisocyanate (CHDI), tolidine diisocyanate (TODI) and the like.

  The reversible thermosensitive recording layer 12 may further contain a curing accelerator. Thereby, hardening of a thermosetting resin can be accelerated | stimulated.

  The curing accelerator is not particularly limited, and examples thereof include tertiary amines such as 1,4-diazabicyclo [2,2,2] octane, and metal compounds such as organic tin compounds.

  The reversible thermosensitive recording layer 12 may further contain a decolorization accelerator.

  The decoloring accelerator is not particularly limited, but from the viewpoint of color density and erasing properties, examples thereof include compounds having an amide group, a urethane group, a urea group, a ketone group, a diacyl hydrazide group, and the like. Also good. Of these, compounds having an amide group, a secondary amide group or a urethane group are preferred. Specific examples include compounds represented by the following general formula or chemical formula.

（式中、ｎ、ｎ'、ｎ''、ｎ'''及びｎ''''は、それぞれ独立に、０〜２１の整数である。ただし、化合物に含まれるｎ、ｎ'、ｎ''、ｎ'''及びｎ''''の全てが５以下であることはない。）

(In the formula, n, n ′, n ″, n ′ ″ and n ″ ″ are each independently an integer of 0 to 21, provided that n, n ′, n ′ contained in the compound are included. ', N''' and n '''' are not all 5 or less.)

（式中、ｎ、ｎ'、ｎ''、ｎ'''及びｎ''''は、それぞれ独立に、０〜２１の整数である。ただし、化合物に含まれるｎ、ｎ'、ｎ''、ｎ'''及びｎ''''の全てが５以下であることはない。Ｘとしては、化学式

(In the formula, n, n ′, n ″, n ′ ″ and n ″ ″ are each independently an integer of 0 to 21, provided that n, n ′, n ′ contained in the compound are included. ', N''' and n '''' are not all less than 5. X is a chemical formula

で表される基が挙げられる。）

The group represented by these is mentioned. )

Ｃ_１１Ｈ_２３ＣＯＮＨＣ_１２Ｈ_２５、Ｃ_１５Ｈ_３１ＣＯＮＨＣ_１６Ｈ_３３、Ｃ_１７Ｈ_３５ＣＯＮＨＣ_１８Ｈ_３７、Ｃ_１７Ｈ_３５ＣＯＮＨＣ_１８Ｈ_３５、Ｃ_２１Ｈ_４１ＣＯＮＨＣ_１８Ｈ_３７、Ｃ_１５Ｈ_３１ＣＯＮＨＣ_１８Ｈ_３７、Ｃ_１７Ｈ_３５ＣＯＮＨＣＨ_２ＮＨＣＯＣ_１７Ｈ_３５、Ｃ_１１Ｈ_２３ＣＯＮＨＣＨ_２ＮＨＣＯＣ_１１Ｈ_２３、Ｃ_７Ｈ_１５ＣＯＮＨＣ_２Ｈ_４ＮＨＣＯＣ_１７Ｈ_３５、Ｃ_９Ｈ_１９ＣＯＮＨＣ_２Ｈ_４ＮＨＣＯＣ_９Ｈ_１９、Ｃ_１１Ｈ_２３ＣＯＮＨＣ_２Ｈ_４ＮＨＣＯＣ_１１Ｈ_２３、Ｃ_１７Ｈ_３５ＣＯＮＨＣ_２Ｈ_４ＮＨＣＯＣ_１７Ｈ_３５、（ＣＨ_３）_２ＣＨＣ_１４Ｈ_３５ＣＯＮＨＣ_２Ｈ_４ＮＨＣＯＣ_１４Ｈ_３５（ＣＨ_３）_２、Ｃ_２１Ｈ_４３ＣＯＮＨＣ_２Ｈ_４ＮＨＣＯＣ_２１Ｈ_４３、Ｃ_１７Ｈ_３５ＣＯＮＨＣ_６Ｈ_１２ＮＨＣＯＣ_１７Ｈ_３５、Ｃ_２１Ｈ_４３ＣＯＮＨＣ_６Ｈ_１２ＮＨＣＯＣ_２１Ｈ_４３、Ｃ_１７Ｈ_３３ＣＯＮＨＣＨ_２ＮＨＣＯＣ_１７Ｈ_３３、Ｃ_１７Ｈ_３３ＣＯＮＨＣ_２Ｈ_４ＮＨＣＯＣ_１７Ｈ_３３、Ｃ_２１Ｈ_４１ＣＯＮＨＣ_２Ｈ_４ＮＨＣＯＣ_２１Ｈ_４１、Ｃ_１７Ｈ_３３ＣＯＮＨＣ_６Ｈ_１２ＮＨＣＯＣ_１７Ｈ_３３、Ｃ_８Ｈ_１７ＮＨＣＯＣ_２Ｈ_４ＣＯＮＨＣ_１８Ｈ_３７、Ｃ_１０Ｈ_２１ＮＨＣＯＣ_２Ｈ_４ＣＯＮＨＣ_１０Ｈ_２１、Ｃ_１２Ｈ_２５ＮＨＣＯＣ_２Ｈ_４ＣＯＮＨＣ_１２Ｈ_２５、Ｃ_１８Ｈ_３７ＮＨＣＯＣ_２Ｈ_４ＣＯＮＨＣ_１８Ｈ_３７、Ｃ_２１Ｈ_４３ＮＨＣＯＣ_２Ｈ_４ＣＯＮＨＣ_２１Ｈ_４３、Ｃ_１８Ｈ_３７ＮＨＣＯＣ_６Ｈ_１２ＣＯＮＨＣ_１８Ｈ_３７、Ｃ_１８Ｈ_３５ＮＨＣＯＣ_４Ｈ_８ＣＯＮＨＣ_１８Ｈ_３５、Ｃ_１８Ｈ_３５ＮＨＣＯＣ_８Ｈ_１６ＣＯＮＨＣ_１８Ｈ_３５、Ｃ_１２Ｈ_２５ＯＣＯＮＨＣ_１８Ｈ_３７、Ｃ_１３Ｈ_２７ＯＣＯＮＨＣ_１８Ｈ_３７、Ｃ_１６Ｈ_３３ＯＣＯＮＨＣ_１８Ｈ_３７、Ｃ_１８Ｈ_３７ＯＣＯＮＨＣ_１８Ｈ_３７、Ｃ_２１Ｈ_４３ＯＣＯＮＨＣ_１８Ｈ_３７、Ｃ_１２Ｈ_２５ＯＣＯＮＨＣ_１６Ｈ_３３、Ｃ_１３Ｈ_２７ＯＣＯＮＨＣ_１６Ｈ_３３、Ｃ_１６Ｈ_３３ＯＣＯＮＨＣ_１６Ｈ_３３、Ｃ_１８Ｈ_３７ＯＣＯＮＨＣ_１６Ｈ_３３、Ｃ_２１Ｈ_４３ＯＣＯＮＨＣ_１６Ｈ_３３、Ｃ_１２Ｈ_２５ＯＣＯＮＨＣ_１４Ｈ_２９、Ｃ_１３Ｈ_２７ＯＣＯＮＨＣ_１４Ｈ_２９、Ｃ_１６Ｈ_３３ＯＣＯＮＨＣ_１４Ｈ_２９、Ｃ_１８Ｈ_３７ＯＣＯＮＨＣ_１４Ｈ_２９、Ｃ_２２Ｈ_４５ＯＣＯＮＨＣ_１４Ｈ_２９、Ｃ_１２Ｈ_２５ＯＣＯＮＨＣ_１２Ｈ_３７、Ｃ_１３Ｈ_２７ＯＣＯＮＨＣ_１２Ｈ_３７、Ｃ_１６Ｈ_３３ＯＣＯＮＨＣ_１２Ｈ_３７、Ｃ_１８Ｈ_３７ＯＣＯＮＨＣ_１２Ｈ_３７、Ｃ_２１Ｈ_４３ＯＣＯＮＨＣ_１２Ｈ_３７、Ｃ_２２Ｈ_４５ＯＣＯＮＨＣ_１８Ｈ_３７、Ｃ_１８Ｈ_３７ＮＨＣＯＯＣ_２Ｈ_４ＯＣＯＮＨＣ_１８Ｈ_３７、Ｃ_１８Ｈ_３７ＮＨＣＯＯＣ_３Ｈ_６ＯＣＯＮＨＣ_１８Ｈ_３７、Ｃ_１８Ｈ_３７ＮＨＣＯＯＣ_４Ｈ_８ＯＣＯＮＨＣ_１８Ｈ_３７、Ｃ_１８Ｈ_３７ＮＨＣＯＯＣ_６Ｈ_１２ＯＣＯＮＨＣ_１８Ｈ_３７、Ｃ_１８Ｈ_３７ＮＨＣＯＯＣ_８Ｈ_１６ＯＣＯＮＨＣ_１８Ｈ_３７、Ｃ_１８Ｈ_３７ＮＨＣＯＯＣ_２Ｈ_４ＯＣ_２Ｈ_４ＯＣＯＮＨＣ_１８Ｈ_３７、Ｃ_１８Ｈ_３７ＮＨＣＯＯＣ_３Ｈ_６ＯＣ_３Ｈ_６ＯＣＯＮＨＣ_１８Ｈ_３７、Ｃ_１８Ｈ_３７ＮＨＣＯＯＣ_１２Ｈ_２４ＯＣＯＮＨＣ_１８Ｈ_３７、Ｃ_１８Ｈ_３７ＮＨＣＯＯＣ_２Ｈ_４ＯＣ_２Ｈ_４ＯＣ_２Ｈ_４ＯＣＯＮＨＣ_１８Ｈ_３７、Ｃ_１６Ｈ_３３ＮＨＣＯＯＣ_２Ｈ_４ＯＣＯＮＨＣ_１６Ｈ_３３、Ｃ_１６Ｈ_３３ＮＨＣＯＯＣ_３Ｈ_６ＯＣＯＮＨＣ_１６Ｈ_３３、Ｃ_１６Ｈ_３３ＮＨＣＯＯＣ_４Ｈ_８ＯＣＯＮＨＣ_１６Ｈ_３３、Ｃ_１６Ｈ_３３ＮＨＣＯＯＣ_６Ｈ_１２ＯＣＯＮＨＣ_１６Ｈ_３３、Ｃ_１６Ｈ_３３ＮＨＣＯＯＣ_８Ｈ_１６ＯＣＯＮＨＣ_１６Ｈ_３３、Ｃ_１８Ｈ_３７ＯＣＯＮＨＣ_６Ｈ_１２ＮＨＣＯＯＣ_１８Ｈ_３７、Ｃ_１６Ｈ_３３ＯＣＯＮＨＣ_６Ｈ_１２ＮＨＣＯＯＣ_１６Ｈ_３３、Ｃ_１４Ｈ_２９ＯＣＯＮＨＣ_６Ｈ_１２ＮＨＣＯＯＣ_１４Ｈ_２９、Ｃ_１２Ｈ_２５ＯＣＯＮＨＣ_６Ｈ_１２ＮＨＣＯＯＣ_１２Ｈ_２５、Ｃ_１０Ｈ_２１ＯＣＯＮＨＣ_６Ｈ_１２ＮＨＣＯＯＣ_１０Ｈ_２１、Ｃ_８Ｈ_１７ＯＣＯＮＨＣ_６Ｈ_１２ＮＨＣＯＯＣ_８Ｈ_１７

_{C 11 H 23 CONHC 12 H 25} , C 15 H 31 CONHC 16 H 33, C 17 H 35 CONHC 18 H 37, C 17 H 35 CONHC 18 H 35, C 21 H 41 CONHC 18 H 37, C 15 H 31 CONHC _{18 H 37, C 17 H 35} CONHCH 2 NHCOC 17 H 35, C 11 H 23 CONHCH 2 NHCOC 11 H 23, C 7 H 15 CONHC 2 H 4 NHCOC 17 H 35, C 9 H 19 CONHC 2 H 4 NHCOC 9 H _{19, C 11 H 23 CONHC 2} H 4 NHCOC 11 H 23, C 17 H 35 CONHC 2 H 4 NHCOC 17 H 35, (CH 3) 2 CHC 14 H 35 CONHC 2 H 4 NHCOC 14 H 35 (CH 3) 2 , C _{1 H 43 CONHC 2 H 4 NHCOC} 21 H 43, C 17 H 35 CONHC 6 H 12 NHCOC 17 H 35, C 21 H 43 CONHC 6 H 12 NHCOC 21 H 43, C 17 H 33 CONHCH 2 NHCOC 17 H 33, C _{17 H 33 CONHC 2 H 4 NHCOC} 17 H 33, C 21 H 41 CONHC 2 H 4 NHCOC 21 H 41, C 17 H 33 CONHC 6 H 12 NHCOC 17 H 33, C 8 H 17 NHCOC 2 H 4 CONHC 18 H 37 _{, C 10 H 21 NHCOC 2 H} 4 CONHC 10 H 21, C 12 H 25 NHCOC 2 H 4 CONHC 12 H 25, C 18 H 37 NHCOC 2 H 4 CONHC 18 H 37, C 21 H 43 NHCOC 2 H _{CONHC 21 H 43, C 18 H} 37 NHCOC 6 H 12 CONHC 18 H 37, C 18 H 35 NHCOC 4 H 8 CONHC 18 H 35, C 18 H 35 NHCOC 8 H 16 CONHC 18 H 35, C 12 H 25 OCONHC 18 H ₃₇ , C ₁₃ H ₂₇ OCONHC ₁₈ H ₃₇ , C ₁₆ H ₃₃ OCONHC ₁₈ H ₃₇ , C ₁₈ H ₃₇ OCONHC ₁₈ H ₃₇ , C ₂₁ H ₄₃ OCONHC ₁₈ H ₃₇ , C ₁₂ H ₂₅ OCONHC ₁₆ H ₃₃ , C _{13 H 27 OCONHC 16 H 33, C} 16 H 33 OCONHC 16 H 33, C 18 H 37 OCONHC 16 H 33, C 21 H 43 OCONHC 16 H 33, C 12 H 25 OCONHC 14 H 29, C 13 _{27 OCONHC 14 H 29, C 16} H 33 OCONHC 14 H 29, C 18 H 37 OCONHC 14 H 29, C 22 H 45 OCONHC 14 H 29, C 12 H 25 OCONHC 12 H 37, C 13 H 27 OCONHC 12 H 37 C ₁₆ H ₃₃ OCONHC ₁₂ H ₃₇ , C ₁₈ H ₃₇ OCONHC ₁₂ H ₃₇ , C ₂₁ H ₄₃ OCONHC ₁₂ H ₃₇ , C ₂₂ H ₄₅ OCONHC ₁₈ H ₃₇ , C ₁₈ H ₃₇ NHCOOC ₂ H ₄ OCONHC ₁₈ H ₃₇ , _{C 18 H 37 NHCOOC 3 H 6} OCONHC 18 H 37, C 18 H 37 NHCOOC 4 H 8 OCONHC 18 H 37, C 18 H 37 NHCOOC 6 H 12 OCONHC 18 H 37, C 18 H _{7 NHCOOC 8 H 16 OCONHC 18 H} 37, C 18 H 37 NHCOOC 2 H 4 OC 2 H 4 OCONHC 18 H 37, C 18 H 37 NHCOOC 3 H 6 OC 3 H 6 OCONHC 18 H 37, C 18 H 37 NHCOOC 12 H ₂₄ OCONHC ₁₈ H ₃₇ , C ₁₈ H ₃₇ NHCOOC ₂ H ₄ OC ₂ H ₄ OC ₂ H ₄ OCONHC ₁₈ H ₃₇ , C ₁₆ H ₃₃ NHCOOC ₂ H ₄ OCONHC ₁₆ H ₃₃ , C ₁₆ H ₃₃ NHCOOC ₃ H ₆ OCN ₁₆ H ₃₃ , C ₁₆ H ₃₃ NHCOOC ₄ H ₈ OCONHC ₁₆ H ₃₃ , C ₁₆ H ₃₃ NHCOOC ₆ H ₁₂ OCONHC ₁₆ H ₃₃ , C ₁₆ H ₃₃ NHCOOC ₈ H ₁₆ OCONHC ₁₆ H _{33 , C 18 H 37 OCONHC 6 H} 12 NHCOOC 18 H 37, C 16 H 33 OCONHC 6 H 12 NHCOOC 16 H 33, C 14 H 29 OCONHC 6 H 12 NHCOOC 14 H 29, C 12 H 25 OCONHC 6 H 12 NHCOOC 12 H ₂₅ , C ₁₀ H ₂₁ OCONHC ₆ H ₁₂ NHCOOC ₁₀ H ₂₁ , C ₈ H ₁₇ OCONHC ₆ H ₁₂ NHCOOC ₈ H ₁₇

電子受容性化合物に対する消色促進剤の質量比は、通常、０．００１〜３であり、０．０３〜１が好ましい。

The mass ratio of the decolorization accelerator to the electron-accepting compound is usually 0.001 to 3, preferably 0.03 to 1.

  The reversible thermosensitive recording layer 12 may further contain a surfactant, a conductive agent, a filler, an antioxidant, a light stabilizer, a color stabilizer, and the like.

  The thickness of the reversible thermosensitive recording layer 12 is usually 1 to 20 μm, preferably 3 to 15 μm. If the thickness of the reversible thermosensitive recording layer 12 is less than 1 μm, the contrast during color development may be insufficient, and if it exceeds 20 μm, the thermal sensitivity of the reversible thermosensitive recording layer 12 may be reduced. .

  The reversible thermosensitive recording layer 12 comprises a non-curable resin as a binder resin and / or a thermosetting resin as a precursor of a binder resin, an electron donating color-forming compound, an electron accepting property on a support 11. It can be formed by applying a coating solution in which a composition containing a compound is dispersed or dissolved in a solvent.

  The solvent is not particularly limited, but water; alcohols such as methanol, ethanol, isopropanol, n-butanol and methyl isocarbinol; ketones such as acetone, 2-butanone, ethyl amyl ketone, diacetone alcohol, isophorone and cyclohexanone Amides such as N, N-dimethylformamide and N, N-dimethylacetamide; ethers such as diethyl ether, isopropyl ether, tetrahydrofuran, 1,4-dioxane and 3,4-dihydro-2H-pyran; Glycol ethers such as methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol dimethyl ether; 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, etc. Recall ether acetates; Esters such as methyl acetate, ethyl acetate, isobutyl acetate, amyl acetate, ethyl lactate and ethylene carbonate; Aromatic hydrocarbons such as benzene, toluene and xylene; Fats such as hexane, heptane, isooctane and cyclohexane Group hydrocarbons; halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, dichloropropane, chlorobenzene; sulfoxides such as dimethyl sulfoxide; N-methyl-2-pyrrolidone, N-octyl-2-pyrrolidone, etc. Examples include pyrrolidones.

  The apparatus for preparing the coating liquid is not particularly limited, and examples thereof include a paint shaker, a ball mill, an attritor, a three-roll mill, a keddy mill, a sand mill, a dyno mill, and a colloid mill.

  The method for preparing the coating liquid is not particularly limited, but each component contained in the composition is dispersed or dissolved in a solvent and then mixed, and the composition is dispersed or dissolved in a solvent. Examples include a method in which an object is heated and dissolved in a solvent, and then cooled and precipitated.

  The method for applying the coating solution is not particularly limited, but blade coating method, wire bar coating method, spray coating method, air knife coating method, bead coating method, curtain coating method, gravure coating method, kiss coating method, reverse roll coating. Method, dip coating method, die coating method and the like.

  When a coating liquid contains a thermosetting resin, it is preferable to heat using a thermostat etc. after apply | coating a coating liquid. The heating conditions are usually about 30 to 130 ° C. for about 1 minute to 150 hours, and preferably 40 to 100 ° C. for about 2 minutes to 120 hours.

  The protective layer 14 includes a UV curable resin that is UV cured, an electron beam curable resin that is electron beam cured, or a thermosetting resin that is thermally cured with a curing agent.

  The ultraviolet curable resin and the electron beam curable resin are not particularly limited, but urethane acrylate, epoxy acrylate, polyester acrylate, polyether acrylate, vinyl, unsaturated polyester oligomer, acrylate, methacrylate, vinyl. Monofunctional or polyfunctional monomers such as esters, ethylene derivatives, and allyl compounds are exemplified.

  In addition, when using an ultraviolet curable resin, you may use a photoinitiator and a photoinitiator together.

  The thermosetting resin is not particularly limited, and examples thereof include acrylic polyol resin, polyester polyol, polyurethane polyol, polyvinyl butyral, cellulose acetate propionate, and cellulose acetate butyrate.

  Although it does not specifically limit as a hardening | curing agent, An isocyanate type compound etc. are mentioned.

  The isocyanate compound is not particularly limited, but tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), naphthylene diisocyanate (NDI), paraphenylene diisocyanate (PPDI), Tetramethylxylylene diisocyanate (TMXDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI), lysine diisocyanate (LDI), isopropylidenebis (4-cyclohexylisocyanate) (IPC), cyclohexyl diisocyanate (CHDI), tolidine diisocyanate (TODI) and the like.

  The protective layer 14 may further include an organic filler, an inorganic filler, an ultraviolet absorber, a lubricant, a color pigment, and the like.

  The material constituting the organic filler is not particularly limited, but silicone resin, cellulose resin, epoxy resin, nylon, phenol resin, polyurethane, urea resin, melamine resin, polyester, polycarbonate, styrene resin, acrylic resin, polyethylene, Examples include formaldehyde resins and polymethyl methacrylate.

  Although it does not specifically limit as a material which comprises an inorganic filler, A carbonate, a silicate, a metal oxide, a sulfate compound, etc. are mentioned.

  Although it does not specifically limit as a ultraviolet absorber, A salicylate type compound, a cyanoacrylate type compound, a benzotriazole type compound, a benzophenone type compound etc. are mentioned.

  Examples of the lubricant include, but are not limited to, synthetic waxes, vegetable waxes, animal waxes, higher alcohols, higher fatty acids, higher fatty acid esters, amides and the like.

  The thickness of the protective layer 14 is usually 0.1 to 10 μm.

  FIG. 2 shows a second embodiment of the reversible thermosensitive recording medium of the present invention. The reversible thermosensitive recording medium 20 has the same configuration as the reversible thermosensitive recording medium 10 except that a primer layer 21 is further formed between the gas barrier layer 13 and the protective layer 14.

  The primer layer 21 includes a thermosetting resin that is thermoset by a curing agent.

  The thermosetting resin is not particularly limited, and examples thereof include polyvinyl butyral, acrylic polyol resin, polyester polyol, polyurethane polyol, and phenoxy resin. Among these, a polyol resin is preferable.

  Although it does not specifically limit as a hardening | curing agent, Polyisocyanate etc. are mentioned.

  Polyisocyanates include tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), naphthylene diisocyanate (NDI), paraphenylene diisocyanate (PPDI), tetramethylxylylene diisocyanate ( TMXDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI), lysine diisocyanate (LDI), isopropylidenebis (4-cyclohexylisocyanate) (IPC), cyclohexyl diisocyanate (CHDI), tolidine diisocyanate (TODI).

  The thickness of the primer layer 21 is usually 0.1 to 3 μm, and preferably 0.2 to 2 μm. If the thickness of the primer layer 21 is less than 0.1 μm, the adhesion between the gas barrier layer 13 and the protective layer 14 may be reduced. If the thickness exceeds 3 μm, the thickness of the reversible thermosensitive recording medium 10 increases. Sometimes.

  The primer layer 21 can be formed by applying a coating liquid in which a composition containing a thermosetting resin and a curing agent is dispersed or dissolved in a solvent on the gas barrier layer 13 and then curing.

  FIG. 3 shows a third embodiment of the reversible thermosensitive recording medium of the present invention. The reversible thermosensitive recording medium 30 has the same configuration as the reversible thermosensitive recording medium 20 except that an anchor layer 31 is further formed between the reversible thermosensitive recording layer 12 and the gas barrier layer 13.

  The anchor layer 31 includes a thermosetting resin that is thermoset by a curing agent.

  The thermosetting resin is not particularly limited, and examples thereof include polyvinyl butyral, acrylic polyol resin, polyester polyol, polyurethane polyol, and phenoxy resin. Among these, a polyol resin is preferable.

  Although it does not specifically limit as a hardening | curing agent, Polyisocyanate etc. are mentioned.

  Polyisocyanates include tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), naphthylene diisocyanate (NDI), paraphenylene diisocyanate (PPDI), tetramethylxylylene diisocyanate ( TMXDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI), lysine diisocyanate (LDI), isopropylidenebis (4-cyclohexylisocyanate) (IPC), cyclohexyl diisocyanate (CHDI), tolidine diisocyanate (TODI).

  The thickness of the anchor layer 31 is usually 0.1 to 3 μm, and preferably 0.2 to 2 μm. When the thickness of the anchor layer 31 is less than 0.1 μm, the adhesion between the reversible thermosensitive recording layer 12 and the gas barrier layer 13 may be lowered. When the thickness exceeds 3 μm, the thickness of the reversible thermosensitive recording medium 10 is decreased. May increase.

  The anchor layer 31 may be formed by applying a coating liquid in which a composition containing a thermosetting resin and a curing agent is dispersed or dissolved in a solvent on the reversible thermosensitive recording layer 12 and then curing. it can.

  FIG. 4 shows a fourth embodiment of the reversible thermosensitive recording medium of the present invention. The reversible thermosensitive recording medium 40 has the same configuration as the reversible thermosensitive recording medium 30 except that an undercoat layer 41 is further formed between the support 11 and the reversible thermosensitive recording layer 12.

  The undercoat layer 41 includes a binder resin and hollow particles. Thereby, when the reversible thermosensitive recording layer 12 is heated, heat transfer to the support 11 can be suppressed.

  The binder resin is not particularly limited as long as the adhesion between the support 11 and the reversible thermosensitive recording layer 12 can be improved, but the styrene / butadiene copolymer, styrene / butadiene / acrylic ester copolymer is not limited. Polymer, polyvinyl acetate, vinyl acetate / acrylic acid copolymer, styrene / acrylic ester copolymer, acrylic ester resin, polyurethane, fully saponified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, partly valence polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol Silyl-modified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol and the like.

  The hollow particles are not particularly limited as long as the heat insulating properties of the undercoat layer 41 can be improved. However, the hollow particles include a shell made of a thermoplastic resin such as acrylonitrile resin or methacrylonitrile resin, and contain a gas such as air inside. Examples include minute hollow particles.

  The average particle diameter of the hollow particles is usually 0.4 to 10 μm. When the average particle diameter of the hollow particles is less than 0.4 μm, it may be difficult to control the hollow ratio of the hollow particles. When the average particle diameter exceeds 10 μm, the smoothness of the surface of the reversible thermosensitive recording medium 30 decreases. There are things to do.

  The average particle diameter of the hollow particles can be measured using a laser analysis / scattering method.

  The hollow ratio of the hollow particles is usually 30 to 98%, preferably 70 to 98%, and more preferably 90 to 98%.

  The hollow ratio is the ratio of the inner diameter to the outer diameter, and can be calculated by measuring the inner diameter and the outer diameter in the same direction for each hollow particle observed in the micrograph. At this time, the hollow ratio is an average value of the hollow ratios of the hollow particles dispersed so as to be spread over an area of 100 μm square or more.

  Specific examples of the hollow particles are described in JP-A No. 2005-199704.

  The undercoat layer 41 may be colored. Thereby, there is no restriction on the color of the support 11 on the side where the reversible thermosensitive recording layer 12 is formed.

  The undercoat layer 41 can be formed by applying a coating solution containing a binder resin and hollow particles on the support 11.

  The undercoat layer 41 may be formed by applying a coating liquid containing a precursor such as a urethane-based material on the support 11 and then foaming.

  FIG. 5 shows a fifth embodiment of the reversible thermosensitive recording medium of the present invention. The reversible thermosensitive recording medium 50 has the same configuration as the reversible thermosensitive recording medium 40 except that an ultraviolet absorbing layer 51 is further formed between the reversible thermosensitive recording layer 12 and the anchor layer 31.

  The ultraviolet absorbing layer 51 includes a thermosetting resin and a filler that are thermally cured by a curing agent contained in the anchor layer 31.

  Although it does not specifically limit as a filler, An inorganic filler, an organic filler, etc. are mentioned, You may use 2 or more types together.

  As materials constituting the inorganic filler, calcium carbonate, magnesium carbonate, anhydrous silicic acid, hydrous silicic acid, hydrous aluminum silicate, hydrous calcium silicate, alumina, iron oxide, calcium oxide, magnesium oxide, chromium oxide, manganese oxide, Silica, talc, mica and the like can be mentioned.

  The materials constituting the organic filler include silicone resin, cellulose, epoxy resin, nylon, phenol resin, polyurethane, urea resin, melamine resin, polyester, polycarbonate, polystyrene, styrene / isoprene copolymer, styrene / divinylbenzene copolymer. Styrene resin such as vinylidene chloride / acrylic copolymer, acrylic urethane resin, acrylic resin such as ethylene / acrylic copolymer, polyethylene, benzoguanamine / formaldehyde condensate, formaldehyde resin such as melamine / formaldehyde condensate, poly Examples include methyl methacrylate and vinyl chloride resin.

  The shape of the filler is not particularly limited, and examples thereof include a spherical shape, a granular shape, a plate shape, and a needle shape.

  Content of the filler in the ultraviolet absorption layer 51 is 5-50 volume% normally.

  The thickness of the ultraviolet absorbing layer 51 is usually 0.1 to 20 μm. If the thickness of the ultraviolet absorbing layer 51 is less than 0.1 μm, the absorption of ultraviolet rays may be insufficient, and if it exceeds 20 μm, the thermal conductivity of the reversible thermosensitive recording medium 40 may be reduced.

  The ultraviolet absorbing layer 51 is formed on the reversible thermosensitive recording layer 12 by applying a coating solution in which a composition containing a thermosetting resin, a curing agent and a filler is dispersed or dissolved in a solvent and then curing. can do.

  The reversible thermosensitive recording layer 12, the gas barrier layer 13, the primer layer 21, and the anchor layer 31 may further contain the same filler as the ultraviolet absorbing layer 51.

  The filler content in each layer is usually 5 to 50% by volume.

  The reversible thermosensitive recording layer 12, the gas barrier layer 13, the primer layer 21, and the anchor layer 31 may further contain a lubricant.

  The lubricant is not particularly limited, but synthetic waxes such as ester wax, paraffin wax and polyethylene wax; vegetable waxes such as hardened castor oil; animal waxes such as beef tallow hardened oil; higher alcohols such as stearyl alcohol and behenyl alcohol Higher fatty acids such as margaric acid, lauric acid, mytynolic acid, palmitic acid, stearic acid, behenic acid, and fumenic acid; higher fatty acid esters such as sorbitan fatty acid ester; stearic acid amide, oleic acid amide, lauric acid amide Amides such as ethylene bis stearamide, methylene bis stearamide, and methylol stearamide.

  The content of the lubricant in each layer is usually 0.1 to 95% by volume, preferably 1 to 75% by volume.

  In the reversible thermosensitive recording medium of the present invention, a reversible thermosensitive recording layer, a gas barrier layer, and a protective layer are sequentially laminated on a support, and a primer layer, an anchor layer, an undercoat layer, an ultraviolet absorbing layer, and the like. Further, it may be formed.

  In the reversible thermosensitive recording medium of the present invention, an adhesive layer may be formed on the surface of the support on which the reversible thermosensitive recording layer is not formed. Thereby, the reversible thermosensitive recording medium of this invention can be affixed on another medium.

  Further, the reversible thermosensitive recording medium of the present invention has a back coat layer formed on the back surface, and a release layer, a protective layer, a gas barrier layer, a reversible thermosensitive recording layer and an undercoat layer are sequentially laminated on the front surface. It may be produced by transferring from a PET film or the like to a support using a thermal transfer printer.

  The reversible thermosensitive recording medium of the present invention may be processed into a sheet shape or a card shape.

  Moreover, printing processing can be performed on the front surface or the back surface of the reversible thermosensitive recording medium of the present invention.

  Further, in the reversible thermosensitive recording medium of the present invention, a reversible thermosensitive recording layer, a gas barrier layer and a protective layer may be sequentially laminated on both sides, or an irreversible thermosensitive recording layer may be used in combination. At this time, the color tone of the color of each heat-sensitive recording layer may be the same or different.

  The reversible thermosensitive recording member of the present invention has an information storage unit and a reversible display unit, and the reversible display unit has the reversible thermosensitive recording medium of the present invention. For example, a reversible display unit, a magnetic recording layer, a magnetic card provided with an information storage unit such as an IC memory, and a card such as an IC card display a part of information stored in the information storage unit on the reversible display unit Can do. Thereby, the owner of the card can confirm the information only by looking at the card. In addition, when the contents of the information storage unit are rewritten, the card can be repeatedly used by rewriting the display of the reversible display unit.

  As the reversible thermosensitive recording member of the present invention, a part of the member having the information recording portion also serves as a support for the reversible thermosensitive recording medium, and the reversible thermosensitive recording medium is bonded to the member having the information recording portion. The one that is.

  At this time, the information storage unit may be provided on the surface opposite to the side on which the reversible thermosensitive recording layer is formed, or may be provided between the support and the reversible thermosensitive recording layer, or the reversible You may provide in a part on thermal recording layer.

  The information storage unit is not particularly limited, and examples thereof include a magnetic recording layer, a magnetic stripe, an IC memory, an optical memory, a hologram, an RF-ID tag card, a disk, a disk cartridge, and a tape cassette. In particular, an IC memory and an RF-ID tag are preferable for a sheet medium having a size larger than the card size.

  Note that the RF-ID tag includes an IC chip and an antenna connected to the IC chip.

  EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not restrict | limited by an Example. In addition, a part means a mass part.

Example 1
[Preparation of coating solution for undercoat layer]
30 parts of a styrene-butadiene copolymer PA-9159 (manufactured by Nippon A & L Co., Ltd.), 12 parts of polyvinyl alcohol POVAL PVA103 (manufactured by Kuraray Co., Ltd.), 20 parts of microsphere R-300 (manufactured by Matsumoto Yushi Co., Ltd.) 40 parts of water was stirred for about 1 hour until it became uniform to obtain a coating solution for an undercoat layer.

[Preparation of coating liquid for reversible thermosensitive recording layer]
Chemical formula

で表される電子受容性化合物３部、ジアルキル尿素のハクリーンＳＢ（日本化成社製）１部、アクリルポリオールの５０質量％メチルエチルケトン溶液ＬＲ３２７（三菱レイヨン社製）９部及びメチルエチルケトン７０部を、ボールミルを用いて、平均粒径が１μｍになるように粉砕した。次に、電子供与性呈色体化合物の２−アニリノ−３−メチル−６−ジ−ｎ−ブチルアミノフルオラン１部及びポリイソシアネートのコロネートＨＬ（日本ポリウレタン社製）３部を加えた後、撹拌して、可逆性感熱記録層用塗布液を得た。

3 parts of an electron-accepting compound represented by the following formula: 1 part of a dialkylurea HACLEAN SB (manufactured by Nippon Kasei Co., Ltd.), 9 parts of an acrylic polyol 50% by weight methyl ethyl ketone solution LR327 (manufactured by Mitsubishi Rayon) and 70 parts of methyl ethyl ketone, And milled to an average particle size of 1 μm. Next, after adding 1 part of 2-anilino-3-methyl-6-di-n-butylaminofluorane of electron donating color former compound and 3 parts of coronate HL (manufactured by Nippon Polyurethane Co., Ltd.) of polyisocyanate, The mixture was stirred to obtain a reversible thermosensitive recording layer coating solution.

[Preparation of UV absorbing layer coating solution]
40 parts by weight of a UV-absorbing polymer having a hydroxyl value of 39 mgKOH / g, 20 parts UV-A11 (manufactured by Nippon Shokubai Co., Ltd.), 2 parts of isocyanate compound D-110N (manufactured by Mitsui Takeda Polyurethanes) and 18 parts of methyl ethyl ketone, And stirred to obtain a coating solution for an ultraviolet absorbing layer.

[Preparation of coating solution for anchor layer]
125 parts of ethyl acetate, 15 parts of polyester polyol Takelac A-3210 (manufactured by Mitsui Chemicals Polyurethane) and 10 parts of isocyanate compound Takenate A-3070 (manufactured by Mitsui Chemicals Polyurethanes) were mixed to obtain a coating solution for an anchor layer. .

[Preparation of coating solution for gas barrier layer]
After mixing 30 parts of purified water, 30 parts of isopropyl alcohol, and 30 parts of ethylene-vinyl alcohol copolymer Soarnol D-2908 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), 10 parts of 30% by mass hydrogen peroxide water was added, While stirring, the temperature was raised to 80 ° C. and reacted for about 2 hours. Next, after cooling, catalase was added to 3000 ppm to remove hydrogen peroxide, and a 30% by mass ethylene-vinyl alcohol copolymer solution was obtained.

  To 95 parts of water, 5 parts of montmorillonite Kunipia F (manufactured by Kunimine Kogyo Co., Ltd.) was added with stirring, dispersed using a high-speed stirrer, and then kept warm at 40 ° C. for 1 day. Got.

  After mixing 30.35 parts of water, 30.35 parts of n-propyl alcohol, and 15.7 parts of an ethylene-vinyl alcohol copolymer solution, 23.6 parts of an inorganic layered compound dispersion was added with stirring. Next, after adding 3 parts of cation exchange resin particles and stirring for 1 hour to remove the cations, only the cation exchange resin particles were filtered off with a strainer. Further, 0.06 part of magnesium hydroxide was added and dispersed using a high-pressure dispersion apparatus at a pressure of 50 MPa, followed by filtration using a 300 mesh filter to obtain a 5.9 mass% filtrate. It was. To 10 parts of the obtained filtrate, 0.008 part of a 65 mass% solution of titanium tetraacetylacetonate TC-401 (manufactured by Matsumoto Fine Chemical Co., Ltd.) was added with stirring to obtain a coating solution for gas barrier layer.

[Preparation of coating solution for primer layer]
After mixing 15 parts of methyl ethyl ketone, 10 parts of isopropyl alcohol, 25 parts of ethyl acetate and 50 parts of polyvinyl butyral SRECK BL-1 (manufactured by Sekisui Chemical Co., Ltd.), 3 parts of Lamiol R curing agent (manufactured by Sakata Inx Corporation) of an isocyanate compound was added. To obtain a primer layer coating solution.

[Preparation of coating solution for protective layer]
Pentaerythritol hexaacrylate KAYARAD DPHA (Nippon Kayaku Co., Ltd.) 3 parts, urethane acrylate oligomer art resin UN-3320HA (Negami Kogyo Co., Ltd.) 3 parts, dipentaerythritol caprolactone acrylate ester KAYARAD DPCA-120 (Japan) 3 parts, manufactured by Kayaku Co., Ltd., 1 part of silica P-526 (manufactured by Mizusawa Chemical Co., Ltd.), 0.5 part of photopolymerization initiator Irgacure 184 (manufactured by Ciba Geigy Japan, Inc.), lubricant ST102PA (manufactured by Toray Dow Co., Ltd.) 0.001 Part and 11 parts of isopropyl alcohol were dispersed using a ball mill so that the average particle diameter was 3 μm, to obtain a coating solution for a protective layer.

[Production of reversible thermosensitive recording medium]
Using a wire bar, an undercoat layer coating solution was applied on Tetron film U2L98W (manufactured by Teijin DuPont), a cloudy polyester film having a thickness of 100 μm, and then dried at 80 ° C. for 2 minutes. The thickness was 20 μm. An undercoat layer was formed.

  Next, a reversible thermosensitive recording layer coating solution is applied onto the undercoat layer using a wire bar, dried at 100 ° C. for 2 minutes, cured at 60 ° C. for 24 hours, and a thickness of 11 μm. A heat-sensitive recording layer was formed.

  Next, a coating solution for an ultraviolet absorbing layer was applied onto the reversible thermosensitive recording layer using a wire bar, and then dried at 80 ° C. for 1 minute to form an ultraviolet absorbing layer having a thickness of 2 μm.

  Next, after applying the anchor layer coating solution onto the ultraviolet absorbing layer using a wire bar, the anchor layer was dried at 80 ° C. for 1 minute to form an anchor layer having a thickness of 0.7 μm.

  Next, after applying the coating solution for gas barrier layer on the anchor layer using a wire bar, it was dried at 80 ° C. for 1 minute to form a gas barrier layer (first layer) having a thickness of 0.2 μm. The gas barrier layer (first layer) had a Ti content of 0.10% by mass.

  Next, using a wire bar, the gas barrier layer coating solution is applied onto the gas barrier layer (first layer), and then dried at 80 ° C. for 1 minute, and the thickness of the gas barrier layer (second layer) is 0.8 μm. ) Was formed. The gas barrier layer (second layer) had a Ti content of 0.10% by mass.

  Next, using a wire bar, a gas barrier layer coating solution is applied onto the gas barrier layer (second layer), and then dried at 80 ° C. for 1 minute, and the thickness of the gas barrier layer (third layer) is 0.2 μm. ) Was formed. The gas barrier layer (third layer) had a Ti content of 0.10% by mass.

  The gas barrier layer was identified using a scanning electron microscope ULTRA 55 (manufactured by Carl Zeiss), and the Ti content was measured using an energy dispersive X-ray analyzer EMAX ENERGY (manufactured by Horiba, Ltd.).

  Next, a primer layer coating solution was applied onto the gas barrier layer using a wire bar, and then dried at 80 ° C. for 1 minute to form a primer layer having a thickness of 0.8 μm.

  Using a wire bar, the protective layer coating solution was applied onto the primer layer, and then dried at 90 ° C. for 1 minute. Next, using an 80 W / cm ultraviolet lamp, it was cured by irradiating light and cured at 60 ° C. for 24 hours to form a protective layer having a thickness of 4 μm, thereby obtaining a reversible thermosensitive recording medium.

(Example 2)
The gas barrier layer (first layer) was the same as the coating solution for the gas barrier layer except that the addition amount of the titanium tetraacetylacetonate 65 mass% solution TC-401 (Matsumoto Fine Chemical Co., Ltd.) was changed to 0.012 part. A coating solution was obtained.

  A reversible thermosensitive recording medium was obtained in the same manner as in Example 1 except that the gas barrier layer (first layer) coating solution was used when forming the gas barrier layer (first layer).

  The gas barrier layer (first layer) had a Ti content of 0.15% by mass.

Example 3
Except for changing the addition amount of a titanium tetraacetylacetonate 65 mass% solution TC-401 (manufactured by Matsumoto Fine Chemical Co., Ltd.) to 0.012 part, the gas barrier layer (first layer, A coating solution for the third layer) was obtained.

  When forming the gas barrier layer (first layer) and the gas barrier layer (third layer), reversible in the same manner as in Example 1 except that the coating liquid for the gas barrier layer (first layer, third layer) was used. A heat-sensitive recording medium was obtained.

  The gas barrier layer (first layer) and the gas barrier layer (third layer) had a Ti content of 0.15% by mass.

Example 4
Except for changing the addition amount of a 65 mass% solution TC-401 of titanium tetraacetylacetonate to 0.042 parts, the gas barrier layer (first layer, A coating solution for the third layer) was obtained.

  When forming the gas barrier layer (first layer) and the gas barrier layer (third layer), reversible in the same manner as in Example 1 except that the coating liquid for the gas barrier layer (first layer, third layer) was used. A heat-sensitive recording medium was obtained.

  The gas barrier layer (first layer) and the gas barrier layer (third layer) had a Ti content of 0.50% by mass.

(Example 5)
The gas barrier layer (first layer, the same as the coating solution for the gas barrier layer) except that the addition amount of the titanium tetraacetylacetonate 65 mass% solution TC-401 (manufactured by Matsumoto Fine Chemical Co., Ltd.) was changed to 0.129 part. A coating solution for the third layer) was obtained.

  Gas barrier layer (second layer) in the same manner as the coating solution for gas barrier layer, except that the addition amount of titanium tetraacetylacetonate 65 mass% solution TC-401 (manufactured by Matsumoto Fine Chemical Co., Ltd.) was changed to 0.084 parts. A coating solution was obtained.

  When forming the gas barrier layer (first layer) and the gas barrier layer (third layer), the coating liquid for the gas barrier layer (first layer, third layer) is used and the gas barrier layer (second layer) is formed. In addition, a reversible thermosensitive recording medium was obtained in the same manner as in Example 1 except that the gas barrier layer (second layer) coating solution was used.

  The gas barrier layer (first layer), the gas barrier layer (second layer), and the gas barrier layer (third layer) each have a Ti content of 1.5 mass%, 1.0 mass%, and 1.5 mass%, respectively. Met.

(Example 6)
Except for changing the addition amount of 65% by weight titanium tetraacetylacetonate solution TC-401 (manufactured by Matsumoto Fine Chemical Co., Ltd.) to 0.442 parts, the gas barrier layer (first layer, A coating solution for the third layer) was obtained.

  Gas barrier layer (second layer) in the same manner as the coating solution for gas barrier layer, except that the addition amount of titanium tetraacetylacetonate 65 mass% solution TC-401 (manufactured by Matsumoto Fine Chemical Co., Ltd.) was changed to 0.084 parts. A coating solution was obtained.

  When forming the gas barrier layer (first layer) and the gas barrier layer (third layer), the coating liquid for the gas barrier layer (first layer, third layer) is used and the gas barrier layer (second layer) is formed. In addition, a reversible thermosensitive recording medium was obtained in the same manner as in Example 1 except that the gas barrier layer (second layer) coating solution was used.

  The gas barrier layer (first layer), the gas barrier layer (second layer), and the gas barrier layer (third layer) each have a Ti content of 5.0 mass%, 1.0 mass%, and 5.0 mass%, respectively. Met.

(Example 7)
Except for changing the addition amount of titanium tetraacetylacetonate 65 mass% solution TC-401 (manufactured by Matsumoto Fine Chemical Co., Ltd.) to 0.26 parts, the gas barrier layer (first layer, A coating solution for the third layer) was obtained.

  Gas barrier layer (second layer) in the same manner as the coating solution for gas barrier layer, except that the addition amount of 65% by weight solution of titanium tetraacetylacetonate TC-401 (manufactured by Matsumoto Fine Chemical Co., Ltd.) was changed to 0.172 parts. A coating solution was obtained.

  When forming the gas barrier layer (first layer) and the gas barrier layer (third layer), the coating liquid for the gas barrier layer (first layer, third layer) is used and the gas barrier layer (second layer) is formed. In addition, a reversible thermosensitive recording medium was obtained in the same manner as in Example 1 except that the gas barrier layer (second layer) coating solution was used.

  The gas barrier layer (first layer), the gas barrier layer (second layer), and the gas barrier layer (third layer) each have a Ti content of 3.0 mass%, 2.0 mass%, and 3.0 mass%, respectively. Met.

(Example 8)
The gas barrier layer (first layer, the same as the coating solution for the gas barrier layer) except that the addition amount of titanium tetraacetylacetonate 65% by weight solution TC-401 (manufactured by Matsumoto Fine Chemical Co., Ltd.) was changed to 0.94 parts. A coating solution for the third layer) was obtained.

  Gas barrier layer (second layer) in the same manner as the coating solution for gas barrier layer, except that the addition amount of 65% by weight solution of titanium tetraacetylacetonate TC-401 (manufactured by Matsumoto Fine Chemical Co., Ltd.) was changed to 0.172 parts. A coating solution was obtained.

  When forming the gas barrier layer (first layer) and the gas barrier layer (third layer), the coating liquid for the gas barrier layer (first layer, third layer) is used and the gas barrier layer (second layer) is formed. In addition, a reversible thermosensitive recording medium was obtained in the same manner as in Example 1 except that the gas barrier layer (second layer) coating solution was used.

  The gas barrier layer (first layer), the gas barrier layer (second layer), and the gas barrier layer (third layer) each had a Ti content of 10 mass%, 2.0 mass%, and 10 mass%.

Example 9
Except for changing the addition amount of 65% by weight titanium tetraacetylacetonate solution TC-401 (manufactured by Matsumoto Fine Chemical Co., Ltd.) to 1.49 parts, the gas barrier layer (first layer, A coating solution for the third layer) was obtained.

  The gas barrier layer (second layer) was the same as the coating solution for the gas barrier layer except that the addition amount of the titanium tetraacetylacetonate 65 mass% solution TC-401 (Matsumoto Fine Chemical Co., Ltd.) was changed to 0.94 parts. A coating solution was obtained.

  When forming the gas barrier layer (first layer) and the gas barrier layer (third layer), the coating liquid for the gas barrier layer (first layer, third layer) is used and the gas barrier layer (second layer) is formed. In addition, a reversible thermosensitive recording medium was obtained in the same manner as in Example 1 except that the gas barrier layer (second layer) coating solution was used.

  The gas barrier layer (first layer), the gas barrier layer (second layer), and the gas barrier layer (third layer) each had a Ti content of 15 mass%, 10 mass%, and 15 mass%.

(Example 10)
The gas barrier layer (first layer, the same as the coating solution for gas barrier layer) except that the addition amount of titanium tetraacetylacetonate 65 mass% solution TC-401 (Matsumoto Fine Chemical Co., Ltd.) was changed to 8.4 parts. A coating solution for the third layer) was obtained.

  The gas barrier layer (second layer) was the same as the coating solution for the gas barrier layer except that the addition amount of the titanium tetraacetylacetonate 65 mass% solution TC-401 (Matsumoto Fine Chemical Co., Ltd.) was changed to 0.94 parts. A coating solution was obtained.

  When forming the gas barrier layer (first layer) and the gas barrier layer (third layer), the coating liquid for the gas barrier layer (first layer, third layer) is used and the gas barrier layer (second layer) is formed. In addition, a reversible thermosensitive recording medium was obtained in the same manner as in Example 1 except that the gas barrier layer (second layer) coating solution was used.

  The gas barrier layer (first layer), the gas barrier layer (second layer), and the gas barrier layer (third layer) each had a Ti content of 50 mass%, 10 mass%, and 50 mass%.

(Example 11)
The gas barrier layer (first layer, the same as the coating solution for gas barrier layer) except that the addition amount of titanium tetraacetylacetonate 65 mass% solution TC-401 (Matsumoto Fine Chemical Co., Ltd.) was changed to 8.4 parts. A coating solution for the second layer and the third layer) was obtained.

  When forming the gas barrier layer (first layer), the gas barrier layer (second layer), and the gas barrier layer (third layer), the coating liquid for the gas barrier layer (first layer, second layer, third layer) was used. Except for this, a reversible thermosensitive recording medium was obtained in the same manner as in Example 1.

  The gas barrier layer (first layer), the gas barrier layer (second layer), and the gas barrier layer (third layer) had a Ti content of 50% by mass.

(Example 12)
Except for changing the addition amount of titanium tetraacetylacetonate 65 mass% solution TC-401 (made by Matsumoto Fine Chemical Co., Ltd.) to 12.65 parts, the gas barrier layer (first layer, A coating solution for the third layer) was obtained.

  The gas barrier layer (second layer) was the same as the coating solution for the gas barrier layer except that the addition amount of the titanium tetraacetylacetonate 65 mass% solution TC-401 (made by Matsumoto Fine Chemical Co., Ltd.) was changed to 8.4 parts. A coating solution was obtained.

  When forming the gas barrier layer (first layer) and the gas barrier layer (third layer), the coating liquid for the gas barrier layer (first layer, third layer) is used and the gas barrier layer (second layer) is formed. In addition, a reversible thermosensitive recording medium was obtained in the same manner as in Example 1 except that the gas barrier layer (second layer) coating solution was used.

  The gas barrier layer (first layer), the gas barrier layer (second layer), and the gas barrier layer (third layer) each had a Ti content of 60% by mass, 50% by mass, and 60% by mass.

(Example 13)
The gas barrier layer (first layer) was the same as the coating solution for the gas barrier layer except that the addition amount of the titanium tetraacetylacetonate 65 mass% solution TC-401 (manufactured by Matsumoto Fine Chemical Co., Ltd.) was changed to 0.26 parts. A coating solution was obtained.

  Gas barrier layer (second layer) in the same manner as the coating solution for gas barrier layer, except that the addition amount of 65% by weight solution of titanium tetraacetylacetonate TC-401 (manufactured by Matsumoto Fine Chemical Co., Ltd.) was changed to 0.172 parts. A coating solution was obtained.

  When forming the gas barrier layer (first layer) and the gas barrier layer (second layer), a gas barrier layer (first layer) coating solution and a gas barrier layer (second layer) coating solution are used, respectively. Reversible thermosensitive recording medium was obtained in the same manner as in Example 1 except that the thickness of one layer) and the gas barrier layer (second layer) was 0.6 μm, and the gas barrier layer (third layer) was not formed. It was.

  In the gas barrier layer (first layer) and the gas barrier layer (second layer), the Ti content was 3.0% by mass and 2.0% by mass, respectively.

(Comparative Example 1)
The gas barrier layer (first layer) was the same as the coating solution for the gas barrier layer except that the addition amount of the titanium tetraacetylacetonate 65 mass% solution TC-401 (manufactured by Matsumoto Fine Chemical Co., Ltd.) was changed to 0.172 parts. A coating solution was obtained.

  When forming the gas barrier layer (first layer), the gas barrier layer (first layer) coating solution is used, the thickness of the gas barrier layer (first layer) is 1.2 μm, and the gas barrier layer (second layer) and A reversible thermosensitive recording medium was obtained in the same manner as in Example 1 except that the gas barrier layer (third layer) was not formed.

  The gas barrier layer (first layer) had a Ti content of 2.0% by mass.

(Comparative Example 2)
Reversible thermosensitive recording in the same manner as in Example 1 except that a 65 mass% solution of titanium tetraacetylacetonate TC-401 (manufactured by Matsumoto Fine Chemical Co., Ltd.) was not added when preparing the coating solution for the gas barrier layer. A medium was obtained.

(Comparative Example 3)
Coating for gas barrier layer (first layer, second layer) in the same manner as the coating solution for gas barrier layer, except that 65% by mass solution of titanium tetraacetylacetonate TC-401 (manufactured by Matsumoto Fine Chemical Co., Ltd.) was not added A liquid was obtained.

  When forming the gas barrier layer (first layer) and the gas barrier layer (second layer), reversible in the same manner as in Example 1 except that the gas barrier layer (first layer, second layer) coating solution was used. A heat-sensitive recording medium was obtained.

  Table 1 shows the characteristics of the gas barrier layers of the reversible thermosensitive recording media of Examples 1 to 13 and Comparative Examples 1 to 3.

（可逆性感熱記録媒体の評価）
実施例１〜１３及び比較例１〜３の可逆性感熱記録媒体の耐久性、耐湿性及び耐光性を評価した。

(Evaluation of reversible thermosensitive recording media)
The durability, moisture resistance and light resistance of the reversible thermosensitive recording media of Examples 1 to 13 and Comparative Examples 1 to 3 were evaluated.

[durability]
Using a card printer R-28000 (manufactured by Panasonic Communications), printing and erasing of printing were repeated 300 times on a reversible thermosensitive recording medium. The printing conditions and the printing erasing conditions were such that the printing energy was 0.57 mJ / dot, the erasing temperature was 130 ° C., and the conveyance speed was 56 mm / sec. When the test was repeated once, 100 times and 300 times, the printing state on the surface of the reversible thermosensitive recording medium was visually observed to evaluate the durability. It should be noted that the color development state of the printing part and the erasing state of the erasing part are good and the level at which no peeling of the gas barrier layer is observed, the color development state of the printing part and the erasing state of the erasing part are good, but the gas barrier layer The level at which slight peeling is observed is judged as ◯, the printing part is concealed and slightly whitened, the level at which gas barrier layer peeling is observed is marked as △, and the level at which gas barrier layer peeling is severely observed is marked as x. did.

  The gas barrier layer peeling means in-layer peeling and / or delamination of the gas barrier layer.

[Moisture resistance]
After printing on a reversible thermosensitive recording medium using a card printer R-28000 (manufactured by Panasonic Communications), it was stored in an environment of 40 ° C. and 90% RH for 1 day, 1 week and 1 month. Next, after the printing on the reversible thermosensitive recording medium was erased, printing was performed on the reversible thermosensitive recording medium in the same manner as described above. The printing conditions and the printing erasing conditions were such that the printing energy was 0.57 mJ / dot, the erasing temperature was 130 ° C., and the conveyance speed was 56 mm / sec. The printed state on the surface of the reversible thermosensitive recording medium was visually observed to evaluate the moisture resistance. It should be noted that the color development state of the printing part and the erasing state of the erasing part are good and the level at which no peeling of the gas barrier layer is observed, the color development state of the printing part and the erasing state of the erasing part are good, but the gas barrier layer The level at which the peeling of the gas barrier is slightly observed is evaluated as ◯, the level at which the printing is concealed and slightly whitened, the level at which the peeling of the gas barrier layer is observed is Δ, and the level at which the peeling of the gas barrier layer is observed intensely is determined as X. .

[Light resistance]
After printing on a reversible thermosensitive recording medium using a card printer R-28000 (manufactured by Panasonic Communications Co., Ltd.), using an artificial solar device (manufactured by Seric Co., Ltd.) at an environment of 35 ° C. and 80% RH at 20000 Lx. The reversible thermosensitive recording medium was irradiated with light for 200 hours, and an exposure test was performed. Next, the print on the reversible thermosensitive recording medium was erased. The printing conditions and the printing erasing conditions were such that the printing energy was 0.57 mJ / dot, the erasing temperature was 130 ° C., and the conveyance speed was 56 mm / sec. The density of the background portion and the erased portion of the reversible thermosensitive recording medium was measured using X-RITE 918, and light resistance was evaluated. In addition, formula (concentration of erased part)-(concentration of background part)
When the difference in density is less than 0.05, ◎, when 0.05 or more and less than 0.20, ◯, when 0.20 or more and less than 0.50, Δ, 0.50 or more A case was determined as x.

表２から、実施例１〜１３の可逆性感熱記録媒体は、耐久性、耐湿性及び耐光性に優れることがわかる。

From Table 2, it can be seen that the reversible thermosensitive recording media of Examples 1 to 13 are excellent in durability, moisture resistance and light resistance.

  On the other hand, the reversible thermosensitive recording medium of Comparative Example 1 has low light resistance because the gas barrier layer is formed as a single layer.

  Since the reversible thermosensitive recording medium of Comparative Example 2 does not contain titanium tetraacetylacetonate in the gas barrier layer, durability and moisture resistance are lowered.

  Since the reversible thermosensitive recording medium of Comparative Example 3 does not contain titanium tetraacetylacetonate in the gas barrier layer (first layer) and the gas barrier layer (second layer), durability and moisture resistance are lowered.

10, 20, 30, 40, 50 Reversible thermosensitive recording medium 11 Support 12 Reversible thermosensitive recording layer 13 Gas barrier layer 14 Protective layer 21 Primer layer 31 Anchor layer 41 Undercoat layer 51 Ultraviolet absorbing layer

JP 2011-136557 A

Claims (7)

On the support, a reversible thermosensitive recording layer, a gas barrier layer and a protective layer are sequentially laminated,
The reversible thermosensitive recording layer comprises an electron donating color-forming compound and an electron accepting compound,
In the gas barrier layer, three or more layers containing a resin, an organometallic compound, and an inorganic stratiform compound are laminated. Out of the layers laminated, the outermost layer is more than a layer other than the outermost layer. The metal content is large,
The resin is a polyvinyl alcohol resin and / or an ethylene-vinyl alcohol copolymer resin,
The reversible thermosensitive recording medium, wherein the organometallic compound is an organotitanium compound and / or an organozirconium compound. In the layers other than the outermost layer, the metal content is 0.10% by mass or more and 10% by mass or less,
2. The reversible thermosensitive recording medium according to claim 1, wherein the ratio of the metal content of the outermost layer to the metal content of a layer other than the outermost layer is 1.5 or more and 5 or less.   The reversible thermosensitive recording medium according to claim 1 or 2, wherein the gas barrier layer has a thickness of 0.1 µm or more and 10 µm or less. An anchor layer is formed between the reversible thermosensitive recording layer and the gas barrier layer,
A primer layer is formed between the gas barrier layer and the protective layer,
The anchor layer and the primer layer are independently reversible thermosensitive recording medium according to any one of claims 1 to 3, characterized in that it comprises a cured product of a thermosetting resin and a curing agent. The thermosetting resin is a polyol resin,
The reversible thermosensitive recording medium according to claim 4, wherein the curing agent is a polyisocyanate.   6. The reversible thermosensitive recording medium according to any one of claims 1 to 5, wherein an undercoat layer is formed between the support and the reversible thermosensitive recording layer. An information storage unit and a reversible display unit;
A reversible thermosensitive recording member comprising the reversible thermosensitive recording medium according to any one of claims 1 to 6.

Images