Thermal recording laminate, packaging material using the same, and label

Abstract

The present invention aims to provide a thermal recording laminate that has low residual solvent, is less prone to blocking, has stain resistance, transparency, adhesion, high color density, and high laminate strength. [Solution] A thermal recording laminate characterized by having a base layer on one side of a plastic film substrate, consisting of a primer containing a resin and an organic solvent; a thermal coloring layer on the base layer, consisting of a thermal coloring agent containing a leuco dye, at least one color developer from compounds represented by general formulas (1) to (4), an aqueous resin, an alcohol, and water; and a barrier coat layer on the thermal coloring layer, consisting of a barrier coat agent containing a water-soluble resin, an inorganic layered compound, and water.

Description

Technical Field

[0001] The present invention relates to a heat-sensitive recording laminate, a packaging material using the same, and a label.

Background Art

[0002] Generally, a heat-sensitive recording medium is obtained by applying a coating liquid containing an electron-donating leuco dye (hereinafter also referred to as "leuco dye"), which is usually colorless or light-colored, and an electron-accepting developer such as a phenolic compound (hereinafter also referred to as "developer") to a support such as paper, synthetic paper, film, or plastic. It develops color by an instantaneous chemical reaction caused by heating with a thermal head, hot stamp, thermal pen, laser light, etc., and a recorded image can be obtained. Heat-sensitive recording media are widely used as recording media for facsimiles, computer terminal printers, automatic ticket vending machines, measurement recorders, receipts at supermarkets and convenience stores, etc.

[0003] Since it can record in a short time using a relatively simple device and has the advantage of low cost, in recent years, it can contribute to the reliability of images, reduction of conventional labels, designability, and cost reduction of packaging materials, and is rapidly being used in the food packaging field such as food, bento, and prepared foods. There is a demand for label-less, transparency, non-color development at low temperatures (soil stain resistance), adhesion, and laminate strength.

[0004] Patent Document 1 discloses a heat-sensitive recording medium having a heat-sensitive recording layer containing a leuco dye and a urethane-urea compound as a developer on a plastic film, and a protective layer as the outermost layer on the heat-sensitive recording layer, the protective layer containing an acrylic resin and a polyolefin resin. <00,00104>However, there is no description of forming an anchor coat layer between the plastic film and the heat-sensitive recording layer, and the adhesion between the plastic film and the heat-sensitive recording layer may be poor, and the laminate strength may be poor.

[0005] Patent Document 2 discloses a thermal recording medium having a support, a thermal recording layer on the support containing a developer which is an N,N'-diarylurea derivative and a styrene-acrylic resin. Furthermore, a printed layer of white ink is formed on the surface of the support, and a protective layer is provided on the thermal recording layer (Example 10). It is also stated that an underlayer may be formed. Patent Document 3 discloses a thermal recording layer forming solution containing a leuco dye, a developer with a specific solubility, and a solvent, and a thermal recording layer on a portion of the support. Furthermore, a printed layer of white ink is formed on the surface of the support, and a protective layer is provided on the thermal recording layer (Example 22). It is also stated that an underlayer may be formed. However, Patent Documents 2 and 3 do not describe the adhesion to the substrate or the adhesion to the thermal recording layer by forming a printed layer or underlayer with the above-mentioned white ink, and there is a risk that the lamination strength may be inferior.

[0006] Patent Document 4 discloses a reversible thermal recording medium in which a reversible thermal recording layer, a gas barrier layer, and a protective layer are sequentially laminated on a support, and multiple layers containing resin, organometallic compounds, and inorganic layered compounds are laminated in the gas barrier layer. It also discloses that an undercoat layer is formed between the support and the reversible thermal recording layer. However, since the resin contained in the undercoat layer is a styrene-butadiene copolymer and polyvinyl alcohol, the resin lacks flexibility and is prone to cohesive failure upon curing, which may result in inferior laminate strength. Furthermore, the undercoat layer is intended to suppress heat transfer to the support during heating of the reversible thermal recording layer, and there is no description of the effect of forming the undercoat layer on adhesion to the substrate or adhesion to the thermal recording layer, which may result in inferior laminate strength. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2013-199054 [Patent Document 2] Japanese Patent Publication No. 2022-146283 [Patent Document 3] Japanese Patent Publication No. 2022-151636 [Patent Document 4] Japanese Patent Publication No. 2013-103354 [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] Therefore, the present invention aims to provide a thermal recording laminate that has low residual solvent, is less prone to blocking, has stain resistance, transparency, adhesion, high color density, and high laminate strength. [Means for solving the problem]

[0009] As a result of diligent research, the present inventors have found that the above objective can be achieved by providing a thermal recording laminate characterized by having a base layer on one side of a plastic film substrate, consisting of a base agent comprising a resin and an organic solvent; a thermal coloring layer on the base layer, consisting of a leuco dye, at least one of the compounds represented by the following general formula (1), the following general formula (2), the following general formula (3), and the following general formula (4), a thermal coloring agent comprising an aqueous resin, an alcohol, and water; and a barrier coat layer on the thermal coloring layer, consisting of a barrier coat agent comprising a water-soluble resin, an inorganic layered compound, and water. This led to the completion of the present invention.

[0010] In other words, the present invention provides the following thermal recording laminate, packaging material using the same, and label. (1) A base layer consisting of a primer containing a resin and an organic solvent is provided on one side of the plastic film substrate, On the aforementioned base layer, a heat-sensitive coloring layer is provided, comprising a leuco dye, at least one color developer from among the compounds represented by the following general formula (1), the compounds represented by the following general formula (2), the compounds represented by the following general formula (3), and the compounds represented by the following general formula (4), an aqueous resin, an alcohol, and a heat-sensitive coloring agent containing water. A thermal recording laminate characterized by having a barrier coat layer on the thermal color-developing layer, the barrier coat layer comprising a water-soluble resin, an inorganic layered compound, and a barrier coat agent containing water.

[0011] [ka] (R 1 R is a linear, branched, or alicyclic alkyl group having 1 to 12 carbon atoms, an unsubstituted or C1 to 12 alkyl group, a C1 to 12 alkoxy group, a C6 to 12 aryl group, or a C7 to 12 aralkyl group substituted with a halogen atom, or an unsubstituted or C1 to 12 alkyl group, a C1 to 12 alkoxy group, a C6 to 12 aryl group, or a C6 to 12 aryl group substituted with a halogen atom, and each may be the same or different. 2 Z is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and these may be the same or different. 1 (This is a sulfonyloxy group, a sulfonyl group, or a sulfonamide group.)

[0012] [ka] (R 3is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkyloxyalkyl group having 3 to 12 carbon atoms, a polyoxyalkylene alkyl group having 3 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms, an alkylsulfanyl group having 1 to 12 carbon atoms, an aralkylsulfanyl group having 7 to 12 carbon atoms, an arylsulfanyl group having 6 to 14 carbon atoms, an alkylsulfonyl group having 1 to 12 carbon atoms, an aralkylsulfonyl group having 7 to 12 carbon atoms, an arylsulfonyl group having 6 to 15 carbon atoms, an aralkylsulfonylamino group having 7 to 12 carbon atoms, an arylsulfonylamino group having 6 to 15 carbon atoms, an acyl group having 2 to 10 carbon atoms, an acylamino group having 2 to 10 carbon atoms, an (acyl having 2 to 10 carbon atoms)oxycarbonylamino group, an (alkyl having 1 to 12 carbon atoms)oxycarbonylamino group, an aralkyloxycarbonylamino group, an (aralkyl having 7 to 12 carbon atoms)oxycarbonylamino group, or an (aryl having 6 to 15 carbon atoms)oxycarbonylamino group, and two adjacent Rs 3 may be bonded to each other to form an aromatic ring or a non-aromatic ring together with the carbon atoms to which they are respectively bonded, and R 4 , R 5 is a hydrogen atom or a methyl group, a, b, c are independently integers from 0 to 4, a + c is an integer from 0 to 5, n is 0 or​​​​​​​​​​​​​​is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, where l and m are 0 or 1, and Z 3 (This is a sulfonyloxy group, a sulfonyl group, or a sulfonamide group.)

[0014] [ka] (R 8 R is a linear, branched, or alicyclic alkyl group having 1 to 12 carbon atoms, an unsubstituted or C1 to 12 alkyl group, a C1 to 12 alkoxy group, a C6 to 12 aryl group, or a C7 to 12 aralkyl group substituted with a halogen atom, or an unsubstituted or C1 to 12 alkyl group, a C1 to 12 alkoxy group, a C6 to 12 aryl group, or a C6 to 12 aryl group substituted with a halogen atom, and each may be the same or different. 9 is a methyl group, d is an integer from 0 to 4, and Z 4 and Z 5 (These are a sulfonyloxy group, a sulfonyl group, or a sulfonamide group, and may be the same or different.)

[0015] (2) A base layer consisting of a primer containing a resin and an organic solvent is provided on one side of the plastic film substrate, On the aforementioned base layer, a heat-sensitive coloring layer is provided, comprising a heat-sensitive coloring agent containing a leuco dye, a compound represented by the following general formula (5), an aqueous resin, an alcohol, and water. A thermal recording laminate characterized by having a barrier coat layer on the thermal color-developing layer, the barrier coat layer comprising a water-soluble resin, an inorganic layered compound, and a barrier coat agent containing water.

[0016] [ka] (R 10These are linear, branched, or alicyclic alkyl groups having 1 to 12 carbon atoms, unsubstituted or alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, aryl groups having 6 to 12 carbon atoms, or aralkyl groups having 7 to 12 carbon atoms substituted with a halogen atom, or unsubstituted or alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, or aryl groups having 6 to 12 carbon atoms substituted with a halogen atom, and these may be the same or different.

[0017] (3) The thermal recording laminate according to (1) or (2), characterized in that the inorganic layered compound is montmorillonite. (4) The thermal recording laminate according to any one of (1) to (3), characterized in that the resin of the base material is at least one resin selected from vinyl chloride-vinyl acetate copolymer and polyurethane resin. (5) The thermal recording laminate according to any one of (1) to (4), further characterized by having a sealant layer or a sealing layer on the barrier coat layer. (6) A packaging material characterized by using a thermal recording laminate described in any of (1) to (5), (7) A label characterized by being made using a thermal recording laminate described in any of (1) to (5). [Effects of the Invention]

[0018] According to the present invention, it is possible to provide a thermal recording laminate that has low residual solvent, is less prone to blocking, has stain resistance, transparency, adhesion, high color density, and high laminate strength. [Modes for carrying out the invention]

[0019] The embodiments for carrying out the present invention will be described in detail below. It should be noted that this embodiment is merely one embodiment for carrying out the present invention, and the present invention is not limited to this embodiment. Various modified embodiments are possible without departing from the spirit of the present invention.

[0020] The thermal recording laminate of the present invention preferably has a base layer on one side of a plastic film substrate, consisting of a primer containing a resin and an organic solvent; a thermal coloring layer on the base layer, consisting of a leuco dye, at least one color developer from among the compounds represented by the following general formula (1), the compounds represented by the following general formula (2), the compounds represented by the following general formula (3), and the compounds represented by the following general formula (4), an aqueous resin, an alcohol, and water; and a barrier coat layer on the thermal coloring layer, consisting of a barrier coat agent containing a water-soluble resin, an inorganic layered compound, and water.

[0021] The resin of the aforementioned primer is preferably at least one resin selected from vinyl chloride-vinyl acetate copolymer (hereinafter also referred to as vinyl chloride acetate) and polyurethane resin (hereinafter also referred to as urethane).

[0022] The vinyl chloride-vinyl acetate copolymer is obtained by copolymerizing vinyl chloride monomer and vinyl acetate monomer. The polymerization method can be conventionally known methods, and the manufacturing method is not particularly limited; it can be carried out by solution polymerization, emulsion polymerization, or suspension polymerization. Furthermore, it may be a modified vinyl chloride-vinyl acetate copolymer, or it may be obtained by copolymerizing vinyl chloride monomer, vinyl acetate monomer, and a monomer having an unsaturated carbon-carbon double bond in one molecule and having an acidic functional group or a hydroxyl group.

[0023] The aforementioned vinyl chloride / vinyl acetate copolymers are commercially available and include the VINNOL series (manufactured by Wacker Chemie), the Solvine series (manufactured by Nisshin Chemical Industry Co., Ltd.), and the Kanevinyl series (manufactured by Kaneka Corporation).

[0024] The polyurethane resin may be obtained by reacting a polyol with an isocyanate compound and a chain extender.

[0025] Examples of the polyols include polyether polyols, low molecular weight polyols, polyester polyols, polycarbonate polyols, polybutadiene glycols, glycols, and acrylic polyols. These polyols can be used individually or in combination of two or more. Examples of the polyisocyanates include aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates. These polyisocyanates can be used individually or in combination of two or more. Examples of the chain extenders include polyamine compounds containing two or more primary or secondary amino groups in one molecule, hydrazide compounds, or low molecular weight polyols with a molecular weight of less than 600. These chain extenders can be used individually or in combination of two or more. In the urethane reaction, it is preferable to use a solvent to control the reaction, and it is more preferable that the solvent is inert or has low activity towards the isocyanate group. Examples of usable solvents include aromatic solvents such as toluene and xylene; aliphatic solvents such as hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate; glycol solvents such as propylene glycol monomethyl ether; and alcohol solvents such as methanol, ethanol, isopropanol, n-propanol, and butanol. These solvents can be used individually or in combination of two or more. In addition, additives may be added as needed. Examples of additives include antioxidants, light stabilizers, hydrolysis inhibitors, UV absorbers, metal deactivators, and reaction retarders. These additives can be added individually or in combination of two or more. They can also be added before, during, or after the reaction as appropriate.

[0026] The aforementioned organic solvents include, for example, aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane; alcoholic solvents such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, 1-butanol, 2-butanol, isobutanol, and tert-butanol; esteric solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, and tert-butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, and ethylene glycol. Examples of glycol ether solvents include glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether, as well as their esterified products. As esterified products, acetate-formed products are mainly selected, such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Among these, toluene, ethyl acetate, n-propyl acetate, isopropyl alcohol, propylene glycol monomethyl ether, and methyl ethyl ketone are more preferred from the viewpoint of printability and versatility. These can be used individually or in mixtures of two or more.

[0027] The primer is more preferably a white ink containing the vinyl chloride / vinyl acetate copolymer, the polyurethane resin, the organic solvent, and a white pigment, or an anchor coating agent containing a hydroxyl group-containing vinyl chloride / vinyl acetate copolymer and the organic solvent.

[0028] The white pigment contained in the white ink is preferably titanium dioxide, but other white pigments may also be used. The titanium dioxide may be of the anatase or rutile type. The average particle size is preferably 0.1 to 0.5 μm, and more preferably 0.15 to 0.45 μm. Here, the average particle size refers to the D50 particle size determined by laser diffraction / scattering.

[0029] The vinyl chloride-vinyl acetate copolymer contained in the white ink is preferably present in an amount of 0.1 to 20% by mass, more preferably 1 to 15% by mass, and even more preferably 5 to 10% by mass, as resin solids per 100% by mass of the white ink.

[0030] The polyurethane resin contained in the white ink is preferably present in an amount of 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 20 to 30% by mass, as resin solids per 100% by mass of the white ink.

[0031] The resin solids content ratio of the vinyl chloride / vinyl acetate copolymer and the polyurethane resin is preferably vinyl chloride / vinyl acetate / urethane = 1 / 99 to 99 / 1, more preferably 2 / 98 to 70 / 30, and even more preferably 5 / 95 to 50 / 50.

[0032] The organic solvent contained in the white ink is preferably present in an amount of 10 to 80% by mass, more preferably 20 to 70% by mass, and even more preferably 30 to 60% by mass, based on 100% by mass of the white ink.

[0033] The white pigment contained in the white ink is preferably present in an amount of 5 to 50% by mass, and more preferably in an amount of 10 to 40% by mass, per 100% by mass of the white ink.

[0034] The white ink may contain other thermoplastic resins in addition to the vinyl chloride-vinyl acetate copolymer and the polyurethane resin. For example, shellacs, rosins, rosin-modified maleic acid resins, rosin-modified phenolic resins, nitrated cotton, cellulose acetate, cellulose acetylpropionate, cellulose acetyl butyrate, chlorinated rubber, cyclized rubber, polyethylene resin, polypropylene resin, vinyl chloride resin, polyamide resin, ethylene-(meth)acrylic acid copolymer, polyester resin, polyvinylidene chloride resin, vinyl acetate resin, ketone resin, butyral resin, chlorinated polypropylene resin, chlorinated polyethylene resin, chlorinated ethylene vinyl acetate resin, ethylene vinyl acetate resin Fat, (meth)acrylic resin, styrene maleic acid resin, polystyrene resin, polyacetal resin, polycarbonate resin, casein, alkyd resin, acrylonitrile resin, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polysulfone resin, polyether resin, polyethersulfone resin, polyetherketone resin, modified polyphenylene ether resin, polyphenylene sulfone resin, polyimide resin, polyamideimide resin, amorphous polyarylate resin, polyetheretherketone resin, etc. are preferred. These resins may be one type or two or more types. When the above-mentioned other thermoplastic resins are included, it is preferable that they be included as resin solids in 5 to 70% by mass, more preferably 10 to 60% by mass, and even more preferably 20 to 50% by mass per 100% by mass of white ink.

[0035] The aforementioned white ink may also contain isocyanate compounds, inorganic fillers, organic fillers, defoamers, leveling agents, antiblocking agents, waxes, pigment dispersants, antistatic agents, slip agents, plasticizers, tackifiers, and the like. Any known and commonly used substances can be appropriately selected as long as they do not impair the properties of the ink composition.

[0036] The aforementioned white ink is preferably used in gravure printing and can be applied as is. However, depending on the application conditions and application effect, it can be diluted with a diluent in Zahn Cup #3 (manufactured by Rigosha Co., Ltd.) to adjust the viscosity to the desired level. In this case, the viscosity is preferably 10 to 40 seconds at 25°C. If it is less than 10 seconds, it will be too fluid, and if it is greater than 40 seconds, the transferability during printing will be poor.

[0037] The aforementioned diluent can be any solvent that can be used to adjust the viscosity of the anchor coating agent, and examples include organic solvents and water. Commercially available solvents can also be used, and there are no particular restrictions. Examples of commercially available solvents include SL9170 solvent (non-toluene solvent), PU515 solvent (non-toluene solvent), CN116 solvent (non-toluene solvent), AC372 solvent (non-toluene solvent), CN104 solvent (non-toluene), TS32 solvent (ester-based), PU53 solvent (toluene-containing), PP575 solvent (toluene-containing), and SL9164 solvent (non-ketone-based) (all manufactured by Tokyo Ink Co., Ltd.).

[0038] The hydroxyl group-containing vinyl chloride / vinyl acetate copolymer contained in the anchor coating agent is obtained by copolymerizing vinyl chloride monomer, vinyl acetate monomer, and monomers having hydroxyl groups.

[0039] Examples of monomers having a hydroxyl group include alkyl alcohols, vinyl alcohols, ethylene glycol monoacrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 2-(2-hydroxyethoxy)ethyl acrylate, and hydroxyalkyl acrylates such as (1-hydroxycyclohexyl)methyl acrylate, among which vinyl alcohols and hydroxyalkyl acrylates are more preferred.

[0040] The aforementioned hydroxyl group-containing vinyl chloride / vinyl acetate copolymers are commercially available and include VINNOL E15 / 45A, VINNOL E15 / 48A, VINNOL E22 / 48A (all manufactured by Wacker Chemie), Solvine A, Solvine AL, Solvine TA5R, Solvine TAO, Solvine TA3 (all manufactured by Nisshin Chemical Industry Co., Ltd.), Kanevinyl T555, Kanevinyl T5HX (both manufactured by Kaneka Corporation), and others.

[0041] The hydroxyl group-containing vinyl chloride / vinyl acetate copolymer contained in the anchor coating agent is preferably present in an amount of 1 to 99% by mass, more preferably 3 to 80% by mass, and even more preferably 5 to 50% by mass, as resin solids per 100% by mass of the anchor coating agent.

[0042] The organic solvent contained in the anchor coating agent is preferably present in an amount of 10 to 80% by mass, more preferably 20 to 70% by mass, and even more preferably 30 to 60% by mass, based on 100% by mass of the anchor coating agent.

[0043] The anchor coating agent may contain other thermoplastic resins in addition to the hydroxyl group-containing vinyl chloride / vinyl acetate copolymer. For example, polyurethane resins, shellacs, rosins, rosin-modified maleic acid resins, rosin-modified phenolic resins, nitrated cotton, cellulose acetate, cellulose acetylpropionate, cellulose acetyl butyrate, chlorinated rubber, cyclized rubber, polyethylene resins, polypropylene resins, vinyl chloride resins, polyamide resins, ethylene-(meth)acrylic acid copolymers, polyester resins, polyvinylidene chloride resins, vinyl acetate resins, ketone resins, butyral resins, chlorinated polypropylene resins, chlorinated polyethylene resins, chlorinated ethylene vinyl acetate resins, ethylene vinyl acetate Cetate resin, (meth)acrylic resin, styrene maleic acid resin, polystyrene resin, polyacetal resin, polycarbonate resin, casein, alkyd resin, acrylonitrile resin, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polysulfone resin, polyether resin, polyethersulfone resin, polyetherketone resin, modified polyphenylene ether resin, polyphenylene sulfone resin, polyimide resin, polyamideimide resin, amorphous polyarylate resin, polyetheretherketone resin, etc. are preferred. Among these, polyurethane resin is more preferred. These resins may be one type or two or more types. When the above-mentioned thermoplastic resins are included, it is preferable that they be included as resin solids in 100% by mass of the anchor coating agent in amounts of 10 to 80% by mass, more preferably 20 to 70% by mass, and even more preferably 30 to 60% by mass.

[0044] The anchor coating agent may also contain colorants, isocyanate compounds, inorganic fillers, organic fillers, defoamers, leveling agents, antiblocking agents, waxes, pigment dispersants, antistatic agents, slip agents, plasticizers, tackifiers, and the like. Any known and commonly used substances can be appropriately selected as long as they do not impair the properties of the anchor coating agent.

[0045] The aforementioned anchor coating agent is preferably used in gravure printing and can be applied as is. However, depending on the coating conditions and coating effect, it can be diluted with a diluent solvent using Zahn Cup #3 (manufactured by Rigosha Co., Ltd.) to adjust the viscosity to the desired level. In this case, the viscosity is preferably 10 to 40 seconds at 25°C. If it is less than 10 seconds, it will be too fluid, and if it is greater than 40 seconds, the transferability during printing will be poor.

[0046] The aforementioned diluent can be any solvent that can be used to adjust the viscosity of the anchor coating agent, and examples include organic solvents and water. Commercially available solvents can also be used, and there are no particular restrictions. Examples of commercially available solvents include SL9170 solvent (non-toluene solvent), PU515 solvent (non-toluene solvent), CN116 solvent (non-toluene solvent), AC372 solvent (non-toluene solvent), CN104 solvent (non-toluene), TS32 solvent (ester-based), PU53 solvent (toluene-containing), PP575 solvent (toluene-containing), and SL9164 solvent (non-ketone-based) (all manufactured by Tokyo Ink Co., Ltd.).

[0047] The thickness of the aforementioned underlayer is preferably 0.1 to 5 μm, and more preferably 0.2 to 3 μm. If the thickness of the underlayer is less than 0.1 μm, the cohesive force may be insufficient, which may reduce the laminate strength, and if it exceeds 5 μm, there is a risk of increased residual solvent and blocking.

[0048] The thermal recording laminate of the present invention preferably has a thermal coloring layer made of a thermal coloring agent on the aforementioned base layer.

[0049] Preferably, the heat-sensitive colorant contains a leuco dye, at least one color developer from among the compounds represented by general formula (1), general formula (2), general formula (3), and general formula (4), an aqueous resin, an alcohol, and water.

[0050] The compounds represented by the general formula (1) are as follows:

[0051] [ka]

[0052] R 1 These are linear, branched, or alicyclic alkyl groups having 1 to 12 carbon atoms, unsubstituted or alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, aryl groups having 6 to 12 carbon atoms, or aralkyl groups having 7 to 12 carbon atoms substituted with a halogen atom, or unsubstituted or alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, or aryl groups having 6 to 12 carbon atoms substituted with a halogen atom, and these may be the same or different.

[0053] Examples of the alkyl groups mentioned above include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, cyclopentyl group, hexyl group, cyclohexyl group, 2-ethylhexyl group, and lauryl group.

[0054] Examples of the aforementioned aralkyl groups include unsubstituted or substituted alkyl groups, alkoxy groups, aralkyl groups, aryl groups, or halogen atoms such as benzyl group, 1-phenylethyl group, 2-phenylethyl group, 3-phenylpropyl group, p-methylbenzyl group, m-methylbenzyl group, m-ethylbenzyl group, p-ethylbenzyl group, p-isopropylbenzyl group, pt-butylbenzyl group, p-methoxybenzyl group, m-methoxybenzyl group, o-methoxybenzyl group, m,p-di-methoxybenzyl group, p-ethoxy-m-methoxybenzyl group, p-phenylmethylbenzyl group, p-cumylbenzyl group, p-phenylbenzyl group, o-phenylbenzyl group, m-phenylbenzyl group, p-tolylbenzyl group, m-tolylbenzyl group, o-tolylbenzyl group, and p-chlorobenzyl group.

[0055] Examples of the aryl group include unsubstituted alkyl groups, alkoxy groups, aralkyl groups, aryl groups, or halogen-substituted aryl groups such as phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, 2,5-dimethylphenyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,3-dimethylphenyl group, 3,4-dimethylphenyl group, mesitylene group, p-ethylphenyl group, p-isopropylphenyl group, p-tert-butylphenyl group, p-methoxyphenyl group, 3,4-dimethoxyphenyl group, p-ethoxyphenyl group, p-chlorophenyl group, 1-naphthyl group, 2-naphthyl group, and tert-butylated naphthyl group.

[0056] R 2 R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and may be the same or different, in the benzene ring of general formula (1). 2 The position may be the same or different, and it can be 3rd, 4th, or 5th. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl groups. Of these, the hydrogen atom is the most preferable.

[0057] Z 1 Examples include a sulfonyloxy group, a sulfonyl group, or a sulfonamide group, and among these, the sulfonyloxy group represented in the general formula (5) below is more preferred, and the R in the benzene ring of general formula (5) 10 The position of -SO2-O- may be the same or different, and is at position 3, 4, or 5, more preferably at position 3.

[0058] The compounds represented by the general formula (5) are as follows:

[0059] [ka]

[0060] R10 These are linear, branched, or alicyclic alkyl groups having 1 to 12 carbon atoms, unsubstituted or alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, aryl groups having 6 to 12 carbon atoms, or aralkyl groups having 7 to 12 carbon atoms substituted with a halogen atom, or unsubstituted or alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, or aryl groups having 6 to 12 carbon atoms substituted with a halogen atom, and these may be the same or different.

[0061] The aforementioned R 10 As for R 1 Similar groups can be cited, and among them, phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, mesitylene group, 2-naphthyl group, methyl group, ethyl group, benzyl group, p-ethylbenzyl group, and p-methoxybenzyl group are more preferred.

[0062] For more details, see N,N'-di-[3-(p-toluenesulfonyloxy)phenyl]urea, N,N'-di-[3-(o-toluenesulfonyloxy)phenyl]urea, N,N'-di-[3-(benzenesulfonyloxy)phenyl]urea, N,N'-di-[(3-benzenesulfonyloxy)phenyl]urea, N,N'-di-[3-(mesitylenesulfonyloxy)phenyl]urea, N,N'-di-[3-(4-ethylbenzenesulfonyloxy)phenyl]urea, N,N'-di-[3-(2-naphthalenesulfonyloxy)phenyl]urea, N,N'-di-[3-(p-methoxyb Examples include N,N'-di-[3-(benzylsulfonyloxy)phenyl]urea, N,N'-di-[3-(ethanesulfonyloxy)phenyl]urea, N,N'-di-[3-(p-toluenesulfonyloxy)-4-methylphenyl]urea, N,N'-di-[4-(p-toluenesulfonyloxy)phenyl]urea, N,N'-di-[4-(benzenesulfonyloxy)phenyl]urea, N,N'-di-[4-(ethanesulfonyloxy)phenyl]urea, and N,N'-di-[2-(p-toluenesulfonyloxy)]phenylurea.

[0063] The compounds represented by the general formula (2) are as follows:

[0064] [ka]

[0065] R 3 These include C1-C12 alkyl groups, C2-C12 alkenyl groups, C3-C12 alkyloxyalkyl groups, C3-C12 polyoxyalkylene alkyl groups, C7-C12 aralkyl groups, C6-C14 aryl groups, C1-C12 alkylsulfanyl groups, C7-C12 aralkylsulfanyl groups, C6-C14 arylsulfanyl groups, C1-C12 alkylsulfonyl groups, C7-C12 aralkylsulfonyl groups, and C6-C15 aryl groups. These are a C1-C15 arylsulfonyl group, an aralkylsulfonylamino group with 7-12 carbon atoms, an arylsulfonylamino group with 6-15 carbon atoms, an acyl group with 2-10 carbon atoms, an acylamino group with 2-10 carbon atoms, an acyloxycarbonylamino group with 2-10 carbon atoms, an alkyloxycarbonylamino group with 1-12 carbon atoms, an aralkyloxycarbonylamino group with 7-12 carbon atoms, or an aryloxycarbonylamino group with 6-15 carbon atoms.

[0066] Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, and lauryl group.

[0067] Examples of the aforementioned alkenyl group include vinyl group, allyl group, propenyl group, and butenyl group.

[0068] Examples of the alkyloxyalkyl groups include C2H5O-C2H4- and C3H7O-C3H6-.

[0069] The polyoxyalkylene alkyl group mentioned above includes HO-(C2H4O)n-C2H4-(n=1~3) and HO-(C3H6O). nExamples include -C3H6- (n=1~3).

[0070] Examples of the aforementioned aralkyl groups include benzyl group, p-methylbenzyl group, p-isopropylbenzyl group, pt-butylbenzyl group, p-chlorobenzyl group, p-methoxybenzyl group, m-methoxybenzyl group, m,p-dimethoxybenzyl group, phenethyl group, α-phenethyl group, and phenylpropyl group.

[0071] Examples of the aryl group include phenyl group, tolyl group, p-ethylphenyl group, p-xylyl group, m-xylyl group, 1,2,3-trimethylphenyl group, mesitylene group, 1,2,4-trimethylphenyl group (pseudocumene group), 1-naphthyl group, 2-naphthyl group, biphenyl group, and dimethylbiphenyl group.

[0072] Examples of the alkylsulfanil group include a methylsulfanil group and a butylsulfanil group.

[0073] Examples of the aforementioned aralkylsulfanyl group include benzylsulfanyl group, 1-phenylethylsulfanyl group, 2-phenylethylsulfanyl group, 1-phenylpropylsulfanyl group, 2-phenylpropylsulfanyl group, 1-phenylbutylsulfanyl group, 2-phenylbutylsulfanyl group, 1-naphthylmethylsulfanyl group, 2-naphthylmethylsulfanyl group, (1-naphthyl)ethylsulfanyl group, and (2-naphthyl)ethylsulfanyl group.

[0074] Examples of the aforementioned arylsulfanil group include the phenylsulfanil group.

[0075] Examples of the alkylsulfonyl group include methanesulfonyl group, ethanesulfonyl group, propanesulfonyl group, and butanesulfonyl group.

[0076] Examples of the aforementioned aralkylsulfonyl group include the benzylsulfonyl group.

[0077] Examples of the arylsulfonyl group include benzenesulfonyl group, toluenesulfonyl group, 2-p-xylenesulfonyl group, mesitylenesulfonyl group, 2,4,6-triisopropylbenzenesulfonyl group, 1-naphthalenesulfonyl group, 2-naphthalenesulfonyl group, and 4-biphenylsulfonyl group.

[0078] Examples of the aforementioned aralkylsulfonylamino group include the benzylsulfonylamino group.

[0079] Examples of the arylsulfonylamino group include benzenesulfonylamino group and toluenesulfonylamino group.

[0080] Examples of the aforementioned acyl group include acetyl group, propionyl group, acryloyl group, methacryloyl group, benzoyl group, toluyl group, and 2-naphthoyl group.

[0081] Examples of the aforementioned acylamino group include acetylamino group, propionylamino group, benzoylamino group, and toluylamino group.

[0082] Examples of the aforementioned (acyl)oxycarbonylamino group having 2 to 10 carbon atoms include acetyloxycarbonylamino group, propionyloxycarbonylamino group, benzoyloxycarbonylamino group, and toluyloxycarbonylamino group.

[0083] Examples of the (alkyl group having 1 to 12 carbon atoms) oxycarbonylamino group include the methoxycarbonylamino group and the butoxycarbonylamino group.

[0084] Examples of the aforementioned aralkyloxycarbonylamino group include the benzyloxycarbonylamino group, the p-methoxybenzyloxycarbonylamino group, and the p-nitrobenzyloxycarbonylamino group.

[0085] Examples of the aforementioned (C7-C12 aralkyl)oxycarbonylamino group include phenethyloxycarbonylamino group, 3-phenylpropyloxycarbonylamino group, 4-phenylbutyloxycarbonylaminoco group, (1-naphthyl)methyloxycarbonylamino group, and (2-naphthyl)methyloxycarbonylamino group.

[0086] Examples of the aforementioned (aryl)oxycarbonylamino group (having 6 to 15 carbon atoms) include the phenoxycarbonylamino group and the tolyloxycarbonylamino group.

[0087] Two adjacent R in general formula (2) 3 They may bond to each other and form an aromatic or non-aromatic ring with the carbon atoms to which they are bonded, preferably an aromatic ring, for example, R 3 It may form a naphthalene ring together with the aromatic ring to which it is bonded.

[0088] Among these, alkyl groups having 1 to 4 carbon atoms are more preferred.

[0089] R 4 , R 5 It is preferable that this is a hydrogen atom or a methyl group.

[0090] a, b, and c are independent integers between 0 and 4, and a + c is an integer between 0 and 5. a and b are more preferably 0, and c is preferably 0 or 1.

[0091] n is preferably 0 or 1, and more preferably 0.

[0092] Y is preferably a divalent organic group, and examples include a divalent organic group obtained by removing two hydrogen atoms from a saturated or unsaturated aliphatic hydrocarbon or alicyclic hydrocarbon; a divalent organic group obtained by removing two hydrogen atoms from an aliphatic or alicyclic hydrocarbon linked by a linking group containing a heteroatom; a divalent organic group obtained by removing two hydrogen atoms from a monocyclic aromatic hydrocarbon; a divalent organic group obtained by removing two hydrogen atoms from a polycyclic aromatic hydrocarbon; a divalent organic group obtained by removing two hydrogen atoms from multiple aromatic hydrocarbons linked by single bonds; a divalent organic group obtained by removing two hydrogen atoms from multiple aromatic hydrocarbons linked by a linking group obtained by removing two hydrogen atoms from a saturated or unsaturated aliphatic hydrocarbon; a divalent organic group obtained by removing two hydrogen atoms from multiple aromatic hydrocarbons linked by a linking group containing a heteroatom; and a divalent organic group obtained by removing two hydrogen atoms from multiple aromatic hydrocarbons linked by a linking group obtained by removing two hydrogen atoms from an aromatic hydrocarbon.

[0093] Examples of divalent organic groups formed by removing two hydrogen atoms from the saturated or unsaturated aliphatic or alicyclic hydrocarbons include methylene, ethylene, trimethylene, tetramethylene, hexamethylene, octamethylene, isopropylidene, cyclohexanediyl, vinylene, propenylene, and 1-butenylene groups.

[0094] Examples of divalent organic groups formed by removing two hydrogen atoms from aliphatic or alicyclic hydrocarbons linked by linking groups containing heteroatoms such as -O-, -S-, -SO2-, and -C(=O)- include -C2H4OC2H4-, -C2H4OC2H4OC2H4-, -C2H4SC2H4-, -C2H4-SO2-C2H4-, and -C2H4COC2H4-.

[0095] Examples of divalent organic groups formed by removing two hydrogen atoms from the aforementioned monocyclic aromatic hydrocarbons include benzene, toluene, xylene, mesitylene, benzyl, and ethylbenzene.

[0096] Examples of divalent organic groups that can be formed by removing two hydrogen atoms from polycyclic aromatic hydrocarbons such as naphthalene and substituted naphthalene include naphthalenediyl, 2,6-naphthalenediyl, 1,8-naphthalenediyl, and 2,3-naphthalenediyl groups.

[0097] Examples of divalent organic groups formed by removing two hydrogen atoms from multiple aromatic hydrocarbons linked by single bonds, such as the aforementioned biphenyl and substituted biphenyl, include the biphenyldiyl group.

[0098] Examples of divalent organic groups formed by removing two hydrogen atoms from multiple aromatic hydrocarbons linked by a linking group formed by removing two hydrogen atoms from the aforementioned saturated or unsaturated aliphatic hydrocarbon include diphenylmethane and 2,2-diphenylpropane.

[0099] Examples of divalent organic groups formed by removing two hydrogen atoms from multiple aromatic hydrocarbons linked by the aforementioned heteroatom-containing linking group include diphenyl ether, diphenoxyethane, di(phenoxyethyl) ether, diphenyl sulfide, and diphenyl sulfone.

[0100] More preferred Y include divalent organic groups formed by removing two hydrogen atoms from monocyclic or polycyclic aromatic hydrocarbons such as phenylene groups, 1,3-phenylene groups, 1,4-phenylene groups, 1,2-phenylene groups, biphenyl groups, 4,4'-biphenyl groups, 3,4'-biphenyl groups, 3,3'-biphenyl groups, oxydiphenyl groups, 4,4'-oxydiphenyl groups, 3,4'-oxydiphenyl groups, and 3,3'-oxydiphenyl groups; divalent organic groups formed by removing two hydrogen atoms from multiple aromatic hydrocarbons linked by single bonds; and divalent organic groups formed by removing two hydrogen atoms from multiple aromatic hydrocarbons linked by linking groups containing heteroatoms.

[0101] Z 2These are a sulfonyloxy group or a sulfonyl group, and may be the same or different. It is more preferable that they be a sulfonyloxy group, and even more preferable that they be the same.

[0102] For more details, see 1,3-bis-(3-[3-phenylureido]phenyloxysulfonyl)benzene, 1,3-bis-(3-[3-{m-tolyl}ureido]phenyloxysulfonyl)benzene, 1,3-bis-(4-[3-{m-tolyl}ureido]phenyloxysulfonyl)benzene, 4,4'-bis-(3-[3-{m-tolyl}ureido]phenyloxysulfonyl)biphenyl, 4,4'-bis-(3-[3-{m-tolyl}ureido] Examples include phenyloxysulfonyl)diphenyl ether, 4,4'-bis-(3-[3-phenylureido]phenyloxysulfonyl)diphenyl ether, 4,4'-bis-(3-[3-phenylureido]phenyloxysulfonyl)biphenyl, 1,3-bis-(3-[3-{p-tolyl}ureido]phenyloxysulfonyl)benzene, and 1,3-bis-(3-[3-{1-naphthyl}ureido]phenyloxysulfonyl)benzene.

[0103] The compounds represented by the general formula (3) are as follows:

[0104] [ka]

[0105] R 6 These are linear, branched, or alicyclic alkyl groups having 1 to 12 carbon atoms, unsubstituted or C1 to 12 alkyl groups, C1 to 12 alkoxy groups, C6 to 12 aryl groups, or C7 to 12 aralkyl groups substituted with halogen atoms, or unsubstituted or C1 to 12 alkyl groups, C1 to 12 alkoxy groups, C6 to 12 aryl groups, or C6 to 12 aryl groups substituted with halogen atoms.

[0106] The aforementioned R6 As for R 1 Similar examples include linear or branched alkyl groups having 1 to 12 carbon atoms, phenyl groups substituted with alkyl groups having 1 to 6 carbon atoms, or alkoxy groups having 1 to 6 carbon atoms, and benzyl groups, among others, which are more preferred.

[0107] R 7 The group is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, such as a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, or tert-butyl group, with the methyl group being more preferred.

[0108] l and m are preferably 0 or 1, and more preferably 0.

[0109] Z 3 The group is preferably a sulfonyloxy group, a sulfonyl group, or a sulfonamide group, and more preferably a sulfonyloxy group or a sulfonamide group.

[0110] More specifically, examples include N-[2-(3-phenylureido)phenyl]benzenesulfonamide, N-benzyl-N'-3-(p-toluenesulfonyloxyphenyl)urea, 3-[(4-methylbenzenesulfonyl)methyl]-1-phenylurea, 3-[4-(octan-1-sulfonyl)phenyl]-1-phenylurea, 1-(benzenesulfonyl)-3-phenylurea, and 1-(4-methylphenylsulfonyl)-3-phenylurea.

[0111] The compounds represented by the general formula (4) are as follows:

[0112] [ka]

[0113] R 8These are linear, branched, or alicyclic alkyl groups having 1 to 12 carbon atoms, unsubstituted or alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, aryl groups having 6 to 12 carbon atoms, or aralkyl groups having 7 to 12 carbon atoms substituted with a halogen atom, or unsubstituted or alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, or aryl groups having 6 to 12 carbon atoms substituted with a halogen atom, and these may be the same or different.

[0114] R 8 As for R 1 Similar groups can be cited, and among them, phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, mesitylene group, 2-naphthyl group, methyl group, ethyl group, benzyl group, p-ethylbenzyl group, and p-methoxybenzyl group are more preferred.

[0115] R 9 It is preferably a methyl group, and R in the benzene ring of general formula (4) 9 Its position is 3rd, 4th, or 5th.

[0116] d is an integer between 0 and 4, and is more preferably 0.

[0117] Z 4 and Z 5 The group is preferably a sulfonyloxy group, a sulfonyl group, or a sulfonamide group, more preferably a sulfonyloxy group or a sulfonyl group, and the -Z in the benzene ring of general formula (4). 5 The position of the hyphen is the 3rd, 4th, or 5th position, and more preferably the 3rd position.

[0118] More specifically, examples include Np-toluenesulfonyl-N'-3-(p-toluenesulfonyloxy)phenylurea and N-benzyl-N'-3-(p-toluenesulfonyloxy)phenylurea.

[0119] At least one of the compounds represented by the general formulas (1) to (5) is preferably contained in the thermochromic agent in an amount of 1 to 70% by mass, more preferably 5 to 50% by mass, and even more preferably 10 to 40% by mass. If the amount of at least one of the compounds represented by the general formulas (1) to (5) is less than 1% by mass, the color development effect is difficult to exhibit, and if it exceeds 70% by mass, the dispersion stability of the thermochromic agent itself may be poor, or it may cause a decrease in heat resistance or solvent resistance during printing.

[0120] It is preferable that the heat-sensitive colorant contains a leuco dye. Any leuco dye known in the field of conventional pressure-sensitive or heat-sensitive recording materials can be used and is not particularly limited, but triarylmethane compounds, fluorane compounds, fluorene compounds, divinyl compounds, diphenylmethane compounds, thiazine compounds, spiro compounds, etc., are preferred. Furthermore, one or more of these leuco dyes can be used.

[0121] Examples of the aforementioned triarylmethane compounds include 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide and 3,3-bis(p-dimethylaminophenyl)phthalide.

[0122] The aforementioned fluorane compounds include 3-diethylamino-6-methylfluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-(o,p-dimethylanilino)fluorane, 3-diethylamino-6-methyl-7-chlorofluorane, 3-diethylamino-6-methyl-7-(m-trifluoromethylanilino)fluorane, 3-diethylamino-6-methyl-7-(o-chloroanilino)fluorane, 3-diethylamino-6-methyl-7-(p-chloroanilino)fluorane, and 3-diethylamino-6-methyl-7-(p-chloroanilino). Diamino-6-methyl-7-(o-fluoroanilino)fluorane, 3-diethylamino-6-methyl-7-(m-methylanilino)fluorane, 3-diethylamino-6-methyl-7-n-octylanilinofluorane, 3-diethylamino-6-methyl-7-n-octylaminofluorane, 3-diethylamino-6-methyl-7-benzylaminofluorane, 3-diethylamino-6-methyl-7-dibenzylaminofluorane, 3-diethylamino-6-methyl-7-(3-methylphenylamino)fluorane, 3-diethylamino-6- 7-methylfluorane, 3-diethylamino-6-chloro-7-anilinofluorane, 3-diethylamino-6-chloro-7-p-methylanilinofluorane, 3-diethylamino-6-ethoxyethyl-7-anilinofluorane, 3-diethylamino-7-methylfluorane, 3-diethylamino-7-octylaminofluorane, 3-diethylamino-7-benzylaminofluorane, 3-diethylamino-7-chlorofluorane, 3-diethylamino-7-bromofluorane, 3-diethylamino-7-phenoxyfluorane, 3-di Ethylamino-7-phenylfluorane, 3-diethylamino-7-(m-trifluoromethylanilino)fluorane, 3-diethylamino-7-(o-chloroanilino)fluorane, 3-diethylamino-7-(p-chloroanilino)fluorane, 3-diethylamino-7-(o-fluoroanilino)fluorane, 3-diethylamino-7-(4-nitroanilino)fluorane, 3-diethylamino-7-(3,4-dichloroanilino)fluorane, 3-diethylamino-benzo[a]fluorane, 3-diethylamino-benzo[c]fluorane,3-Diethylamino-7,8-dibenzofluorane, 3-dibutylamino-6-methylfluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7-(o,p-dimethylanilino)fluorane, 3-dibutylamino-6-methyl-7-(o-chloroanilino)fluorane, 3-dibutylamino-6-methyl-7-(p-chloroanilino)fluorane, 3-dibutylamino-6-methyl-7-(o-fluoroanilino)fluorane, 3-dibutylamino-6-methyl-7-(m-trifluorane) (O-methylanilino)fluorane, 3-dibutylamino-6-methyl-7-chlorofluorane, 3-dibutylamino-6-ethoxyethyl-7-anilinofluorane, 3-dibutylamino-6-chloro-7-anilinofluorane, 3-dibutylamino-6-methyl-7-p-methylanilinofluorane, 3-dibutylamino-7-(o-chloroanilino)fluorane, 3-dibutylamino-7-(o-fluoroanilino)fluorane, 3-di-n-pentylamino-6-methyl-7-anilinofluorane, 3-di-n-pentylamino-6-methyl -7-(p-chloroanilino)fluorane, 3-di-n-pentylamino-7-(m-trifluoromethylanilino)fluorane, 3-di-n-pentylamino-6-chloro-7-anilinofluorane, 3-di-n-pentylamino-7-(p-chloroanilino)fluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3-(N-methyl-N-propylamino)-6-methyl-7-anilinofluorane, 3-(N-methyl-N-cyclohexylamino)-6-methyl-7- Anilinofluorane, 3-(N-methyl-N-isoamylamino)-7-phenoxyfluorane, 3-(N-ethyl-N-cyclohexylamino)-6-methyl-7-anilinofluorane, 3-(N-ethyl-N-hexylamino)-6-methyl-7-(p-chloroanilino)fluorane, 3-(N-ethyl-N-tolyl)amino-6-methyl-7-anilinofluorane, 3-(N-ethyl-N-isoamylamino)-6-methyl-7-anilinofluorane, 3-(N-ethyl-N-isoamylamino)-6-chloro-7-anilinofluorane,3-(N-ethyl-N-tetrahydrofurfurylamino)-6-methyl-7-anilinofluorane, 3-(N-ethyl-N-isobutylamino)-6-methyl-7-anilinofluorane, 3-(N-ethyl-N-ethoxypropylamino)-6-methyl-7-anilinofluorane, 3-(N-ethyl-N-tolyl)amino-6-methyl-7-phenethylaminofluorane, 3-(N-ethyl-Nn-hexylamino)-7-(o-chloroanilino)fluorane, 3-(N-ethyl-Np-tolylamino)-7-(N-phenyl-N-methyl (Tylamino) Fluorane, 3-(N-methyl-N-isoamylamino)-7,8-benzofluorane, 3-cyclohexylamino-6-chlorofluorane, 3-pyrrolidino-6-chlorofluorane, 3-pyrrolidino-7-dibenzylaminofluorane, 2-(4-oxahexyl)-3-dimethylamino-6-methyl-7-anilinofluorane, 2-(4-oxahexyl)-3-diethylamino-6-methyl-7-anilinofluorane, 2-(4-oxahexyl)-3-dipropylamino-6-methyl-7-anilinofluorane, 2-methyl-6-p-(p-dimethylaminophenyl)aminoanilinofluorane, 2-methoxy-6-p-(p-dimethylaminophenyl)aminoanilinofluorane, 2-chloro-3-methyl-6-p-(p-phenylaminophenyl)aminoanilinofluorane, 2-chloro-6-p-(p-dimethylaminophenyl)aminoanilinofluorane, 2-nitro-6-p-(p-diethylaminophenyl)aminoanilinofluorane, 2-amino-6-p-(p-diethylaminophenyl)aminoanilinofluorane, 2-diethyl Luamino-6-p-(p-diethylaminophenyl)aminoanilinofluorane, 2-phenyl-6-methyl-6-p-(p-phenylaminophenyl)aminoanilinofluorane, 2-benzyl-6-p-(p-phenylaminophenyl)aminoanilinofluorane, 2-hydroxy-6-p-(p-phenylaminophenyl)aminoanilinofluorane, 3-methyl-6-p-(p-dimethylaminophenyl)aminoanilinofluorane, 3-diethylamino-6-p-(p-diethylaminophenyl)aminoanilinofluorane,Examples include 3-diethylamino-6-p-(p-dibutylaminophenyl)aminoanilinofluorane, 2,4-dimethyl-6-[(4-dimethylamino)anilino]-fluorane, and 3,6-dimethoxyfluorane.

[0123] Examples of the aforementioned fluorene compounds include 3,6,6'-tris(dimethylamino)spiro[fluorene-9,3'-phthalide] and 3,6,6'-tris(diethylamino)spiro[fluorene-9,3'-phthalide].

[0124] Examples of the aforementioned divinyl compounds include 3,3-bis-[2-(p-dimethylaminophenyl)-2-(p-methoxyphenyl)ethenyl]-4,5,6,7-tetrabromophthalide, 3,3-bis-[2-(p-dimethylaminophenyl)-2-(p-methoxyphenyl)ethenyl]-4,5,6,7-tetrachlorophthalide, 3,3-bis-[1,1-bis(4-pyrrolidinophenyl)ethylene-2-yl]-4,5,6,7-tetrabromophthalide, and 3,3-bis-[1-(4-methoxyphenyl)-1-(4-pyrrolidinophenyl)ethylene-2-yl]-4,5,6,7-tetrachlorophthalide.

[0125] Examples of the aforementioned diphenylmethane-based compounds include 4,4'-bisdimethylaminobenzhydrin benzyl ether, N-halophenylleucoauramine, and N-2,4,5-trichlorophenylleucoauramine.

[0126] Examples of the aforementioned thiazine compounds include benzoylleucomethylene blue and p-nitrobenzoylleucomethylene blue.

[0127] Examples of the aforementioned spiro compounds include 3-methyl-spiro-dinaphthtopyran, 3-ethyl-spiro-dinaphthtopyran, 3,3'-dichloro-spiro-dinaphthtopyran, 3-benzyl-spiro-dinaphthtopyran, 3-methylnaphtho-(3-methoxybenzo)-spiropyran, and 3-propyl-spiro-dibenzopyran.

[0128] Other examples include 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindole-3-yl)-4-azaphthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-octyl-2-methylindole-3-yl)-4-azaphthalide, 3-(4-cyclohexylethylamino-2-methoxyphenyl)-3-(1-ethyl-2-methylindole-3-yl)-4-azaphthalide, and 3-(1-ethyl-2-methylindole-3-yl)-3-(4-diethylamino-2-n-hexyloxyphenyl )-4-azaphthalide, 3-(1-ethyl-2-methylindole-3-yl)-3-(4-diethylamino)-2-methylphenyl-4-azaphthalide, 3-(2-methyl-1-n-octylindole-3-yl)-3-(4-diethylamino-2-ethoxyphenyl)-4-azaphthalide, 3,3-bis(1-ethyl-2-methylindole-3-yl)phthalide, 3,3-bis(1-n-butyl-2-methylindole-3-yl)phthalide, 3,3-bis(1,2-dimethylindole-3-yl)-5-dimethylaminophthalide, 3,3-bis (1,2-dimethylindole-3-yl)-6-dimethylaminophthalide, 3,3-bis(9-ethylcarbazole-3-yl)-5-dimethylaminophthalide, 3,3-bis(2-phenylindole-3-yl)-5-dimethylaminophthalide, 3-(p-dimethylaminophenyl)-3-(1,2-dimethylindole-3-yl)phthalide, 3-(p-dimethylaminophenyl)-3-(2-methylindole-3-yl)phthalide, 3-(p-dimethylaminophenyl)-3-(2-phenylindole-3-yl)phthalide, 3-(p-di Methylaminophenyl)-3-(1-methylpyrrole-2-yl)-6-dimethylaminophthalide, 3-(p-diethylaminophenyl)-3-(1-ethyl-2-methylindole-3-yl)phthalide, 3,6-bis(diethylamino)fluoran-γ-(3'-nitro)anilinolactam, 3,6-bis(diethylamino)fluoran-γ-(4'-nitro)anilinolactam, 1,1-bis-[2',2',2'',2''-tetrakis-(p-dimethylaminophenyl)-ethenyl]-2,2-dinitrileethane, 1,1-bis-[2',2',Examples include 2'',2''-tetrakis-(p-dimethylaminophenyl)-ethenyl]-2-β-naphthoylethane, 1,1-bis-[2',2',2'',2''-tetrakis-(p-dimethylaminophenyl)-ethenyl]-2,2-diacetylethane, bis-[2,2,2',2'-tetrakis-(p-dimethylaminophenyl)-ethenyl]-methylmalonate dimethyl ester, and 2,2-bis{4-[6'-(N-cyclohexyl-N-methylamino)-3'-methylspiro[phthalide-3,9'-xanthene]-2'-ylamino]phenyl}propane.

[0129] The leuco dye is preferably contained in the heat-sensitive colorant at a concentration of 1 to 20% by mass, more preferably at 3 to 15% by mass, and even more preferably at 5 to 10% by mass. If the amount of the leuco dye is less than 1% by mass, the color development effect is difficult to achieve, and if it exceeds 20% by mass, the dispersibility of the heat-sensitive colorant itself is poor, which may result in insufficient cohesive force of the heat-sensitive colored layer film or poor adhesion to the plastic film substrate. The ratio of the developer and the leuco dye contained in the heat-sensitive colorant is preferably developer / leuco dye = 7 / 1 to 0.5 / 1, more preferably 5 / 1 to 1 / 1, and even more preferably 4 / 1 to 2 / 1. A ratio within the above range provides excellent heat-sensitive color development.

[0130] It is preferable that the heat-sensitive colorant contains an aqueous resin. As the aqueous resin, any resin that can be soluble or dispersed in an aqueous medium can be used; any conventionally known resin is acceptable. An aqueous medium refers to one containing water or a hydrophilic solvent as a component. Among these, a water-soluble resin or an aqueous emulsion resin is more preferable.

[0131] The aforementioned water-soluble resins have ionic groups such as sulfonyl groups and carboxyl groups, and water-soluble substituents such as hydroxyl groups within their molecules, and dissolve in water. Examples include water-soluble polyacrylamide, water-soluble acrylic resins, water-soluble polyester resins, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral and other polyvinyl alcohol-based resins, water-soluble nylon resins, water-soluble alkyd resins, water-soluble melamine resins, water-soluble urea resins, water-soluble phenol resins, water-soluble epoxy resins, water-soluble polybutadiene resins, water-soluble urethane resins, water-soluble acrylic / styrene resins, water-soluble vinyl acetate / acrylic copolymer resins, water-soluble styrene / maleic acid copolymer resins, water-soluble fluororesins, water-soluble polyisocyanate resins, polystyrene resins, polyvinylpyrrolidone, polyethylene oxide, polyvinyl acetate, carboxymethylcellulose, water-soluble polyether resins and copolymers thereof, as well as natural polymer compounds such as starch, gelatin, casein, gum arabic, chitosan, dextran, and guar gum. Among these, water-soluble acrylic resins and water-soluble polyester resins are more preferred. Water-soluble polyester resins are particularly preferred.

[0132] The aforementioned aqueous emulsion resin refers to a state in which resin particles are dispersed in an aqueous medium, regardless of whether the resin particles are solid or liquid. Examples of resin particles include polyamides, polyimides, low-density polyethylene, high-density polyethylene, poly(meth)acrylic acid esters, polystyrenes such as polystyrene and its derivatives, polyvinyl chloride, phenolic resins, melamine resins, urea resins, epoxy resins, polybutadiene resins, polycarbonates, alkyd resins, fluororesins, vinyl acetate resins, polyisocyanate resins, chlorinated polyolefin resins, and copolymers thereof. Among these, polystyrenes such as poly(meth)acrylic acid esters and polystyrenes and their derivatives are more preferred. Polystyrenes are particularly preferred, and it is preferable that they contain acidic monomer units such as acrylic acid units and methacrylic acid units.

[0133] The aqueous resin is preferably contained in the heat-sensitive colorant at a concentration of 1 to 50% by mass, more preferably at 5 to 40% by mass, and even more preferably at 10 to 30% by mass. If the amount of aqueous resin is less than 1% by mass, the dispersibility of the heat-sensitive colorant itself is poor, which may result in insufficient cohesive force of the heat-sensitive colorant layer film or poor adhesion to the plastic film substrate. If it exceeds 50% by mass, it may result in reduced print density or poor fluidity.

[0134] It is preferable that the heat-sensitive colorant contains an alcohol. Examples of alcohols include methanol, ethanol, propyl alcohol, isopropyl alcohol, n-propyl alcohol, 1-butanol, 2-butanol, isobutanol, tert-butanol, ethylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,4-pentanediol, 2,5-hexanediol, 1,6-hexanediol, triethylene glycol, 1-methyl-1,3-butylene glycol, 2-methyl-1,3-butylene glycol, 2,4-diethyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, tripropylene glycol, 1,2-propylene glycol, 2-methyl-1,5-pentanediol, and 2-methyl-1,4-pentanediol. Tandiol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,8-octanediol, 2,2,4-trimethyl-1,6-hexanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether are preferred, with methanol, ethanol, propyl alcohol, isopropyl alcohol, n-propyl alcohol, and propylene glycol monomethyl ether being more preferred.

[0135] The alcohol is preferably contained in the heat-sensitive colorant at a concentration of 1 to 50% by mass, more preferably at 2 to 40% by mass, and even more preferably at 5 to 20% by mass. If the amount of alcohol is less than 1% by mass, it may be difficult to dry and may have poor suitability for high-speed printing, and if it exceeds 50% by mass, it may result in a decrease in print density and poor fluidity.

[0136] A sensitizer can be used in the aforementioned heat-sensitive colorant as needed, and conventionally known sensitizers can be used. For example, fatty acid amides such as stearamide, bis-stearamide, N-hydroxymethyl stearamide, N-stearyl stearamide, ethylenebis-stearamide, methylenebis-stearamide, methylol-stearamide, palmitamide, p-toluenesulfonamide, stearic acid, fatty acid metal salts such as calcium, zinc, or aluminum, behenic acid, palmitic acid, N-stearyl urea, benzyl-2-naphthyl ether, 4-benzyl biphenyl, 2,2'-bis(4-methoxyphenoxy)diethyl ether, α,α'-diphenoxyxylene, bis(4-methoxyphenyl) ether, p-benzyl biphenyl, diphenyl sulfone, benzyl benzyl benzoate, 2-benzyloxynaphthalene, 1,2-bis(m-tolyloxy)ethane, 1,2-bis(p-tolyloxy) Examples include bis(phenoxy)ethane, 1,2-bis(m-tolyloxy)ethane, 1,2-bis(3-methylphenoxy)ethane, 1,3-bis(phenoxy)propane, dibenzyl oxalate, p-methylbenzyl oxalate, bis(4-methylbenzyl) ester oxalate, bis(4-chlorobenzyl) ester oxalate, diphenyl adipate, dimethyl terephthalate, dibenzyl terephthalate, phenyl benzenesulfonate, bis(4-allyloxyphenyl)sulfone, 1,2-diphenoxyethane, 4-acetylacetophenone, m-terphenyl, 1-hydroxy-2-naphthoic acid, acetoacetate anilides, fatty acid anilides, etc., among which 1,2-bis(3-methylphenoxy)ethane, 1,2-bis(m-tolyloxy)ethane, 1,2-bis(p-tolyloxy)ethane, and 1,2-bis(phenoxy)ethane are more preferred.

[0137] It is preferable that the heat-sensitive coloring agent contains water. The water is not particularly limited, and tap water, well water, distilled water, deionized water, pure water, etc., can be used. Among these, it is more preferable to use distilled water, deionized water, or pure water.

[0138] The water content is the remainder of each of the aforementioned components.

[0139] The aforementioned thermochromic agent may optionally contain colorants, inorganic fillers, organic fillers, defoamers, leveling agents, antiblocking agents, pigment dispersants, antistatic agents, slip agents, plasticizers, tackifiers, curing agents, silane coupling agents, waxes, and the like. Any known and commonly used substances can be appropriately selected as long as they do not impair the properties of the thermochromic agent.

[0140] Examples of the aforementioned colorants include amorphous silica, amorphous calcium silicate, heavy calcium carbonate, light calcium carbonate, kaolin, calcined kaolin, diatomaceous earth, talc, titanium dioxide, zinc oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, colloidal silica, polystyrene powder, nylon powder, urea-formaldehyde resin filler, styrene-methacrylic acid copolymer, styrene-butadiene copolymer, and other inorganic or organic pigments such as hollow plastic pigments.

[0141] The aforementioned heat-sensitive colorant is preferably used in gravure printing and can be applied as is. However, depending on the coating conditions and coating effect, it can be diluted with a diluent solvent using Zahn Cup #3 (manufactured by Rigosha Co., Ltd.) to adjust the viscosity to the desired level. In this case, the viscosity is preferably 10 to 40 seconds at 25°C. If it is less than 10 seconds, it will be too fluid, and if it is greater than 40 seconds, the transferability during printing will be poor.

[0142] The aforementioned diluent can be any solvent that can be used to adjust the viscosity of the heat-sensitive colorant, and examples include organic solvents and water. Commercially available solvents can also be used, and there are no particular restrictions. Examples of commercially available solvents include WA734 solvent (alcohol-based aqueous solvent), WA735 solvent (alcohol-based aqueous solvent), WA736 solvent (alcohol-based aqueous solvent), TA50 solvent (alcohol-based solvent), and TA52 solvent (alcohol-based solvent) (all manufactured by Tokyo Ink Co., Ltd.).

[0143] The thermal recording laminate of the present invention preferably has a thermal coloring layer made of the thermal coloring agent.

[0144] The thickness of the heat-sensitive color-developing layer is preferably 0.1 to 5 μm, and more preferably 0.2 to 3 μm. If the thickness of the heat-sensitive color-developing layer is less than 0.1 μm, the color density after printing may be insufficient, and if it exceeds 5 μm, blocking may occur.

[0145] The thermal recording laminate of the present invention preferably has a barrier coat layer made of a barrier coat agent on the thermal coloring layer.

[0146] The barrier coating agent preferably contains a water-soluble resin, an inorganic layered compound, and water.

[0147] The water-soluble resin used in the barrier coating agent can be the same water-soluble resin as the heat-sensitive coloring agent. Among these, polyvinyl alcohols are more preferred. These water-soluble resins can be used individually or in combination of two or more types.

[0148] The water-soluble resin is preferably contained in the barrier coating agent in an amount of 1 to 50% by mass, and more preferably in an amount of 2 to 30% by mass. If the amount of the water-soluble resin is less than 1% by mass, the film-forming ability of the barrier coating layer is poor, and if it exceeds 50% by mass, the fluidity of the barrier coating agent is poor, resulting in poor workability.

[0149] Examples of inorganic layered compounds used in the barrier coating agent include clay minerals such as smectite, kaolin, mica, hydrotalcite, and chlorite (including their synthetic counterparts). Specifically, examples include montmorillonite, beiderite, saponite, hectorite, souconite, stevensite, kaolinite, nacrite, dickite, halloysite, hydrated halloysite, tetrasilicic mica, sodium teniolite, muscovite, margalite, phlogopite, talc, antigorite, chrysotile, pyrophyllite, vermiculite, xanthophyllite, and chlorite. Flake silica can also be used. These can be used individually or in combination of two or more. Among these, smectite is more preferred, and montmorillonite is even more preferred. The presence of inorganic layered compounds suppresses the influence of solvents contained in sealant or sealing layers on the barrier coat layer when these layers are laminated, improving printability and enabling printing with thin films.

[0150] The montmorillonite is preferably one that contains redox metal ions, and conventionally known types can be used in terms of printability and versatility. For example, it can be expressed by the following general formula (6). (X,Y)2~3Z4O 10 (OH)2·mH2O·(W ω ) (6)

[0151] X is Al, Fe(III), or Cr(III). Y is Mg, Fe(II), Mn(II), Ni, Zn, or Li. Z is Si, or Al. W is K, Na, or Ca. H2O is intercalated water. m and ω are positive real numbers. Among these, the one in which W in the general formula (6) is Na is preferred because it cleaves in an aqueous medium.

[0152] The size and shape of the inorganic layered compound are not particularly limited, but the particle size (major axis) is preferably 5 μm or less, more preferably 4 μm or less, and even more preferably 3 μm or less. If the particle size is larger than 5 μm, the dispersibility will be poor, and as a result, the coating properties of the barrier coat layer, the appearance of the film, and the effect of suppressing the solvent's influence on the heat-sensitive coloring layer may be poor. The aspect ratio is preferably 50 to 5000, more preferably 100 to 4000, and even more preferably 200 to 3000. The aspect ratio is defined as [average major axis / average thickness].

[0153] The inorganic layered compound is preferably contained in the barrier coating agent at a concentration of 0.1 to 5% by mass, more preferably at 0.5 to 3% by mass, and even more preferably at 1 to 2% by mass. If the amount of the inorganic layered compound is less than 0.1% by mass, the stain resistance of the heat-sensitive coloring layer is poor, and if it exceeds 5% by mass, the fluidity and transparency of the barrier coating agent are poor.

[0154] It is preferable that the barrier coating agent contains water. The water is not particularly limited, and tap water, well water, distilled water, ion-exchanged water, pure water, etc. may be used. It may also contain solvents commonly used in gravure inks. For example, aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane; alcoholic solvents such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, 1-butanol, 2-butanol, isobutanol, and tert-butanol; esteric solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, and tert-butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, and ethylene glycol Examples of glycol ether solvents include toluene monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether, as well as their esterified products. As esterified products, acetate-formed products are mainly selected, such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Among these, toluene, ethyl acetate, n-propyl acetate, isopropyl alcohol, propylene glycol monomethyl ether, and methyl ethyl ketone are more preferred from the viewpoint of printability and versatility. These can be used individually or in combination of two or more.

[0155] The water is preferably contained in the barrier coating agent at a concentration of 50-90% by mass, more preferably at 60-80% by mass, and even more preferably at 70-80% by mass. If the amount of water is less than 50% by mass, the viscosity increases, resulting in poor workability and printability. If it exceeds 90% by mass, wetting during printing becomes poor.

[0156] The barrier coating agent may optionally contain colorants, inorganic fillers, organic fillers, defoamers, leveling agents, antiblocking agents, pigment dispersants, antistatic agents, slip agents, plasticizers, tackifiers, curing agents, silane coupling agents, waxes, and the like. Any known and commonly used substances can be appropriately selected as long as they do not impair the properties of the barrier coating agent.

[0157] The barrier coating agent is preferably used in gravure printing and can be applied as is. However, depending on the coating conditions and coating effect, it can be diluted with a diluent solvent using Zahn Cup #3 (manufactured by Rigosha Co., Ltd.) to adjust the viscosity to the desired level. In this case, the viscosity is preferably 10 to 40 seconds at 25°C. If it is less than 10 seconds, it will be too fluid, and if it is greater than 40 seconds, the transferability during printing will be poor.

[0158] The aforementioned diluent can be any solvent that can be used to adjust the viscosity of the barrier coating agent, and examples include organic solvents and water. Commercially available solvents can also be used, and there are no particular restrictions. Examples of commercially available solvents include WA734 solvent (alcohol-based aqueous solvent), WA735 solvent (alcohol-based aqueous solvent), WA736 solvent (alcohol-based aqueous solvent), TA50 solvent (alcohol-based solvent), and TA52 solvent (alcohol-based solvent) (all manufactured by Tokyo Ink Co., Ltd.).

[0159] The thickness of the barrier coating layer is preferably 0.01 to 2 μm, more preferably 0.05 to 1.4 μm, and even more preferably 0.1 to 1.2 μm. If the thickness of the barrier coating layer is less than 0.01 μm, the film-forming properties of the barrier coating layer will be poor, and if it exceeds 2 μm, it may be difficult to dry and may have poor suitability for high-speed printing.

[0160] The thermal recording laminate of the present invention preferably further has a sealant layer or a sealing layer on the barrier coat layer.

[0161] As long as sufficient sealing strength can be ensured, the bonding method for the sealant layer can be appropriately selected according to the substrate, application, and structure. For example, bonding with a heat-sealable laminate or known sealant film (dry lamination method, non-solvent lamination method, wet lamination method), bonding by heat (thermal lamination method), and resin coating by extrusion lamination method (extrusion lamination method, co-extrusion lamination method, PE sandwich lamination method) can be preferably used.

[0162] Examples of resins that can be used in the aforementioned extruded laminates and co-extruded laminates include polyethylene resins such as LDPE, LLDPE, and HDPE; polypropylene resins (homopolypropylene, random polypropylene, etc.); ethylene-vinyl acetate copolymers; ionomer resins; ethylene-acrylic acid copolymers; ethylene-ethyl acrylate copolymers; ethylene-methyl acrylate copolymers; ethylene-methacrylic acid copolymers; ethylene-methyl methacrylate copolymers; ethylene-propylene copolymers; methylpentene polymers; acid-modified polyolefin resins obtained by modifying polyethylene or polypropylene with maleic acid or fumaric acid; polystyrene resins (general-purpose polystyrene (GPPS), high-impact polystyrene (HIPS), expanded polystyrene (PSP), heat-resistant PSP, etc.); and thermoplastic resins such as polybutylene terephthalate resin. These resins can be used individually or in mixtures of two or more types. For extruded laminates, a thickness of 1 to 100 μm is preferred.

[0163] When using adhesives in the dry lamination method and the non-solvent lamination method, commercially available adhesives are acceptable. Examples include two-component or one-component urethane resin adhesives, acrylic, epoxy, polyester, polyethyleneimine, polybutadiene, water-based urethane, isocyanate, organotitanium, starch-based water-soluble adhesives, and water-based adhesives such as vinyl acetate emulsion. Known application methods can be used for the adhesive, such as roll coaters, reverse roll coaters, gravure coaters, microgravure coaters, knife coaters, bar coaters, wire bar coaters, die coaters, and dip coaters. There are no particular restrictions on the thickness of the adhesive, but a range of 0.001 to 10 μm is preferred, and a range of 0.01 to 5 μm is particularly preferred.

[0164] The sealing layer is formed by methods such as coating with a heat sealant or a hot melt agent. These methods can be used individually or in combination to manufacture the laminate.

[0165] There are no particular restrictions on the thickness of the sealant layer, but it is preferable to have a thickness of 2 to 200 μm for sealant films and 1 to 100 μm for resin coatings by extrusion lamination. The seal layer is preferably 0.01 to 30 μm thick for heat sealant coatings and 1 to 50 μm thick for hot melt coatings.

[0166] Examples of the sealant film include polyolefin films such as polyethylene, polypropylene, ethylene-vinyl acetate, and copolymers thereof, as well as co-extruded and colored films thereof, polystyrene films, polyacrylonitrile films, and ethylene-vinyl alcohol resin films. The film may be stretched or unstretched, and one or more types may be laminated.

[0167] Examples of resins used in heat-sealing agents that form a seal layer include thermoplastic resins such as vinylidene chloride, shellacs, rosins, rosin-modified maleic acid resins, rosin-modified phenolic resins, nitrated cotton, cellulose acetate, cellulose acetylpropionate, cellulose acetyl butyrate, chlorinated rubber, cycloadhesive rubber, polyamide resins, vinyl chloride-vinyl acetate copolymers, polyester resins, ketone resins, butyral resins, chlorinated polypropylene resins, chlorinated polyethylene resins, chlorinated ethylene vinyl acetate resins, ethylene vinyl acetate resins, (meth)acrylic resins, urethane resins, ethylene-vinyl alcohol resins, styrene maleic acid resins, casein, and alkyd resins. These can be used individually or in combination of two or more types. Examples include types in which these resins are dissolved in a solvent, or dispersed in water as acrylic emulsions, urethane emulsions, ethylene-vinyl alcohol emulsions, polyethylene emulsions, polypropylene emulsions, and ethylene vinyl acetate emulsions.

[0168] The thermal recording laminate of the present invention can produce printed materials by using a laser printer (for example, FP-1000, manufactured by Keyence Corporation) to develop color in the thermal color layer. Regarding the color intensity, a heat sealer (manufactured by Tester Industries Co., Ltd.) is used to color the thermal recording laminate, L * a * b * The color density can be evaluated by the L value, which is measured according to the method specified in the color system (CIE1976). A lower L value indicates higher blackness and is considered to be of better quality. Instruments that can be used to measure color density include reflectance meters, spectrophotometers, and spectrophotometers. For example, the portable spectrophotometer eXact 2 (manufactured by X-Rite) is one such instrument.

[0169] The aforementioned plastic film substrate is preferably at least one selected from plastic films or sheets and laminates thereof. Examples include polyester films such as polyethylene terephthalate (PET), polyethylene naphthalate, and polybutylene terephthalate; polyolefin films such as polyethylene, polypropylene, and ethylene-vinyl acetate (e.g., films for body wrap labels); polystyrene films; alcohol-based films such as ethylene-vinyl alcohol and polyvinyl alcohol; polyamide films or barrier polyamide films with a barrier layer in the middle; polycarbonate films; polyacrylonitrile films; polyimide films; cellophane; moisture-proof cellophane; transparent vapor-deposited polyester films or transparent vapor-deposited polyamide films having a vapor-deposited layer of alumina or silica on a PET film or polyamide film; various coated films coated with polyvinylidene chloride resin, polyvinyl alcohol resin, polyacrylic acid resin, etc.; co-extruded films of PET and nylon; polylactic acid films; and heat-shrinkable films (e.g., shrink films). These may be stretched or unstretched, and one or more types may be laminated. Appropriate materials can be selected considering mechanical strength and dimensional stability. Furthermore, to improve the adhesion of the anchor coat layer and laminate layer to the surface, corona treatment, low-temperature plasma treatment, flame treatment, solvent treatment, or coating treatment can be applied, or pre-treated materials can be selected. Among these, PET film, polypropylene film, polyamide film, coated film, transparent vapor-deposited polyester film or transparent vapor-deposited polyamide film, and co-extruded film are preferred. The thickness of the plastic film substrate is not particularly limited as long as it does not impede printability or winding suitability, but 5 to 300 μm is preferred, and 6 to 250 μm is more preferred. Alternatively, a plastic film substrate with the anchor coat agent pre-printed on it may be used.

[0170] The aforementioned base layer, heat-sensitive color-developing layer, and barrier coat layer are preferably created on one side of the plastic film substrate by gravure printing. In particular, it is more preferable to create them by gravure printing using a multi-color gravure printing machine. Since they can be created by gravure printing, each layer can be formed over the entire surface, but it is also easy to form each layer partially.

[0171] The thermal recording laminate of the present invention may have a pattern layer. The pattern layer may be present over the entire surface or in part, and may be a halftone. However, it is preferable to avoid placing a pattern layer between the thermal coloring layer and the barrier coat layer, as this may cause the thermal coloring layer to become contaminated. The aforementioned pattern layer is typically formed using a color printing ink composition commonly used in gravure printing, and is a layer on which patterns, text, or other images are printed.

[0172] The thermal recording laminate of the present invention is preferably used for packaging, food preservation, retort applications, microwave oven applications, agricultural applications, civil engineering applications, fisheries applications, automotive interior and exterior applications, marine applications, daily necessities applications, building material interior and exterior applications, housing equipment applications, medical and medical device applications, pharmaceutical applications, home appliance applications, furniture applications, stationery and office supplies applications, sales promotion applications, commercial applications, electrical and electronic industry applications, and industrial materials applications. Among these, it is more preferably used for packaging, retort applications, and microwave oven applications.

[0173] A method for manufacturing a thermal recording laminate comprises the steps of: preparing a plastic film substrate; a gravure printing step of forming a base layer on one side of the plastic film substrate, consisting of a base agent containing a resin and an organic solvent; a gravure printing step of forming a thermal color layer on the base layer, provided by a thermal color agent containing a leuco dye, a color developer, an aqueous resin, an alcohol, and water; and a coating step of forming a barrier coat layer on the thermal color layer, consisting of a barrier coat agent containing a water-soluble resin, an inorganic layered compound, and water. In this method for manufacturing a thermal recording laminate, it is preferable that the color developer is at least one of the compounds represented by general formula (1), general formula (2), general formula (3), and general formula (4). In particular, it is more preferable that the color developer is a compound represented by general formula (5).

[0174] The resin in the primer used in the gravure printing process for forming the aforementioned base layer is preferably at least one resin selected from vinyl chloride-vinyl acetate copolymer and polyurethane resin.

[0175] The vinyl chloride-vinyl acetate copolymer is obtained by copolymerizing vinyl chloride monomer and vinyl acetate monomer. The polymerization method can be conventionally known methods, and the manufacturing method is not particularly limited; it can be carried out by solution polymerization, emulsion polymerization, or suspension polymerization. Furthermore, it may be a modified vinyl chloride-vinyl acetate copolymer, or it may be obtained by copolymerizing vinyl chloride monomer, vinyl acetate monomer, and a monomer having an unsaturated carbon-carbon double bond in one molecule and having an acidic functional group or a hydroxyl group.

[0176] The aforementioned vinyl chloride / vinyl acetate copolymers are commercially available and include the VINNOL series (manufactured by Wacker Chemie), the Solvine series (manufactured by Nisshin Chemical Industry Co., Ltd.), and the Kanevinyl series (manufactured by Kaneka Corporation).

[0177] The polyurethane resin may be obtained by reacting a polyol with an isocyanate compound and a chain extender.

[0178] Examples of the polyols include polyether polyols, low molecular weight polyols, polyester polyols, polycarbonate polyols, polybutadiene glycols, glycols, and acrylic polyols. These polyols can be used individually or in combination of two or more. Examples of the polyisocyanates include aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates. These polyisocyanates can be used individually or in combination of two or more. Examples of the chain extenders include polyamine compounds containing two or more primary or secondary amino groups in one molecule, hydrazide compounds, or low molecular weight polyols with a molecular weight of less than 600. These chain extenders can be used individually or in combination of two or more. In the urethane reaction, it is preferable to use a solvent to control the reaction, and it is more preferable that the solvent is inert or has low activity towards the isocyanate group. Examples of usable solvents include aromatic solvents such as toluene and xylene; aliphatic solvents such as hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate; glycol solvents such as propylene glycol monomethyl ether; and alcohol solvents such as methanol, ethanol, isopropanol, n-propanol, and butanol. These solvents can be used individually or in combination of two or more. In addition, additives may be added as needed. Examples of additives include antioxidants, light stabilizers, hydrolysis inhibitors, UV absorbers, metal deactivators, and reaction retarders. These additives can be added individually or in combination of two or more. They can also be added before, during, or after the reaction as appropriate.

[0179] The aforementioned organic solvents include, for example, aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane; alcoholic solvents such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, 1-butanol, 2-butanol, isobutanol, and tert-butanol; esteric solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, and tert-butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, and ethylene glycol. Examples of glycol ether solvents include glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether, as well as their esterified products. As esterified products, acetate-formed products are mainly selected, such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Among these, toluene, ethyl acetate, n-propyl acetate, isopropyl alcohol, propylene glycol monomethyl ether, and methyl ethyl ketone are more preferred from the viewpoint of printability and versatility. These can be used individually or in mixtures of two or more.

[0180] The primer is more preferably a white ink containing the vinyl chloride / vinyl acetate copolymer, the polyurethane resin, the organic solvent, and a white pigment, or an anchor coating agent containing a hydroxyl group-containing vinyl chloride / vinyl acetate copolymer and the organic solvent.

[0181] The white pigment contained in the white ink is preferably titanium dioxide, but other white pigments may also be used. The titanium dioxide may be of the anatase or rutile type. The average particle size is preferably 0.1 to 0.5 μm, and more preferably 0.15 to 0.45 μm. Here, the average particle size refers to the D50 particle size determined by laser diffraction / scattering.

[0182] The vinyl chloride-vinyl acetate copolymer contained in the white ink is preferably present in an amount of 0.1 to 20% by mass, more preferably 1 to 15% by mass, and even more preferably 5 to 10% by mass, as resin solids per 100% by mass of the white ink.

[0183] The polyurethane resin contained in the white ink is preferably present in an amount of 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 20 to 30% by mass, as resin solids per 100% by mass of the white ink.

[0184] The resin solids content ratio of the vinyl chloride / vinyl acetate copolymer and the polyurethane resin is preferably vinyl chloride / vinyl acetate / urethane = 1 / 99 to 99 / 1, more preferably 2 / 98 to 70 / 30, and even more preferably 5 / 95 to 50 / 50.

[0185] The organic solvent contained in the white ink is preferably present in an amount of 10 to 80% by mass, more preferably 20 to 70% by mass, and even more preferably 30 to 60% by mass, based on 100% by mass of the white ink.

[0186] The white pigment contained in the white ink is preferably present in an amount of 5 to 50% by mass, and more preferably in an amount of 10 to 40% by mass, per 100% by mass of the white ink.

[0187] The white ink may contain other thermoplastic resins in addition to the vinyl chloride-vinyl acetate copolymer and the polyurethane resin. For example, shellacs, rosins, rosin-modified maleic acid resins, rosin-modified phenolic resins, nitrated cotton, cellulose acetate, cellulose acetylpropionate, cellulose acetyl butyrate, chlorinated rubber, cyclized rubber, polyethylene resin, polypropylene resin, vinyl chloride resin, polyamide resin, ethylene-(meth)acrylic acid copolymer, polyester resin, polyvinylidene chloride resin, vinyl acetate resin, ketone resin, butyral resin, chlorinated polypropylene resin, chlorinated polyethylene resin, chlorinated ethylene vinyl acetate resin, ethylene vinyl acetate resin Fat, (meth)acrylic resin, styrene maleic acid resin, polystyrene resin, polyacetal resin, polycarbonate resin, casein, alkyd resin, acrylonitrile resin, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polysulfone resin, polyether resin, polyethersulfone resin, polyetherketone resin, modified polyphenylene ether resin, polyphenylene sulfone resin, polyimide resin, polyamideimide resin, amorphous polyarylate resin, polyetheretherketone resin, etc. are preferred. These resins may be one type or two or more types. When the above-mentioned other thermoplastic resins are included, it is preferable that they be included as resin solids in 5 to 70% by mass, more preferably 10 to 60% by mass, and even more preferably 20 to 50% by mass per 100% by mass of white ink.

[0188] The aforementioned white ink may also contain isocyanate compounds, inorganic fillers, organic fillers, defoamers, leveling agents, antiblocking agents, waxes, pigment dispersants, antistatic agents, slip agents, plasticizers, tackifiers, and the like. Any known and commonly used substances can be appropriately selected as long as they do not impair the properties of the ink composition.

[0189] The aforementioned white ink is preferably used in gravure printing and can be applied as is. However, depending on the application conditions and application effect, it can be diluted with a diluent in Zahn Cup #3 (manufactured by Rigosha Co., Ltd.) to adjust the viscosity to the desired level. In this case, the viscosity is preferably 10 to 40 seconds at 25°C. If it is less than 10 seconds, it will be too fluid, and if it is greater than 40 seconds, the transferability during printing will be poor.

[0190] The aforementioned diluent can be any solvent that can be used to adjust the viscosity of the anchor coating agent, and examples include organic solvents and water. Commercially available solvents can also be used, and there are no particular restrictions. Examples of commercially available solvents include SL9170 solvent (non-toluene solvent), PU515 solvent (non-toluene solvent), CN116 solvent (non-toluene solvent), AC372 solvent (non-toluene solvent), CN104 solvent (non-toluene), TS32 solvent (ester-based), PU53 solvent (toluene-containing), PP575 solvent (toluene-containing), and SL9164 solvent (non-ketone-based) (all manufactured by Tokyo Ink Co., Ltd.).

[0191] The hydroxyl group-containing vinyl chloride / vinyl acetate copolymer is obtained by copolymerizing vinyl chloride monomer, vinyl acetate monomer, and monomers having hydroxyl groups.

[0192] Examples of monomers having a hydroxyl group include alkyl alcohols, vinyl alcohols, ethylene glycol monoacrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 2-(2-hydroxyethoxy)ethyl acrylate, and hydroxyalkyl acrylates such as (1-hydroxycyclohexyl)methyl acrylate, among which vinyl alcohols and hydroxyalkyl acrylates are more preferred.

[0193] The aforementioned hydroxyl group-containing vinyl chloride / vinyl acetate copolymers are commercially available and include VINNOL E15 / 45A, VINNOL E15 / 48A, VINNOL E22 / 48A (all manufactured by Wacker Chemie), Solvine A, Solvine AL, Solvine TA5R, Solvine TAO, Solvine TA3 (all manufactured by Nisshin Chemical Industry Co., Ltd.), Kanevinyl T555, Kanevinyl T5HX (both manufactured by Kaneka Corporation), and others.

[0194] The hydroxyl group-containing vinyl chloride / vinyl acetate copolymer contained in the anchor coating agent is preferably present in an amount of 1 to 99% by mass, more preferably 3 to 80% by mass, and even more preferably 5 to 50% by mass, as resin solids per 100% by mass of the anchor coating agent.

[0195] The organic solvent contained in the anchor coating agent is preferably present in an amount of 10 to 80% by mass, more preferably 20 to 70% by mass, and even more preferably 30 to 60% by mass, based on 100% by mass of the anchor coating agent.

[0196] The anchor coating agent may contain other thermoplastic resins in addition to the hydroxyl group-containing vinyl chloride / vinyl acetate copolymer. For example, polyurethane resins, shellacs, rosins, rosin-modified maleic acid resins, rosin-modified phenolic resins, nitrated cotton, cellulose acetate, cellulose acetylpropionate, cellulose acetyl butyrate, chlorinated rubber, cyclized rubber, polyethylene resins, polypropylene resins, vinyl chloride resins, polyamide resins, ethylene-(meth)acrylic acid copolymers, polyester resins, polyvinylidene chloride resins, vinyl acetate resins, ketone resins, butyral resins, chlorinated polypropylene resins, chlorinated polyethylene resins, chlorinated ethylene vinyl acetate resins, ethylene vinyl acetate Cetate resin, (meth)acrylic resin, styrene maleic acid resin, polystyrene resin, polyacetal resin, polycarbonate resin, casein, alkyd resin, acrylonitrile resin, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polysulfone resin, polyether resin, polyethersulfone resin, polyetherketone resin, modified polyphenylene ether resin, polyphenylene sulfone resin, polyimide resin, polyamideimide resin, amorphous polyarylate resin, polyetheretherketone resin, etc. are preferred. Among these, polyurethane resin is more preferred. These resins may be one type or two or more types. When the above-mentioned thermoplastic resins are included, it is preferable that they be included as resin solids in 100% by mass of the anchor coating agent in amounts of 10 to 80% by mass, more preferably 20 to 70% by mass, and even more preferably 30 to 60% by mass.

[0197] The anchor coating agent may also contain colorants, isocyanate compounds, inorganic fillers, organic fillers, defoamers, leveling agents, antiblocking agents, waxes, pigment dispersants, antistatic agents, slip agents, plasticizers, tackifiers, and the like. Any known and commonly used substances can be appropriately selected as long as they do not impair the properties of the anchor coating agent.

[0198] The aforementioned anchor coating agent is preferably used in gravure printing and can be applied as is. However, depending on the coating conditions and coating effect, it can be diluted with a diluent solvent using Zahn Cup #3 (manufactured by Rigosha Co., Ltd.) to adjust the viscosity to the desired level. In this case, the viscosity is preferably 10 to 40 seconds at 25°C. If it is less than 10 seconds, it will be too fluid, and if it is greater than 40 seconds, the transferability during printing will be poor.

[0199] The aforementioned diluent can be any solvent that can be used to adjust the viscosity of the anchor coating agent, and examples include organic solvents and water. Commercially available solvents can also be used, and there are no particular restrictions. Examples of commercially available solvents include SL9170 solvent (non-toluene solvent), PU515 solvent (non-toluene solvent), CN116 solvent (non-toluene solvent), AC372 solvent (non-toluene solvent), CN104 solvent (non-toluene), TS32 solvent (ester-based), PU53 solvent (toluene-containing), PP575 solvent (toluene-containing), and SL9164 solvent (non-ketone-based) (all manufactured by Tokyo Ink Co., Ltd.).

[0200] The thickness of the aforementioned underlayer is preferably 0.1 to 5 μm, and more preferably 0.2 to 3 μm. If the thickness of the underlayer is less than 0.1 μm, the cohesive force may be insufficient, which may reduce the laminate strength, and if it exceeds 5 μm, there is a risk of increased residual solvent and blocking.

[0201] It is preferable that the developer in the heat-sensitive colorant used in the gravure printing process for forming the heat-sensitive color layer of the present invention is a compound represented by the following general formula (1).

[0202] [ka]

[0203] R 1These are linear, branched, or alicyclic alkyl groups having 1 to 12 carbon atoms, unsubstituted or alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, aryl groups having 6 to 12 carbon atoms, or aralkyl groups having 7 to 12 carbon atoms substituted with a halogen atom, or unsubstituted or alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, or aryl groups having 6 to 12 carbon atoms substituted with a halogen atom, and these may be the same or different.

[0204] Examples of the alkyl groups mentioned above include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, cyclopentyl group, hexyl group, cyclohexyl group, 2-ethylhexyl group, and lauryl group.

[0205] Examples of the aforementioned aralkyl groups include unsubstituted or substituted alkyl groups, alkoxy groups, aralkyl groups, aryl groups, or halogen atoms such as benzyl group, 1-phenylethyl group, 2-phenylethyl group, 3-phenylpropyl group, p-methylbenzyl group, m-methylbenzyl group, m-ethylbenzyl group, p-ethylbenzyl group, p-isopropylbenzyl group, pt-butylbenzyl group, p-methoxybenzyl group, m-methoxybenzyl group, o-methoxybenzyl group, m,p-di-methoxybenzyl group, p-ethoxy-m-methoxybenzyl group, p-phenylmethylbenzyl group, p-cumylbenzyl group, p-phenylbenzyl group, o-phenylbenzyl group, m-phenylbenzyl group, p-tolylbenzyl group, m-tolylbenzyl group, o-tolylbenzyl group, and p-chlorobenzyl group.

[0206] Examples of the aryl group include unsubstituted alkyl groups, alkoxy groups, aralkyl groups, aryl groups, or halogen-substituted aryl groups such as phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, 2,5-dimethylphenyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,3-dimethylphenyl group, 3,4-dimethylphenyl group, mesitylene group, p-ethylphenyl group, p-isopropylphenyl group, p-tert-butylphenyl group, p-methoxyphenyl group, 3,4-dimethoxyphenyl group, p-ethoxyphenyl group, p-chlorophenyl group, 1-naphthyl group, 2-naphthyl group, and tert-butylated naphthyl group.

[0207] R 2 R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and may be the same or different, in the benzene ring of general formula (1). 2 The position may be the same or different, and it can be 3rd, 4th, or 5th. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl groups. Of these, the hydrogen atom is the most preferable.

[0208] Z 1 Examples include a sulfonyloxy group, a sulfonyl group, or a sulfonamide group, and among these, the sulfonyloxy group represented in the general formula (5) below is more preferred, and the R in the benzene ring of general formula (5) 10 The position of -SO2-O- may be the same or different, and is at position 3, 4, or 5, more preferably at position 3.

[0209] It is more preferable that the color developer in the aforementioned heat-sensitive colorant is a compound represented by the following general formula (5).

[0210] [ka]

[0211] R 10 These are linear, branched, or alicyclic alkyl groups having 1 to 12 carbon atoms, unsubstituted or alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, aryl groups having 6 to 12 carbon atoms, or aralkyl groups having 7 to 12 carbon atoms substituted with a halogen atom, or unsubstituted or alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, or aryl groups having 6 to 12 carbon atoms substituted with a halogen atom, and these may be the same or different.

[0212] The aforementioned R 10 As for R 1 Similar groups can be cited, and among them, phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, mesitylene group, 2-naphthyl group, methyl group, ethyl group, benzyl group, p-ethylbenzyl group, and p-methoxybenzyl group are more preferred.

[0213] For more details, see N,N'-di-[3-(p-toluenesulfonyloxy)phenyl]urea, N,N'-di-[3-(o-toluenesulfonyloxy)phenyl]urea, N,N'-di-[3-(benzenesulfonyloxy)phenyl]urea, N,N'-di-[(3-benzenesulfonyloxy)phenyl]urea, N,N'-di-[3-(mesitylenesulfonyloxy)phenyl]urea, N,N'-di-[3-(4-ethylbenzenesulfonyloxy)phenyl]urea, N,N'-di-[3-(2-naphthalenesulfonyloxy)phenyl]urea, N,N'-di-[3-(p-methoxyb Examples include N,N'-di-[3-(benzylsulfonyloxy)phenyl]urea, N,N'-di-[3-(ethanesulfonyloxy)phenyl]urea, N,N'-di-[3-(p-toluenesulfonyloxy)-4-methylphenyl]urea, N,N'-di-[4-(p-toluenesulfonyloxy)phenyl]urea, N,N'-di-[4-(benzenesulfonyloxy)phenyl]urea, N,N'-di-[4-(ethanesulfonyloxy)phenyl]urea, and N,N'-di-[2-(p-toluenesulfonyloxy)]phenylurea.

[0214] It is preferable that the developer in the heat-sensitive colorant used in the gravure printing process for forming the heat-sensitive color layer of the present invention is a compound represented by the following general formula (2).

[0215] [ka]

[0216] R 3 These include C1-C12 alkyl groups, C2-C12 alkenyl groups, C3-C12 alkyloxyalkyl groups, C3-C12 polyoxyalkylene alkyl groups, C7-C12 aralkyl groups, C6-C14 aryl groups, C1-C12 alkylsulfanyl groups, C7-C12 aralkylsulfanyl groups, C6-C14 arylsulfanyl groups, C1-C12 alkylsulfonyl groups, C7-C12 aralkylsulfonyl groups, and C6-C15 aryl groups. These are a C1-C15 arylsulfonyl group, an aralkylsulfonylamino group with 7-12 carbon atoms, an arylsulfonylamino group with 6-15 carbon atoms, an acyl group with 2-10 carbon atoms, an acylamino group with 2-10 carbon atoms, an acyloxycarbonylamino group with 2-10 carbon atoms, an alkyloxycarbonylamino group with 1-12 carbon atoms, an aralkyloxycarbonylamino group with 7-12 carbon atoms, or an aryloxycarbonylamino group with 6-15 carbon atoms.

[0217] Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, and lauryl group.

[0218] Examples of the aforementioned alkenyl group include vinyl group, allyl group, propenyl group, and butenyl group.

[0219] Examples of the alkyloxyalkyl groups include C2H5O-C2H4- and C3H7O-C3H6-.

[0220] The polyoxyalkylene alkyl group mentioned above includes HO-(C2H4O)n-C2H4-(n=1~3) and HO-(C3H6O). n Examples include -C3H6- (n=1~3).

[0221] Examples of the aforementioned aralkyl groups include benzyl group, p-methylbenzyl group, p-isopropylbenzyl group, pt-butylbenzyl group, p-chlorobenzyl group, p-methoxybenzyl group, m-methoxybenzyl group, m,p-dimethoxybenzyl group, phenethyl group, α-phenethyl group, and phenylpropyl group.

[0222] Examples of the aryl group include phenyl group, tolyl group, p-ethylphenyl group, p-xylyl group, m-xylyl group, 1,2,3-trimethylphenyl group, mesitylene group, 1,2,4-trimethylphenyl group (pseudocumene group), 1-naphthyl group, 2-naphthyl group, biphenyl group, and dimethylbiphenyl group.

[0223] Examples of the alkylsulfanil group include a methylsulfanil group and a butylsulfanil group.

[0224] Examples of the aforementioned aralkylsulfanyl group include benzylsulfanyl group, 1-phenylethylsulfanyl group, 2-phenylethylsulfanyl group, 1-phenylpropylsulfanyl group, 2-phenylpropylsulfanyl group, 1-phenylbutylsulfanyl group, 2-phenylbutylsulfanyl group, 1-naphthylmethylsulfanyl group, 2-naphthylmethylsulfanyl group, (1-naphthyl)ethylsulfanyl group, and (2-naphthyl)ethylsulfanyl group.

[0225] Examples of the aforementioned arylsulfanil group include the phenylsulfanil group.

[0226] Examples of the alkylsulfonyl group include methanesulfonyl group, ethanesulfonyl group, propanesulfonyl group, and butanesulfonyl group.

[0227] Examples of the aforementioned aralkylsulfonyl group include the benzylsulfonyl group.

[0228] Examples of the arylsulfonyl group include benzenesulfonyl group, toluenesulfonyl group, 2-p-xylenesulfonyl group, mesitylenesulfonyl group, 2,4,6-triisopropylbenzenesulfonyl group, 1-naphthalenesulfonyl group, 2-naphthalenesulfonyl group, and 4-biphenylsulfonyl group.

[0229] Examples of the aforementioned aralkylsulfonylamino group include the benzylsulfonylamino group.

[0230] Examples of the arylsulfonylamino group include benzenesulfonylamino group and toluenesulfonylamino group.

[0231] Examples of the aforementioned acyl group include acetyl group, propionyl group, acryloyl group, methacryloyl group, benzoyl group, toluyl group, and 2-naphthoyl group.

[0232] Examples of the aforementioned acylamino group include acetylamino group, propionylamino group, benzoylamino group, and toluylamino group.

[0233] Examples of the aforementioned (acyl)oxycarbonylamino group having 2 to 10 carbon atoms include acetyloxycarbonylamino group, propionyloxycarbonylamino group, benzoyloxycarbonylamino group, and toluyloxycarbonylamino group.

[0234] Examples of the (alkyl group having 1 to 12 carbon atoms) oxycarbonylamino group include the methoxycarbonylamino group and the butoxycarbonylamino group.

[0235] Examples of the aforementioned aralkyloxycarbonylamino group include the benzyloxycarbonylamino group.

[0236] Examples of the (aralkyl having 7 to 12 carbon atoms)oxycarbonylamino group include a phenethyloxycarbonylamino group, a 3-phenylpropyloxycarbonylamino group, a 4-phenylbutyloxycarbonylamino group, a (1-naphthyl)methyloxycarbonylamino group, a (2-naphthyl)methyloxycarbonylamino group, and the like.

[0237] Examples of the (aryl having 6 to 15 carbon atoms)oxycarbonylamino group include a phenoxycarbonylamino group, a tolyloxycarbonylamino group, and the like.

[0238] Two adjacent Rs in the general formula (2) 3 may be bonded to each other to form an aromatic ring or a non-aromatic ring together with the carbon atoms to which they are respectively bonded, preferably an aromatic ring. For example, a naphthalene ring may be formed together with the aromatic ring to which R 3 is bonded.

[0239] Among them, an alkyl group having 1 to 4 carbon atoms is more preferable.

[0240] R 4 and R 5 are preferably a hydrogen atom or a methyl group.

[0241] a, b, and c are independently integers from 0 to 4, and a + c is an integer from 0 to 5. It is more preferable that a and b are 0, and it is preferable that c is 0 or 1.

[0242] n is preferably 0 or 1, and more preferably 0.

[0243] Y is preferably a divalent organic group, and examples include a divalent organic group obtained by removing two hydrogen atoms from a saturated or unsaturated aliphatic hydrocarbon or alicyclic hydrocarbon; a divalent organic group obtained by removing two hydrogen atoms from an aliphatic or alicyclic hydrocarbon linked by a linking group containing a heteroatom; a divalent organic group obtained by removing two hydrogen atoms from a monocyclic aromatic hydrocarbon; a divalent organic group obtained by removing two hydrogen atoms from a polycyclic aromatic hydrocarbon; a divalent organic group obtained by removing two hydrogen atoms from multiple aromatic hydrocarbons linked by single bonds; a divalent organic group obtained by removing two hydrogen atoms from multiple aromatic hydrocarbons linked by a linking group obtained by removing two hydrogen atoms from a saturated or unsaturated aliphatic hydrocarbon; a divalent organic group obtained by removing two hydrogen atoms from multiple aromatic hydrocarbons linked by a linking group containing a heteroatom; and a divalent organic group obtained by removing two hydrogen atoms from multiple aromatic hydrocarbons linked by a linking group obtained by removing two hydrogen atoms from an aromatic hydrocarbon.

[0244] Examples of divalent organic groups formed by removing two hydrogen atoms from the saturated or unsaturated aliphatic or alicyclic hydrocarbons include methylene, ethylene, trimethylene, tetramethylene, hexamethylene, octamethylene, isopropylidene, cyclohexanediyl, vinylene, propenylene, and 1-butenylene groups.

[0245] Examples of divalent organic groups formed by removing two hydrogen atoms from aliphatic or alicyclic hydrocarbons linked by linking groups containing heteroatoms such as -O-, -S-, -SO2-, and -C(=O)- include -C2H4OC2H4-, -C2H4OC2H4OC2H4-, -C2H4SC2H4-, -C2H4-SO2-C2H4-, and -C2H4COC2H4-.

[0246] Examples of divalent organic groups formed by removing two hydrogen atoms from the aforementioned monocyclic aromatic hydrocarbons include benzene, toluene, xylene, mesitylene, benzyl, and ethylbenzene.

[0247] Examples of divalent organic groups that can be formed by removing two hydrogen atoms from polycyclic aromatic hydrocarbons such as naphthalene and substituted naphthalene include naphthalenediyl, 2,6-naphthalenediyl, 1,8-naphthalenediyl, and 2,3-naphthalenediyl groups.

[0248] Examples of divalent organic groups formed by removing two hydrogen atoms from multiple aromatic hydrocarbons linked by single bonds, such as the aforementioned biphenyl and substituted biphenyl, include the biphenyldiyl group.

[0249] Examples of divalent organic groups formed by removing two hydrogen atoms from multiple aromatic hydrocarbons linked by a linking group formed by removing two hydrogen atoms from the aforementioned saturated or unsaturated aliphatic hydrocarbon include diphenylmethane and 2,2-diphenylpropane.

[0250] Examples of divalent organic groups formed by removing two hydrogen atoms from multiple aromatic hydrocarbons linked by the aforementioned heteroatom-containing linking group include diphenyl ether, diphenoxyethane, di(phenoxyethyl) ether, diphenyl sulfide, and diphenyl sulfone.

[0251] More preferred Y include divalent organic groups formed by removing two hydrogen atoms from monocyclic or polycyclic aromatic hydrocarbons such as phenylene groups, 1,3-phenylene groups, 1,4-phenylene groups, 1,2-phenylene groups, biphenyl groups, 4,4'-biphenyl groups, 3,4'-biphenyl groups, 3,3'-biphenyl groups, oxydiphenyl groups, 4,4'-oxydiphenyl groups, 3,4'-oxydiphenyl groups, and 3,3'-oxydiphenyl groups; divalent organic groups formed by removing two hydrogen atoms from multiple aromatic hydrocarbons linked by single bonds; and divalent organic groups formed by removing two hydrogen atoms from multiple aromatic hydrocarbons linked by linking groups containing heteroatoms.

[0252] Z 2These are a sulfonyloxy group or a sulfonyl group, and may be the same or different. It is more preferable that they be a sulfonyloxy group, and even more preferable that they be the same.

[0253] For more details, see 1,3-bis-(3-[3-phenylureido]phenyloxysulfonyl)benzene, 1,3-bis-(3-[3-{m-tolyl}ureido]phenyloxysulfonyl)benzene, 1,3-bis-(4-[3-{m-tolyl}ureido]phenyloxysulfonyl)benzene, 4,4'-bis-(3-[3-{m-tolyl}ureido]phenyloxysulfonyl)biphenyl, 4,4'-bis-(3-[3-{m-tolyl}ureido] Examples include phenyloxysulfonyl)diphenyl ether, 4,4'-bis-(3-[3-phenylureido]phenyloxysulfonyl)diphenyl ether, 4,4'-bis-(3-[3-phenylureido]phenyloxysulfonyl)biphenyl, 1,3-bis-(3-[3-{p-tolyl}ureido]phenyloxysulfonyl)benzene, and 1,3-bis-(3-[3-{1-naphthyl}ureido]phenyloxysulfonyl)benzene.

[0254] It is preferable that the developer in the heat-sensitive colorant used in the gravure printing process for forming the heat-sensitive color layer of the present invention is a compound represented by the following general formula (3).

[0255] [ka]

[0256] R 6 These are linear, branched, or alicyclic alkyl groups having 1 to 12 carbon atoms, unsubstituted or C1 to 12 alkyl groups, C1 to 12 alkoxy groups, C6 to 12 aryl groups, or C7 to 12 aralkyl groups substituted with halogen atoms, or unsubstituted or C1 to 12 alkyl groups, C1 to 12 alkoxy groups, C6 to 12 aryl groups, or C6 to 12 aryl groups substituted with halogen atoms.

[0257] Said R 6 As said R 1 Examples thereof are the same as those of said R. Among them, a linear or branched alkyl group having 1 to 12 carbon atoms, a phenyl group substituted with an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, a benzyl group, etc. are more preferable.

[0258] R 7 is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, etc. Among them, a methyl group is more preferable.

[0259] l and m are preferably 0 or 1, and more preferably 0.

[0260] Z 3 is preferably a sulfonyloxy group, a sulfonyl group or a sulfonamide group, and more preferably a sulfonyloxy group or a sulfonamide group.

[0261] More specifically, N-[2-(3-phenylureido)phenyl]benzenesulfonamide, N-benzyl-N'-3-(p-toluenesulfonyloxyphenyl)urea, 3-[(4-methylbenzenesulfonyl)methyl]-1-phenylurea, 3-[4-(octane-1-sulfonyl)phenyl]-1-phenylurea, 1-(benzenesulfonyl)-3-phenylurea, 1-(4-methylphenylsulfonyl)-3-phenylurea, etc. can be mentioned.

[0262] The developer in the thermochromic agent used in the gravure printing process for forming the thermochromic layer of the present invention is preferably a compound represented by the following general formula (4).

[0263]

Chemical formula

[0264] R 8 These are linear, branched, or alicyclic alkyl groups having 1 to 12 carbon atoms, unsubstituted or C1 to 12 alkyl groups, C1 to 12 alkoxy groups, C6 to 12 aryl groups, or C7 to 12 aralkyl groups substituted with halogen atoms, or unsubstituted or C1 to 12 alkyl groups, C1 to 12 alkoxy groups, C6 to 12 aryl groups, or C6 to 12 aryl groups substituted with halogen atoms, and these may be the same or different.

[0265] The aforementioned R 8 As for R 1 Similar groups can be cited, and among them, phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, mesitylene group, 2-naphthyl group, methyl group, ethyl group, benzyl group, p-ethylbenzyl group, and p-methoxybenzyl group are more preferred.

[0266] R 9 It is preferably a methyl group, and R in the benzene ring of general formula (4) 9 Its position is 3rd, 4th, or 5th.

[0267] d is an integer between 0 and 4, and is more preferably 0.

[0268] Z 4 and Z 5 The group is preferably a sulfonyloxy group, a sulfonyl group, or a sulfonamide group, more preferably a sulfonyloxy group or a sulfonyl group, and the -Z in the benzene ring of general formula (4). 5 The position of the hyphen is the 3rd, 4th, or 5th position, and more preferably the 3rd position.

[0269] More specifically, examples include Np-toluenesulfonyl-N'-3-(p-toluenesulfonyloxy)phenylurea and N-benzyl-N'-3-(p-toluenesulfonyloxy)phenylurea.

[0270] At least one of the compounds represented by the general formulas (1) to (5) is preferably contained in the thermochromic agent in an amount of 1 to 70% by mass, more preferably 5 to 50% by mass, and even more preferably 10 to 40% by mass. If the amount of at least one of the compounds represented by the general formulas (1) to (5) is less than 1% by mass, the color development effect is difficult to exhibit, and if it exceeds 70% by mass, the dispersion stability of the thermochromic agent itself may be poor, or it may cause a decrease in heat resistance or solvent resistance during printing.

[0271] It is preferable that the heat-sensitive colorant used in the gravure printing process for forming the heat-sensitive color layer contains a leuco dye. While all leuco dyes known in the field of conventional pressure-sensitive or heat-sensitive recording materials can be used and are not particularly limited, triarylmethane compounds, fluorane compounds, fluorene compounds, divinyl compounds, diphenylmethane compounds, thiazine compounds, spiro compounds, etc., are preferred. Furthermore, these leuco dyes can be used individually or in combination of two or more types.

[0272] Examples of the aforementioned triarylmethane compounds include 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide and 3,3-bis(p-dimethylaminophenyl)phthalide.

[0273] The aforementioned fluorane compounds include 3-diethylamino-6-methylfluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-(o,p-dimethylanilino)fluorane, 3-diethylamino-6-methyl-7-chlorofluorane, 3-diethylamino-6-methyl-7-(m-trifluoromethylanilino)fluorane, 3-diethylamino-6-methyl-7-(o-chloroanilino)fluorane, 3-diethylamino-6-methyl-7-(p-chloroanilino)fluorane, and 3-diethylamino-6-methyl-7-(p-chloroanilino). Diamino-6-methyl-7-(o-fluoroanilino)fluorane, 3-diethylamino-6-methyl-7-(m-methylanilino)fluorane, 3-diethylamino-6-methyl-7-n-octylanilinofluorane, 3-diethylamino-6-methyl-7-n-octylaminofluorane, 3-diethylamino-6-methyl-7-benzylaminofluorane, 3-diethylamino-6-methyl-7-dibenzylaminofluorane, 3-diethylamino-6-methyl-7-(3-methylphenylamino)fluorane, 3-diethylamino-6- 7-methylfluorane, 3-diethylamino-6-chloro-7-anilinofluorane, 3-diethylamino-6-chloro-7-p-methylanilinofluorane, 3-diethylamino-6-ethoxyethyl-7-anilinofluorane, 3-diethylamino-7-methylfluorane, 3-diethylamino-7-octylaminofluorane, 3-diethylamino-7-benzylaminofluorane, 3-diethylamino-7-chlorofluorane, 3-diethylamino-7-bromofluorane, 3-diethylamino-7-phenoxyfluorane, 3-di Ethylamino-7-phenylfluorane, 3-diethylamino-7-(m-trifluoromethylanilino)fluorane, 3-diethylamino-7-(o-chloroanilino)fluorane, 3-diethylamino-7-(p-chloroanilino)fluorane, 3-diethylamino-7-(o-fluoroanilino)fluorane, 3-diethylamino-7-(4-nitroanilino)fluorane, 3-diethylamino-7-(3,4-dichloroanilino)fluorane, 3-diethylamino-benzo[a]fluorane, 3-diethylamino-benzo[c]fluorane,3-Diethylamino-7,8-dibenzofluorane, 3-dibutylamino-6-methylfluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7-(o,p-dimethylanilino)fluorane, 3-dibutylamino-6-methyl-7-(o-chloroanilino)fluorane, 3-dibutylamino-6-methyl-7-(p-chloroanilino)fluorane, 3-dibutylamino-6-methyl-7-(o-fluoroanilino)fluorane, 3-dibutylamino-6-methyl-7-(m-trifluorane) (O-methylanilino)fluorane, 3-dibutylamino-6-methyl-7-chlorofluorane, 3-dibutylamino-6-ethoxyethyl-7-anilinofluorane, 3-dibutylamino-6-chloro-7-anilinofluorane, 3-dibutylamino-6-methyl-7-p-methylanilinofluorane, 3-dibutylamino-7-(o-chloroanilino)fluorane, 3-dibutylamino-7-(o-fluoroanilino)fluorane, 3-di-n-pentylamino-6-methyl-7-anilinofluorane, 3-di-n-pentylamino-6-methyl -7-(p-chloroanilino)fluorane, 3-di-n-pentylamino-7-(m-trifluoromethylanilino)fluorane, 3-di-n-pentylamino-6-chloro-7-anilinofluorane, 3-di-n-pentylamino-7-(p-chloroanilino)fluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3-(N-methyl-N-propylamino)-6-methyl-7-anilinofluorane, 3-(N-methyl-N-cyclohexylamino)-6-methyl-7- Anilinofluorane, 3-(N-methyl-N-isoamylamino)-7-phenoxyfluorane, 3-(N-ethyl-N-cyclohexylamino)-6-methyl-7-anilinofluorane, 3-(N-ethyl-N-hexylamino)-6-methyl-7-(p-chloroanilino)fluorane, 3-(N-ethyl-N-tolyl)amino-6-methyl-7-anilinofluorane, 3-(N-ethyl-N-isoamylamino)-6-methyl-7-anilinofluorane, 3-(N-ethyl-N-isoamylamino)-6-chloro-7-anilinofluorane,3-(N-ethyl-N-tetrahydrofurfurylamino)-6-methyl-7-anilinofluorane, 3-(N-ethyl-N-isobutylamino)-6-methyl-7-anilinofluorane, 3-(N-ethyl-N-ethoxypropylamino)-6-methyl-7-anilinofluorane, 3-(N-ethyl-N-tolyl)amino-6-methyl-7-phenethylaminofluorane, 3-(N-ethyl-Nn-hexylamino)-7-(o-chloroanilino)fluorane, 3-(N-ethyl-Np-tolylamino)-7-(N-phenyl-N-methyl (Tylamino) Fluorane, 3-(N-methyl-N-isoamylamino)-7,8-benzofluorane, 3-cyclohexylamino-6-chlorofluorane, 3-pyrrolidino-6-chlorofluorane, 3-pyrrolidino-7-dibenzylaminofluorane, 2-(4-oxahexyl)-3-dimethylamino-6-methyl-7-anilinofluorane, 2-(4-oxahexyl)-3-diethylamino-6-methyl-7-anilinofluorane, 2-(4-oxahexyl)-3-dipropylamino-6-methyl-7-anilinofluorane, 2-methyl-6-p-(p-dimethylaminophenyl)aminoanilinofluorane, 2-methoxy-6-p-(p-dimethylaminophenyl)aminoanilinofluorane, 2-chloro-3-methyl-6-p-(p-phenylaminophenyl)aminoanilinofluorane, 2-chloro-6-p-(p-dimethylaminophenyl)aminoanilinofluorane, 2-nitro-6-p-(p-diethylaminophenyl)aminoanilinofluorane, 2-amino-6-p-(p-diethylaminophenyl)aminoanilinofluorane, 2-diethyl Luamino-6-p-(p-diethylaminophenyl)aminoanilinofluorane, 2-phenyl-6-methyl-6-p-(p-phenylaminophenyl)aminoanilinofluorane, 2-benzyl-6-p-(p-phenylaminophenyl)aminoanilinofluorane, 2-hydroxy-6-p-(p-phenylaminophenyl)aminoanilinofluorane, 3-methyl-6-p-(p-dimethylaminophenyl)aminoanilinofluorane, 3-diethylamino-6-p-(p-diethylaminophenyl)aminoanilinofluorane,Examples include 3-diethylamino-6-p-(p-dibutylaminophenyl)aminoanilinofluorane, 2,4-dimethyl-6-[(4-dimethylamino)anilino]-fluorane, and 3,6-dimethoxyfluorane.

[0274] Examples of the aforementioned fluorene compounds include 3,6,6'-tris(dimethylamino)spiro[fluorene-9,3'-phthalide] and 3,6,6'-tris(diethylamino)spiro[fluorene-9,3'-phthalide].

[0275] Examples of the aforementioned divinyl compounds include 3,3-bis-[2-(p-dimethylaminophenyl)-2-(p-methoxyphenyl)ethenyl]-4,5,6,7-tetrabromophthalide, 3,3-bis-[2-(p-dimethylaminophenyl)-2-(p-methoxyphenyl)ethenyl]-4,5,6,7-tetrachlorophthalide, 3,3-bis-[1,1-bis(4-pyrrolidinophenyl)ethylene-2-yl]-4,5,6,7-tetrabromophthalide, and 3,3-bis-[1-(4-methoxyphenyl)-1-(4-pyrrolidinophenyl)ethylene-2-yl]-4,5,6,7-tetrachlorophthalide.

[0276] Examples of the aforementioned diphenylmethane-based compounds include 4,4'-bisdimethylaminobenzhydrin benzyl ether, N-halophenylleucoauramine, and N-2,4,5-trichlorophenylleucoauramine.

[0277] Examples of the aforementioned thiazine compounds include benzoylleucomethylene blue and p-nitrobenzoylleucomethylene blue.

[0278] Examples of the aforementioned spiro compounds include 3-methyl-spiro-dinaphthtopyran, 3-ethyl-spiro-dinaphthtopyran, 3,3'-dichloro-spiro-dinaphthtopyran, 3-benzyl-spiro-dinaphthtopyran, 3-methylnaphtho-(3-methoxybenzo)-spiropyran, and 3-propyl-spiro-dibenzopyran.

[0279] Other examples include 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindole-3-yl)-4-azaphthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-octyl-2-methylindole-3-yl)-4-azaphthalide, 3-(4-cyclohexylethylamino-2-methoxyphenyl)-3-(1-ethyl-2-methylindole-3-yl)-4-azaphthalide, and 3-(1-ethyl-2-methylindole-3-yl)-3-(4-diethylamino-2-n-hexyloxyphenyl )-4-azaphthalide, 3-(1-ethyl-2-methylindole-3-yl)-3-(4-diethylamino)-2-methylphenyl-4-azaphthalide, 3-(2-methyl-1-n-octylindole-3-yl)-3-(4-diethylamino-2-ethoxyphenyl)-4-azaphthalide, 3,3-bis(1-ethyl-2-methylindole-3-yl)phthalide, 3,3-bis(1-n-butyl-2-methylindole-3-yl)phthalide, 3,3-bis(1,2-dimethylindole-3-yl)-5-dimethylaminophthalide, 3,3-bis (1,2-dimethylindole-3-yl)-6-dimethylaminophthalide, 3,3-bis(9-ethylcarbazole-3-yl)-5-dimethylaminophthalide, 3,3-bis(2-phenylindole-3-yl)-5-dimethylaminophthalide, 3-(p-dimethylaminophenyl)-3-(1,2-dimethylindole-3-yl)phthalide, 3-(p-dimethylaminophenyl)-3-(2-methylindole-3-yl)phthalide, 3-(p-dimethylaminophenyl)-3-(2-phenylindole-3-yl)phthalide, 3-(p-di Methylaminophenyl)-3-(1-methylpyrrole-2-yl)-6-dimethylaminophthalide, 3-(p-diethylaminophenyl)-3-(1-ethyl-2-methylindole-3-yl)phthalide, 3,6-bis(diethylamino)fluoran-γ-(3'-nitro)anilinolactam, 3,6-bis(diethylamino)fluoran-γ-(4'-nitro)anilinolactam, 1,1-bis-[2',2',2'',2''-tetrakis-(p-dimethylaminophenyl)-ethenyl]-2,2-dinitrileethane, 1,1-bis-[2',2',Examples include 2'',2''-tetrakis-(p-dimethylaminophenyl)-ethenyl]-2-β-naphthoylethane, 1,1-bis-[2',2',2'',2''-tetrakis-(p-dimethylaminophenyl)-ethenyl]-2,2-diacetylethane, bis-[2,2,2',2'-tetrakis-(p-dimethylaminophenyl)-ethenyl]-methylmalonate dimethyl ester, and 2,2-bis{4-[6'-(N-cyclohexyl-N-methylamino)-3'-methylspiro[phthalide-3,9'-xanthene]-2'-ylamino]phenyl}propane.

[0280] The leuco dye is preferably contained in the heat-sensitive colorant at a concentration of 1 to 20% by mass, more preferably at 3 to 15% by mass, and even more preferably at 5 to 10% by mass. If the amount of the leuco dye is less than 1% by mass, the color development effect is difficult to achieve, and if it exceeds 20% by mass, the dispersibility of the heat-sensitive colorant itself is poor, which may result in insufficient cohesive force of the heat-sensitive colored layer film or poor adhesion to the plastic film substrate. The ratio of the developer and the leuco dye contained in the heat-sensitive colorant is preferably developer / leuco dye = 7 / 1 to 0.5 / 1, more preferably 5 / 1 to 1 / 1, and even more preferably 4 / 1 to 2 / 1. A ratio within the above range provides excellent heat-sensitive color development.

[0281] It is preferable that the heat-sensitive colorant used in the gravure printing process for forming the heat-sensitive color-developing layer contains an aqueous resin. As the aqueous resin, any resin that can be soluble or dispersed in an aqueous medium can be used; any conventionally known resin can be used. An aqueous medium refers to one containing water or a hydrophilic solvent as a component. Among these, a water-soluble resin or an aqueous emulsion resin is more preferable.

[0282] The aforementioned water-soluble resins have ionic groups such as sulfonyl groups and carboxyl groups, and water-soluble substituents such as hydroxyl groups within their molecules, and dissolve in water. Examples include water-soluble polyacrylamide, water-soluble acrylic resins, water-soluble polyester resins, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral and other polyvinyl alcohol-based resins, water-soluble nylon resins, water-soluble alkyd resins, water-soluble melamine resins, water-soluble urea resins, water-soluble phenol resins, water-soluble epoxy resins, water-soluble polybutadiene resins, water-soluble urethane resins, water-soluble acrylic / styrene resins, water-soluble vinyl acetate / acrylic copolymer resins, water-soluble styrene / maleic acid copolymer resins, water-soluble fluororesins, water-soluble polyisocyanate resins, polystyrene resins, polyvinylpyrrolidone, polyethylene oxide, polyvinyl acetate, carboxymethylcellulose, water-soluble polyether resins and copolymers thereof, as well as natural polymer compounds such as starch, gelatin, casein, gum arabic, chitosan, dextran, and guar gum. Among these, water-soluble acrylic resins and water-soluble polyester resins are more preferred. Water-soluble polyester resins are particularly preferred.

[0283] The aforementioned aqueous emulsion resin refers to a state in which resin particles are dispersed in an aqueous medium, regardless of whether the resin particles are solid or liquid. Examples of resin particles include polyamides, polyimides, low-density polyethylene, high-density polyethylene, poly(meth)acrylic acid esters, polystyrenes such as polystyrene and its derivatives, polyvinyl chloride, phenolic resins, melamine resins, urea resins, epoxy resins, polybutadiene resins, polycarbonates, alkyd resins, fluororesins, vinyl acetate resins, polyisocyanate resins, chlorinated polyolefin resins, and copolymers thereof. Among these, polystyrenes such as poly(meth)acrylic acid esters and polystyrenes and their derivatives are more preferred. Polystyrenes are particularly preferred, and it is preferable that they contain acidic monomer units such as acrylic acid units and methacrylic acid units.

[0284] The aqueous resin is preferably contained in the heat-sensitive colorant at a concentration of 1 to 50% by mass, more preferably at 5 to 40% by mass, and even more preferably at 10 to 30% by mass. If the amount of aqueous resin is less than 1% by mass, the dispersibility of the heat-sensitive colorant itself is poor, which may result in insufficient cohesive force of the heat-sensitive colorant layer film or poor adhesion to the plastic film substrate. If it exceeds 50% by mass, it may result in reduced print density or poor fluidity.

[0285] It is preferable that the heat-sensitive colorant used in the gravure printing process for forming the heat-sensitive color layer contains an alcohol. Examples of alcohols include methanol, ethanol, propyl alcohol, isopropyl alcohol, n-propyl alcohol, 1-butanol, 2-butanol, isobutanol, tert-butanol, ethylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,4-pentanediol, 2,5-hexanediol, 1,6-hexanediol, triethylene glycol, 1-methyl-1,3-butylene glycol, 2-methyl-1,3-butylene glycol, 2,4-diethyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, tripropylene glycol, 1,2-propylene glycol, 2-methyl-1,5-pentanediol, and 2-methyl-1,4-pentanediol. Tandiol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,8-octanediol, 2,2,4-trimethyl-1,6-hexanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether are preferred, with methanol, ethanol, propyl alcohol, isopropyl alcohol, n-propyl alcohol, and propylene glycol monomethyl ether being more preferred.

[0286] The alcohol is preferably contained in the heat-sensitive colorant at a concentration of 1 to 50% by mass, more preferably at 2 to 40% by mass, and even more preferably at 5 to 20% by mass. If the amount of alcohol is less than 1% by mass, it may be difficult to dry and may have poor suitability for high-speed printing, and if it exceeds 50% by mass, it may result in a decrease in print density and poor fluidity.

[0287] A sensitizer can be used in the heat-sensitive colorant used in the gravure printing process for forming the aforementioned heat-sensitive color layer, as needed, and conventionally known sensitizers can be used. For example, fatty acid amides such as stearamide, bis-stearamide, N-hydroxymethyl stearamide, N-stearyl stearamide, ethylenebis-stearamide, methylenebis-stearamide, methylol-stearamide, palmitamide, p-toluenesulfonamide, stearic acid, fatty acid metal salts such as calcium, zinc, or aluminum, behenic acid, palmitic acid, N-stearyl urea, benzyl-2-naphthyl ether, 4-benzyl biphenyl, 2,2'-bis(4-methoxyphenoxy)diethyl ether, α,α'-diphenoxyxylene, bis(4-methoxyphenyl) ether, p-benzyl biphenyl, diphenyl sulfone, benzyl benzyl benzoate, 2-benzyloxynaphthalene, 1,2-bis(p-tri Examples include bis(phenoxy)ethane, 1,2-bis(phenoxy)ethane, 1,2-bis(3-methylphenoxy)ethane, 1,3-bis(phenoxy)propane, dibenzyl oxalate, p-methylbenzyl oxalate, bis(4-methylbenzyl) ester oxalate, bis(4-chlorobenzyl) ester oxalate, diphenyl adipate, dimethyl terephthalate, dibenzyl terephthalate, phenyl benzenesulfonate, bis(4-allyloxyphenyl)sulfone, 1,2-diphenoxyethane, 4-acetylacetophenone, m-terphenyl, 1-hydroxy-2-naphthoic acid, acetoacetate anilides, fatty acid anilides, etc., among which 1,2-bis(3-methylphenoxy)ethane, 1,2-bis(p-tolyloxy)ethane, and 1,2-bis(phenoxy)ethane are more preferred.

[0288] It is preferable that the heat-sensitive colorant used in the gravure printing process for forming the heat-sensitive color layer contains water. The water is not particularly limited, and tap water, well water, distilled water, deionized water, pure water, etc., can be used. Among these, the use of distilled water, deionized water, or pure water is more preferable.

[0289] The water content is the remainder of each of the aforementioned components.

[0290] The thermochromic agent used in the gravure printing process for forming the aforementioned thermochromic layer may optionally contain colorants, inorganic fillers, organic fillers, defoamers, leveling agents, antiblocking agents, pigment dispersants, antistatic agents, slip agents, plasticizers, tackifiers, curing agents, silane coupling agents, waxes, and the like. Any known and commonly used substances can be appropriately selected as long as they do not impair the properties of the thermochromic agent.

[0291] Examples of the aforementioned colorants include amorphous silica, amorphous calcium silicate, heavy calcium carbonate, light calcium carbonate, kaolin, calcined kaolin, diatomaceous earth, talc, titanium dioxide, zinc oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, colloidal silica, polystyrene powder, nylon powder, urea-formaldehyde resin filler, styrene-methacrylic acid copolymer, styrene-butadiene copolymer, and other inorganic or organic pigments such as hollow plastic pigments.

[0292] The method for manufacturing the thermal recording laminate preferably includes a gravure printing step to form a thermal color layer provided by the thermal coloring agent. The thermal coloring agent can be used as is in the gravure printing step, but depending on the coating conditions and coating effect, the process may also include diluting it with a diluting solvent using Zahn Cup #3 (manufactured by Rigosha Co., Ltd.) to adjust it to a desired viscosity. In this case, the viscosity is preferably 10 to 40 seconds at 25°C. If it is less than 10 seconds, it will be easy to move, and if it is greater than 40 seconds, the transferability during printing will be poor.

[0293] The aforementioned diluent can be any solvent that can be used to adjust the viscosity of the heat-sensitive colorant, and examples include organic solvents and water. Commercially available solvents can also be used, and there are no particular restrictions. Examples of commercially available solvents include WA734 solvent (alcohol-based aqueous solvent), WA735 solvent (alcohol-based aqueous solvent), WA736 solvent (alcohol-based aqueous solvent), TA50 solvent (alcohol-based solvent), and TA52 solvent (alcohol-based solvent) (all manufactured by Tokyo Ink Co., Ltd.).

[0294] The thickness of the heat-sensitive color-developing layer is preferably 0.1 to 5 μm, and more preferably 0.2 to 3 μm. If the thickness of the heat-sensitive color-developing layer is less than 0.1 μm, the color density after printing may be insufficient, and if it exceeds 5 μm, blocking may occur.

[0295] The present invention's method for manufacturing a thermal recording laminate preferably includes a coating step of forming a barrier coat layer on the thermal color-developing layer using a barrier coat agent.

[0296] The barrier coating agent used in the coating step for forming the barrier coating layer preferably contains a water-soluble resin, an inorganic layered compound, and water.

[0297] The water-soluble resin used in the barrier coating agent can be the same water-soluble resin as the heat-sensitive coloring agent. Among these, polyvinyl alcohols are more preferred. These water-soluble resins can be used individually or in combination of two or more types.

[0298] The water-soluble resin is preferably contained in the barrier coating agent used in the coating process for forming the barrier coating layer in an amount of 1 to 50% by mass, and more preferably in an amount of 2 to 30% by mass. If the amount of the water-soluble resin is less than 1% by mass, the film-forming ability of the barrier coating layer is poor, and if it exceeds 50% by mass, the fluidity of the barrier coating agent is poor, resulting in poor workability.

[0299] Examples of inorganic layered compounds used in the barrier coating agent include clay minerals such as smectite, kaolin, mica, hydrotalcite, and chlorite (including their synthetic counterparts). Specifically, examples include montmorillonite, beiderite, saponite, hectorite, souconite, stevensite, kaolinite, nacrite, dickite, halloysite, hydrated halloysite, tetrasilicic mica, sodium teniolite, muscovite, margalite, phlogopite, talc, antigorite, chrysotile, pyrophyllite, vermiculite, xanthophyllite, and chlorite. Flake silica can also be used. These can be used individually or in combination of two or more. Among these, smectite is more preferred, and montmorillonite is even more preferred. The presence of inorganic layered compounds suppresses the influence of solvents contained in sealant or sealing layers on the barrier coat layer when these layers are laminated, improving printability and enabling printing with thin films.

[0300] The montmorillonite is preferably one that contains redox metal ions, and conventionally known types can be used in terms of printability and versatility. For example, it can be expressed by the following general formula (6). (X,Y)2~3Z4O 10 (OH)2·mH2O·(W ω ) (6)

[0301] X is Al, Fe(III), or Cr(III). Y is Mg, Fe(II), Mn(II), Ni, Zn, or Li. Z is Si, or Al. W is K, Na, or Ca. H2O is intercalated water. m and ω are positive real numbers. Among these, the one in which W in the general formula (6) is Na is preferred because it cleaves in an aqueous medium.

[0302] The size and shape of the inorganic layered compound are not particularly limited, but the particle size (major axis) is preferably 5 μm or less, more preferably 4 μm or less, and even more preferably 3 μm or less. If the particle size is larger than 5 μm, the dispersibility will be poor, and as a result, the coating properties of the barrier coat layer, the appearance of the film, and the effect of suppressing the solvent's influence on the heat-sensitive coloring layer may be poor. The aspect ratio is preferably 50 to 5000, more preferably 100 to 4000, and even more preferably 200 to 3000. The aspect ratio is defined as [average major axis / average thickness].

[0303] The inorganic layered compound is preferably contained in the barrier coating agent at a concentration of 0.1 to 5% by mass, more preferably at 0.5 to 3% by mass, and even more preferably at 1 to 2% by mass. If the amount of the inorganic layered compound is less than 0.1% by mass, the stain resistance of the heat-sensitive coloring layer is poor, and if it exceeds 5% by mass, the fluidity and transparency of the barrier coating agent are poor.

[0304] It is preferable that the barrier coating agent contains water. The water is not particularly limited, and tap water, well water, distilled water, ion-exchanged water, pure water, etc. may be used. It may also contain solvents commonly used in gravure inks. For example, aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane; alcoholic solvents such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, 1-butanol, 2-butanol, isobutanol, and tert-butanol; esteric solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, and tert-butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, and ethylene glycol Examples of glycol ether solvents include toluene monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether, as well as their esterified products. As esterified products, acetate-formed products are mainly selected, such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Among these, toluene, ethyl acetate, n-propyl acetate, isopropyl alcohol, propylene glycol monomethyl ether, and methyl ethyl ketone are more preferred from the viewpoint of printability and versatility. These can be used individually or in combination of two or more.

[0305] The water is preferably contained in the barrier coating agent at a concentration of 50-90% by mass, more preferably at 60-80% by mass, and even more preferably at 70-80% by mass. If the amount of water is less than 50% by mass, the viscosity increases, resulting in poor workability and printability. If it exceeds 90% by mass, wetting during printing becomes poor.

[0306] The barrier coating agent may optionally contain colorants, inorganic fillers, organic fillers, defoamers, leveling agents, antiblocking agents, pigment dispersants, antistatic agents, slip agents, plasticizers, tackifiers, curing agents, silane coupling agents, waxes, and the like. Any known and commonly used substances can be appropriately selected as long as they do not impair the properties of the barrier coating agent.

[0307] The coating step for forming the barrier coating layer provided by the barrier coating agent is preferably a gravure printing step. The barrier coating agent can be used directly in the gravure printing step, but depending on the coating conditions and coating effect, a step of diluting it with a diluent solvent using Zahn Cup #3 (manufactured by Rigosha Co., Ltd.) may be included, and it can be used after adjusting to the desired viscosity. In this case, the viscosity is preferably 10 to 40 seconds at 25°C. If it is less than 10 seconds, it will be easy to move, and if it is greater than 40 seconds, the transferability during printing will be poor.

[0308] The aforementioned diluent can be any solvent that can be used to adjust the viscosity of the barrier coating agent, and examples include organic solvents and water. Commercially available solvents can also be used, and there are no particular restrictions. Examples of commercially available solvents include WA734 solvent (alcohol-based aqueous solvent), WA735 solvent (alcohol-based aqueous solvent), WA736 solvent (alcohol-based aqueous solvent), TA50 solvent (alcohol-based solvent), and TA52 solvent (alcohol-based solvent) (all manufactured by Tokyo Ink Co., Ltd.).

[0309] The thickness of the barrier coating layer formed by the barrier coating agent is preferably 0.01 to 2 μm, more preferably 0.05 to 1.4 μm, and even more preferably 0.1 to 1.2 μm. If the thickness of the barrier coating layer is less than 0.01 μm, the film-forming ability of the barrier coating layer is poor, and if it exceeds 2 μm, it may be difficult to dry and may have poor suitability for high-speed printing.

[0310] The method for manufacturing the thermal recording laminate preferably further comprises a lamination step of forming a sealant layer on the barrier coat layer or a coating step of forming a seal layer.

[0311] The lamination process for forming the sealant layer can be appropriately selected depending on the substrate, application, and structure, as long as sufficient seal strength can be ensured. For example, lamination processes with heat-sealable laminates or known sealant films (dry lamination, non-solvent lamination, wet lamination), heat lamination (thermal lamination), and resin coating by extrusion lamination (extrusion lamination, co-extrusion lamination, PE sandwich lamination) can be preferably used.

[0312] Examples of resins that can be used in the extrusion lamination process and co-extrusion lamination process include polyethylene resins such as LDPE, LLDPE, and HDPE; polypropylene resins (homopolypropylene, random polypropylene, etc.); ethylene-vinyl acetate copolymers; ionomer resins; ethylene-acrylic acid copolymers; ethylene-ethyl acrylate copolymers; ethylene-methyl acrylate copolymers; ethylene-methacrylic acid copolymers; ethylene-methyl methacrylate copolymers; ethylene-propylene copolymers; methylpentene polymers; acid-modified polyolefin resins obtained by modifying polyethylene or polypropylene with maleic acid or fumaric acid; polystyrene resins (general-purpose polystyrene (GPPS), high-impact polystyrene (HIPS), expanded polystyrene (PSP), heat-resistant PSP, etc.); and thermoplastic resins such as polybutylene terephthalate resin. These resins can be used individually or in mixtures of two or more. In the extrusion lamination process, a thickness of 1 to 100 μm is preferred.

[0313] When adhesives are used in the dry lamination and non-solvent lamination processes, commercially available adhesives are acceptable. Examples include two-component or one-component urethane resin adhesives, acrylic, epoxy, polyester, polyethyleneimine, polybutadiene, water-based urethane, isocyanate, organotitanium, starch-based water-soluble adhesives, and water-based adhesives such as vinyl acetate emulsion. Known application processes can be used for the adhesive application, such as roll coaters, reverse roll coaters, gravure coaters, microgravure coaters, knife coaters, bar coaters, wire bar coaters, die coaters, and dip coaters. There are no particular restrictions on the thickness of the adhesive, but a range of 0.001 to 10 μm is preferred, and a range of 0.01 to 5 μm is particularly preferred.

[0314] The coating process for forming the sealing layer includes coating processes for heat sealants and hot melt agents. These processes can be used individually or in combination to manufacture the laminate.

[0315] The thickness of the sealant layer formed by the lamination process is not particularly limited, but it is preferably 2 to 200 μm for sealant films and 1 to 100 μm for resin coatings formed by the extrusion lamination process. The seal layer formed by the coating process is preferably 0.01 to 30 μm for heat sealant coatings and 1 to 50 μm for hot melt coatings.

[0316] Examples of the sealant film include polyolefin films such as polyethylene, polypropylene, ethylene-vinyl acetate, and copolymers thereof, as well as co-extruded and colored films thereof, polystyrene films, polyacrylonitrile films, and ethylene-vinyl alcohol resin films. The film may be stretched or unstretched, and one or more types may be laminated.

[0317] Examples of resins used in the coating process for forming a seal layer include thermoplastic resins such as vinylidene chloride, shellacs, rosins, rosin-modified maleic acid resins, rosin-modified phenolic resins, nitrated cotton, cellulose acetate, cellulose acetylpropionate, cellulose acetyl butyrate, chlorinated rubber, cyclic rubber, polyamide resins, vinyl chloride-vinyl acetate copolymers, polyester resins, ketone resins, butyral resins, chlorinated polypropylene resins, chlorinated polyethylene resins, chlorinated ethylene vinyl acetate resins, ethylene vinyl acetate resins, (meth)acrylic resins, urethane resins, ethylene-vinyl alcohol resins, styrene maleic acid resins, casein, and alkyd resins. These can be used individually or in combination of two or more types. These resins can be dissolved in a solvent, or dispersed in water as acrylic emulsions, urethane emulsions, ethylene-vinyl alcohol emulsions, polyethylene emulsions, polypropylene emulsions, or ethylene vinyl acetate emulsions.

[0318] The thermal recording laminate produced by the manufacturing method of the present invention can be used to produce printed materials by using a laser printer (for example, FP-1000, manufactured by Keyence Corporation) to colorize the thermal coloring layer. Regarding the color intensity, a heat sealer (manufactured by Tester Industries Co., Ltd.) is used to color the thermal recording laminate, L * a * b * The color density can be evaluated by the L value, which is measured according to the method specified in the color system (CIE1976). A lower L value indicates higher blackness and is considered to be of better quality. Instruments that can be used to measure color density include reflectance meters, spectrophotometers, and spectrophotometers. For example, the portable spectrophotometer eXact 2 (manufactured by X-Rite) is one such instrument.

[0319] The step of preparing the aforementioned plastic film substrate is preferably a step of preparing at least one selected from plastic films or sheets and laminates thereof. Examples include polyester films such as polyethylene terephthalate (PET), polyethylene naphthalate, and polybutylene terephthalate; polyolefin films such as polyethylene, polypropylene, and ethylene-vinyl acetate (e.g., films for body wrap labels); polystyrene films; alcohol-based films such as ethylene-vinyl alcohol and polyvinyl alcohol; polyamide films or barrier polyamide films with a barrier layer in the middle; polycarbonate films; polyacrylonitrile films; polyimide films; cellophane; moisture-proof cellophane; transparent vapor-deposited polyester films or transparent vapor-deposited polyamide films having a vapor-deposited layer of alumina or silica on a PET film or polyamide film; various coated films coated with polyvinylidene chloride resin, polyvinyl alcohol resin, polyacrylic acid resin, etc.; co-extruded films of PET and nylon; polylactic acid films; and heat-shrinkable films (e.g., shrink films). These may be stretched or unstretched, and the step may involve preparing one or more types laminated together. Appropriate materials can be selected considering mechanical strength and dimensional stability. Furthermore, to improve the adhesion of the anchor coat layer and laminate layer to the surface, corona treatment, low-temperature plasma treatment, flame treatment, solvent treatment, or coating treatment can be applied, or pre-treated materials can be selected and prepared. Among these, PET film, polypropylene film, polyamide film, coated film, transparent vapor-deposited polyester film or transparent vapor-deposited polyamide film, and co-extruded film are preferred. The thickness of the plastic film substrate is not particularly limited as long as it does not impede printability or winding suitability, but 5 to 300 μm is preferred, and 6 to 250 μm is more preferred.

[0320] The process of forming the base layer provided by the primer, the heat-sensitive color-developing layer provided by the heat-sensitive color-developing agent, and the barrier coat layer provided by the barrier coat agent on one of the plastic film substrates is preferably a gravure printing process, and more preferably a gravure printing process using a multi-color gravure printing machine. Since it can be created by a gravure printing process, each layer can be formed over the entire surface, but it is also easy to form each layer partially.

[0321] The method for manufacturing the thermal recording laminate of the present invention may include a gravure printing step for forming a pattern layer. The pattern layer may be formed over the entire surface or on a portion of it, or it may be formed using halftones. However, it is preferable to avoid the step of forming the pattern layer between the thermal coloring layer and the barrier coat layer, as this may cause the thermal coloring layer to become stained. The aforementioned pattern layer is typically formed using a color printing ink composition commonly used in gravure printing, and is a layer on which patterns, text, or other images are printed.

[0322] The packaging material and label according to the embodiment of the present invention are preferably made using the laminate, and the packaging material may be a packaging bag, a lid, or the like.

[0323] The laminate that will become the packaging bag may be composed of a plastic film substrate / underlayment / thermal coloring layer / barrier coat layer / sealant layer, a plastic film substrate / underlayment / thermal coloring layer / barrier coat layer / seal layer, a plastic film substrate / pattern layer / underlayment / thermal coloring layer / barrier coat layer / sealant layer, a plastic film substrate / pattern layer / underlayment / thermal coloring layer / barrier coat layer / seal layer, a plastic film substrate / pattern layer / underlayment / pattern layer / thermal coloring layer / barrier coat layer / sealant layer, a plastic film substrate / pattern layer / underlayment / pattern layer / thermal coloring layer / barrier coat layer / seal layer, a plastic film substrate / underlayment / thermal coloring layer / barrier coat layer / pattern layer / sealant layer, a plastic film substrate / underlayment / thermal coloring layer / barrier coat layer / pattern layer / sealant layer, or the like. The packaging bag may be any of the well-known forms, such as two-side seals, three-side seals, four-side seals, pillow seals, standing pouches, envelope seals, gussets, or heat-sealed seals.

[0324] The lid material may be any of the well-known forms such as a cover, lid, or cap. The laminate that serves as the lid material may be composed of a plastic film substrate / underlayment / thermochromic layer / barrier coat layer / sealant layer, a plastic film substrate / underlayment / thermochromic layer / barrier coat layer / seal layer, a plastic film substrate / pattern layer / underlayment / thermochromic layer / barrier coat layer / sealant layer, a plastic film substrate / pattern layer / underlayment / thermochromic layer / barrier coat layer / seal layer, a plastic film substrate / pattern layer / underlayment / pattern layer / thermochromic layer / barrier coat layer / sealant layer, a plastic film substrate / pattern layer / underlayment / pattern layer / thermochromic layer / barrier coat layer / sealant layer, a plastic film substrate / underlayment / thermochromic layer / barrier coat layer / pattern layer / sealant layer, a plastic film substrate / underlayment / thermochromic layer / barrier coat layer / pattern layer / sealant layer, or the like.

[0325] Furthermore, it is preferable that the container be sealed by making close contact with it. This sealing can be done manually, or by using machinery such as an automatic sealing device. The appropriate method can be selected depending on the type, form, size, and quantity of food, the container to be sealed, the equipment, and the environment. This can be done by heat sealing (heat pressure sealing), surface sealing, or by using adhesives or bonding agents. The container is more preferably a cylindrical container with a bottom. In this case, it is preferable that the lid material covers the opening of the cylindrical container with a bottom and seals it, and it is even more preferable that the seal is made by heat sealing. Examples of resins used in the aforementioned containers include thermoplastic resins such as polyethylene, polypropylene, polyethylene terephthalate, polyvinyl chloride, polystyrene, and polyacrylonitrile.

[0326] The aforementioned label can also be formed by forming an adhesive layer or bonding layer on a plastic film substrate on the other side of which a sealant layer or sealing layer has been formed on a barrier coat layer, and further forming a release layer. The adhesive layer or bonding layer can be any material that adheres closely to the plastic film substrate and the release layer, and allows the release layer to be easily peeled off, such as a rubber-based adhesive material or an acrylic resin-based adhesive material. The release layer can be any material such as polyethylene film, polyester film, or paper (release paper). The laminate that forms the label consists of an adhesive layer / plastic film substrate / underlayment / thermochromic layer / barrier coat layer / sealant layer, an adhesive layer / plastic film substrate / underlayment / thermochromic layer / barrier coat layer / seal layer, a hot melt layer / plastic film substrate / underlayment / thermochromic layer / barrier coat layer / sealant layer, a hot melt layer / plastic film substrate / underlayment / thermochromic layer / barrier coat layer / seal layer, an adhesive layer / plastic film substrate / pattern layer / underlayment / thermochromic layer / barrier coat layer / sealant layer, an adhesive layer / plastic film substrate / underlayment / thermochromic layer / barrier coat layer / sealant layer, an adhesive layer / plastic film substrate / pattern layer / underlayment / thermochromic layer / barrier coat layer / seal layer, an adhesive layer / plastic film substrate / pattern layer / underlayment / thermochromic layer / barrier coat layer / seal layer, an adhesive layer / plastic It may also be a stick film substrate / underlay / pattern layer / thermal color layer / barrier coat layer / seal layer, adhesive layer / plastic film substrate / underlay / thermal color layer / barrier coat layer / pattern layer / seal layer, hot melt layer / plastic film substrate / pattern layer / underlay / thermal color layer / barrier coat layer / sealant layer, hot melt layer / plastic film substrate / underlay / thermal color layer / barrier coat layer / sealant layer, hot melt layer / plastic film substrate / underlay / thermal color layer / barrier coat layer / pattern layer / sealant layer, hot melt layer / plastic film substrate / pattern layer / underlay / thermal color layer / barrier coat layer / seal layer, hot melt layer / plastic film substrate / underlay / thermal color layer / barrier coat layer / pattern layer, hot melt layer / plastic film substrate / underlay / thermal color layer / barrier coat layer / pattern layer, etc. [Examples]

[0327] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these. In the examples and comparative examples, "parts" refers to parts by mass, and "%" refers to weight percent.

[0328] [Preparation of heat-sensitive colorants] Manufacturing Example 1 (Preparation of Chromogen Dispersion) 30 parts of N,N'-di-3-(p-toluenesulfonyl)oxy)phenylurea, 30 parts of aqueous resin (Hyros M-141, aqueous acrylic emulsion resin, manufactured by Seikoh PMC Co., Ltd.), 20 parts of methanol, and 20 parts of water were added, mixed, and dispersed to prepare Agent A1. Agents A2 to A10 were prepared in the same manner as Agent A1, according to the formulations in Table 1.

[0329] [Table 1]

[0330] Production example 21 (leuco dye dispersion) 30 parts of leuco dye (3-dibutylamino-6-methyl-7-anilinofluorane, manufactured by Yamamoto Kasei Co., Ltd.), 40 parts of aqueous resin (Pluscoat RZ-570, water-soluble polyester resin, manufactured by Go-o Chemical Industry Co., Ltd.), 15 parts of isopropyl alcohol, and 15 parts of water were added and stirred to prepare Agent B1. Agents B2 to B5 were prepared in the same manner as Agent B1, according to the formulations in Table 2.

[0331] [Table 2]

[0332] The materials used were as follows: JONCRYL PDX7741, water-based acrylic emulsion resin, manufactured by BASF. JONCRYL PDX7779, water-based acrylic emulsion resin, manufactured by BASF. JONCRYL PDX7326, water-based acrylic emulsion resin, manufactured by BASF. JONCRYL HPD-96J, water-soluble acrylic resin, manufactured by BASF. JONCRYL HPD-196, water-soluble acrylic resin, manufactured by BASF. JONCRYL PDX7356, water-based acrylic emulsion resin, manufactured by BASF. 1,3-Bis-(3-[3-phenylureido]phenyloxysulfonyl)benzene, color developer N-[2-(3-phenylureido)phenyl]benzenesulfonamide, color developer Np-toluenesulfonyl-N'-3-(p-toluenesulfonyloxy)phenylurea, color developer

[0333] Manufacturing Example 31 (Preparation of Thermochromic Agent) Next, 70 parts of Agent A1 and 30 parts of Agent B1 were mixed to prepare Thermochromic Agent 1. Thermochromic Agents 2 to 14 were prepared in the same manner as Thermochromic Agent 1, according to the formulations shown in Tables 3 and 4.

[0334] [Table 3]

[0335] [Table 4]

[0336] Manufacturing Example 51 (Preparation of White Ink) White ink 1 was prepared by adding 6 parts of LG-FK R medium A (hydroxyl group-containing vinyl acetate copolymer solution, 18% solids, manufactured by Tokyo Ink Co., Ltd.), 29 parts of LAMREK R medium (urethane resin solution, 15% solids, manufactured by Tokyo Ink Co., Ltd.), 32 parts of titanium dioxide (JR-805, D50 average particle size 0.29 μm, manufactured by Teika Co., Ltd.), 11 parts of ethyl acetate, 16 parts of n-propyl acetate, 6 parts of isopropyl alcohol, and 100 parts of ceramic beads, and dispersing them in a paint shaker for 1 hour.

[0337] [Table 5]

[0338] Manufacturing Example 61 (Preparation of Anchor Coating Agent) Anchor coating agent 1 was prepared by adding 45 parts of LG-FK R medium A (hydroxyl group-containing vinyl chloride copolymer solution, 18% solids, manufactured by Tokyo Ink Co., Ltd.), 8 parts of LAMREK R medium (urethane resin solution, 15% solids, manufactured by Tokyo Ink Co., Ltd.), 30 parts of propylene glycol monomethyl ether, and 17 parts of n-propyl acetate, and stirring. Anchor coating agent 2 was prepared in the same manner as anchor coating agent 1, according to the formulation in Table 6. Furthermore, the anchor coating agent 2 is similar to the coating liquid for the undercoat layer in Example 1 of Patent Document 4.

[0339] [Table 6]

[0340] Manufacturing Example 71 (Preparation of Barrier Coating Agent) Barrier coating agent 1 was prepared by adding 31 parts of a 10% polyvinyl alcohol aqueous solution (manufactured by Nippon Vinegar & Polyvinyl Alcohol Co., Ltd.), 2 parts of montmorillonite (Kunipia F, manufactured by Kunimine Industries Co., Ltd.), 8 parts of n-propyl alcohol, 9 parts of isopropyl alcohol, and 50 parts of water, stirring, and then dispersing using a nanomill. Barrier coating agents 2 to 5 were prepared in the same manner as barrier coating agent 1, according to the formulations in Table 7. Barrier coating agent 2 does not contain montmorillonite. Barrier coating agent 3 is similar to protective layer coating liquid 1 of Example 1 in Patent Document 1. Barrier coating agent 4 is similar to protective layer coating liquid of Example 6 in Patent Document 2. Barrier coating agent 5 is similar to protective layer coating liquid 1 of Example 21 in Patent Document 3.

[0341] [Table 7]

[0342] The materials used were as follows: Sma-Tex PA-9159: Styrene-butadiene copolymer latex aqueous dispersion (synthetic rubber), solids content 47.5%, manufactured by Nippon A&L Co., Ltd. Poval 3-98: Fully saponified polyvinyl alcohol, solids content 94.0% or more, Kuraray Co., Ltd. Microsphere M-600: Polymethyl methacrylate hollow particle microbeads, manufactured by Matsumoto Oil & Fat Pharmaceutical Co., Ltd. ASN1004K: Acrylic resin emulsion, 18% solids content, manufactured by Mitsui Chemicals, Inc. NeoCryl A-1125: Acrylic resin emulsion, 19.5% solids content, manufactured by DSM Coating Resin.

[0343] [Fabrication of thermal recording laminates] <Example 1> Using a 5-color gravure printing press, a 12μm thick double-treated PET film (E-5202, abbreviated as double-treated PET, manufactured by Toyobo Co., Ltd.) was printed on one side with the first unit to a film thickness of 1μm, with the second unit to a film thickness of 2μm for the thermal colorant 1, and with the third unit to a film thickness of 1μm for the barrier coating agent 1, and then wound up. At this time, the white ink 1 was diluted with SL9170 (non-toluene solvent, manufactured by Tokyo Ink Co., Ltd.), the thermal colorant 1 with WA734 (alcohol-based water solvent, manufactured by Tokyo Ink Co., Ltd.), and the barrier coating agent 1 with water, and the viscosity was adjusted to 17 seconds using a Zahn cup No. 3. Furthermore, using a dry laminating machine, Takelac A-525 / Takenate A-52 (abbreviated as DL, manufactured by Mitsui Chemicals, Inc.) and ZK207 (abbreviated as RetoCP, manufactured by Toray Film Processing Co., Ltd.), a 60 μm thick unoriented polypropylene film for retort processing, were laminated together. After aging at 40°C for 72 hours, a thermal recording laminate 1 consisting of both treated PET / white ink 1 / thermal coloring agent 1 / barrier coating agent 1 / RetoCP was obtained.

[0344] As shown in Table 8, thermal recording laminates 2 to 14 (Examples 2 to 14) were obtained in the same manner as in Example 1.

[0345] <Example 15> Furthermore, using a 5-color gravure printing press, a 12 μm thick double-treated PET film (E-5202, abbreviated as double-treated PET, manufactured by Toyobo Co., Ltd.) was printed on one side with the first unit to a film thickness of 1.1 μm, the second unit to a film thickness of 2 μm for the heat-sensitive colorant 1, and the third unit to a film thickness of 1 μm for the barrier coating agent 1, and then wound up. At this time, the anchor coating agent 1 was diluted with SL9170 (non-toluene solvent, manufactured by Tokyo Ink Co., Ltd.), the heat-sensitive colorant 1 with WA734 (alcohol-based water solvent, manufactured by Tokyo Ink Co., Ltd.), and the barrier coating agent 1 with water, and the viscosity was adjusted to 17 seconds using a Zahn cup No. 3. Furthermore, using a dry laminating machine, Takelac A-525 / Takenate A-52 (abbreviated as DL, manufactured by Mitsui Chemicals, Inc.) and ZK207 (abbreviated as RetoCP, manufactured by Toray Film Processing Co., Ltd.), a 60 μm thick unoriented polypropylene film for retort processing, were laminated together. After aging at 40°C for 72 hours, a thermal recording laminate 15 was obtained consisting of both treated PET / anchor coating agent 1 / thermochromic coloring agent 1 / barrier coating agent 1 / RetoCP.

[0346] As shown in Tables 9 to 10, thermal recording laminates 16 to 31 (Examples 16 to 31) were obtained in the same manner as in Example 15.

[0347] The following plastic film substrates were used: Transparent vapor-deposited PET film, Barrierox 1011HG-CR, 12μm thickness, manufactured by Toray Film Processing Co., Ltd., abbreviation: Transparent vapor-deposited PET (printed on the vapor-deposited surface) OPP film, OP U-2, 20μm thickness, manufactured by Mitsui Chemicals Tohcello Co., Ltd., abbreviation: OPP Double-treated nylon film, ONMB, 15μm thickness, manufactured by Unitika Ltd., abbreviation: Double-treated NY

[0348] [Table 8]

[0349] [Table 9]

[0350] [Table 10]

[0351] As shown in Table 11, a thermal recording laminate 32 (Comparative Example 1) was obtained in the same manner as in Example 1, except that the base coat was not printed. Furthermore, a thermal recording laminate 33 (Comparative Example 2) was obtained in the same manner as in Example 15, with barrier coat agent 1 replaced by barrier coat agent 2. In addition, a thermal recording laminate 34 (Comparative Example 3) similar to Example 1 of Patent Document 1 was obtained. Furthermore, a thermal recording laminate 35 (Comparative Example 4) similar to Example 6 of Patent Document 2 was obtained. Furthermore, a thermal recording laminate 36 (Comparative Example 5) similar to Example 21 of Patent Document 3 was obtained. Furthermore, a thermal recording laminate 37 (Comparative Example 6) similar to Example 1 of Patent Document 4 was obtained.

[0352] [Table 11]

[0353] For the thermal recording laminate, stain resistance, blocking, transparency, residual solvent, and, for the thermal recording laminate after lamination, color density and lamination strength were evaluated and are shown in Tables 8 to 11.

[0354] <Stain resistance> For thermal recording laminates, the degree of blackening of the coated layer (undercoat layer, thermal coloring layer, barrier coat layer; hereinafter collectively referred to as "coated layer") immediately after fabrication was evaluated. The evaluation was performed visually by five observers. A coating layer that was not blackened (little blackening) was judged to be good. For resistance to soiling, it was evaluated on a four-point scale: ◎: All five judged that there was no blackening, ○: Three judged that there was no blackening, △: Three or more judged that there was slight blackening (no practical problem), ×: All five judged that there was blackening.

[0355] <Blocking> For the same thermal recording laminate described above as having <stain resistance>, two pieces were prepared by cutting them to a size of 3 cm x 3 cm immediately after fabrication. These were then stacked with the coated layer side and the plastic film substrate side facing each other, and tested at 50°C for 24 hours at 5 N / cm². 2 After applying the load, the delamination state and delamination resistance were evaluated when the overlapping portion between the coated layer surface and the plastic film substrate surface was separated. A sample that peeled off without resistance and showed no delamination was judged as good. Blocking was evaluated in two stages: ○: peeled off without resistance and no delamination; ×: high resistance during peeling and delamination observed.

[0356] <Transparency> For the same thermal recording laminate described above as <Stain Resistance>, three pieces were prepared, each cut to a size of 2cm x 3cm immediately after fabrication. Using HAZE GARD II (manufactured by Toyo Seiki Seisakusho Co., Ltd.), the haze value of the coated layer surface was measured, and the average value was evaluated as transparency. A lower haze value was judged to be good. Transparency was evaluated in three stages: ○: haze value less than 45, △: haze value between 45 and 70, ×: haze value of 70 or more.

[0357] <Residual solvent> For the same thermal recording laminate described above as <resistance to soil staining>, after 24 hours at room temperature following fabrication, 0.1m 2 The sample was cut into specimens, placed in vials, preheated at 80°C for 30 minutes, and the headspace was analyzed using a gas chromatograph-mass spectrometer (HS-20, detector: TCD type, manufactured by Shimadzu Corporation) to quantify the residual solvent. Samples with low residual solvent levels were considered good. Regarding residual solvent, ○: 5 mg / m² 2 Less than △ = 5-10 mg / m² 2 Less than 10 mg / m² 2 The evaluation was based on the three stages described above.

[0358] <Color intensity> After lamination, the thermal recording laminate was stored in a 40°C constant temperature bath for 24 hours, and then sealed using a heat sealer (manufactured by Tester Industries Co., Ltd.) at 150°C with a printing pressure of 2 kgf / cm². 2The L value was measured using a portable spectrophotometer eXact 2 (manufactured by X-Rite) when color was developed under the condition of a printing pressure time of 0.5 seconds, and this was used as the color development density. A lower L value (higher blackness) was judged to be good. The color development density was evaluated on a three-point scale: ○: L value less than 20, △: L value between 20 and 40, ×: L value 40 or higher.

[0359] <Lamination Strength> The laminated thermal recording laminate was cut into 15mm wide strips to form test specimens. These specimens were tested using a universal tensile testing machine (RTE-1210, manufactured by Orientec Co., Ltd.) under T-type peeling conditions at a tensile speed of 300mm / min. The maximum load at the time of peeling was measured as the laminate strength. A higher laminate strength indicated better lamination. The laminate strength was evaluated in three stages: ○: 80g or more, △: 50g or more, less than 80g, and ×: less than 50g.

[0360] Tables 8 to 11 clearly show that the thermal recording laminates of Examples 1 to 31 have good stain resistance, blocking, transparency, color density, and laminate strength. On the other hand, the thermal recording laminate 32 of Comparative Example 1, which lacks a base layer, clearly exhibits inferior stain resistance, blocking, and lamination strength. The thermal recording laminate 33 of Comparative Example 2, which uses a barrier coating agent that does not contain an inorganic layered compound, clearly exhibits inferior stain resistance. It is clear that the thermal recording laminate 34 of Comparative Example 3, which is similar to Patent Document 1, has inferior blocking, residual solvent, and laminate strength. It is clear that the thermal recording laminate 35 of Comparative Example 4, which is similar to Patent Document 2, has inferior blocking, residual solvent, and laminate strength. It is clear that the thermal recording laminate 36 of Comparative Example 5, which is similar to Patent Document 3, has inferior blocking, residual solvent, and laminate strength. It is clear that the thermal recording laminate 37 of Comparative Example 6, which is similar to Patent Document 4, has inferior blocking, transparency, residual solvent, and laminate strength.

Claims

1. A base layer consisting of a primer containing a resin and an organic solvent is provided on one side of the plastic film substrate. On the aforementioned base layer, a heat-sensitive coloring layer is provided, comprising a leuco dye, at least one color developer from among the compounds represented by the following general formula (1), the compounds represented by the following general formula (2), the compounds represented by the following general formula (3), and the compounds represented by the following general formula (4), an aqueous resin, an alcohol, and water. A thermal recording laminate characterized by having a barrier coat layer on the thermal color-developing layer, the barrier coat layer comprising a water-soluble resin, an inorganic layered compound, and a barrier coat agent containing water. 【Chemistry 1】 (R １ R is a linear, branched, or alicyclic alkyl group having 1 to 12 carbon atoms, an unsubstituted or C1 to 12 alkyl group, a C1 to 12 alkoxy group, a C6 to 12 aryl group, or a C7 to 12 aralkyl group substituted with a halogen atom, or an unsubstituted or C1 to 12 alkyl group, a C1 to 12 alkoxy group, a C6 to 12 aryl group, or a C6 to 12 aryl group substituted with a halogen atom, and each may be the same or different. ２ Z is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and these may be the same or different. １ (This is a sulfonyloxy group, a sulfonyl group, or a sulfonamide group.) 【Chemistry 2】 (R ３ This includes C1-C12 alkyl groups, C2-C12 alkenyl groups, C3-C12 alkyloxyalkyl groups, C3-C12 polyoxyalkylene alkyl groups, C7-C12 aralkyl groups, C6-C14 aryl groups, C1-C12 alkylsulfanyl groups, C7-C12 aralkylsulfanyl groups, C6-C14 arylsulfanyl groups, C1-C12 alkylsulfonyl groups, C7-C12 aralkylsulfonyl groups, and C6-C15 arylsulfonyl groups. A honyl group, a C7-C12 aralkylsulfonylamino group, a C6-C15 arylsulfonylamino group, a C2-C10 acyl group, a C2-C10 acylamino group, a C2-C10 acyloxycarbonylamino group, a C1-C12 alkyloxycarbonylamino group, an aralkyloxycarbonylamino group, a C7-C12 aralkyloxycarbonylamino group, or a C6-C15 aryloxycarbonylamino group, with two adjacent R groups. ３ They may bond to each other and form an aromatic or non-aromatic ring with the carbon atoms to which they are bonded, R ４ , R ５ a is a hydrogen atom or a methyl group, a, b, and c are independently integers from 0 to 4, a + c is an integer from 0 to 5, n is 0 or 1, Y is a divalent organic group, and Z ２ (This is a sulfonyloxy group or a sulfonyl group.) 【Transformation 3】 (R ６ is a linear, branched or alicyclic alkyl group having 1 to 12 carbon atoms, an unsubstituted or alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms substituted with a halogen atom, or an unsubstituted or aryl group having 6 to 12 carbon atoms substituted with an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or a halogen atom, and R ７ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, l and m are 0 or 1, and Z ３ is a sulfonyloxy group, a sulfonyl group or a sulfonamide group.) 【Chemistry 4】 (R ８ R is a linear, branched, or alicyclic alkyl group having 1 to 12 carbon atoms, an unsubstituted or C1 to 12 alkyl group, a C1 to 12 alkoxy group, a C6 to 12 aryl group, or a C7 to 12 aralkyl group substituted with a halogen atom, or an unsubstituted or C1 to 12 alkyl group, a C1 to 12 alkoxy group, a C6 to 12 aryl group, or a C6 to 12 aryl group substituted with a halogen atom, and each may be the same or different. ９ is a methyl group, d is an integer from 0 to 4, and Z ４ and Z ５ (These are a sulfonyloxy group, a sulfonyl group, or a sulfonamide group, and may be the same or different.)

2. A base layer consisting of a primer containing a resin and an organic solvent is provided on one side of the plastic film substrate. On the aforementioned base layer, a heat-sensitive coloring layer is provided, comprising a heat-sensitive coloring agent containing a leuco dye, a compound represented by the following general formula (5), an aqueous resin, an alcohol, and water. A thermal recording laminate characterized by having a barrier coat layer on the thermal color-developing layer, the barrier coat layer comprising a water-soluble resin, an inorganic layered compound, and a barrier coat agent containing water. 【Transformation 5】 (R １０ These are linear, branched, or alicyclic alkyl groups having 1 to 12 carbon atoms, unsubstituted or alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, aryl groups having 6 to 12 carbon atoms, or aralkyl groups having 7 to 12 carbon atoms substituted with a halogen atom, or unsubstituted or alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, or aryl groups having 6 to 12 carbon atoms substituted with a halogen atom, and these may be the same or different.

3. The thermal recording laminate according to claim 1 or 2, characterized in that the inorganic layered compound is montmorillonite.

4. The thermal recording laminate according to claim 1 or 2, characterized in that the resin of the primer is at least one resin selected from vinyl chloride / vinyl acetate copolymer and polyurethane resin.

5. Furthermore, the thermal recording laminate according to claim 1 or 2 is characterized by having a sealant layer or a sealing layer on the barrier coat layer.

6. A packaging material characterized by using the thermal recording laminate described in claim 5.

7. A label characterized by being made using the thermal recording laminate described in claim 1 or 2.

8. A label characterized by being made using the thermal recording laminate described in claim 5.

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