WO2023190314A1 - Heat-sensitive recording body - Google Patents

Heat-sensitive recording body Download PDF

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Publication number
WO2023190314A1
WO2023190314A1 PCT/JP2023/012159 JP2023012159W WO2023190314A1 WO 2023190314 A1 WO2023190314 A1 WO 2023190314A1 JP 2023012159 W JP2023012159 W JP 2023012159W WO 2023190314 A1 WO2023190314 A1 WO 2023190314A1
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WO
WIPO (PCT)
Prior art keywords
heat
sensitive recording
ethylene
parts
resin
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PCT/JP2023/012159
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French (fr)
Japanese (ja)
Inventor
達朗 越
佳美 緑川
健二 平井
Original Assignee
日本製紙株式会社
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Application filed by 日本製紙株式会社 filed Critical 日本製紙株式会社
Priority to JP2023544159A priority Critical patent/JP7354483B1/en
Publication of WO2023190314A1 publication Critical patent/WO2023190314A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/323—Organic colour formers, e.g. leuco dyes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography

Definitions

  • the present invention relates to a heat-sensitive recording material having water vapor barrier properties on the back surface.
  • a thermal recording material contains a colorless or light-colored electron-donating leuco dye (hereinafter also referred to as “leuco dye”) and an electron-accepting color developer (hereinafter also referred to as “color developer”).
  • a heat-sensitive recording layer is provided by applying a coating liquid to a support such as paper, synthetic paper, film, or plastic, and instant chemical recording is performed by heating with a thermal head, hot stamp, thermal pen, laser beam, etc. Color develops due to the reaction, and a recorded image is obtained.
  • Thermosensitive recording media are widely used as recording media for facsimiles, computer terminal printers, automatic ticket vending machines, measurement recorders, receipts at supermarkets, convenience stores, etc.
  • Patent Document 1 In order to obtain good water resistance, heat-sensitive recording materials are known that are provided with a back coat layer containing an adhesive such as polyvinyl alcohol (Patent Document 1, etc.). Furthermore, it is known that paper base materials containing ethylene copolymerized polyvinyl alcohol or ethylene/acrylic copolymers have water vapor barrier properties (Patent Documents 2 to 4, etc.).
  • the thermal head becomes hot. If printing continues at high temperatures for a long time, the moisture in the thermal recording material will evaporate, causing the thermal head to become hot. There was a problem in that water droplets were generated from the back side that was not in contact, causing equipment failure. Therefore, the present invention provides a heat-sensitive recording material having water vapor barrier properties against moisture in the heat-sensitive recording material.
  • a heat-sensitive recording layer is provided on the support of a heat-sensitive recording medium, and a back coat layer is provided on the opposite side of the heat-sensitive recording layer.
  • the present invention was completed based on the discovery that the above-mentioned problems can be solved by incorporating an ethylene-acrylic copolymer. That is, in the present invention, a heat-sensitive recording layer containing a colorless or light-colored electron-donating leuco dye and an electron-accepting color developer is provided on a support, and a back coat layer is provided on the opposite side of the heat-sensitive recording layer.
  • the present invention is a heat-sensitive recording material in which the back coat layer contains an ethylene-vinyl alcohol copolymer and an ethylene-acrylic copolymer.
  • a heat-sensitive recording material that has excellent water vapor barrier properties on the back surface (that is, the surface opposite to the heat-sensitive recording layer of the support) and that does not generate water vapor from the back side even when printing is performed for a long time. Obtainable.
  • the heat-sensitive recording material of the present invention has a heat-sensitive recording layer containing a leuco dye and a color developer on a support, and a back coat layer on the opposite surface of the support from the heat-sensitive recording layer.
  • the back coat layer of the present invention contains an ethylene-vinyl alcohol copolymer and an ethylene-acrylic copolymer.
  • the ethylene-vinyl alcohol copolymer used in the present invention is a polymer having ethylene units and vinyl alcohol units. Ethylene-vinyl alcohol copolymers are usually obtained by polymerizing ethylene and vinyl ester and saponifying the resulting ethylene-vinyl ester copolymer. From the viewpoint of using a water-based paint, the ethylene content is preferably 3 to 20 mol%. Further, in order to impart barrier properties, the degree of saponification is preferably 80 to 100 mol%. If the degree of saponification is less than 80 mol%, sufficient barrier properties and moisture resistance cannot be obtained.
  • the ethylene-acrylic copolymer used in the present invention is a copolymer obtained by emulsion polymerization of ethylene and an acrylic monomer.
  • acrylic monomer acrylic acid and methacrylic acid are preferred, and acrylic acid is more preferred.
  • ethylene-acrylic copolymers include ethylene/acrylic acid copolymer, ethylene/methacrylic acid copolymer, ethylene/methyl acrylate copolymer, ethylene/methyl methacrylate copolymer, and ethylene/ethyl acrylate copolymer.
  • ethylene/ethyl methacrylate copolymer ethylene/butyl acrylate copolymer, and ethylene/butyl methacrylate copolymer.
  • the copolymer may contain a small amount of a monomer made of ethylene and another compound copolymerizable with the acrylic monomer. Among these, ethylene/acrylic acid copolymer and ethylene/methacrylic acid copolymer are more preferred, and ethylene/acrylic acid copolymer is even more preferred.
  • an aqueous dispersion of an ethylene-acrylic acid copolymer ammonium salt may be used as Zaixen (registered trademark) AC (copolymerization ratio of acrylic acid 20%, manufactured by Sumitomo Seika Co., Ltd.). ) etc.
  • the back coat layer of the present invention may also contain a water-soluble polymer, a water-dispersed resin, a pigment, etc., as long as there is no problem with water vapor barrier properties.
  • water-soluble polymers include polyvinyl alcohols other than ethylene-vinyl alcohol copolymers such as fully saponified polyvinyl alcohol and partially saponified polyvinyl alcohol, proteins such as casein, soy protein, and synthetic proteins, oxidized starch, Examples include starches such as cationized starch, urea phosphate starch, and hydroxyethyl etherified starch, cellulose derivatives such as carboxymethyl cellulose, hydroxymethyl cellulose, and hydroxyethyl cellulose, polyvinylpyrrolidone, and sodium alginate.
  • water-dispersed resin examples include natural rubber, diene rubber, non-diene rubber, and thermoplastic elastomer.
  • this pigment any pigment that can be used in a heat-sensitive recording layer can be used as appropriate, but aluminum hydroxide, silica, kaolin, and calcined kaolin are preferable, and aluminum hydroxide is more preferable.
  • This back coat layer may contain lubricants, crosslinking agents, ultraviolet absorbers, dispersants, antifoaming agents, fluorescent dyes, etc., which can be used in the heat-sensitive recording layer, as necessary, within a range that does not impede the desired effects for the above-mentioned problems. may be included as appropriate.
  • the content (solid content) of the ethylene-vinyl alcohol copolymer in the back coat layer is preferably 10 to 80% by weight, more preferably 10 to 50% by weight.
  • the content (solid content) of the ethylene-acrylic copolymer in the back coat layer is preferably 10 to 80% by weight, more preferably 50 to 80% by weight.
  • the total content (solid content) of the ethylene-vinyl alcohol copolymer and ethylene-acrylic copolymer in the back coat layer is preferably 50 to 100% by weight, more preferably 50 to 90% by weight, and even more preferably is 70 to 90% by weight.
  • the content ratio (solid content) of the ethylene-acrylic copolymer to the ethylene-vinyl alcohol copolymer is preferably 2.5 parts to 40 parts, more preferably is 10 to 40 parts.
  • the pigment content (solid content) in the back coat layer is preferably 50 to 10% by weight, more preferably 30 to 10% by weight.
  • the coating amount of the back coat layer is determined according to the required performance and recording suitability, and is not particularly limited, but the general coating amount is about 0.1 to 5 g/m 2 in terms of solid content. Among these, it is preferable to have an amount of about 2.5 to 4.5 g/m 2 because it has excellent water vapor barrier properties and has good quality as a heat-sensitive recording material.
  • the heat-sensitive recording layer of the present invention contains a leuco dye and a color developer, and may optionally further contain a sensitizer, a binder, a pigment, a crosslinking agent, an image stabilizer, and other components.
  • the leuco dye used in the present invention all those known in the field of conventional pressure-sensitive or heat-sensitive recording paper can be used, and there are no particular restrictions on the leuco dye, including triphenylmethane compounds, fluoran compounds, fluorene compounds, etc. and divinyl-based compounds are preferred. Specific examples of typical colorless to light-colored leuco dyes (dye precursors) are shown below. Further, these dye precursors may be used alone or in combination of two or more.
  • Triphenylmethane-based leuco dye 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide [also known as crystal violet lactone]; 3,3-bis(p-dimethylaminophenyl) phthalide; [also known as malachite green lactone]
  • ⁇ Fluorene-based leuco dye > 3,6,6'-tris(dimethylamino)spiro[fluorene-9,3'-phthalide];3,6,6'-tris(diethylamino)spiro[fluorene-9,3'-phthalide]
  • ⁇ Divinyl leuco dye> 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; 3,3-bis-[1-(4-methoxyphenyl)-1-(4-pyrrolidinophenyl)ethylene-2- ]-4,5,6,7-tetrachlorophthalide
  • color developer that can be used in the heat-sensitive recording medium of the present invention
  • those known in the field of conventional pressure-sensitive or heat-sensitive recording paper can be used, and are not particularly limited, but for example, Inorganic acidic substances such as activated clay, attapulgite, colloidal silica, aluminum silicate, 4,4'-isopropylidenediphenol, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxyphenyl) -4-Methylpentane, 4,4'-dihydroxydiphenyl sulfide, hydroquinone monobenzyl ether, benzyl 4-hydroxybenzoate, 4,4'-dihydroxydiphenyl sulfone, 2,4'-dihydroxydiphenyl sulfone, 4-hydroxy-4 '-isopropoxydiphenylsulfone, 4-hydroxy-4'-n-propoxydiphenylsulfone, bis(3-allyl-4-hydroxyphenyl)
  • thiourea compounds such as N,N'-di-m-chlorophenylthiourea, p-chlorobenzoic acid, stearyl gallate, zinc bis[4-(n-octyloxycarbonylamino)salicylate] Dihydrate, 4-[2-(p-methoxyphenoxy)ethyloxy]salicylic acid, 4-[3-(p-tolylsulfonyl)propyloxy]salicylic acid, 5-[p-(2-p-methoxyphenoxyethoxy) Aromatic carboxylic acids such as [cumyl] salicylic acid, salts of these aromatic carboxylic acids with polyvalent metal salts such as zinc, magnesium, aluminum, calcium, titanium, manganese, tin, and nickel, and antipyrine complexes of zinc thiocyanate.
  • WO 97/16420 is available from Nippon Soda Co., Ltd. It is available under the trade name D-90. Furthermore, the compounds described in WO02/081229 and the like are available as trade names NKK-395 and D-100 manufactured by Nippon Soda Co., Ltd.
  • sensitizers include fatty acid amides such as stearic acid amide and palmitic acid amide, ethylene bisamide, montanic acid wax, polyethylene wax, 1,2-di-(3-methylphenoxy)ethane, p-benzylbiphenyl, ⁇ - Benzyloxynaphthalene, 4-biphenyl-p-tolyl ether, m-terphenyl, 1,2-diphenoxyethane, dibenzyl oxalate, di(p-chlorobenzyl) oxalate, di(p-methylbenzyl) oxalate, Dibenzyl terephthalate, benzyl p-benzyloxybenzoate, di-p-tolyl carbonate, phenyl- ⁇ -naphthyl carbonate, 1,4-diethoxynaphthalene
  • fatty acid amides such as stearic acid amide and palmitic acid amide
  • ethylene bisamide monta
  • Binders that can be used in the present invention include fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, and butyral.
  • Polyvinyl alcohols such as modified polyvinyl alcohol, olefin-modified polyvinyl alcohol, nitrile-modified polyvinyl alcohol, pyrrolidone-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, terminal alkyl-modified polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, Starches such as cellulose ether and its derivatives such as acetyl cellulose, starch, enzyme-modified starch, thermochemically modified starch, oxidized starch, esterified starch, etherified starch (e.g.
  • polyester Polyacrylamides such as acrylamide, cationic polyacrylamide, anionic polyacrylamide, and amphoteric polyacrylamide, urethane resins such as polyester polyurethane resin, polyether polyurethane resin, and polyurethane ionomer resin, (meth)acrylic acid and ( Acrylic resins consisting of monomer components (excluding olefins) that can be copolymerized with meth)acrylic acid, styrene-butadiene copolymers, styrene-butadiene-acrylonitrile copolymers, styrene-butadiene-acrylic copolymers, etc.
  • Polyolefin resins such as styrene-butadiene resins, polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, ethylene-vinyl acetate copolymers, polyvinyl chloride, polyvinylidene chloride, polyacrylic esters, gum arabic, polyvinyl butyral, Examples include polystyrose and copolymers thereof, silicone resins, petroleum resins, terpene resins, ketone resins, coumaron resins, and the like. These may be used alone or in combination of two or more.
  • pigments examples include inorganic or organic fillers such as silica, calcium carbonate, kaolin, calcined kaolin, diatomaceous earth, talc, titanium oxide, and aluminum hydroxide. These may be used alone or in combination of two or more.
  • Crosslinking agents that can be used in the present invention include glyoxal, methylolmelamine, melamine formaldehyde resin, melamine urea resin, polyamine epichlorohydrin resin, polyamide epichlorohydrin resin, potassium persulfate, ammonium persulfate, sodium persulfate, chloride
  • Examples include ferric iron, magnesium chloride, borax, boric acid, alum, and ammonium chloride agents.
  • the types and amounts of the electron-donating leuco dye, electron-accepting color developer, and other various components used in the thermal recording medium of the present invention are determined according to the required performance and recording suitability, and are not particularly limited. Usually, about 0.5 to 10 parts by weight of an electron-accepting color developer and 0.5 to 10 parts by weight of a sensitizer are used per 1 part by weight of an electron-donating leuco dye.
  • the types and amounts of other optional components such as binders, pigments, crosslinking agents, image stabilizers, and other components are determined according to the required performance and recording suitability, and are not particularly limited.
  • the solid content is about 5 to 50 parts by weight per 100 parts by weight of the heat-sensitive recording layer (solid content), and the pigment is suitably about 0 to 50 parts by weight in terms of solid content per 100 parts by weight of the heat-sensitive recording layer (solid content).
  • the content of the lubricant is suitably about 5 to 10 parts by weight based on 100 parts by weight of the heat-sensitive recording layer (solid content).
  • a protective layer may be further provided on the heat-sensitive recording layer.
  • the protective layer often contains a pigment and a resin as main components, and binders, pigments, crosslinking agents, etc., which are exemplified as materials that can be used in the heat-sensitive recording layer, can be used.
  • binders that can be used in the above-mentioned heat-sensitive recording layer can be used as appropriate, but carboxy-modified polyvinyl alcohol and non-core-shell type acrylic resin are preferable. These binders may be used alone or in combination of two or more.
  • any crosslinking agent that can be used in the heat-sensitive recording layer mentioned above can be used as appropriate, but epichlorohydrin resins and polyamine/polyamide resins (those contained in epichlorohydrin resins) can be used as appropriate. ) is preferred. It is more preferable that the protective layer contains an epichlorohydrin resin and a polyamine/polyamide resin together with carboxy-modified polyvinyl alcohol, thereby further improving the coloring performance.
  • This carboxy-modified polyvinyl alcohol is, for example, a reaction product of polyvinyl alcohol and a polyhydric carboxylic acid such as fumaric acid, phthalic anhydride, mellitic anhydride, itaconic anhydride, or an esterified product of these reactants, and also a reaction product of vinyl acetate. It is obtained as a saponified copolymer with ethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, crotonic acid, acrylic acid, and methacrylic acid. Specific manufacturing methods include, for example, the method exemplified in JP-A-53-91995. Further, the degree of saponification of the carboxy-modified polyvinyl alcohol is preferably 72 to 100 mol%, and the degree of polymerization is preferably 500 to 2,400, more preferably 1,000 to 2,000.
  • the glass transition point (Tg) of this non-core-shell type acrylic resin is preferably 95°C or lower, more preferably higher than 50°C. This Tg is measured by differential scanning calorimetry (DSC).
  • This non-core-shell type acrylic resin contains (meth)acrylic acid and a monomer component copolymerizable with (meth)acrylic acid, and (meth)acrylic acid is 1 part by weight in 100 parts by weight of the non-core-shell type acrylic resin. The amount is preferably 10 parts by weight.
  • (Meth)acrylic acid is alkali-soluble and has the property of making a non-core-shell type acrylic resin a water-soluble resin by adding a neutralizing agent.
  • the bonding property to the pigment is significantly improved, especially when the protective layer contains a pigment, and the protective layer has excellent strength even when containing a large amount of pigment.
  • components copolymerizable with (meth)acrylic acid include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate,
  • alkyl acrylate resins such as pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, epoxy resin, silicone resin, styrene or its derivatives.
  • modified alkyl acrylate resins such as the above-mentioned modified alkyl acrylate resins, (meth)acrylonitrile, acrylic esters, and hydroxyalkyl acrylic esters, but in particular, (meth)acrylonitrile and/or methyl methacrylate should be blended. is preferred.
  • (Meth)acrylonitrile is preferably blended in an amount of 15 to 70 parts per 100 parts of the non-core-shell type acrylic resin.
  • methyl methacrylate be contained in an amount of 20 to 80 parts per 100 parts of the non-core-shell type acrylic resin.
  • This epichlorohydrin resin is a resin characterized by containing an epoxy group in its molecule, and includes, for example, polyamide epichlorohydrin resin, polyamine epichlorohydrin resin, etc. These can be used alone or in combination. Furthermore, as the amine present in the main chain of the epichlorohydrin resin, primary to quaternary amines can be used, and there are no particular limitations. Further, in order to have good water resistance, the degree of cationization and molecular weight are preferably 5 meq/g ⁇ Solid or less (measured value at pH 7) and a molecular weight of 500,000 or more.
  • epichlorohydrin resins include violet resin 650 (30), violet resin 675A, violet resin 6615 (manufactured by Sumitomo Chemical Co., Ltd.), WS4002, WS4020, WS4024, WS4030, WS4046, WS4010, Examples include CP8970 (manufactured by Seiko PMC).
  • This polyamine/polyamide resin does not have an epoxy group in its molecule, and includes, for example, polyamide urea resin, polyalkylene polyamine resin, polyalkylene polyamide resin, polyamine polyurea resin, modified polyamine resin, modified polyamide resin, polyalkylene polyamine Examples include urea-formalin resin, polyalkylene polyamine polyamide polyurea resin, and these can be used alone or in combination.
  • polyamine/polyamide-based resins include violet resin 302 (manufactured by Sumitomo Chemical Co., Ltd.: polyamine polyurea resin), violet resin 712 (manufactured by Sumitomo Chemical Co., Ltd.: polyamine polyurea resin), and violet resin 703 (manufactured by Sumitomo Chemical Co., Ltd.: polyamine polyurea resin).
  • polyamine resins polyalkylene polyamine resin, polyamine polyurea resin, modified polyamine resin, polyalkylene polyamine urea formalin resin, polyalkylene polyamine polyamide polyurea resin
  • polyamine resins polyalkylene polyamine resin, polyamine polyurea resin, modified polyamine resin, polyalkylene polyamine urea formalin resin, polyalkylene polyamine polyamide polyurea resin
  • the content thereof is preferably 1 to 100 parts by weight per 100 parts by weight of carboxy-modified polyvinyl alcohol. , more preferably 5 to 50 parts by weight, and still more preferably 10 to 40 parts by weight.
  • the pigments that can be used in the heat-sensitive recording layer described above can be used as appropriate, but kaolin, calcined kaolin, aluminum hydroxide, and silica are preferable. These pigments may be used alone or in combination of two or more.
  • the binder content (solid content) in the protective layer is preferably 20% by weight or more, more preferably about 20 to 80% by weight.
  • the content of the pigment and binder is 100 parts by weight of the pigment.
  • the binder preferably has a solid content of about 30 to 300 parts by weight.
  • the coating solution for the protective layer may contain crosslinking agents, lubricants, stabilizers, ultraviolet absorbers, dispersants, antifoaming agents, antioxidants, fluorescent dyes, etc. that can be used in the heat-sensitive recording layer as described above.
  • Various auxiliary agents may be blended as appropriate.
  • an undercoat layer may be provided between the support and the heat-sensitive recording layer.
  • This undercoat layer mainly consists of a binder and a pigment.
  • the binder used in the undercoat layer the various binders used in the above-mentioned heat-sensitive recording layer can be used. These binders may be used alone or in combination of two or more.
  • the pigment used in the undercoat layer the various pigments used in the heat-sensitive recording layer described above can be used. These pigments may be used alone or in combination of two or more.
  • the amount of pigment in the undercoat layer is usually 50 to 95 parts by weight, preferably 70 to 90 parts by weight, based on 100 parts by weight of the total solid content of the undercoat layer.
  • auxiliary agents such as a dispersant, a plasticizer, a pH adjuster, an antifoaming agent, a water retention agent, a preservative, a coloring dye, and an ultraviolet light inhibitor may be appropriately blended into the undercoat layer as required.
  • the desired thermal sensitivity can be achieved by coating a coating liquid with the composition formulated for each of the above coating layers onto any support such as paper, recycled paper, synthetic paper, film, plastic film, foamed plastic film, non-woven fabric, etc.
  • a recording body is obtained.
  • a composite sheet obtained by combining these may be used as a support.
  • the electron-donating leuco dye, electron-accepting color developer, electron acceptor, electron donor, and other materials to be added as necessary are crushed to a size of several microns or less by a grinder such as a ball mill, attritor, or sand glider, or by an appropriate emulsifying device.
  • the means for applying each of the above-mentioned coating layers is not particularly limited, and can be applied according to well-known and commonly used techniques.
  • an off-machine coating machine or an on-machine coating machine equipped with various coaters such as an air knife coater, a rod blade coater, a bent blade coater, a bevel blade coater, a roll coater, a curtain coater, and a spray coater is appropriately selected and used.
  • the coating amount of the heat-sensitive recording layer is determined according to the required performance and recording suitability, and is not particularly limited, but the general coating amount is about 2 to 12 g/m 2 in terms of solid content.
  • various known techniques in the field of heat-sensitive recording materials may be added as appropriate, such as applying a smoothing treatment such as super calendering after coating each coating layer.
  • a coating solution for an undercoat layer was prepared by stirring and dispersing a composition having the following composition.
  • ⁇ Coating liquid for undercoat layer> Calcined kaolin (manufactured by Imerys, Alphatex HP) 50 parts Plastic hollow particles (manufactured by Zeon, MH8109) 50 parts Styrene-butadiene copolymer latex (manufactured by Nippon Zeon, ST5526, solid content 48%) 10 parts Water 50 parts
  • backcoat layer coating solutions 1 to 6 were prepared by mixing formulations having the following proportions.
  • a color developer dispersion, a leuco dye dispersion, and a sensitizer dispersion having the following formulations were wet-ground separately using a sand grinder until the average particle size was 0.5 microns.
  • Color developer dispersion (A1 liquid) N-[2-(3-phenylureido)phenyl]benzenesulfonamide (manufactured by Nippon Soda Co., Ltd., NKK1304, hereinafter referred to as "urea compound”) 6.0 parts fully saponified polyvinyl alcohol aqueous solution (manufactured by Kuraray Co., Ltd., PVA117, Solid content 10%) 5.0 parts Water 1.5 parts
  • each dispersion liquid was mixed in the following proportions to prepare a coating liquid for a heat-sensitive recording layer.
  • a coating solution for a protective layer was prepared by mixing a formulation having the following proportions.
  • ⁇ Coating liquid for protective layer> Aluminum hydroxide dispersion (manufactured by Martinsberg, product name: Martiffin OL, solid content 50%) 9.0 parts Carboxy-modified polyvinyl alcohol aqueous solution (manufactured by Kuraray Co., Ltd., product name: KL318, degree of polymerization: about 1700, degree of saponification: 95 to 99 mol%, Solid content 10%) 30.0 parts
  • Polyamide epichlorohydrin resin manufactured by Seiko PMC, trade name: WS4030, solid content 25%
  • Modified polyamine resin manufactured by Sumitomo Chemical Co., Ltd., product name: Sumiraze Resin SPI-102A, solid content 45%
  • Zinc stearate manufactured by Chukyo Yushi Co., Ltd., product name : Hydrin Z-7-30, Solid content
  • Example 1 After applying the coating solution for the undercoat layer to one side of the support (high-quality paper with a basis weight of 60 g/m 2 ) using a bent blade method so that the coating amount in terms of solid content was 6.0 g/m 2 , It was dried to obtain an undercoat coated paper.
  • Coating liquid 1 for heat-sensitive recording layer was coated on the undercoat layer of the undercoat layer-coated paper using a rod blade method in a coating amount of 3.0 g/ m2 in terms of solid content, and then dried.
  • a paper coated with a heat-sensitive recording layer was prepared by treating the paper with a super calender to give a smoothness of 500 to 1000 seconds.
  • a coating solution for a protective layer was applied using a rod blade method so that the coating amount was 3.0 g/ m2 in terms of solid content, and then It was dried to produce a protective layer coated paper.
  • coating liquid 1 for back coat layer was applied using a rod blade method to a coating amount of 3.5 g/ m2 in terms of solid content. After that, it was dried to produce a heat-sensitive recording material.
  • Example 2 A heat-sensitive recording material was produced in the same manner as in Example 1, except that the coating amount of the backcoat layer coating liquid was 2.0 g/m 2 .
  • Example 3 A heat-sensitive recording material was produced in the same manner as in Example 1 except that the coating amount of the backcoat layer coating liquid was 2.5 g/m 2 .
  • Example 4 A heat-sensitive recording material was produced in the same manner as in Example 1, except that the coating amount of the back coat layer coating liquid was 4.5 g/m 2 .
  • Example 5 A thermosensitive recording material was produced in the same manner as in Example 1, except that the coating solution for the back coat layer was 30 parts of ethylene-vinyl alcohol copolymer and 20 parts of ethylene-acrylic copolymer.
  • Example 6 A thermosensitive recording material was produced in the same manner as in Example 1, except that the coating solution for the back coat layer was 40 parts of ethylene-vinyl alcohol copolymer and 10 parts of ethylene-acrylic copolymer.
  • Example 7 A heat-sensitive recording material was produced in the same manner as in Example 1 except that Coating Solution 2 for heat-sensitive recording layer was used in place of Coating Solution 1 for heat-sensitive recording layer.
  • Example 8 A heat-sensitive recording material was produced in the same manner as in Example 1 except that Coating Solution 2 for back coat layer was used in place of Coating Solution 1 for back coat layer.
  • a heat-sensitive recording material was produced in the same manner as in Example 1 except that Coating Liquid 3 for back coat layer was used in place of Coating Liquid 1 for back coat layer.
  • a heat-sensitive recording material was produced in the same manner as in Example 1 except that Coating Liquid 4 for back coat layer was used in place of Coating Liquid 1 for back coat layer.
  • a heat-sensitive recording material was produced in the same manner as in Example 1 except that Coating Liquid 5 for back coat layer was used in place of Coating Liquid 1 for back coat layer.
  • the produced heat-sensitive recording material was evaluated as follows. ⁇ Color development performance (print density)> The produced thermal recording material was printed in a checkered pattern using a TH-PMD (thermal recording paper printing tester manufactured by Okura Electric Co., Ltd., equipped with a thermal head manufactured by Kyocera Corporation) at an applied energy of 0.35 mJ/dot and a printing speed of 50 mm/sec. was printed. The print density of the print area was measured using a Macbeth densitometer (RD-914, using an amber filter) to evaluate the color development performance.
  • TH-PMD thermal recording paper printing tester manufactured by Okura Electric Co., Ltd., equipped with a thermal head manufactured by Kyocera Corporation
  • the print density of the print area was measured using a Macbeth densitometer (RD-914, using an amber filter) to evaluate the color development performance.
  • the heat-sensitive recording material of the present invention has excellent water vapor barrier properties that prevent water droplets from adhering to the back surface without adversely affecting color development sensitivity.

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Abstract

[Problem] To provide a heat-sensitive recording body having water vapor barrier properties against moisture in the heat-sensitive recording body.　[Solution] A heat-sensitive recording body in which provided on a support body are a heat-sensitive recording layer containing a colorless to light-colored electron-donating leuco dye and an electron-accepting developer, and a back coat layer on the side opposite to the heat-sensitive recording layer, the back coat layer containing an ethylene-vinyl alcohol copolymer and an ethylene-acrylic copolymer.　

Description

感熱記録体heat sensitive recording material
　この発明は、背面に水蒸気バリア性を有する感熱記録体に関する。 The present invention relates to a heat-sensitive recording material having water vapor barrier properties on the back surface.
　一般に、感熱記録体は、無色ないし淡色の電子供与性ロイコ染料（以下、「ロイコ染料」ともいう。）と電子受容性顕色剤（以下、「顕色剤」ともいう。）とを含有する塗工液を、紙、合成紙、フィルム、プラスチック等の支持体に塗工して感熱記録層を設けたものであり、サーマルヘッド、ホットスタンプ、熱ペン、レーザー光等の加熱による瞬時の化学反応により発色し、記録画像が得られる。感熱記録体は、ファクシミリ、コンピューターの端末プリンター、自動券売機、計測用レコーダー、スーパーマーケットやコンビニなどのレシート等の記録媒体として広範囲に使用されている。
　良好な耐水性を得るために、ポリビニルアルコール等の接着剤を含有するバックコート層を設けた感熱記録材料が知られている（特許文献1等）。また、エチレン共重合ポリビニルアルコールやエチレン・アクリル共重合体を含む紙基材が水蒸気バリア性を有することが知られている（特許文献２～４等）。 Generally, a thermal recording material contains a colorless or light-colored electron-donating leuco dye (hereinafter also referred to as "leuco dye") and an electron-accepting color developer (hereinafter also referred to as "color developer"). A heat-sensitive recording layer is provided by applying a coating liquid to a support such as paper, synthetic paper, film, or plastic, and instant chemical recording is performed by heating with a thermal head, hot stamp, thermal pen, laser beam, etc. Color develops due to the reaction, and a recorded image is obtained. Thermosensitive recording media are widely used as recording media for facsimiles, computer terminal printers, automatic ticket vending machines, measurement recorders, receipts at supermarkets, convenience stores, etc.
In order to obtain good water resistance, heat-sensitive recording materials are known that are provided with a back coat layer containing an adhesive such as polyvinyl alcohol (Patent Document 1, etc.). Furthermore, it is known that paper base materials containing ethylene copolymerized polyvinyl alcohol or ethylene/acrylic copolymers have water vapor barrier properties (Patent Documents 2 to 4, etc.).
特開２００３－１７５６７１JP2003-175671 特開２０１３－１６９９８８JP2013-169988 特開２０１４－１７３２０１JP2014-173201 特開２０２０－１９００６３JP2020-190063
　医療用など高感度が必要とされるプリンターは、高エネルギーで印字するため、サーマルヘッドが高温となり、長時間高温のまま印字が続くと、感熱記録体中の水分が気化して、サーマルヘッドと接触していない背面側から水滴が発生し、機器不良を引き起こすという問題があった。
　そこで、本発明は、感熱記録体中の水分に対して水蒸気バリア性を有する感熱記録体を提供する。 Printers that require high sensitivity, such as medical printers, print with high energy, so the thermal head becomes hot. If printing continues at high temperatures for a long time, the moisture in the thermal recording material will evaporate, causing the thermal head to become hot. There was a problem in that water droplets were generated from the back side that was not in contact, causing equipment failure.
Therefore, the present invention provides a heat-sensitive recording material having water vapor barrier properties against moisture in the heat-sensitive recording material.
　本発明者らは鋭意検討の結果、感熱記録体の支持体上に感熱記録層と、この感熱記録層とは反対面にバックコート層とを設け、このバックコート層にエチレン－ビニルアルコール共重合体及びエチレン－アクリル共重合体を含有させることにより、上記課題を解決することができることを見出し、本発明を完成させた。
　即ち、本発明は、支持体上に、無色ないし淡色の電子供与性ロイコ染料及び電子受容性顕色剤を含有する感熱記録層と、該感熱記録層とは反対面にバックコート層を設けた感熱記録体であって、該バックコート層がエチレン－ビニルアルコール共重合体及びエチレン－アクリル共重合体を含有する、感熱記録体である。 As a result of extensive studies, the present inventors found that a heat-sensitive recording layer is provided on the support of a heat-sensitive recording medium, and a back coat layer is provided on the opposite side of the heat-sensitive recording layer. The present invention was completed based on the discovery that the above-mentioned problems can be solved by incorporating an ethylene-acrylic copolymer.
That is, in the present invention, a heat-sensitive recording layer containing a colorless or light-colored electron-donating leuco dye and an electron-accepting color developer is provided on a support, and a back coat layer is provided on the opposite side of the heat-sensitive recording layer. The present invention is a heat-sensitive recording material in which the back coat layer contains an ethylene-vinyl alcohol copolymer and an ethylene-acrylic copolymer.
　本発明によれば、背面（即ち、支持体の感熱記録層とは反対の面）に優れた水蒸気バリア性を有し、長時間印字された場合でも背面側から水蒸気が発生しない感熱記録体を得ることができる。 According to the present invention, there is provided a heat-sensitive recording material that has excellent water vapor barrier properties on the back surface (that is, the surface opposite to the heat-sensitive recording layer of the support) and that does not generate water vapor from the back side even when printing is performed for a long time. Obtainable.
　本発明の感熱記録体は、支持体上に、ロイコ染料及び顕色剤を含有する感熱記録層を有し、支持体の感熱記録層とは反対面にバックコート層を有する。
　本発明のバックコート層は、エチレン－ビニルアルコール共重合体及びエチレン－アクリル共重合体を含有する。 The heat-sensitive recording material of the present invention has a heat-sensitive recording layer containing a leuco dye and a color developer on a support, and a back coat layer on the opposite surface of the support from the heat-sensitive recording layer.
The back coat layer of the present invention contains an ethylene-vinyl alcohol copolymer and an ethylene-acrylic copolymer.
　本発明で使用するエチレン－ビニルアルコール共重合体は、エチレン単位及びビニルアルコール単位を有する重合体である。エチレン－ビニルアルコール共重合体は、通常、エチレンとビニルエステルとを重合し、得られるエチレン－ビニルエステル共重合体をケン化して得られる。
　水系塗料を用いる観点から、エチレン含有量は３～２０モル％が好適である。またバリア性を付与するため、ケン化度は８０～１００モル％が好適である。ケン化度が８０モル％未満では、バリア性、耐湿性が十分に得られない。 The ethylene-vinyl alcohol copolymer used in the present invention is a polymer having ethylene units and vinyl alcohol units. Ethylene-vinyl alcohol copolymers are usually obtained by polymerizing ethylene and vinyl ester and saponifying the resulting ethylene-vinyl ester copolymer.
From the viewpoint of using a water-based paint, the ethylene content is preferably 3 to 20 mol%. Further, in order to impart barrier properties, the degree of saponification is preferably 80 to 100 mol%. If the degree of saponification is less than 80 mol%, sufficient barrier properties and moisture resistance cannot be obtained.
　本発明で使用するエチレン－アクリル共重合体は、エチレンとアクリル単量体とを乳化重合することによって得られる共重合体である。アクリル単量体としては、アクリル酸、メタクリル酸が好ましく、アクリル酸がより好ましい。
　エチレン－アクリル共重合体としては、エチレン・アクリル酸共重合体、エチレン・メタクリル酸共重合体、エチレン・アクリル酸メチル共重合体、エチレン・メタクリル酸メチル共重合体、エチレン・アクリル酸エチル共重合体、エチレン・メタクリル酸エチル共重合体、エチレン・アクリル酸ブチル共重合体およびエチレン・メタクリル酸ブチル共重合体のうちいずれか１種以上であることが好ましい。共重合体には、エチレンおよびアクリル単量体と共重合可能なその他の化合物からなる単量体が少量共重合されていてもよい。
　これらの中でもエチレン・アクリル酸共重合体、エチレン・メタクリル酸共重合体がより好ましく、エチレン・アクリル酸共重合体がさらに好ましい。
　エチレン－アクリル共重合体の具体例として、例えば、エチレン・アクリル酸共重合体アンモニウム塩の水性分散液が、ザイクセン（登録商標）ＡＣ（アクリル酸の共重合比率２０％、住友精化株式会社製）等として入手可能である。 The ethylene-acrylic copolymer used in the present invention is a copolymer obtained by emulsion polymerization of ethylene and an acrylic monomer. As the acrylic monomer, acrylic acid and methacrylic acid are preferred, and acrylic acid is more preferred.
Examples of ethylene-acrylic copolymers include ethylene/acrylic acid copolymer, ethylene/methacrylic acid copolymer, ethylene/methyl acrylate copolymer, ethylene/methyl methacrylate copolymer, and ethylene/ethyl acrylate copolymer. It is preferable to use one or more of ethylene/ethyl methacrylate copolymer, ethylene/butyl acrylate copolymer, and ethylene/butyl methacrylate copolymer. The copolymer may contain a small amount of a monomer made of ethylene and another compound copolymerizable with the acrylic monomer.
Among these, ethylene/acrylic acid copolymer and ethylene/methacrylic acid copolymer are more preferred, and ethylene/acrylic acid copolymer is even more preferred.
As a specific example of the ethylene-acrylic copolymer, for example, an aqueous dispersion of an ethylene-acrylic acid copolymer ammonium salt may be used as Zaixen (registered trademark) AC (copolymerization ratio of acrylic acid 20%, manufactured by Sumitomo Seika Co., Ltd.). ) etc.
　本発明のバックコート層は、この他に、水蒸気バリア性に問題がない程度であれば、水溶性高分子、水分散系樹脂、顔料などを含有してもよい。
　この水溶性高分子としては、完全ケン化ポリビニルアルコール、部分ケン化ポリビニルアルコールなどの、エチレン－ビニルアルコール共重合体以外のポリビニルアルコール類、カゼイン、大豆タンパク、合成タンパクなどのタンパク質類、酸化澱粉、カチオン化澱粉、尿素リン酸エステル化澱粉、ヒドロキシエチルエーテル化澱粉などの澱粉類、カルボキシメチルセルロース、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース等のセルロース誘導体、ポリビニルピロリドン、アルギン酸ナトリウムなどが挙げられる。
　この水分散系樹脂としては、天然ゴム、ジエン系ゴム、非ジエン系ゴム及び熱可塑性エラストマーなどが挙げられる。
　この顔料としては、感熱記録層に使用可能な顔料が適宜使用可能であるが、水酸化アルミニウム、シリカ、カオリン、焼成カオリンが好ましく、水酸化アルミニウムがより好ましい。
　このバックコート層は、上記課題に対する所望の効果を阻害しない範囲で、さらに必要に応じて、感熱記録層に使用可能な滑剤、架橋剤、紫外線吸収剤、分散剤、消泡剤、蛍光染料等を適宜含有してもよい。 The back coat layer of the present invention may also contain a water-soluble polymer, a water-dispersed resin, a pigment, etc., as long as there is no problem with water vapor barrier properties.
Examples of water-soluble polymers include polyvinyl alcohols other than ethylene-vinyl alcohol copolymers such as fully saponified polyvinyl alcohol and partially saponified polyvinyl alcohol, proteins such as casein, soy protein, and synthetic proteins, oxidized starch, Examples include starches such as cationized starch, urea phosphate starch, and hydroxyethyl etherified starch, cellulose derivatives such as carboxymethyl cellulose, hydroxymethyl cellulose, and hydroxyethyl cellulose, polyvinylpyrrolidone, and sodium alginate.
Examples of the water-dispersed resin include natural rubber, diene rubber, non-diene rubber, and thermoplastic elastomer.
As this pigment, any pigment that can be used in a heat-sensitive recording layer can be used as appropriate, but aluminum hydroxide, silica, kaolin, and calcined kaolin are preferable, and aluminum hydroxide is more preferable.
This back coat layer may contain lubricants, crosslinking agents, ultraviolet absorbers, dispersants, antifoaming agents, fluorescent dyes, etc., which can be used in the heat-sensitive recording layer, as necessary, within a range that does not impede the desired effects for the above-mentioned problems. may be included as appropriate.
　バックコート層中のエチレン－ビニルアルコール共重合体の含有量（固形分）は、好ましくは１０～８０重量％、より好ましくは１０～５０重量％である。
　バックコート層中のエチレン－アクリル共重合体の含有量（固形分）は、好ましくは１０～８０重量％、より好ましくは５０～８０重量％である。
　但し、バックコート層中のエチレン－ビニルアルコール共重合体及びエチレン－アクリル共重合体の合計含有量（固形分）は、好ましくは５０～１００重量％、より好ましくは５０～９０重量％、更に好ましくは７０～９０重量％である。
　またエチレン－ビニルアルコール共重合体に対するエチレン－アクリル共重合体の含有比（固形分）は、エチレン－ビニルアルコール共重合体１０質量部に対して、好ましくは２．５部～４０部、より好ましくは１０～４０部である。
　また、バックコート層中の顔料の含有量（固形分）は、好ましくは５０～１０重量％、より好ましくは３０～１０重量％である。
　バックコート層の塗布量は要求される性能及び記録適性に従って決定され、特に限定されるものではないが、一般的な塗布量は固形分で０．１～５ｇ／ｍ２程度である。このうち、２．５～４．５ｇ／ｍ２程度であると、優れた水蒸気バリア性を有し、かつ、感熱記録体としての品質が良好であるため好ましい。 The content (solid content) of the ethylene-vinyl alcohol copolymer in the back coat layer is preferably 10 to 80% by weight, more preferably 10 to 50% by weight.
The content (solid content) of the ethylene-acrylic copolymer in the back coat layer is preferably 10 to 80% by weight, more preferably 50 to 80% by weight.
However, the total content (solid content) of the ethylene-vinyl alcohol copolymer and ethylene-acrylic copolymer in the back coat layer is preferably 50 to 100% by weight, more preferably 50 to 90% by weight, and even more preferably is 70 to 90% by weight.
The content ratio (solid content) of the ethylene-acrylic copolymer to the ethylene-vinyl alcohol copolymer is preferably 2.5 parts to 40 parts, more preferably is 10 to 40 parts.
Further, the pigment content (solid content) in the back coat layer is preferably 50 to 10% by weight, more preferably 30 to 10% by weight.
The coating amount of the back coat layer is determined according to the required performance and recording suitability, and is not particularly limited, but the general coating amount is about 0.1 to 5 g/m 2 in terms of solid content. Among these, it is preferable to have an amount of about 2.5 to 4.5 g/m 2 because it has excellent water vapor barrier properties and has good quality as a heat-sensitive recording material.
　本発明の感熱記録層は、ロイコ染料及び顕色剤を含有し、更に、任意に、増感剤、バインダー、顔料、架橋剤、画像安定剤、その他の成分を含有してもよい。 The heat-sensitive recording layer of the present invention contains a leuco dye and a color developer, and may optionally further contain a sensitizer, a binder, a pigment, a crosslinking agent, an image stabilizer, and other components.
　本発明で使用するロイコ染料としては、従来の感圧あるいは感熱記録紙分野で公知のものは全て使用可能であり、特に制限されるものではないが、トリフェニルメタン系化合物、フルオラン系化合物、フルオレン系、ジビニル系化合物等が好ましい。以下に代表的な無色ないし淡色のロイコ染料（染料前駆体）の具体例を示す。また、これらの染料前駆体は単独又は２種以上混合して使用してもよい。 As the leuco dye used in the present invention, all those known in the field of conventional pressure-sensitive or heat-sensitive recording paper can be used, and there are no particular restrictions on the leuco dye, including triphenylmethane compounds, fluoran compounds, fluorene compounds, etc. and divinyl-based compounds are preferred. Specific examples of typical colorless to light-colored leuco dyes (dye precursors) are shown below. Further, these dye precursors may be used alone or in combination of two or more.
＜トリフェニルメタン系ロイコ染料＞
　３、３－ビス（ｐ－ジメチルアミノフェニル）－６－ジメチルアミノフタリド〔別名クリスタルバイオレットラクトン〕；３，３－ビス（ｐ－ジメチルアミノフェニル）フタリド；〔別名マラカイトグリーンラクトン〕 <Triphenylmethane-based leuco dye>
3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide [also known as crystal violet lactone]; 3,3-bis(p-dimethylaminophenyl) phthalide; [also known as malachite green lactone]
＜フルオラン系ロイコ染料＞
　３－ジエチルアミノ－６－メチルフルオラン；　３－ジエチルアミノ－６－メチル－７－アニリノフルオラン；　３－ジエチルアミノ－６－メチル－７－（ｏ、ｐ－ジメチルアニリノ）フルオラン；　３－ジエチルアミノ－６－メチル－７－クロロフルオラン；　３－ジエチルアミノ－６－メチル－７－（ｍ－トリフルオロメチルアニリノ）フルオラン；　３－ジエチルアミノ－６－メチル－７－（ｏ－クロロアニリノ）フルオラン；　３－ジエチルアミノ－６－メチル－７－（ｐ－クロロアニリノ）フルオラン；　３－ジエチルアミノ－６－メチル－７－（ｏ－フルオロアニリノ）フルオラン；　３－ジエチルアミノ－６－メチル－７－（ｍ－メチルアニリノ）フルオラン；　３－ジエチルアミノ－６－メチル－７－ｎ－オクチルアニリノフルオラン；　３－ジエチルアミノ－６－メチル－７－ｎ－オクチルアミノフルオラン；　３－ジエチルアミノ－６－メチル－７－ベンジルアミノフルオラン；　３－ジエチルアミノ－６－メチル－７－ジベンジルアミノフルオラン；　３－ジエチルアミノ－６－クロロ－７－メチルフルオラン；　３－ジエチルアミノ－６－クロロ－７－アニリノフルオラン；　３－ジエチルアミノ－６－クロロ－７－ｐ－メチルアニリノフルオラン；　３－ジエチルアミノ－６－エトキシエチル－７－アニリノフルオラン；　３－ジエチルアミノ－７－メチルフルオラン；　３－ジエチルアミノ－７－クロロフルオラン；　３－ジエチルアミノ－７－（ｍ－トリフルオロメチルアニリノ）フルオラン；　３－ジエチルアミノ－７－（ｏ－クロロアニリノ）フルオラン；　３－ジエチルアミノ－７－（ｐ－クロロアニリノ）フルオラン；　３－ジエチルアミノ－７－（ｏ－フルオロアニリノ）フルオラン；　３－ジエチルアミノ－ベンゾ〔ａ〕フルオラン；　３－ジエチルアミノ－ベンゾ〔ｃ〕フルオラン；　３－ジブチルアミノ－６－メチル－フルオラン；　３－ジブチルアミノ－６－メチル－７－アニリノフルオラン；　３－ジブチルアミノ－６－メチル－７－（ｏ、ｐ－ジメチルアニリノ）フルオラン；　３－ジブチルアミノ－６－メチル－７－（ｏ－クロロアニリノ）フルオラン；　３－ジブチルアミノ－６－メチル－７－（ｐ－クロロアニリノ）フルオラン；　３－ジブチルアミノ－６－メチル－７－（ｏ－フルオロアニリノ）フルオラン；　３－ジブチルアミノ－６－メチル－７－（ｍ－トリフルオロメチルアニリノ）フルオラン；　３－ジブチルアミノ－６－メチル－クロロフルオラン；　３－ジブチルアミノ－６－エトキシエチル－７－アニリノフルオラン；　３－ジブチルアミノ－６－クロロ－７－アニリノフルオラン；　３－ジブチルアミノ－６－メチル－７－ｐ－メチルアニリノフルオラン；　３－ジブチルアミノ－７－（ｏ－クロロアニリノ）フルオラン；　３－ジブチルアミノ－７－（ｏ－フルオロアニリノ）フルオラン；　３－ジ－ｎ－ペンチルアミノ－６－メチル－７－アニリノフルオラン；　３－ジ－ｎ－ペンチルアミノ－６－メチル－７－（ｐ－クロロアニリノ）フルオラン；　３－ジ－ｎ－ペンチルアミノ－７－（ｍ－トリフルオロメチルアニリノ）フルオラン；　３－ジ－ｎ－ペンチルアミノ－６－クロロ－７－アニリノフルオラン；　３－ジ－ｎ－ペンチルアミノ－７－（ｐ－クロロアニリノ）フルオラン；　３－ピロリジノ－６－メチル－７－アニリノフルオラン；　３－ピペリジノ－６－メチル－７－アニリノフルオラン；　３－（Ｎ－メチル－Ｎ－プロピルアミノ）－６－メチル－７－アニリノフルオラン；　３－（Ｎ－メチル－Ｎ－シクロヘキシルアミノ）－６－メチル－７－アニリノフルオラン；　３－（Ｎ－エチル－Ｎ－シクロヘキシルアミノ）－６－メチル－７－アニリノフルオラン；　３－（Ｎ－エチル－Ｎ－キシルアミノ）－６－メチル－７－（ｐ－クロロアニリノ）フルオラン；　３－（Ｎ－エチル－ｐ－トルイディノ）－６－メチル－７－アニリノフルオラン；　３－（Ｎ－エチル－Ｎ－イソアミルアミノ）－６－メチル－７－アニリノフルオラン；　３－（Ｎ－エチル－Ｎ－イソアミルアミノ）－６－クロロ－７－アニリノフルオラン；　３－（Ｎ－エチル－Ｎ－テトラヒドロフルフリルアミノ）－６－メチル－７－アニリノフルオラン；　３－（Ｎ－エチル－Ｎ－イソブチルアミノ）－６－メチル－７－アニリノフルオラン；　３－（Ｎ－エチル－Ｎ－エトキシプロピルアミノ）－６－メチル－７－アニリノフルオラン；　３－シクロヘキシルアミノ－６－クロロフルオラン；　２－（４－オキサヘキシル）－３－ジメチルアミノ－６－メチル－７－アニリノフルオラン；　２－（４－オキサヘキシル）－３－ジエチルアミノ－６－メチル－７－アニリノフルオラン；　２－（４－オキサヘキシル）－３－ジプロピルアミノ－６－メチル－７－アニリノフルオラン；　２－メチル－６－ｐ－（ｐ－ジメチルアミノフェニル）アミノアニリノフルオラン；　２－メトキシ－６－ｐ－（ｐ－ジメチルアミノフェニル）アミノアニリノフルオラン；　２－クロロ－３－メチル－６－ｐ－（ｐ－フェニルアミノフェニル）アミノアニリノフルオラン；　２－クロロ－６－ｐ－（ｐ－ジメチルアミノフェニル）アミノアニリノフルオラン；　２－ニトロ－６－ｐ－（ｐ－ジエチルアミノフェニル）アミノアニリノフルオラン；　２－アミノ－６－ｐ－（ｐ－ジエチルアミノフェニル）アミノアニリノフルオラン；　２－ジエチルアミノ－６－ｐ－（ｐ－ジエチルアミノフェニル）アミノアニリノフルオラン；　２－フェニル－６－メチル－６－ｐ－（ｐ－フェニルアミノフェニル）アミノアニリノフルオラン；　２－ベンジル－６－ｐ－（ｐ－フェニルアミノフェニル）アミノアニリノフルオラン；　２－ヒドロキシ－６－ｐ－（ｐ－フェニルアミノフェニル）アミノアニリノフルオラン；　３－メチル－６－ｐ－（ｐ－ジメチルアミノフェニル）アミノアニリノフルオラン；　３－ジエチルアミノ－６－ｐ－（ｐ－ジエチルアミノフェニル）アミノアニリノフルオラン；　３－ジエチルアミノ－６－ｐ－（ｐ－ジブチルアミノフェニル）アミノアニリノフルオラン；　２、４－ジメチル－６－〔（４－ジメチルアミノ）アニリノ〕－フルオラン <Fluorane-based leuco dye>
3-diethylamino-6-methylfluorane; 3-diethylamino-6-methyl-7-anilinofluorane; 3-diethylamino-6-methyl-7-(o, p-dimethylanilino)fluorane; 3-diethylamino- 6-Methyl-7-chlorofluoran; 3-diethylamino-6-methyl-7-(m-trifluoromethylanilino)fluoran; 3-diethylamino-6-methyl-7-(o-chloroanilino)fluoran; 3- Diethylamino-6-methyl-7-(p-chloroanilino)fluoran; 3-diethylamino-6-methyl-7-(o-fluoroanilino)fluoran; 3-diethylamino-6-methyl-7-(m-methylanilino)fluoran ; 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-chloro-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-chlorofluorane; 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-benzo[a]fluorane; 3-diethylamino-benzo[c]fluorane; 3-dibutylamino-6-methyl-fluorane; 3-dibutylamino-6-methyl-7- Anilinofluoran; 3-dibutylamino-6-methyl-7-(o,p-dimethylanilino)fluoran; 3-dibutylamino-6-methyl-7-(o-chloroanilino)fluoran; 3-dibutylamino- 6-Methyl-7-(p-chloroanilino)fluoran; 3-dibutylamino-6-methyl-7-(o-fluoroanilino)fluoran; 3-dibutylamino-6-methyl-7-(m-trifluoromethyl 3-dibutylamino-6-methyl-chlorofluoran; 3-dibutylamino-6-ethoxyethyl-7-anilinofluoran; 3-dibutylamino-6-chloro-7-anilinofluoran ; 3-dibutylamino-6-methyl-7-p-methylanilinofluorane; 3-dibutylamino-7-(o-chloroanilino)fluoran; 3-dibutylamino-7-(o-fluoroanilino)fluoran; 3-di-n-pentylamino-6-methyl-7-anilinofluorane; 3-di-n-pentylamino-6-methyl-7-(p-chloroanilino)fluoran; 3-di-n-pentylamino -7-(m-trifluoromethylanilino)fluorane; 3-di-n-pentylamino-6-chloro-7-anilinofluorane; 3-di-n-pentylamino-7-(p-chloroanilino) Fluoran; 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-ethyl-N-cyclohexylamino)-6-methyl-7-ani Linofluorane; 3-(N-ethyl-N-xylamino)-6-methyl-7-(p-chloroanilino)fluoran; 3-(N-ethyl-p-toluidino)-6-methyl-7-anilinofluoran Orane; 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-cyclohexylamino-6-chlorofluorane; 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)aminoanilino Fluoran; 2-chloro-3-methyl-6-p-(p-phenylaminophenyl)aminoanilinofluoran; 2-chloro-6-p-(p-dimethylaminophenyl)aminoanilinofluoran; 2 -nitro-6-p-(p-diethylaminophenyl)aminoanilinofluorane; 2-amino-6-p-(p-diethylaminophenyl)aminoanilinofluorane; 2-diethylamino-6-p-(p- diethylaminophenyl)aminoanilinofluorane; 2-phenyl-6-methyl-6-p-(p-phenylaminophenyl)aminoanilinofluorane; 2-benzyl-6-p-(p-phenylaminophenyl)amino Anilinofluoran; 2-hydroxy-6-p-(p-phenylaminophenyl)aminoanilinofluoran; 3-methyl-6-p-(p-dimethylaminophenyl)aminoanilinofluoran; 3-diethylamino -6-p-(p-diethylaminophenyl)aminoanilinofluorane; 3-diethylamino-6-p-(p-dibutylaminophenyl)aminoanilinofluorane; 2,4-dimethyl-6-[(4- dimethylamino)anilino]-fluorane
＜フルオレン系ロイコ染料＞
　３、６、６'－トリス（ジメチルアミノ）スピロ〔フルオレン－９、３´－フタリド〕；　３、６、６'－トリス（ジエチルアミノ）スピロ〔フルオレン－９、３´－フタリド〕 <Fluorene-based leuco dye>
3,6,6'-tris(dimethylamino)spiro[fluorene-9,3'-phthalide];3,6,6'-tris(diethylamino)spiro[fluorene-9,3'-phthalide]
＜ジビニル系ロイコ染料＞
　３、３－ビス－〔２－（ｐ－ジメチルアミノフェニル）－２－（ｐ－メトキシフェニル）エテニル〕－４、５、６、７－テトラブロモフタリド；　３、３－ビス－〔２－（ｐ－ジメチルアミノフェニル）－２－（ｐ－メトキシフェニル）エテニル〕－４、５、６、７－テトラクロロフタリド；　３、３－ビス－〔１、１－ビス（４－ピロリジノフェニル）エチレン－２－イル〕－４、５、６、７－テトラブロモフタリド；　３、３－ビス－〔１－（４－メトキシフェニル）－１－（４－ピロリジノフェニル）エチレン－２－イル〕－４、５、６、７－テトラクロロフタリド <Divinyl leuco dye>
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; 3,3-bis-[1-(4-methoxyphenyl)-1-(4-pyrrolidinophenyl)ethylene-2- ]-4,5,6,7-tetrachlorophthalide
＜その他＞
　３－（４－ジエチルアミノ－２－エトキシフェニル）－３－（１－エチル－２－メチルインドール－３－イル）－４－アザフタリド；　３－（４－ジエチルアミノ－２－エトキシフェニル）－３－（１－オクチル－２－メチルインドール－３－イル）－４－アザフタリド；　３－（４－シクロヘキシルエチルアミノ－２－メトキシフェニル）－３－（１－エチル－２－メチルインドール－３－イル）－４－アザフタリド；　３、３－ビス（１－エチル－２－メチルインドール－３－イル）フタリド；　３、６－ビス（ジエチルアミノ）フルオラン－γ－（３´－ニトロ）アニリノラクタム；　３、６－ビス（ジエチルアミノ）フルオラン－γ－（４´－ニトロ）アニリノラクタム；　１、１－ビス－〔２'、２'、２''、２''－テトラキス－（ｐ－ジメチルアミノフェニル）－エテニル〕－２、２－ジニトリルエタン；　１、１－ビス－〔２'、２'、２''、２''－テトラキス－（ｐ－ジメチルアミノフェニル）－エテニル〕－２－β－ナフトイルエタン；　１、１－ビス－〔２'、２'、２''、２''－テトラキス－（ｐ－ジメチルアミノフェニル）－エテニル〕－２、２－ジアセチルエタン；　ビス－〔２、２、２'、２'－テトラキス－（ｐ－ジメチルアミノフェニル）－エテニル〕－メチルマロン酸ジメチルエステル <Others>
3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide; 3-(4-diethylamino-2-ethoxyphenyl)-3-( 1-octyl-2-methylindol-3-yl)-4-azaphthalide; 3-(4-cyclohexylethylamino-2-methoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)- 4-Azaphthalide; 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide; 3,6-bis(diethylamino)fluoran-γ-(3′-nitro)anilinolactam; 3,6 -Bis(diethylamino)fluorane-γ-(4'-nitro)anilinolactam;1,1-bis-[2',2',2'',2''-tetrakis-(p-dimethylaminophenyl)- ethenyl]-2,2-dinitrile ethane; 1,1-bis-[2',2',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]-methylmalonic acid dimethyl ester
　本発明の感熱記録体に使用することのできる顕色剤としては、従来の感圧あるいは感熱記録紙の分野で公知のものを使用することができ、特に制限されるものではないが、例えば、活性白土、アタパルジャイト、コロイダルシリカ、珪酸アルミニウムなどの無機酸性物質、４，４'－イソプロピリデンジフェノール、１，１－ビス（４－ヒドロキシフェニル）シクロヘキサン、２，２－ビス（４－ヒドロキシフェニル）－４－メチルペンタン、４，４'－ジヒドロキシジフェニルスルフィド、ヒドロキノンモノベンジルエーテル、４－ヒドロキシ安息香酸ベンジル、４，４'－ジヒドロキシジフェニルスルホン、２，４'－ジヒドロキシジフェニルスルホン、４－ヒドロキシ－４'－イソプロポキシジフェニルスルホン、４－ヒドロキシ－４'－ｎ－プロポキシジフェニルスルホン、ビス（３－アリル－４－ヒドロキシフェニル）スルホン、４－ヒドロキシ－４'－メチルジフェニルスルホン、４－ヒドロキシフェニル－４'－ベンジルオキシフェニルスルホン、３，４－ジヒドロキシフェニル－４'－メチルフェニルスルホン、１－［４－（４－ヒドロキシフェニルスルホニル）フェノキシ］－４－［４－（４－イソプロポキシフェニルスルホニル）フェノキシ］ブタン、特開２００３－１５４７６０号公報記載のフェノール縮合組成物、特開平８－５９６０３号公報記載のアミノベンゼンスルホンアミド誘導体、ビス（４－ヒドロキシフェニルチオエトキシ）メタン、１，５－ジ（４－ヒドロキシフェニルチオ）－３－オキサペンタン、ビス（ｐ－ヒドロキシフェニル）酢酸ブチル、ビス（ｐ－ヒドロキシフェニル）酢酸メチル、１，１－ビス（４－ヒドロキシフェニル）－１－フェニルエタン、１，４－ビス［α－メチル－α－（４'－ヒドロキシフェニル）エチル］ベンゼン、１，３－ビス［α－メチル－α－（４'－ヒドロキシフェニル）エチル］ベンゼン、ジ（４－ヒドロキシ－３－メチルフェニル）スルフィド、２，２'－チオビス（３－tert－オクチルフェノール）、２，２'－チオビス（４－tert－オクチルフェノール）、Ｎ－［２－（３－フェニルウレイド）フェニル］ベンゼンスルホンアミド、Ｎ，Ｎ'－ジ－［３－（ｐ－トルエンスルホニルオキシ）フェニル］尿素、ＷＯ９７／１６４２０号に記載のジフェニルスルホン架橋型化合物等のフェノール性化合物、ＷＯ０２／０８１２２９号あるいは特開２００２－３０１８７３号公報記載の化合物、またＮ，Ｎ'－ジ－ｍ－クロロフェニルチオウレア等のチオ尿素化合物、ｐ－クロロ安息香酸、没食子酸ステアリル、ビス［４－（ｎ－オクチルオキシカルボニルアミノ）サリチル酸亜鉛］２水和物、４－［２－（ｐ－メトキシフェノキシ）エチルオキシ］サリチル酸、４－［３－（ｐ－トリルスルホニル）プロピルオキシ］サリチル酸、５－［ｐ－（２－ｐ－メトキシフェノキシエトキシ）クミル］サリチル酸の芳香族カルボン酸、及びこれらの芳香族カルボン酸の亜鉛、マグネシウム、アルミニウム、カルシウム、チタン、マンガン、スズ、ニッケル等の多価金属塩との塩、さらにはチオシアン酸亜鉛のアンチピリン錯体、テレフタルアルデヒド酸と他の芳香族カルボン酸との複合亜鉛塩等が挙げられる。これらの顕色剤は、単独で又は２種以上混合して使用することもできる。１－［４－（４－ヒドロキシフェニルスルホニル）フェノキシ］－４－［４－（４－イソプロポキシフェニルスルホニル）フェノキシ］ブタンは、例えば、三菱ケミカル株式会社製商品名ＴＯＭＩＬＡＣ２１４として入手可能であり、特開２００３－１５４７６０号公報記載のフェノール縮合組成物は、例えば、三菱ケミカル株式会社製商品名ＴＯＭＩＬＡＣ２２４として入手可能であり、国際公開ＷＯ９７／１６４２０号に記載のジフェニルスルホン架橋型化合物は、日本曹達株式会社製商品名Ｄ－９０として入手可能である。また、ＷＯ０２／０８１２２９号等に記載の化合物は、日本曹達株式会社製商品名ＮＫＫ－３９５、Ｄ－１００として入手可能である。 As the color developer that can be used in the heat-sensitive recording medium of the present invention, those known in the field of conventional pressure-sensitive or heat-sensitive recording paper can be used, and are not particularly limited, but for example, Inorganic acidic substances such as activated clay, attapulgite, colloidal silica, aluminum silicate, 4,4'-isopropylidenediphenol, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxyphenyl) -4-Methylpentane, 4,4'-dihydroxydiphenyl sulfide, hydroquinone monobenzyl ether, benzyl 4-hydroxybenzoate, 4,4'-dihydroxydiphenyl sulfone, 2,4'-dihydroxydiphenyl sulfone, 4-hydroxy-4 '-isopropoxydiphenylsulfone, 4-hydroxy-4'-n-propoxydiphenylsulfone, bis(3-allyl-4-hydroxyphenyl)sulfone, 4-hydroxy-4'-methyldiphenylsulfone, 4-hydroxyphenyl-4 '-Benzyloxyphenylsulfone, 3,4-dihydroxyphenyl-4'-methylphenylsulfone, 1-[4-(4-hydroxyphenylsulfonyl)phenoxy]-4-[4-(4-isopropoxyphenylsulfonyl)phenoxy ] Butane, phenol condensation compositions described in JP-A No. 2003-154760, aminobenzenesulfonamide derivatives described in JP-A-8-59603, bis(4-hydroxyphenylthioethoxy)methane, 1,5-di(4 -hydroxyphenylthio)-3-oxapentane, bis(p-hydroxyphenyl)butyl acetate, bis(p-hydroxyphenyl)methyl acetate, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1, 4-bis[α-methyl-α-(4'-hydroxyphenyl)ethyl]benzene, 1,3-bis[α-methyl-α-(4'-hydroxyphenyl)ethyl]benzene, di(4-hydroxy- 3-methylphenyl) sulfide, 2,2'-thiobis(3-tert-octylphenol), 2,2'-thiobis(4-tert-octylphenol), N-[2-(3-phenylureido)phenyl]benzenesulfone Phenolic compounds such as amides, N,N'-di-[3-(p-toluenesulfonyloxy)phenyl]urea, diphenylsulfone crosslinked compounds described in WO 97/16420, WO 02/081229 or JP-A-2002- Compounds described in Publication No. 301873, thiourea compounds such as N,N'-di-m-chlorophenylthiourea, p-chlorobenzoic acid, stearyl gallate, zinc bis[4-(n-octyloxycarbonylamino)salicylate] Dihydrate, 4-[2-(p-methoxyphenoxy)ethyloxy]salicylic acid, 4-[3-(p-tolylsulfonyl)propyloxy]salicylic acid, 5-[p-(2-p-methoxyphenoxyethoxy) Aromatic carboxylic acids such as [cumyl] salicylic acid, salts of these aromatic carboxylic acids with polyvalent metal salts such as zinc, magnesium, aluminum, calcium, titanium, manganese, tin, and nickel, and antipyrine complexes of zinc thiocyanate. , complex zinc salts of terephthalaldehydic acid and other aromatic carboxylic acids, and the like. These color developers can be used alone or in combination of two or more. 1-[4-(4-Hydroxyphenylsulfonyl)phenoxy]-4-[4-(4-isopropoxyphenylsulfonyl)phenoxy]butane is available, for example, under the trade name TOMILAC214 manufactured by Mitsubishi Chemical Corporation. The phenol condensation composition described in Publication No. 2003-154760 is available, for example, under the trade name TOMILAC224 manufactured by Mitsubishi Chemical Corporation, and the diphenylsulfone crosslinked compound described in International Publication No. WO 97/16420 is available from Nippon Soda Co., Ltd. It is available under the trade name D-90. Furthermore, the compounds described in WO02/081229 and the like are available as trade names NKK-395 and D-100 manufactured by Nippon Soda Co., Ltd.
　本発明の感熱記録体に使用することのできる増感剤としては、従来公知の増感剤を使用することができる。かかる増感剤としては、ステアリン酸アミド、パルミチン酸アミド等の脂肪酸アマイド、エチレンビスアミド、モンタン酸ワックス、ポリエチレンワックス、１，２－ジ－（３－メチルフェノキシ）エタン、ｐ－ベンジルビフェニル、β－ベンジルオキシナフタレン、４－ビフェニル－ｐ－トリルエーテル、ｍ－ターフェニル、１，２－ジフェノキシエタン、シュウ酸ジベンジル、シュウ酸ジ（ｐ－クロロベンジル）、シュウ酸ジ（ｐ－メチルベンジル）、テレフタル酸ジベンジル、ｐ－ベンジルオキシ安息香酸ベンジル、ジ－ｐ－トリルカーボネート、フェニル－α－ナフチルカーボネート、１，４－ジエトキシナフタレン、１－ヒドロキシ－２－ナフトエ酸フェニルエステル、ｏ－キシレン－ビス－（フェニルエーテル）、４－（ｍ－メチルフェノキシメチル）ビフェニル、４，４'－エチレンジオキシ－ビス－安息香酸ジベンジルエステル、ジベンゾイルオキシメタン、１，２－ジ（３－メチルフェノキシ）エチレン、ビス［２－（４－メトキシ－フェノキシ）エチル］エーテル、ｐ－ニトロ安息香酸メチル、ｐ－トルエンスルホン酸フェニルなどを例示することができるが、特にこれらに制限されるものではない。これらの増感剤は、単独又は２種以上混合して使用してもよい。 As the sensitizer that can be used in the heat-sensitive recording material of the present invention, conventionally known sensitizers can be used. Such sensitizers include fatty acid amides such as stearic acid amide and palmitic acid amide, ethylene bisamide, montanic acid wax, polyethylene wax, 1,2-di-(3-methylphenoxy)ethane, p-benzylbiphenyl, β- Benzyloxynaphthalene, 4-biphenyl-p-tolyl ether, m-terphenyl, 1,2-diphenoxyethane, dibenzyl oxalate, di(p-chlorobenzyl) oxalate, di(p-methylbenzyl) oxalate, Dibenzyl terephthalate, benzyl p-benzyloxybenzoate, di-p-tolyl carbonate, phenyl-α-naphthyl carbonate, 1,4-diethoxynaphthalene, 1-hydroxy-2-naphthoic acid phenyl ester, o-xylene-bis -(phenyl ether), 4-(m-methylphenoxymethyl)biphenyl, 4,4'-ethylenedioxy-bis-benzoic acid dibenzyl ester, dibenzoyloxymethane, 1,2-di(3-methylphenoxy) Examples include ethylene, bis[2-(4-methoxy-phenoxy)ethyl]ether, methyl p-nitrobenzoate, phenyl p-toluenesulfonate, but are not particularly limited thereto. These sensitizers may be used alone or in combination of two or more.
　本発明で使用可能なバインダーとしては、完全ケン化ポリビニルアルコール、部分ケン化ポリビニルアルコール、カルボキシ変性ポリビニルアルコール、ジアセトン変性ポリビニルアルコール、アセトアセチル変性ポリビニルアルコール、アマイド変性ポリビニルアルコール、スルホン酸変性ポリビニルアルコール、ブチラール変性ポリビニルアルコール、オレフィン変性ポリビニルアルコール、ニトリル変性ポリビニルアルコール、ピロリドン変性ポリビニルアルコール、シラノール変性ポリビニルアルコール、カチオン変性ポリビニルアルコール、末端アルキル変性ポリビニルアルコールなどのポリビニルアルコール類、ヒドロキシエチルセルロース、メチルセルロース、エチルセルロース、カルボキシメチルセルロース、アセチルセルロースなどのセルロースエーテル及びその誘導体、澱粉、酵素変性澱粉、熱化学変性澱粉、酸化澱粉、エステル化澱粉、エーテル化澱粉（例えば、ヒドロキシエチル化澱粉など）、カチオン化澱粉などの澱粉類、ポリアクリルアミド、カチオン性ポリアクリルアミド、アニオン性ポリアクリルアミド、両性ポリアクリルアミドなどのポリアクリルアミド類、ポリエステルポリウレタン系樹脂、ポリエーテルポリウレタン系樹脂、ポリウレタン系アイオノマー樹脂などのウレタン系樹脂、（メタ）アクリル酸及び、（メタ）アクリル酸と共重合可能な単量体成分（オレフィンを除く）からなるアクリル系樹脂、スチレン－ブタジエン共重合体、スチレン－ブタジエン－アクリロニトリル共重合体、スチレン－ブタジエン－アクリル共重合体などのスチレン－ブタジエン系樹脂、ポリ酢酸ビニル、塩化ビニル－酢酸ビニル共重合体、エチレン－酢酸ビニル共重合体などのポリオレフィン系樹脂、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリアクリル酸エステル、アラビヤゴム、ポリビニルブチラール、ポリスチロース及びそれらの共重合体、シリコーン樹脂、石油樹脂、テルペン樹脂、ケトン樹脂、クマロン樹脂などを例示することができる。これらは単独で又は２種以上混合して使用してもよい。 Binders that can be used in the present invention include fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, and butyral. Polyvinyl alcohols such as modified polyvinyl alcohol, olefin-modified polyvinyl alcohol, nitrile-modified polyvinyl alcohol, pyrrolidone-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, terminal alkyl-modified polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, Starches such as cellulose ether and its derivatives such as acetyl cellulose, starch, enzyme-modified starch, thermochemically modified starch, oxidized starch, esterified starch, etherified starch (e.g. hydroxyethylated starch, etc.), cationized starch, polyester Polyacrylamides such as acrylamide, cationic polyacrylamide, anionic polyacrylamide, and amphoteric polyacrylamide, urethane resins such as polyester polyurethane resin, polyether polyurethane resin, and polyurethane ionomer resin, (meth)acrylic acid and ( Acrylic resins consisting of monomer components (excluding olefins) that can be copolymerized with meth)acrylic acid, styrene-butadiene copolymers, styrene-butadiene-acrylonitrile copolymers, styrene-butadiene-acrylic copolymers, etc. Polyolefin resins such as styrene-butadiene resins, polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, ethylene-vinyl acetate copolymers, polyvinyl chloride, polyvinylidene chloride, polyacrylic esters, gum arabic, polyvinyl butyral, Examples include polystyrose and copolymers thereof, silicone resins, petroleum resins, terpene resins, ketone resins, coumaron resins, and the like. These may be used alone or in combination of two or more.
　本発明で使用可能な顔料としては、シリカ、炭酸カルシウム、カオリン、焼成カオリン、ケイソウ土、タルク、酸化チタン、水酸化アルミニウムなどの無機又は有機充填剤などを例示することができる。これらは単独で又は２種以上混合して使用してもよい。 Examples of pigments that can be used in the present invention include inorganic or organic fillers such as silica, calcium carbonate, kaolin, calcined kaolin, diatomaceous earth, talc, titanium oxide, and aluminum hydroxide. These may be used alone or in combination of two or more.
　本発明で使用可能な架橋剤としては、グリオキザール、メチロールメラミン、メラミンホルムアルデヒド樹脂、メラミン尿素樹脂、ポリアミンエピクロロヒドリン樹脂、ポリアミドエピクロロヒドリン樹脂、過硫酸カリウム、過硫酸アンモニウム、過硫酸ソーダ、塩化第二鉄、塩化マグネシウム、ホウ砂、ホウ酸、ミョウバン、塩化アンモニウム剤などを例示することができる。 Crosslinking agents that can be used in the present invention include glyoxal, methylolmelamine, melamine formaldehyde resin, melamine urea resin, polyamine epichlorohydrin resin, polyamide epichlorohydrin resin, potassium persulfate, ammonium persulfate, sodium persulfate, chloride Examples include ferric iron, magnesium chloride, borax, boric acid, alum, and ammonium chloride agents.
　また、本発明においては、前記課題に対する所望の効果を阻害しない範囲で、記録画像の耐油性効果などを示す画像安定剤として、４，４'－ブチリデン（６－ｔ－ブチル－３－メチルフェノール）、２，２'－ジ－ｔ－ブチル－５，５'－ジメチル－４，４'－スルホニルジフェノール、１，１，３－トリス（２－メチル－４－ヒドロキシ－５－シクロヘキシルフェニル）ブタン、１，１，３－トリス（２－メチル－４－ヒドロキシ－５－ｔ－ブチルフェニル）ブタン、４－ベンジルオキシ－４'－（２，３－エポキシ－２－メチルプロポキシ）ジフェニルスルホン等を使用することもできる。
　このほかにベンゾフェノン系やトリアゾール系の紫外線吸収剤、滑剤、分散剤、消泡剤、酸化防止剤、蛍光染料等を使用することができる。 In the present invention, 4,4'-butylidene (6-t-butyl-3-methylphenol ), 2,2'-di-t-butyl-5,5'-dimethyl-4,4'-sulfonyldiphenol, 1,1,3-tris(2-methyl-4-hydroxy-5-cyclohexylphenyl) Butane, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 4-benzyloxy-4'-(2,3-epoxy-2-methylpropoxy)diphenylsulfone, etc. You can also use
In addition, benzophenone-based or triazole-based ultraviolet absorbers, lubricants, dispersants, antifoaming agents, antioxidants, fluorescent dyes, and the like can be used.
　本発明の感熱記録体に使用する電子供与性ロイコ染料、電子受容性顕色剤、その他の各種成分の種類及び量は要求される性能及び記録適性に従って決定され、特に限定されるものではないが、通常、電子供与性ロイコ染料１重量部に対して電子受容性顕色剤０．５～１０重量部、増感剤０．５～１０重量部程度が使用される。
　その他の任意成分である、バインダー、顔料、架橋剤、画像安定剤、その他の成分の種類及び量は、要求される性能及び記録適性に従って決定され、特に限定されるものではないが、通常、バインダーは感熱記録層（固形分）１００重量部に対し固形分で５～５０重量部程度、顔料は感熱記録層（固形分）１００重量部に対し固形分で０～５０重量部程度が適当である。滑剤を使用する場合には、滑剤の含有量は感熱記録層（固形分）１００重量部に対し固形分で５～１０重量部程度が適当である。 The types and amounts of the electron-donating leuco dye, electron-accepting color developer, and other various components used in the thermal recording medium of the present invention are determined according to the required performance and recording suitability, and are not particularly limited. Usually, about 0.5 to 10 parts by weight of an electron-accepting color developer and 0.5 to 10 parts by weight of a sensitizer are used per 1 part by weight of an electron-donating leuco dye.
The types and amounts of other optional components such as binders, pigments, crosslinking agents, image stabilizers, and other components are determined according to the required performance and recording suitability, and are not particularly limited. Appropriately, the solid content is about 5 to 50 parts by weight per 100 parts by weight of the heat-sensitive recording layer (solid content), and the pigment is suitably about 0 to 50 parts by weight in terms of solid content per 100 parts by weight of the heat-sensitive recording layer (solid content). . When a lubricant is used, the content of the lubricant is suitably about 5 to 10 parts by weight based on 100 parts by weight of the heat-sensitive recording layer (solid content).
　本発明の感熱記録体においては、感熱記録層上に更に保護層を設けてもよい。保護層は、顔料と樹脂を主成分とすることが多く、感熱記録層に使用できる材料として例示したバインダー、顔料、架橋剤などを用いることができる。
　このバインダーとしては、上述の感熱記録層に使用可能なバインダーが適宜使用可能であるが、カルボキシ変性ポリビニルアルコール及び非コアシェル型アクリル系樹脂が好ましい。これらのバインダーは１種又は２種以上用いてもよい。
　また、架橋剤としては、上述の感熱記録層に使用可能な架橋剤が適宜使用可能であるが、エピクロロヒドリン系樹脂及びポリアミン／ポリアミド系樹脂（エピクロロヒドリン系樹脂に含まれるものを除く。）が好ましい。
　保護層にカルボキシ変性ポリビニルアルコールと共に、エピクロロヒドリン系樹脂及びポリアミン／ポリアミド系樹脂を含有させることがより好ましく、これにより発色性能が更に改善される。 In the heat-sensitive recording material of the present invention, a protective layer may be further provided on the heat-sensitive recording layer. The protective layer often contains a pigment and a resin as main components, and binders, pigments, crosslinking agents, etc., which are exemplified as materials that can be used in the heat-sensitive recording layer, can be used.
As this binder, binders that can be used in the above-mentioned heat-sensitive recording layer can be used as appropriate, but carboxy-modified polyvinyl alcohol and non-core-shell type acrylic resin are preferable. These binders may be used alone or in combination of two or more.
In addition, as the crosslinking agent, any crosslinking agent that can be used in the heat-sensitive recording layer mentioned above can be used as appropriate, but epichlorohydrin resins and polyamine/polyamide resins (those contained in epichlorohydrin resins) can be used as appropriate. ) is preferred.
It is more preferable that the protective layer contains an epichlorohydrin resin and a polyamine/polyamide resin together with carboxy-modified polyvinyl alcohol, thereby further improving the coloring performance.
　このカルボキシ変性ポリビニルアルコールは、例えば、ポリビニルアルコールとフマル酸、無水フタル酸、無水メリト酸、無水イタコン酸などの多価カルボン酸との反応物、あるいはこれらの反応物のエステル化物、さらに酢酸ビニルとマレイン酸、フマル酸、イタコン酸、クロトン酸、アクリル酸、メタアクリル酸などのエチレン性不飽和ジカルボン酸との共重合物の鹸化物として得られる。具体的な製造方法としては、例えば特開昭５３－９１９９５号公報などに例示されている方法が挙げられる。また、カルボキシ変性ポリビニルアルコールの鹸化度は７２～１００ｍｏｌ％であることが好ましく、重合度は５００～２４００、より好ましくは１０００～２０００である。 This carboxy-modified polyvinyl alcohol is, for example, a reaction product of polyvinyl alcohol and a polyhydric carboxylic acid such as fumaric acid, phthalic anhydride, mellitic anhydride, itaconic anhydride, or an esterified product of these reactants, and also a reaction product of vinyl acetate. It is obtained as a saponified copolymer with ethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, crotonic acid, acrylic acid, and methacrylic acid. Specific manufacturing methods include, for example, the method exemplified in JP-A-53-91995. Further, the degree of saponification of the carboxy-modified polyvinyl alcohol is preferably 72 to 100 mol%, and the degree of polymerization is preferably 500 to 2,400, more preferably 1,000 to 2,000.
　この非コアシェル型アクリル系樹脂のガラス転移点（Ｔｇ）は、好ましくは９５℃以下であり、更に好ましくは５０℃より高い。このＴｇは示差走査熱量測定（ＤＳＣ）によって測定する。
　この非コアシェル型アクリル系樹脂は、（メタ）アクリル酸、及び（メタ）アクリル酸と共重合可能な単量体成分を含み、（メタ）アクリル酸が非コアシェル型アクリル系樹脂１００重量部中１～１０重量部であることが好ましい。（メタ）アクリル酸は、アルカリ可溶性であり、中和剤の添加により非コアシェル型アクリル系樹脂を水溶性樹脂にする特性を有している。非コアシェル型アクリル系樹脂を水溶性樹脂に変化させることによって、特に保護層中に顔料を含有する場合、顔料への結合性が著しく向上し、多量の顔料含有下でも優れた強度を有する保護層を形成することができる。（メタ）アクリル酸と共重合可能な成分としては、例えば（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸－２－エチルへキシル、（メタ）アクリル酸オクチルなどのアクリル酸アルキル樹脂及びエポキシ樹脂、シリコーン樹脂、スチレン又はその誘導体によって変性された上記アクリル酸アルキル樹脂などの変性アクリル酸アルキル樹脂、（メタ）アクリロニトリル、アクリル酸エステル、ヒドロキシアルキルアクリル酸エステルを例示できるが、特に（メタ）アクリロニトリル及び／又はメタクリル酸メチルを配合することが好ましい。（メタ）アクリロニトリルは非コアシェル型アクリル系樹脂１００部中１５～７０部配合することが好ましい。また、メタクリル酸メチルは非コアシェル型アクリル系樹脂１００部中２０～８０部含むことが好ましい。（メタ）アクリロニトリル及びメタクリル酸メチルを含む場合、（メタ）アクリロニトリルを非コアシェル型アクリル系樹脂１００部中１５～１８部、メタクリル酸メチルを非コアシェル型アクリル系樹脂１００部中２０～８０部配合することが好ましい。 The glass transition point (Tg) of this non-core-shell type acrylic resin is preferably 95°C or lower, more preferably higher than 50°C. This Tg is measured by differential scanning calorimetry (DSC).
This non-core-shell type acrylic resin contains (meth)acrylic acid and a monomer component copolymerizable with (meth)acrylic acid, and (meth)acrylic acid is 1 part by weight in 100 parts by weight of the non-core-shell type acrylic resin. The amount is preferably 10 parts by weight. (Meth)acrylic acid is alkali-soluble and has the property of making a non-core-shell type acrylic resin a water-soluble resin by adding a neutralizing agent. By changing the non-core-shell type acrylic resin to a water-soluble resin, the bonding property to the pigment is significantly improved, especially when the protective layer contains a pigment, and the protective layer has excellent strength even when containing a large amount of pigment. can be formed. Examples of components copolymerizable with (meth)acrylic acid include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, By alkyl acrylate resins such as pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, epoxy resin, silicone resin, styrene or its derivatives. Examples include modified alkyl acrylate resins such as the above-mentioned modified alkyl acrylate resins, (meth)acrylonitrile, acrylic esters, and hydroxyalkyl acrylic esters, but in particular, (meth)acrylonitrile and/or methyl methacrylate should be blended. is preferred. (Meth)acrylonitrile is preferably blended in an amount of 15 to 70 parts per 100 parts of the non-core-shell type acrylic resin. Furthermore, it is preferable that methyl methacrylate be contained in an amount of 20 to 80 parts per 100 parts of the non-core-shell type acrylic resin. When containing (meth)acrylonitrile and methyl methacrylate, mix 15 to 18 parts of (meth)acrylonitrile to 100 parts of non-core-shell acrylic resin, and 20 to 80 parts of methyl methacrylate to 100 parts of non-core-shell acrylic resin. It is preferable.
　このエピクロロヒドリン系樹脂は、分子中にエポキシ基を含有していることを特徴とする樹脂であり、例えば、ポリアミドエピクロロヒドリン樹脂、ポリアミンエピクロロヒドリン樹脂などを挙げることができ、これらを単独又は併用することができる。また、エピクロロヒドリン系樹脂の主鎖に存在するアミンとしては第１級から第４級までのものを使用することができ、特に制限はない。さらに、耐水性が良好なことから、カチオン化度および分子量はカチオン化度５ｍｅｑ／ｇ・Ｓｏｌｉｄ以下（ｐＨ７での測定値）、分子量５０万以上が好ましい。エピクロロヒドリン系樹脂の具体例としては、スミレーズレジン６５０（３０）、スミレーズレジン６７５Ａ、スミレーズレジン６６１５（以上、住友化学社製）、ＷＳ４００２、ＷＳ４０２０、ＷＳ４０２４、ＷＳ４０３０、ＷＳ４０４６、ＷＳ４０１０、ＣＰ８９７０（以上、星光ＰＭＣ社製）などが挙げられる。 This epichlorohydrin resin is a resin characterized by containing an epoxy group in its molecule, and includes, for example, polyamide epichlorohydrin resin, polyamine epichlorohydrin resin, etc. These can be used alone or in combination. Furthermore, as the amine present in the main chain of the epichlorohydrin resin, primary to quaternary amines can be used, and there are no particular limitations. Further, in order to have good water resistance, the degree of cationization and molecular weight are preferably 5 meq/g·Solid or less (measured value at pH 7) and a molecular weight of 500,000 or more. Specific examples of epichlorohydrin resins include violet resin 650 (30), violet resin 675A, violet resin 6615 (manufactured by Sumitomo Chemical Co., Ltd.), WS4002, WS4020, WS4024, WS4030, WS4046, WS4010, Examples include CP8970 (manufactured by Seiko PMC).
　このポリアミン／ポリアミド系樹脂は、分子中にエポキシ基を有さず、例えば、ポリアミド尿素樹脂、ポリアルキレンポリアミン樹脂、ポリアルキレンポリアミド樹脂、ポリアミンポリ尿素樹脂、変性ポリアミン樹脂、変性ポリアミド樹脂、ポリアルキレンポリアミン尿素ホルマリン樹脂、ポリアルキレンポリアミンポリアミドポリ尿素樹脂などを挙げることができ、これらを単独又は併用することができる。ポリアミン／ポリアミド系樹脂の具体例としては、スミレーズレジン３０２（住友化学社製：ポリアミンポリ尿素樹脂）、スミレーズレジン７１２（住友化学社製：ポリアミンポリ尿素樹脂）、スミレーズレジン７０３（住友化学社製：ポリアミンポリ尿素樹脂）、スミレーズレジン６３６（住友化学社製：ポリアミンポリ尿素樹脂）、スミレーズレジンＳＰＩ－１００（住友化学社製：変性ポリアミン樹脂）、スミレーズレジンＳＰＩ－１０２Ａ（住友化学社製：変性ポリアミン樹脂）、スミレーズレジンＳＰＩ－１０６Ｎ（住友化学社製：変性ポリアミド樹脂）、スミレーズレジンＳＰＩ－２０３（５０）（住友化学社製）、スミレーズレジンＳＰＩ－１９８（住友化学社製）、プリンティブＡ－７００、プリンティブＡ－６００（以上、旭化成社製）、ＰＡ６５００、ＰＡ６５０４、ＰＡ６６３４、ＰＡ６６３８、ＰＡ６６４０、ＰＡ６６４４、ＰＡ６６４６、ＰＡ６６５４、ＰＡ６７０２、ＰＡ６７０４（以上、星光ＰＭＣ社製：ポリアルキレンポリアミンポリアミドポリ尿素樹脂）、ＣＰ８９９４（星光ＰＭＣ社製：ポリエチレンイミン樹脂）などが挙げられる。特に制限はないが、印字濃度が良好なことから、ポリアミン系樹脂（ポリアルキレンポリアミン樹脂、ポリアミンポリ尿素樹脂、変性ポリアミン樹脂、ポリアルキレンポリアミン尿素ホルマリン樹脂、ポリアルキレンポリアミンポリアミドポリ尿素樹脂）を使用することが好ましい。 This polyamine/polyamide resin does not have an epoxy group in its molecule, and includes, for example, polyamide urea resin, polyalkylene polyamine resin, polyalkylene polyamide resin, polyamine polyurea resin, modified polyamine resin, modified polyamide resin, polyalkylene polyamine Examples include urea-formalin resin, polyalkylene polyamine polyamide polyurea resin, and these can be used alone or in combination. Specific examples of polyamine/polyamide-based resins include violet resin 302 (manufactured by Sumitomo Chemical Co., Ltd.: polyamine polyurea resin), violet resin 712 (manufactured by Sumitomo Chemical Co., Ltd.: polyamine polyurea resin), and violet resin 703 (manufactured by Sumitomo Chemical Co., Ltd.: polyamine polyurea resin). Sumitomo Chemical Co., Ltd.: Polyamine Polyurea Resin), Sumitomo Chemical Co., Ltd.: Polyamine Polyurea Resin), Sumitomo Chemical Co., Ltd.: Polyamine Polyurea Resin), Sumitomo Chemical Co., Ltd.: Polyamine Polyurea Resin), Sumitomo Chemical Co., Ltd.: Polyamine Polyurea Resin), Sumitomo Chemical Co., Ltd.: Modified Polyamine Resin), Sumitomo Resin SPI-102A (Sumitomo (manufactured by Kagaku Co., Ltd.: modified polyamine resin), Sumirezu Resin SPI-106N (manufactured by Sumitomo Chemical Co., Ltd.: modified polyamide resin), Sumireze Resin SPI-203 (50) (manufactured by Sumitomo Chemical Co., Ltd.), Sumiraze Resin SPI-198 (manufactured by Sumitomo Chemical Co., Ltd.) Printive A-700, Printive A-600 (all manufactured by Asahi Kasei), PA6500, PA6504, PA6634, PA6638, PA6640, PA6644, PA6646, PA6654, PA6702, PA6704 (all manufactured by Seiko PMC) : polyalkylene polyamine polyamide polyurea resin), CP8994 (manufactured by Seiko PMC Co., Ltd.: polyethylene imine resin), and the like. Although there are no particular restrictions, polyamine resins (polyalkylene polyamine resin, polyamine polyurea resin, modified polyamine resin, polyalkylene polyamine urea formalin resin, polyalkylene polyamine polyamide polyurea resin) are used because of their good print density. It is preferable.
　保護層にカルボキシ変性ポリビニルアルコールと共にエピクロロヒドリン系樹脂及びポリアミン／ポリアミド系樹脂を使用する場合の含有量は、カルボキシ変性ポリビニルアルコール１００重量部に対してそれぞれ１～１００重量部であることが好ましく、５～５０重量部であることがより好ましく、１０～４０重量部であることが更に好ましい。 When epichlorohydrin resin and polyamine/polyamide resin are used together with carboxy-modified polyvinyl alcohol in the protective layer, the content thereof is preferably 1 to 100 parts by weight per 100 parts by weight of carboxy-modified polyvinyl alcohol. , more preferably 5 to 50 parts by weight, and still more preferably 10 to 40 parts by weight.
　保護層に用いる顔料としては、上記の感熱記録層に使用可能な顔料が適宜使用可能であるが、カオリン、焼成カオリン、水酸化アルミニウム、シリカが好ましい。これらの顔料は１種又は２種以上用いてもよい。
　保護層中のバインダーの含有量（固形分）は好ましくは２０重量％以上、２０～８０重量％程度がより好ましく、保護層が顔料を含む場合、顔料およびバインダーの含有量は、顔料１００重量部に対しバインダーは固形分で３０～３００重量部程度が好ましい。
　保護層の塗工液には必要に応じて、上述の感熱記録層に使用可能な架橋剤、滑剤、安定剤や、紫外線吸収剤、分散剤、消泡剤、酸化防止剤、蛍光染料等の各種助剤を適宜配合してもよい。 As the pigment used in the protective layer, the pigments that can be used in the heat-sensitive recording layer described above can be used as appropriate, but kaolin, calcined kaolin, aluminum hydroxide, and silica are preferable. These pigments may be used alone or in combination of two or more.
The binder content (solid content) in the protective layer is preferably 20% by weight or more, more preferably about 20 to 80% by weight. When the protective layer contains a pigment, the content of the pigment and binder is 100 parts by weight of the pigment. On the other hand, the binder preferably has a solid content of about 30 to 300 parts by weight.
The coating solution for the protective layer may contain crosslinking agents, lubricants, stabilizers, ultraviolet absorbers, dispersants, antifoaming agents, antioxidants, fluorescent dyes, etc. that can be used in the heat-sensitive recording layer as described above. Various auxiliary agents may be blended as appropriate.
　また、支持体と感熱記録層の間に下塗り層を設けてもよい。この下塗り層は、主としてバインダーと顔料とから成る。
　下塗り層に使用するバインダーとしては、上述の感熱記録層に使用する各種バインダーが使用可能である。これらのバインダーは１種又は２種以上使用してもよい。
　下塗り層に使用する顔料としては、上述の感熱記録層に使用する各種顔料が使用可能である。これらの顔料は１種又は２種以上使用してもよい。
　下塗り層中の顔料は、下塗り層の全固形分１００重量部に対して、通常５０～９５重量部、好ましくは７０～９０重量部である。
　下塗り層には、必要に応じて分散剤、可塑剤、ｐＨ調整剤、消泡剤、保水剤、防腐剤、着色染料、紫外線防止剤等の各種助剤を適宜配合してもよい。 Further, an undercoat layer may be provided between the support and the heat-sensitive recording layer. This undercoat layer mainly consists of a binder and a pigment.
As the binder used in the undercoat layer, the various binders used in the above-mentioned heat-sensitive recording layer can be used. These binders may be used alone or in combination of two or more.
As the pigment used in the undercoat layer, the various pigments used in the heat-sensitive recording layer described above can be used. These pigments may be used alone or in combination of two or more.
The amount of pigment in the undercoat layer is usually 50 to 95 parts by weight, preferably 70 to 90 parts by weight, based on 100 parts by weight of the total solid content of the undercoat layer.
Various auxiliary agents such as a dispersant, a plasticizer, a pH adjuster, an antifoaming agent, a water retention agent, a preservative, a coloring dye, and an ultraviolet light inhibitor may be appropriately blended into the undercoat layer as required.
　上記各塗工層用に処方された組成からなる塗工液を紙、再生紙、合成紙、フィルム、プラスチックフィルム、発泡プラスチックフィルム、不織布等任意の支持体に塗工することによって目的とする感熱記録体が得られる。またこれらを組み合わせた複合シートを支持体として使用してもよい。
　電子供与性ロイコ染料、電子受容性顕色剤、電子受容体、電子供与体及び必要に応じて添加する材料は、ボールミル、アトライター、サンドグライダーなどの粉砕機あるいは適当な乳化装置によって数ミクロン以下の粒子径になるまで微粒化し、目的に応じて各種の添加材料を加えて塗工液とする。
　上記各塗工層を塗工する手段は特に限定されるものではなく、周知慣用技術に従って塗工することができる。例えばエアーナイフコーター、ロッドブレードコーター、ベントブレードコーター、ベベルブレードコーター、ロールコーター、カーテンコーター、スプレーコーターなど各種コーターを備えたオフマシン塗工機やオンマシン塗工機が適宜選択され使用される。感熱記録層の塗工量は要求される性能及び記録適性に従って決定され、特に限定されるものではないが、一般的な塗工量は固形分で２～１２ｇ／ｍ２程度である。
　また、各塗工層の塗工後にスーパーカレンダーがけ等の平滑化処理を施すなど、感熱記録体分野における各種公知の技術を適宜付加してもよい。
The desired thermal sensitivity can be achieved by coating a coating liquid with the composition formulated for each of the above coating layers onto any support such as paper, recycled paper, synthetic paper, film, plastic film, foamed plastic film, non-woven fabric, etc. A recording body is obtained. Moreover, a composite sheet obtained by combining these may be used as a support.
The electron-donating leuco dye, electron-accepting color developer, electron acceptor, electron donor, and other materials to be added as necessary are crushed to a size of several microns or less by a grinder such as a ball mill, attritor, or sand glider, or by an appropriate emulsifying device. It is atomized until it has a particle size of , and various additive materials are added depending on the purpose to make a coating liquid.
The means for applying each of the above-mentioned coating layers is not particularly limited, and can be applied according to well-known and commonly used techniques. For example, an off-machine coating machine or an on-machine coating machine equipped with various coaters such as an air knife coater, a rod blade coater, a bent blade coater, a bevel blade coater, a roll coater, a curtain coater, and a spray coater is appropriately selected and used. The coating amount of the heat-sensitive recording layer is determined according to the required performance and recording suitability, and is not particularly limited, but the general coating amount is about 2 to 12 g/m 2 in terms of solid content.
Further, various known techniques in the field of heat-sensitive recording materials may be added as appropriate, such as applying a smoothing treatment such as super calendering after coating each coating layer.
　以下、実施例にて本発明を例証するが、本発明を限定することを意図するものではない。なお、各実施例及び比較例中、特にことわらない限り「部」は「重量部」、「％」は「重量％」を示す。 Hereinafter, the present invention will be illustrated by Examples, but the present invention is not intended to be limited. In each of the Examples and Comparative Examples, "part" means "part by weight" and "%" means "% by weight" unless otherwise specified.
［各塗工液の調製］
　下記配合からなる配合物を攪拌分散して、下塗り層用塗工液を調製した。
＜下塗り層用塗工液＞
　焼成カオリン（イメリス社製、アルファテックスＨＰ）　　　　　５０部
　プラスチック中空粒子（ゼオン社製、ＭＨ８１０９）　　　　　　５０部
　スチレン・ブタジエン共重合体ラテックス（日本ゼオン社製、
　　ＳＴ５５２６、固形分４８％）　　　　　　　　　　　　　　　１０部
　水　　　　　　　　　　　　　　　　　　　　　　　　　　　　　５０部 [Preparation of each coating fluid]
A coating solution for an undercoat layer was prepared by stirring and dispersing a composition having the following composition.
<Coating liquid for undercoat layer>
Calcined kaolin (manufactured by Imerys, Alphatex HP) 50 parts Plastic hollow particles (manufactured by Zeon, MH8109) 50 parts Styrene-butadiene copolymer latex (manufactured by Nippon Zeon,
ST5526, solid content 48%) 10 parts Water 50 parts
　次いで、下記割合からなる配合物を混合してバックコート層用塗工液１～６を調製した。
＜バックコート層用塗工液１＞
　カオリン（イメリス社製、商品名：コンツァー１５００）　　　　２０部
　エチレン－ビニルアルコール共重合体(クラレ社製、商品名：
　　エクセバール　ＲＳ４１０４)　　　　　　　　　　　　　　　１０部
　エチレン－アクリル共重合体（住友精化社製、商品名：ザイクセンＡＣ、
　　融点：８０～９５℃）　　　　　　　　　　　　　　　　　　　４０部
＜バックコート層用塗工液２＞
　カオリン（イメリス社製、商品名：コンツァー１５００）　　　　２０部
　エチレン－ビニルアルコール共重合体（ＲＳ４１０４）　　　　　１０部
　エチレン－アクリル共重合体（ザイクセンＡＣ）　　　　　　　　２０部
　スチレン・ブタジエン共重合体ラテックス（ＳＴ５５２６）　　　２０部 Next, backcoat layer coating solutions 1 to 6 were prepared by mixing formulations having the following proportions.
<Coating liquid 1 for back coat layer>
Kaolin (manufactured by Imerys, trade name: Conzer 1500) 20 parts Ethylene-vinyl alcohol copolymer (manufactured by Kuraray, trade name:
Excelval RS4104) 10 parts Ethylene-acrylic copolymer (manufactured by Sumitomo Seika Co., Ltd., product name: Zaixen AC,
Melting point: 80-95°C) 40 parts <Coating liquid 2 for back coat layer>
Kaolin (manufactured by Imerys, trade name: Conzer 1500) 20 parts Ethylene-vinyl alcohol copolymer (RS4104) 10 parts Ethylene-acrylic copolymer (Zaixen AC) 20 parts Styrene-butadiene copolymer latex (ST5526) 20 parts
＜バックコート層用塗工液３＞
　カオリン（コンツァー１５００）　　　　　　　　　　　　　　　２０部
　エチレン・アクリル酸共重合体（ザイクセンＡＣ）　　　　　　　５０部
＜バックコート層用塗工液４＞
　カオリン（コンツァー１５００）　　　　　　　　　　　　　　　２０部
　エチレン－ビニルアルコール共重合体（ＲＳ４１０４）　　　　　５０部
＜バックコート層用塗工液５＞
　カオリン（コンツァー１５００）　　　　　　　　　　　　　　　２０部
　完全ケン化型ポリビニルアルコール水溶液（ＰＶＡ１１７）　　　１０部
　エチレン－アクリル共重合体（ザイクセンＡＣ）　　　　　　　　４０部
＜バックコート層用塗工液６＞
　カオリン（コンツァー１５００）　　　　　　　　　　　　　　　２０部
　エチレン－ビニルアルコール共重合体（ＲＳ４１０４）　　　　　１０部
　スチレン・ブタジエン共重合体ラテックス（ＳＴ５５２６）　　　４０部 <Coating liquid 3 for back coat layer>
Kaolin (Conzer 1500) 20 parts Ethylene-acrylic acid copolymer (Zaixen AC) 50 parts <Coating liquid 4 for back coat layer>
Kaolin (Conzer 1500) 20 parts Ethylene-vinyl alcohol copolymer (RS4104) 50 parts <Coating liquid for back coat layer 5>
Kaolin (Conzer 1500) 20 parts Completely saponified polyvinyl alcohol aqueous solution (PVA117) 10 parts Ethylene-acrylic copolymer (Zaixen AC) 40 parts <Coating liquid 6 for back coat layer>
Kaolin (Conzer 1500) 20 parts Ethylene-vinyl alcohol copolymer (RS4104) 10 parts Styrene-butadiene copolymer latex (ST5526) 40 parts
　下記配合の顕色剤分散液、ロイコ染料分散液、および増感剤分散液を、それぞれ別々にサンドグラインダーで平均粒子径０．５ミクロンになるまで湿式磨砕を行った。
顕色剤分散液（Ａ１液）
　Ｎ－［２－（３－フェニルウレイド）フェニル］ベンゼンスルホンアミド
（日本曹達社製、ＮＫＫ１３０４、以下"ウレア系化合物"という。）
　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　６．０部
　完全ケン化型ポリビニルアルコール水溶液（クラレ社製、ＰＶＡ１１７、
　　固形分１０％）　　　　　　　　　　　　　　　　　　　　　５．０部
　水　　　　　　　　　　　　　　　　　　　　　　　　　　　　１．５部
顕色剤分散液（Ａ２液）
　４－ベンジルオキシ－４'－ヒドロキシジフェニルスルホン
　　（日華化学社製、ＢＰＳ－ＭＡ３）　　　　　　　　　　　　６．０部
　完全ケン化型ポリビニルアルコール水溶液（ＰＶＡ１１７）　　５．０部
　水　　　　　　　　　　　　　　　　　　　　　　　　　　　　１．５部
ロイコ染料分散液（Ｂ液）
　３－ジブチルアミノ－６－メチル－７－アニリノフルオラン
　　（山本化成社製、ＯＤＢ－２）　　　　　　　　　　　　　　６．０部
　完全ケン化型ポリビニルアルコール水溶液（ＰＶＡ１１７）　　５．０部
　水　　　　　　　　　　　　　　　　　　　　　　　　　　　　１．５部
増感剤分散液（Ｃ液）
　１，２－ビス－（３－メチルフェノキシ）エタン（三光社製、
　　ＫＳ２３２）　　　　　　　　　　　　　　　　　　　　　　６．０部
　完全ケン化型ポリビニルアルコール水溶液（ＰＶＡ１１７）　　５．０部
　水　　　　　　　　　　　　　　　　　　　　　　　　　　　　１．５部 A color developer dispersion, a leuco dye dispersion, and a sensitizer dispersion having the following formulations were wet-ground separately using a sand grinder until the average particle size was 0.5 microns.
Color developer dispersion (A1 liquid)
N-[2-(3-phenylureido)phenyl]benzenesulfonamide (manufactured by Nippon Soda Co., Ltd., NKK1304, hereinafter referred to as "urea compound")
6.0 parts fully saponified polyvinyl alcohol aqueous solution (manufactured by Kuraray Co., Ltd., PVA117,
Solid content 10%) 5.0 parts Water 1.5 parts
Color developer dispersion (A2 liquid)
4-Benzyloxy-4'-hydroxydiphenylsulfone (manufactured by NICCA Chemical Co., Ltd., BPS-MA3) 6.0 parts Completely saponified polyvinyl alcohol aqueous solution (PVA117) 5.0 parts Water 1.5 parts
Leuco dye dispersion (liquid B)
3-dibutylamino-6-methyl-7-anilinofluorane (manufactured by Yamamoto Kasei Co., Ltd., ODB-2) 6.0 parts Completely saponified polyvinyl alcohol aqueous solution (PVA117) 5.0 parts Water 1.5 parts
Sensitizer dispersion liquid (C liquid)
1,2-bis-(3-methylphenoxy)ethane (manufactured by Sankosha,
KS232) 6.0 parts Completely saponified polyvinyl alcohol aqueous solution (PVA117) 5.0 parts Water 1.5 parts
　次いで、下記の割合で各分散液を混合して感熱記録層用塗工液を調製した。
＜感熱記録層用塗工液１＞
　顕色剤分散液（Ａ１液）　　　　　　　　　　　　　　　　　１８．０部
　ロイコ染料分散液（Ｂ液）　　　　　　　　　　　　　　　　１８．０部
　増感剤分散液（Ｃ液）　　　　　　　　　　　　　　　　　　３６．０部
　シリカ分散液（水澤化学社製、ミズカシルＰ－５３７、固形分２５％）
　　　　　　　　　　　　　　　　　　　　　　　　　　　　　１７．５部
　完全ケン化型ポリビニルアルコール水溶液（ＰＶＡ１１７）　３０．０部
＜感熱記録層用塗工液２＞
　顕色剤分散液（Ａ２液）　　　　　　　　　　　　　　　　　１８．０部
　ロイコ染料分散液（Ｂ液）　　　　　　　　　　　　　　　　１８．０部
　増感剤分散液（Ｃ液）　　　　　　　　　　　　　　　　　　３６．０部
　シリカ分散液（ミズカシルＰ－５３７）　　　　　　　　　　１７．５部
　完全ケン化型ポリビニルアルコール水溶液（ＰＶＡ１１７）　３０．０部 Next, each dispersion liquid was mixed in the following proportions to prepare a coating liquid for a heat-sensitive recording layer.
<Coating liquid 1 for heat-sensitive recording layer>
Color developer dispersion (Liquid A1) 18.0 parts Leuco dye dispersion (Liquid B) 18.0 parts Sensitizer dispersion (Liquid C) 36.0 parts Silica dispersion (manufactured by Mizusawa Chemical Co., Ltd., Mizukasil P- 537, solid content 25%)
17.5 parts Completely saponified polyvinyl alcohol aqueous solution (PVA117) 30.0 parts <Coating liquid 2 for heat-sensitive recording layer>
Color developer dispersion (A2 solution) 18.0 parts Leuco dye dispersion (B solution) 18.0 parts Sensitizer dispersion (C solution) 36.0 parts Silica dispersion (Mizukasil P-537) 17.5 Part: Completely saponified polyvinyl alcohol aqueous solution (PVA117) 30.0 parts
　次いで、下記割合からなる配合物を混合して保護層用塗工液を調製した。
＜保護層用塗工液＞
　水酸化アルミニウム分散液（マーティンスベルグ社製、商品名：
　　マーティフィンＯＬ、固形分５０％）　　　　　　　　　　　９．０部
　カルボキシ変性ポリビニルアルコール水溶液（クラレ社製、商品名：
　　ＫＬ３１８、重合度：約１７００、鹸化度：９５～９９ｍｏｌ％、
　　固形分１０％）　　　　　　　　　　　　　　　　　　　　３０．０部
　ポリアミドエピクロロヒドリン樹脂（星光ＰＭＣ社製、商品名：
　　ＷＳ４０３０、固形分２５％）　　　　　　　　　　　　　　４．０部
　変性ポリアミン樹脂（住友化学社製、商品名：スミレーズレジン
　　ＳＰＩ－１０２Ａ、固形分４５％）　　　　　　　　　　　　２．２部
　ステアリン酸亜鉛（中京油脂社製、商品名：ハイドリンＺ－７－３０、
　　固形分３０％）　　　　　　　　　　　　　　　　　　　　　２．０部
　水　　　　　　　　　　　　　　　　　　　　　　　　　　　２２．８部 Next, a coating solution for a protective layer was prepared by mixing a formulation having the following proportions.
<Coating liquid for protective layer>
Aluminum hydroxide dispersion (manufactured by Martinsberg, product name:
Martiffin OL, solid content 50%) 9.0 parts Carboxy-modified polyvinyl alcohol aqueous solution (manufactured by Kuraray Co., Ltd., product name:
KL318, degree of polymerization: about 1700, degree of saponification: 95 to 99 mol%,
Solid content 10%) 30.0 parts Polyamide epichlorohydrin resin (manufactured by Seiko PMC, trade name:
WS4030, solid content 25%) 4.0 parts Modified polyamine resin (manufactured by Sumitomo Chemical Co., Ltd., product name: Sumiraze Resin SPI-102A, solid content 45%) 2.2 parts Zinc stearate (manufactured by Chukyo Yushi Co., Ltd., product name : Hydrin Z-7-30,
Solid content 30%) 2.0 parts Water 22.8 parts
［実施例１］
　支持体（坪量６０ｇ／ｍ２の上質紙）の片面に、下塗り層用塗工液を、固形分で塗工量６．０ｇ／ｍ２となるようにベントブレード法で塗工した後、乾燥を行ない、下塗り層塗工紙を得た。
　この下塗り層塗工紙の下塗り層上に、感熱記録層用塗工液１を、固形分で塗工量３．０ｇ／ｍ２となるようにロッドブレード法で塗工した後、乾燥を行い、スーパーカレンダーで平滑度が５００～１０００秒になるように処理して感熱記録層塗工紙を作製した。
　次いで、この感熱記録層塗工紙の感熱記録層上に、保護層用塗工液を、固形分で塗工量３．０ｇ／ｍ２となるように、ロッドブレード法で塗工した後、乾燥を行ない、保護層塗工紙を作製した。
　次いで、この保護層塗工紙の保護層とは反対面に、バックコート層用塗工液１を、固形分で塗工量３．５ｇ／ｍ２となるように、ロッドブレード法で塗工した後、乾燥を行ない、感熱記録体を作製した。 [Example 1]
After applying the coating solution for the undercoat layer to one side of the support (high-quality paper with a basis weight of 60 g/m 2 ) using a bent blade method so that the coating amount in terms of solid content was 6.0 g/m 2 , It was dried to obtain an undercoat coated paper.
Coating liquid 1 for heat-sensitive recording layer was coated on the undercoat layer of the undercoat layer-coated paper using a rod blade method in a coating amount of 3.0 g/ m2 in terms of solid content, and then dried. A paper coated with a heat-sensitive recording layer was prepared by treating the paper with a super calender to give a smoothness of 500 to 1000 seconds.
Next, on the heat-sensitive recording layer of this heat-sensitive recording layer-coated paper, a coating solution for a protective layer was applied using a rod blade method so that the coating amount was 3.0 g/ m2 in terms of solid content, and then It was dried to produce a protective layer coated paper.
Next, on the opposite side of the protective layer-coated paper from the protective layer, coating liquid 1 for back coat layer was applied using a rod blade method to a coating amount of 3.5 g/ m2 in terms of solid content. After that, it was dried to produce a heat-sensitive recording material.
［実施例２］
　バックコート層用塗工液の塗工量を２．０ｇ／ｍ２にした以外は実施例１と同様にして感熱記録体を作製した。
［実施例３］
　バックコート層用塗工液の塗工量を２．５ｇ／ｍ２にした以外は実施例１と同様にして感熱記録体を作製した。
［実施例４］
　バックコート層用塗工液の塗工量を４．５ｇ／ｍ２にした以外は実施例１と同様にして感熱記録体を作製した。
［実施例５］
　バックコート層用塗工液について、エチレン－ビニルアルコール共重合体３０部、エチレン－アクリル共重合体２０部にした以外は実施例１と同様にして感熱記録体を作製した。
［実施例６］
　バックコート層用塗工液について、エチレン－ビニルアルコール共重合体４０部、エチレン－アクリル共重合体１０部にした以外は実施例１と同様にして感熱記録体を作製した。 [Example 2]
A heat-sensitive recording material was produced in the same manner as in Example 1, except that the coating amount of the backcoat layer coating liquid was 2.0 g/m 2 .
[Example 3]
A heat-sensitive recording material was produced in the same manner as in Example 1 except that the coating amount of the backcoat layer coating liquid was 2.5 g/m 2 .
[Example 4]
A heat-sensitive recording material was produced in the same manner as in Example 1, except that the coating amount of the back coat layer coating liquid was 4.5 g/m 2 .
[Example 5]
A thermosensitive recording material was produced in the same manner as in Example 1, except that the coating solution for the back coat layer was 30 parts of ethylene-vinyl alcohol copolymer and 20 parts of ethylene-acrylic copolymer.
[Example 6]
A thermosensitive recording material was produced in the same manner as in Example 1, except that the coating solution for the back coat layer was 40 parts of ethylene-vinyl alcohol copolymer and 10 parts of ethylene-acrylic copolymer.
［実施例７］
　感熱記録層用塗工液１に代えて感熱記録層用塗工液２を使用した以外は実施例１と同様にして感熱記録体を作製した。
［実施例８］
　バックコート層用塗工液１に代えてバックコート層用塗工液２を使用した以外は実施例１と同様にして感熱記録体を作製した。 [Example 7]
A heat-sensitive recording material was produced in the same manner as in Example 1 except that Coating Solution 2 for heat-sensitive recording layer was used in place of Coating Solution 1 for heat-sensitive recording layer.
[Example 8]
A heat-sensitive recording material was produced in the same manner as in Example 1 except that Coating Solution 2 for back coat layer was used in place of Coating Solution 1 for back coat layer.
［比較例１］
　バックコート層用塗工液１に代えてバックコート層用塗工液３を使用した以外は実施例１と同様にして感熱記録体を作製した。
［比較例２］
　バックコート層用塗工液１に代えてバックコート層用塗工液４を使用した以外は実施例１と同様にして感熱記録体を作製した。
［比較例３］
　バックコート層用塗工液１に代えてバックコート層用塗工液５を使用した以外は実施例１と同様にして感熱記録体を作製した。
［比較例４］
　バックコート層用塗工液１に代えてバックコート層用塗工液６を使用した以外は実施例１と同様にして感熱記録体を作製した。
［比較例５］
　バックコート層用塗工液を塗工しない以外は実施例１と同様にして感熱記録体を作製した。 [Comparative example 1]
A heat-sensitive recording material was produced in the same manner as in Example 1 except that Coating Liquid 3 for back coat layer was used in place of Coating Liquid 1 for back coat layer.
[Comparative example 2]
A heat-sensitive recording material was produced in the same manner as in Example 1 except that Coating Liquid 4 for back coat layer was used in place of Coating Liquid 1 for back coat layer.
[Comparative example 3]
A heat-sensitive recording material was produced in the same manner as in Example 1 except that Coating Liquid 5 for back coat layer was used in place of Coating Liquid 1 for back coat layer.
[Comparative example 4]
A heat-sensitive recording material was produced in the same manner as in Example 1 except that Coating Liquid 6 for back coat layer was used in place of Coating Liquid 1 for Back Coat Layer.
[Comparative example 5]
A heat-sensitive recording material was produced in the same manner as in Example 1 except that the coating liquid for the back coat layer was not applied.
　作製した感熱記録体について、下記評価を行った。
＜発色性能（印字濃度）＞
　作製した感熱記録体について、大倉電機社製のＴＨ－ＰＭＤ（感熱記録紙印字試験機、京セラ社製サーマルヘッドを装着）を用い、印加エネルギー０．３５ｍＪ／ｄｏｔ、印字速度５０ｍｍ／ｓｅｃで市松模様を印字した。印字部の印字濃度をマクベス濃度計（ＲＤ－９１４、アンバーフィルター使用）で測定し、発色性能を評価した。 The produced heat-sensitive recording material was evaluated as follows.
<Color development performance (print density)>
The produced thermal recording material was printed in a checkered pattern using a TH-PMD (thermal recording paper printing tester manufactured by Okura Electric Co., Ltd., equipped with a thermal head manufactured by Kyocera Corporation) at an applied energy of 0.35 mJ/dot and a printing speed of 50 mm/sec. was printed. The print density of the print area was measured using a Macbeth densitometer (RD-914, using an amber filter) to evaluate the color development performance.
＜裏面防湿性能＞
　作製した感熱記録体について、以下の２種類の条件下で性能評価を行った。
　　（１）２３℃×５０％ＲＨ×２４時間保管→２３℃×５０％ＲＨ条件下で印字
　　（２）３５℃×８０％ＲＨ×２４時間保管→２３℃×５０％ＲＨ条件下で印字
　即ち、ＳＯＮＹ社製のＵＰ－Ｘ８９８ＭＤ（医療用感熱印字機）を用い、Ｓモードの条件で１巻（２０ｍ）、ベタ模様を印字した後、サーマルヘッドとは反対側、プリンターのダンパー部に水滴が付着しているかを目視にて観察し、防湿性能を以下の基準で評価した。
　○：水滴が付着しない
　△：水滴が付着するが、すぐに消える
　×：水滴が付着し、数分間消えない
　××：水滴が付着し、数時間消えない <Backside moisture proofing performance>
Performance evaluation of the produced heat-sensitive recording material was performed under the following two types of conditions.
(1) Storage at 23°C x 50% RH x 24 hours → Printing under conditions of 23°C x 50% RH (2) Storage at 35°C x 80% RH x 24 hours → Printing under conditions of 23°C x 50% RH That is, After printing a solid pattern for one roll (20m) in S mode using SONY's UP-X898MD (thermal printing machine for medical use), water droplets adhered to the damper part of the printer on the opposite side of the thermal head. The moisture-proof performance was evaluated based on the following criteria.
○: Water droplets do not adhere △: Water droplets adhere but disappear quickly ×: Water droplets adhere and do not disappear for several minutes ××: Water droplets adhere and do not disappear for several hours
＜巻取りブロッキング＞
　作成した感熱記録体について小巻加工（１１０ｍｍ×２０ｍ）を行い、３５℃×８０％ＲＨ環境条件下に２４時間静置した後、以下の基準で目視評価した。
　○：ブロッキングが全く発生せず、保護層及びバックコート層の剥がれがない
　×：ブロッキングが発生し、保護層及もしくはバックコート層が剥がれる <Take-up blocking>
The produced heat-sensitive recording material was subjected to a small roll process (110 mm x 20 m), left for 24 hours under 35° C. x 80% RH environmental conditions, and then visually evaluated according to the following criteria.
○: Blocking does not occur at all, and the protective layer and back coat layer do not peel off. ×: Blocking occurs, and the protective layer and/or back coat layer peels off.
　結果を表１に示す。
Figure JPOXMLDOC01-appb-T000001
 The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
　表１に示すように、本発明の感熱記録体は、発色感度に悪影響を及ぼさずに裏面の水滴付着を防止する、水蒸気バリア性に優れた効果を有する。 As shown in Table 1, the heat-sensitive recording material of the present invention has excellent water vapor barrier properties that prevent water droplets from adhering to the back surface without adversely affecting color development sensitivity.

Claims (4)

  1. 支持体上に、無色ないし淡色の電子供与性ロイコ染料及び電子受容性顕色剤を含有する感熱記録層と、該感熱記録層とは反対面にバックコート層を設けた感熱記録体であって、該バックコート層がエチレン－ビニルアルコール共重合体及びエチレン－アクリル共重合体を含有する、感熱記録体。 A heat-sensitive recording material comprising, on a support, a heat-sensitive recording layer containing a colorless or light-colored electron-donating leuco dye and an electron-accepting color developer, and a back coat layer on the opposite side of the heat-sensitive recording layer. A thermosensitive recording material, wherein the back coat layer contains an ethylene-vinyl alcohol copolymer and an ethylene-acrylic copolymer.
  2. エチレン－ビニルアルコール共重合体に対するエチレン－アクリル共重合体の含有比（固形分）が、エチレン－ビニルアルコール共重合体１０質量部に対して２．５部～４０部である、請求項１に記載の感熱記録体。 Claim 1, wherein the content ratio (solid content) of the ethylene-acrylic copolymer to the ethylene-vinyl alcohol copolymer is 2.5 parts to 40 parts per 10 parts by mass of the ethylene-vinyl alcohol copolymer. The heat-sensitive recording medium described above.
  3. バックコート層中のエチレン－ビニルアルコール共重合体及びエチレン－アクリル共重合体の合計含有量（固形分）が、５０～９０重量％である、請求項１又は２に記載の感熱記録体。 The heat-sensitive recording material according to claim 1 or 2, wherein the total content (solid content) of the ethylene-vinyl alcohol copolymer and the ethylene-acrylic copolymer in the back coat layer is 50 to 90% by weight.
  4. バックコート層の塗布量が、２．５～４．５ｇ／ｍ２である、請求項１～３のいずれか一項に記載の感熱記録体。 The heat-sensitive recording material according to any one of claims 1 to 3, wherein the coating amount of the back coat layer is 2.5 to 4.5 g/m 2 .
PCT/JP2023/012159 2022-03-30 2023-03-27 Heat-sensitive recording body WO2023190314A1 (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0532044A (en) * 1991-07-31 1993-02-09 Kanzaki Paper Mfg Co Ltd Manufacture of double-side thermal recording sheet
JPH09265149A (en) * 1996-03-28 1997-10-07 Fuji Photo Film Co Ltd Recording material
JPH11208115A (en) * 1998-01-22 1999-08-03 Ricoh Co Ltd Thermal recording material
JP2006084607A (en) * 2004-09-15 2006-03-30 Ricoh Co Ltd Thermally adhesive label, method for thermally activating label, and method for manufacturing thermally adhesive label
JP2009255551A (en) * 2008-03-18 2009-11-05 Ricoh Co Ltd Heat resistance improver and reversible thermosensitive recording medium
JP2011008089A (en) * 2009-06-26 2011-01-13 Nippon Paper Industries Co Ltd Band label

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0532044A (en) * 1991-07-31 1993-02-09 Kanzaki Paper Mfg Co Ltd Manufacture of double-side thermal recording sheet
JPH09265149A (en) * 1996-03-28 1997-10-07 Fuji Photo Film Co Ltd Recording material
JPH11208115A (en) * 1998-01-22 1999-08-03 Ricoh Co Ltd Thermal recording material
JP2006084607A (en) * 2004-09-15 2006-03-30 Ricoh Co Ltd Thermally adhesive label, method for thermally activating label, and method for manufacturing thermally adhesive label
JP2009255551A (en) * 2008-03-18 2009-11-05 Ricoh Co Ltd Heat resistance improver and reversible thermosensitive recording medium
JP2011008089A (en) * 2009-06-26 2011-01-13 Nippon Paper Industries Co Ltd Band label

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