WO2023190314A1 - Corps d'impression thermosensible - Google Patents

Corps d'impression thermosensible 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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English (en)
Japanese (ja)
Inventor
達朗 越
佳美 緑川
健二 平井
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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/ja
Publication of WO2023190314A1 publication Critical patent/WO2023190314A1/fr

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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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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)

Abstract

[Problème] Fournir un corps d'enregistrement thermosensible ayant des propriétés de barrière à la vapeur d'eau contre l'humidité dans le corps d'enregistrement thermosensible.　[Solution] Un corps d'enregistrement thermosensible dans lequel sont disposés sur un corps de support une couche d'enregistrement thermosensible contenant un leuco-colorant donneur d'électrons incolore à de couleur claire et un révélateur accepteur d'électrons, et une couche de revêtement arrière sur le côté opposé à la couche d'enregistrement thermosensible, la couche de revêtement arrière contenant un copolymère éthylène-alcool vinylique et un copolymère éthylène-acrylique.　
PCT/JP2023/012159 2022-03-30 2023-03-27 Corps d'impression thermosensible WO2023190314A1 (fr)

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JP2023544159A JP7354483B1 (ja) 2022-03-30 2023-03-27 感熱記録体

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0532044A (ja) * 1991-07-31 1993-02-09 Kanzaki Paper Mfg Co Ltd 両面感熱記録シートの製造方法
JPH09265149A (ja) * 1996-03-28 1997-10-07 Fuji Photo Film Co Ltd 記録材料
JPH11208115A (ja) * 1998-01-22 1999-08-03 Ricoh Co Ltd 感熱記録材料
JP2006084607A (ja) * 2004-09-15 2006-03-30 Ricoh Co Ltd 熱粘着性ラベル及び該ラベルの熱活性化方法並びに熱粘着性ラベルの製造方法
JP2009255551A (ja) * 2008-03-18 2009-11-05 Ricoh Co Ltd 耐熱性向上剤及び可逆性感熱記録媒体
JP2011008089A (ja) * 2009-06-26 2011-01-13 Nippon Paper Industries Co Ltd 帯ラベル

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0532044A (ja) * 1991-07-31 1993-02-09 Kanzaki Paper Mfg Co Ltd 両面感熱記録シートの製造方法
JPH09265149A (ja) * 1996-03-28 1997-10-07 Fuji Photo Film Co Ltd 記録材料
JPH11208115A (ja) * 1998-01-22 1999-08-03 Ricoh Co Ltd 感熱記録材料
JP2006084607A (ja) * 2004-09-15 2006-03-30 Ricoh Co Ltd 熱粘着性ラベル及び該ラベルの熱活性化方法並びに熱粘着性ラベルの製造方法
JP2009255551A (ja) * 2008-03-18 2009-11-05 Ricoh Co Ltd 耐熱性向上剤及び可逆性感熱記録媒体
JP2011008089A (ja) * 2009-06-26 2011-01-13 Nippon Paper Industries Co Ltd 帯ラベル

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