WO2014097881A1 - Thermal recording body - Google Patents

Thermal recording body Download PDF

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Publication number
WO2014097881A1
WO2014097881A1 PCT/JP2013/082451 JP2013082451W WO2014097881A1 WO 2014097881 A1 WO2014097881 A1 WO 2014097881A1 JP 2013082451 W JP2013082451 W JP 2013082451W WO 2014097881 A1 WO2014097881 A1 WO 2014097881A1
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WO
WIPO (PCT)
Prior art keywords
heat
sensitive recording
parts
methyl
recording layer
Prior art date
Application number
PCT/JP2013/082451
Other languages
French (fr)
Japanese (ja)
Inventor
荻野　明人
平井　健二
Original Assignee
日本製紙株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2012275299A external-priority patent/JP2016028847A/en
Priority claimed from JP2013117692A external-priority patent/JP2016028848A/en
Application filed by 日本製紙株式会社 filed Critical 日本製紙株式会社
Publication of WO2014097881A1 publication Critical patent/WO2014097881A1/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
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333—Non-macromolecular compounds

Definitions

  • the present invention utilizes a coloring reaction between a colorless or light-colored electron-donating leuco dye (hereinafter also referred to as “leuco dye”) and an electron-accepting developer (hereinafter also referred to as “developer”).
  • leuco dye colorless or light-colored electron-donating leuco dye
  • developer electron-accepting developer
  • the present invention relates to a heat-sensitive recording material, which is excellent in heat discoloration at a white paper portion and particularly excellent in barcode reading ability.
  • a thermal recording material is usually a colorless or light leuco dye and a developer such as a phenolic compound, each of which is ground and dispersed into fine particles, and then mixed together to form a binder, a filler, a sensitivity improver,
  • a coating solution obtained by adding a lubricant and other auxiliary agents is applied to a support such as paper, synthetic paper, film, plastic, etc., such as thermal head, hot stamp, thermal pen, laser beam, etc. Color is generated by an instantaneous chemical reaction by heating, and a recorded image is obtained.
  • Thermosensitive recording media are widely used as recording media for facsimiles, computer terminal printers, automatic ticket vending machines, recorders for measurement, receipts for supermarkets and convenience stores, and the like.
  • the media used has been miniaturized, such as for handy terminals, and for recording and labeling and ticketing applications, color sensitivity and image quality, especially barcode readability, are required. It has been.
  • it is often used outdoors for labels and used for food, etc., so that it is not difficult to read the image part due to moisture and moisture such as rain, etc.
  • the plasticizer contained in the synthetic leather used in these materials does not make it difficult to read the image area.
  • storage stability such as plasticizer properties
  • excellent performance has begun to be required.
  • As a method for improving the storage stability of the image area it is generally known to provide a protective layer on the thermosensitive recording layer.
  • the protective layer absorbs the thermal energy given from the thermal head, so that there is a problem that the color development performance, that is, the color development sensitivity and image quality are inferior.
  • the color development sensitivity decreases and the difference in contrast between the print area and the white paper area becomes small, when the barcode is printed, it cannot be read by a reader even if it can be visually observed.
  • aptitude was insufficient.
  • Patent Document 1 a heat-sensitive recording material that improves the storage stability of the image area, or by using a combination of a specific sensitizer and a stabilizer.
  • thermal recording media Patent Documents 2 to 4 etc.
  • storage stability such as water resistance and plasticizer resistance
  • a heat-sensitive recording material Patent Document 5, etc.
  • the color development performance and the storage stability of the image part are improved by using a combination of two specific color developers. Due to the inferior properties, the white paper portion will develop color when the thermal recording material is stored in a high temperature environment. For this reason, the difference in contrast (contrast) between the printed portion and the white paper portion is reduced, and the barcode readability is insufficient.
  • an object of the present invention is to provide a heat-sensitive recording material that is excellent in both the color development performance and the heat discoloration property of the white paper portion even under a harsh environment, and as a result, has good barcode readability.
  • the present invention is a heat-sensitive recording material provided with a heat-sensitive recording layer containing a colorless or light-colored electron-donating leuco dye and an electron-accepting developer on a support, and the heat-sensitive recording layer comprises an electron As a receptive developer (i) the following chemical formula (Ii) 4-hydroxy-4′-allyloxydiphenyl sulfone and the following general formula (Formula 2)
  • a heat-sensitive recording material comprising at least one selected from the group consisting of urea urethane compounds represented by the formula:
  • the present invention it is possible to provide a heat-sensitive recording material that is excellent in both color development performance and heat discoloration resistance of a white paper portion even under a harsh environment, and as a result, has good barcode readability. Furthermore, by providing a protective layer on the heat-sensitive recording material, it is possible to provide a heat-sensitive recording material that is particularly excellent in water resistance, plasticizer resistance in the image area, and heat discoloration resistance in the white paper area, and also has good color development performance. It is.
  • the heat-sensitive recording layer of the heat-sensitive recording material of the present invention comprises (i) the following chemical formula (Formula 1) as a developer. And (ii) 4-hydroxy-4′-allyloxydiphenyl sulfone represented by the following general formula (Formula 2): Containing at least one selected from the group consisting of urea urethane compounds represented by the formula:
  • the heat-sensitive recording layer of the present invention uses, as a developer, the sulfonic acid compound represented by the above chemical formula (Chemical Formula 1) and another developer having a structure that interacts therewith, the following It is considered effective. That is, when the heat-sensitive recording layer of the present invention contains a sulfonic acid compound represented by the above chemical formula (Formula 1) and 4-hydroxy-4′-allyloxydiphenyl sulfone as a developer, the heat-sensitive recording layer is heated and melted.
  • the heat-sensitive recording layer of the present invention contains a sulfonic acid compound represented by the above chemical formula (Chemical Formula 1) and a urethane urea compound represented by the above General Formula (Chemical Formula 2) as a developer, the heat-sensitive recording layer.
  • the protective layer when a protective layer is provided on the thermal recording material, that is, when the protective layer absorbs part of the thermal energy given from the thermal head or the like and the thermal energy is low, the developer and leuco It is presumed that the stability of the electron transfer complex, which is a reaction product with the dye, is sufficiently high so that the color development sensitivity does not decrease and the bar code reading suitability of the resulting thermal recording material is good.
  • urea urethane compounds are specifically three types represented by the following formulas (Chemical Formula 3) to (Chemical Formula 5), and these may be used alone or in combination of two or more.
  • a developer other than the above compounds may be used in combination.
  • WO 02/081229 The compounds described in WO 02/081229 and the like are available as trade names NKK-395 and D-100 manufactured by Nippon Soda Co., Ltd.
  • a metal chelate color-developing component such as a higher fatty acid metal double salt and a polyvalent hydroxyaromatic compound described in JP-A-10-258577 can also be contained.
  • 4-hydroxy-4′-allyloxydiphenyl sulfone or the urea urethane type represented by the general formula (Chemical Formula 2) is used per 1 part by weight of the sulfonic acid type compound represented by the chemical formula (Chemical Formula 1).
  • the compound is preferably used in a proportion of 0.01 to 10.0 parts by weight, more preferably 0.1 to 5.0 parts by weight.
  • 4-hydroxy-4'-allyloxydiphenyl sulfone or urea urethane compound represented by the above general formula (Chemical Formula 2) is 0.01% per 1 part by weight of the sulfonic acid type compound represented by the chemical formula (Chemical Formula 1).
  • the heat-sensitive recording layer of the present invention comprises a sulfonic acid compound represented by the above chemical formula (Chemical Formula 1), 4-hydroxy-4′-allyloxydiphenyl sulfone, or a urea urethane compound represented by the above General Formula (Chemical Formula 2)
  • a developer other than the above is contained, the sulfonic acid compound represented by the above chemical formula (Chemical Formula 1), 4-hydroxy-4′-allyloxydiphenyl sulfone, and the urea urethane represented by the above general formula (Chemical Formula 2)
  • the total content of the series compounds is the total developer contained in the thermosensitive recording layer (the sulfonic acid series compound represented by the above chemical formula (Chemical Formula 1), 4-hydroxy-4′-allyloxy
  • binders, cross-linking agents, pigments, and the like may be used as necessary as long as they do not hinder the desired effects on the above-described problems. It can also be used for each coating layer such as a provided protective layer.
  • any known leuco dyes in the field of conventional pressure-sensitive or thermal recording paper can be used, and are not particularly limited, but include triphenylmethane compounds, fluoran compounds, fluorenes. Of these, divinyl compounds and divinyl compounds are preferred. Specific examples of typical colorless or light-colored dyes (dye precursors) are shown below. These dye precursors may be used alone or in combination of two or more.
  • Triphenylmethane 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)
  • sensitizer used in the present invention, a conventionally known sensitizer can be used.
  • sensitizers include fatty acid amides such as stearamide and palmitic acid amide, ethylene bisamide, montanic acid wax, polyethylene wax, 1,2-bis- (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, 1-hydroxy-2-naphthoic acid
  • pigment used in the present invention examples include kaolin, calcined kaolin, calcium carbonate, aluminum oxide, titanium oxide, magnesium carbonate, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, and silica, depending on the required quality. It can also be used together.
  • the binder used in the present invention includes fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, acetoacetylated polyvinyl alcohol, carboxy-modified polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, butyral-modified polyvinyl alcohol, and olefin-modified.
  • crosslinking agent used in the present invention examples include glyoxal, methylol melamine, melamine formaldehyde resin, melamine urea resin, polyamine epichlorohydrin resin, polyamide epichlorohydrin resin, potassium persulfate, ammonium persulfate, sodium persulfate, chloride chloride
  • examples include ferric iron, magnesium chloride, borax, boric acid, alum, ammonium chloride and the like.
  • lubricant used in the present invention examples include fatty acid metal salts such as zinc stearate and calcium stearate, waxes, silicone resins and the like.
  • 2,2'-di-t-butyl-5,5'-dimethyl-4,4'-sulfonyldiphenol, 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane, 1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane and the like can also be added.
  • benzophenone and triazole ultraviolet absorbers, dispersants, antifoaming agents, antioxidants, fluorescent dyes, and the like can be used.
  • the types and amounts of the leuco dye, developer, sensitizer, and other various components used in the heat-sensitive recording layer of the present invention are determined according to the required performance and recording suitability, and are not particularly limited. Usually, 0.5 to 10 parts by weight of developer, 0.1 to 10 parts by weight of sensitizer, 0.5 to 20 parts by weight of pigment, and 0.01 to 10 parts by weight of stabilizer for 1 part by weight of leuco dye. Parts and other components of about 0.01 to 10 parts by weight.
  • the binder is suitably about 5 to 25% by weight in the solid content of the heat-sensitive recording layer.
  • the leuco dye, the developer, and the material to be added as necessary are finely divided to a particle size of several microns or less by a pulverizer such as a ball mill, an attritor, or a sand glider, or a suitable emulsifying device, Depending on the purpose, various additive materials are added to obtain a coating solution.
  • a pulverizer such as a ball mill, an attritor, or a sand glider, or a suitable emulsifying device
  • various additive materials are added to obtain a coating solution.
  • the solvent used in the coating solution water or alcohol can be used, and its solid content is about 20 to 40% by weight.
  • a protective layer can be further provided on the heat-sensitive recording layer.
  • the protective layer is mainly composed of a pigment and a resin, and binders, pigments, crosslinking agents and the like exemplified as materials that can be used for the heat-sensitive recording layer can be used.
  • the content of the pigment and binder in the protective layer is about 30 to 300 parts by weight in solid content of the binder with respect to 100 parts by weight of the pigment.
  • the heat-sensitive recording material of the present invention has a heat-sensitive recording layer on a support, but an undercoat layer can be provided between the support and the heat-sensitive recording layer.
  • This undercoat layer mainly comprises a binder and a pigment.
  • the binder used for the undercoat layer a commonly used water-soluble polymer or hydrophobic polymer emulsion or the like can be appropriately used.
  • cellulose derivatives such as polyvinyl alcohol, polyvinyl acetal, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, starch and derivatives thereof, polysodium acrylate, polyvinyl pyrrolidone, acrylate / acrylate copolymers, acrylic acid Water-soluble polymers such as amide / acrylic acid ester / methacrylic acid copolymer, styrene / maleic anhydride copolymer alkali salt, isobutylene / maleic anhydride copolymer alkali salt, polyacrylamide, sodium alginate, gelatin, casein, Polyvinyl acetate, polyurethane, styrene / butadiene copolymer, polyacrylic acid, polyacrylate ester, vinyl chloride / vinyl acetate copolymer, polybutyl methacrylate, ethylene / acetic acid Cycloalkenyl copolymer, can be used
  • pigments used in the undercoat layer known pigments generally used conventionally, specific examples include calcium carbonate, silica, zinc oxide, titanium oxide, aluminum hydroxide, magnesium hydroxide, calcined kaolin, clay, talc, etc.
  • Inorganic pigments can be used. These pigments may be used alone or in combination of two or more.
  • the pigment in the undercoat layer is usually 50 to 95 parts by weight, preferably 70 to 90 parts by weight with respect to 100 parts by weight of the total solid content.
  • Various additives such as a dispersant, a plasticizer, a pH adjuster, an antifoaming agent, a water retention agent, an antiseptic, a coloring dye, and an ultraviolet ray inhibitor may be appropriately blended in the undercoat layer coating liquid as necessary. Good.
  • the means for coating the heat-sensitive recording layer and the coating layer other than the heat-sensitive recording layer is not particularly limited, and can be applied according to a well-known conventional technique.
  • 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 vent blade coater, a bevel blade coater, a roll coater, and a curtain coater is appropriately selected and used.
  • the coating amount of the coating layer other than the heat-sensitive recording layer and 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 of the heat-sensitive recording layer is solid. It is about 2 to 12 g / m 2 per minute.
  • various known techniques in the heat-sensitive recording material field can be added as appropriate, such as applying a smoothing process such as supercalendering after coating each layer.
  • Example 1 A composition comprising the following composition was stirred and dispersed to prepare an undercoat layer coating solution.
  • the coating amount of the undercoat layer coating solution is 10.0 g in solid content on one side of the support (basis weight 47 g / m 2 fine paper). After coating by the vent blade method so as to be / m 2 , drying was performed to obtain an undercoat layer coated paper.
  • First developer dispersions 1 to 2 (A1 liquid to A2 liquid), second developer dispersions 1 to 2 (B1 liquid to B2 liquid), leuco dye dispersion liquid (C liquid) and sensitization of the following composition
  • the agent dispersion liquid (liquid D) was separately wet-ground with a sand grinder until the average particle size became 0.5 microns.
  • First developer dispersion 1 A sulfonic acid compound represented by the chemical formula (Chemical Formula 1) (manufactured by BASF, trade name: DP201) 6.0 parts Completely saponified polyvinyl alcohol aqueous solution (Kuraray Co., Ltd., trade name: PVA) 117, solid content 10%) 5.0 parts water 1.5 parts first developer dispersion 2 (liquid A2) Diphenylsulfone cross-linking compound (Nippon Soda Co., Ltd., trade name: D90) 6.0 parts Completely saponified polyvinyl alcohol aqueous solution (Kuraray Co., Ltd., trade name: PVA) 117, solid content 10%) 5.0 parts water 1.5 parts
  • Second developer dispersion 1 (B1 solution) 4-hydroxy-4′-allyloxydiphenyl sulfone (manufactured by Nikka Chemical Co., Ltd.)
  • Product name: BPS-MAE 6.0 parts Completely saponified polyvinyl alcohol aqueous solution (Kuraray Co., Ltd., product name: PVA) 117, solid content 10%) 5.0 parts water 1.5 parts
  • second developer dispersion 2 (B2 liquid) Urethane urea compound represented by the chemical formula (Chemical Formula 3) (Chemipro Kasei Co., Ltd., Product name: UU) 6.0 parts Completely saponified polyvinyl alcohol aqueous solution (Kuraray Co., Ltd., product name: PVA) 117, solid content 10%) 5.0 parts water 1.5 parts
  • Leuco dye dispersion liquid C
  • Libibutylamino-6-methyl-7-anilinofluorane manufactured by Yamamoto Kasei Co., Ltd., trade name: ODB-2
  • 6.0 parts fully saponified polyvinyl alcohol aqueous solution manufactured by Kuraray Co., Ltd., trade name: PVA
  • 117, solid content 10% 5.0 parts water
  • sensitizer dispersion liquid D
  • 1,2-bis- (3-methylphenoxy) ethane manufactured by Sanko Co., Ltd., trade name: KS232
  • 6.0 parts Completely saponified polyvinyl alcohol aqueous solution (Kuraray Co., Ltd., trade name: PVA) 117, solid content 10%) 5.0 parts water 1.5 parts
  • thermal recording layer coating solution 1 > 1st developer dispersion 1 (A1 liquid) 18.0 parts 2nd developer dispersion 1 (B1 liquid) 18.0 parts Leuco dye dispersion (liquid C) 18.0 parts Sensitizer dispersion ( Liquid D) 36.0 parts Silica dispersion (manufactured by Mizusawa Chemical Co., Ltd., trade name: Mizukasil P-537, solid content 25%) 17.5 parts Complete saponified polyvinyl alcohol aqueous solution (Kuraray Co., Ltd., trade name: PVA) 117, solid content 10%) 25.0 parts
  • heat-sensitive recording layer coating solution 1 is applied onto the undercoat layer of the undercoat layer-coated paper so that the solid coating amount is 6.0 g / m 2. After coating by the blade method, drying was performed, and processing was performed with a super calender so that the smoothness became 500 to 1000 seconds, thereby
  • Example 2 6.0 parts of 1,2-bis- (3-methylphenoxy) ethane (manufactured by Sanko Co., Ltd., trade name: KS232) in the sensitizer dispersion (liquid D) was mixed with stearic acid amide / paltimic acid amide mixture (mixing ratio). : 7/3, Nippon Kasei Co., Ltd., trade name: AP-1) A heat-sensitive recording material was produced in the same manner as in Example 1 except that 6.0 parts were used.
  • Example 3 6.0 parts of 3-dibutylamino-6-methyl-7-anilinofluorane (manufactured by Yamamoto Kasei Co., Ltd., trade name: ODB-2) in the leuco dye dispersion (liquid C) was mixed with 3-di-n-pentyl.
  • a thermosensitive recording material was produced in the same manner as in Example 1 except that 6.0 parts of amino-6-methyl-7-anilinofluorane (trade name: BLACK305, manufactured by Yamada Chemical Co., Ltd.) was used.
  • Example 4 The amount of silica dispersion in the heat-sensitive recording layer coating liquid 1 is changed from 17.5 parts to 7.5 parts to obtain a heat-sensitive recording layer coating liquid 2, and the heat-sensitive recording layer coating liquid 2 is applied to the undercoat layer coating.
  • the undercoat layer of paper After coating by the rod blade method so that the coating amount is 6.0 g / m 2 in terms of solid content, drying is performed so that the smoothness becomes 500 to 1000 seconds with a super calendar.
  • the heat-sensitive recording layer coated paper was produced by processing. Subsequently, the mixture which consists of the following ratio was mixed and the protective layer coating liquid was prepared.
  • ⁇ Protective layer coating solution Aluminum hydroxide dispersion (manufactured by Martinsberg, Product name: Martyfin OL, solid content 50%) 9.0 parts Carboxy-modified polyvinyl alcohol aqueous solution (manufactured by Kuraray Co., Ltd., product name: KL) 318, solid content 10%) 30.0 parts Polyamide epichlorohydrin resin (manufactured by Seiko PMC, trade name: WS40) 30, solid content 25%) 4.0 parts Zinc stearate (manufactured by Chukyo Yushi Co., Ltd., trade name: Hydrin Z-7-30, (Solid content: 30%) 2.0 parts Next, the protective layer coating liquid was applied onto the heat-sensitive recording layer of the heat-sensitive recording layer-coated paper so that the coating amount was 3.0 g / m 2 in terms of solid content. After coating by the method, drying was performed to produce a heat-sensitive recording material.
  • Example 5 6.0 parts of 1,2-bis- (3-methylphenoxy) ethane (manufactured by Sanko Co., Ltd., trade name: KS232) in the sensitizer dispersion (liquid D) was mixed with stearic acid amide / paltimic acid amide mixture (mixing ratio). : 7/3, manufactured by Nippon Kasei Co., Ltd., trade name: AP-1) A heat-sensitive recording material was produced in the same manner as in Example 4 except that 6.0 parts was used.
  • Example 6 6.0 parts of 3-dibutylamino-6-methyl-7-anilinofluorane (manufactured by Yamamoto Kasei Co., Ltd., trade name: ODB-2) in the leuco dye dispersion (liquid C) was mixed with 3-di-n-pentyl.
  • a thermosensitive recording material was produced in the same manner as in Example 4 except that 6.0 parts of amino-6-methyl-7-anilinofluorane (trade name: BLACK305, manufactured by Yamada Chemical Co., Ltd.) was used.
  • Example 7 The second developer dispersion liquid 1 (B1 liquid) of the heat-sensitive recording layer coating liquid 1 is replaced with the second developer dispersion liquid 2 (B2 liquid) to form a heat-sensitive recording layer coating liquid 3, and the heat-sensitive recording layer coating is performed.
  • a heat-sensitive recording material was produced in the same manner as in Example 1 except that the liquid 1 was replaced with the heat-sensitive recording layer coating liquid 3.
  • Example 8 6.0 parts of 1,2-bis- (3-methylphenoxy) ethane (manufactured by Sanko Co., Ltd., trade name: KS232) in the sensitizer dispersion (liquid D) was mixed with stearic acid amide / paltimic acid amide mixture (mixing ratio).
  • Example 9 A heat-sensitive recording material was produced in the same manner as in Example 7 except that 6.0 parts were used.
  • 6.0 parts of 3-dibutylamino-6-methyl-7-anilinofluorane (manufactured by Yamamoto Kasei Co., Ltd., trade name: ODB-2) in the leuco dye dispersion (liquid C) was mixed with 3-di-n-pentyl.
  • a thermosensitive recording material was produced in the same manner as in Example 7 except that 6.0 parts of amino-6-methyl-7-anilinofluorane (trade name: BLACK305, manufactured by Yamada Chemical Co., Ltd.) was used.
  • Example 10 The second developer dispersion liquid 1 (B1 liquid) of the heat-sensitive recording layer coating liquid 2 is replaced with the second developer dispersion liquid 2 (B2 liquid) to obtain a heat-sensitive recording layer coating liquid 4, and the heat-sensitive recording layer coating is applied.
  • the liquid 4 was applied on the undercoat layer of the undercoat layer coated paper by the rod blade method so that the coating amount was 6.0 g / m 2 as a solid content, and then dried, and the smoothness was measured with a super calendar.
  • the heat-sensitive recording layer-coated paper was obtained by processing for 500 to 1000 seconds.
  • the protective layer coating solution is applied onto the heat-sensitive recording layer of the heat-sensitive recording layer-coated paper by the rod blade method so that the coating amount is 3.0 g / m 2 in solids, and then dried.
  • a heat-sensitive recording material was produced.
  • Example 12 A heat-sensitive recording material was produced in the same manner as in Example 10 except that 6.0 parts were used.
  • Example 12 6.0 parts of 3-dibutylamino-6-methyl-7-anilinofluorane (manufactured by Yamamoto Kasei Co., Ltd., trade name: ODB-2) in the leuco dye dispersion (liquid C) was mixed with 3-di-n-pentyl.
  • a thermosensitive recording material was produced in the same manner as in Example 10, except that 6.0 parts of amino-6-methyl-7-anilinofluorane (trade name: BLACK305, manufactured by Yamada Chemical Co., Ltd.) were used.
  • thermosensitive recording material was produced in the same manner as described above.
  • Comparative Example 2 Example 1 except that 0 parts of the first developer dispersion 1 (A1 liquid) and 36.0 parts of the second developer dispersion 1 (B1 liquid) in the thermosensitive recording layer coating liquid 1 were used. A thermosensitive recording material was produced in the same manner as described above.
  • Example 7 except that 0 parts of the first developer dispersion 1 (A1 liquid) and 36.0 parts of the second developer dispersion 2 (B2 liquid) in the thermosensitive recording layer coating liquid 3 were used.
  • a thermosensitive recording material was produced in the same manner as described above.
  • the first developer dispersion liquid 1 (A1 liquid) of the heat-sensitive recording layer coating liquid 1 is replaced with the first developer dispersion liquid 2 (A2 liquid) to obtain a heat-sensitive recording layer coating liquid 5, and the heat-sensitive recording layer coating is applied.
  • a heat-sensitive recording material was produced in the same manner as in Example 1 except that the liquid 1 was replaced with the heat-sensitive recording layer coating liquid 5.
  • thermosensitive recording material The following evaluation was performed about the produced thermosensitive recording material.
  • the produced thermal recording medium is a checkered pattern using a TH-PMD manufactured by Okura Electric Co., Ltd. (with thermal recording paper printing tester and Kyocera thermal head installed) with an applied energy of 0.35 mJ / dot and a printing speed of 50 mm / sec. Is printed.
  • the printing density of the printing part was measured with a Macbeth densitometer (RD-914, using an amber filter) to evaluate the color development performance.
  • Ground color development value (density of non-printed area after processing)-(density of non-printed area before processing) Excellent: Ground color development value is less than 0.1 Good: Ground color development value is 0.1 or more and less than 0.3 Possible: Ground color development value is 0.3 or more and less than 0.5 Impossibility: Ground color development value is 0.00. 5 or more

Abstract

[Problem] The purpose of the present invention is to provide a thermal recording body that has both excellent color development performance and thermal discoloration resistance in blank sections, and that offers excellent barcode readability. [Solution] Provided is a thermal recording body in which a thermal recording layer including a colorless or light-colored electron-donating leuco dye and an electron-accepting developer is provided on a support body, the thermal recording body being characterized in that the thermal recording layer includes, as the electron-accepting developer, a specific sulfonic acid-based compound and at least one type of compound selected from the group consisting of 4-hydroxy-4'-allyloxydiphenylsulfone and specific urea urethane-based compounds.

Description

感熱記録体Thermal recording material
　この発明は、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。）との発色反応を利用した感熱記録体であって、白紙部の耐熱変色性に優れ、特にバーコード読み取り適性に優れた感熱記録体に関する。 The present invention utilizes a coloring reaction between a colorless or light-colored electron-donating leuco dye (hereinafter also referred to as “leuco dye”) and an electron-accepting developer (hereinafter also referred to as “developer”). The present invention relates to a heat-sensitive recording material, which is excellent in heat discoloration at a white paper portion and particularly excellent in barcode reading ability.
　一般に、感熱記録体は通常無色ないし淡色のロイコ染料とフェノール性化合物等の顕色剤とを、それぞれ微細な粒子に磨砕分散した後、両者を混合し、バインダー、充填剤、感度向上剤、滑剤及びその他の助剤を添加して得られた塗液を、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、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。
　近年、用いる媒体はハンディターミナル用途など小型化が進んでおり、また、ラベル、チケット用途などでは、発色感度や画質、特にバーコード読み取り適性が求められるなど、感熱記録体は優れた発色性能を求められている。さらに、例えばラベル用では屋外で使用されたり、食品用途などに使用されたりすることが多いため、雨などの水分や湿気によって画像部の判読が困難とならないこと、また、チケット用では財布などに収納されることが多いため、これらに使用される合成皮革が含有する可塑剤によって画像部の判読が困難とならないことなど、感熱記録体に対して従来では問題になっていなかった耐水性、耐可塑剤性等の保存性に関して、優れた性能が要求され始めている。
　画像部の保存性を向上させる方法として、感熱記録層上に保護層を設けることは一般に知られている。しかし、感熱記録体上に保護層を設けた場合、保護層がサーマルヘッドから与えられた熱エネルギーを吸収してしまうため、発色性能、すなわち発色感度や画質が劣るという問題がある。特に、発色感度が低下して印字部と白紙部の濃淡差（コントラスト）が小さくなると、バーコードを印字した場合に、目視は可能であっても読み取り機で読み取ることができず、バーコード読み取り適性が不十分になるという問題があった。
　また、特定の顕色剤と安定剤を組み合わせて用いることにより画像部の保存性を向上させた感熱記録体（特許文献１等）や、特定の増感剤と安定剤を組み合わせて用いることにより画像部の保存性を向上させた感熱記録体（特許文献２～４等）が開示されているが、前述のラベル用、チケット用等の過酷な環境下で用いられる用途に使用される場合、耐水性、耐可塑剤性等の保存性は不十分である。
　さらに、特定の２種類の顕色剤を組み合わせて用いることにより、発色性能と画像部の保存性を向上させた感熱記録体（特許文献５等）が開示されているが、白紙部の耐熱変色性が劣るため、感熱記録体を高温環境で保管すると白紙部が発色してしまう。そのため、印字部と白紙部の濃淡差（コントラスト）が小さくなり、バーコード読み取り適性が不十分であった。 In general, a thermal recording material is usually a colorless or light leuco dye and a developer such as a phenolic compound, each of which is ground and dispersed into fine particles, and then mixed together to form a binder, a filler, a sensitivity improver, A coating solution obtained by adding a lubricant and other auxiliary agents is applied to a support such as paper, synthetic paper, film, plastic, etc., such as thermal head, hot stamp, thermal pen, laser beam, etc. Color is generated by an instantaneous chemical reaction by heating, and a recorded image is obtained. Thermosensitive recording media are widely used as recording media for facsimiles, computer terminal printers, automatic ticket vending machines, recorders for measurement, receipts for supermarkets and convenience stores, and the like.
In recent years, the media used has been miniaturized, such as for handy terminals, and for recording and labeling and ticketing applications, color sensitivity and image quality, especially barcode readability, are required. It has been. In addition, for example, it is often used outdoors for labels and used for food, etc., so that it is not difficult to read the image part due to moisture and moisture such as rain, etc. Since it is often stored, the plasticizer contained in the synthetic leather used in these materials does not make it difficult to read the image area. With respect to storage stability such as plasticizer properties, excellent performance has begun to be required.
As a method for improving the storage stability of the image area, it is generally known to provide a protective layer on the thermosensitive recording layer. However, when a protective layer is provided on the heat-sensitive recording material, the protective layer absorbs the thermal energy given from the thermal head, so that there is a problem that the color development performance, that is, the color development sensitivity and image quality are inferior. In particular, if the color development sensitivity decreases and the difference in contrast between the print area and the white paper area becomes small, when the barcode is printed, it cannot be read by a reader even if it can be visually observed. There was a problem that aptitude was insufficient.
In addition, by using a combination of a specific developer and a stabilizer, a heat-sensitive recording material (Patent Document 1 or the like) that improves the storage stability of the image area, or by using a combination of a specific sensitizer and a stabilizer. Although thermal recording media (Patent Documents 2 to 4 etc.) with improved storage stability of the image portion are disclosed, when used for applications used in harsh environments such as for labels and tickets described above, Storage stability such as water resistance and plasticizer resistance is insufficient.
Furthermore, a heat-sensitive recording material (Patent Document 5, etc.) is disclosed in which the color development performance and the storage stability of the image part are improved by using a combination of two specific color developers. Due to the inferior properties, the white paper portion will develop color when the thermal recording material is stored in a high temperature environment. For this reason, the difference in contrast (contrast) between the printed portion and the white paper portion is reduced, and the barcode readability is insufficient.
特開２００１－３４７７５７JP 2001-347757 A 特開２００１－３４１４３２JP 2001-341432 A 特開２００２－１７８６４６JP 2002-178646 A ＷＯ２００４／００２７４８WO2004 / 002748 特開２００６－２６４２５５JP 2006-264255 A
　上記のように、バーコード読み取り適性が良好であるためには、発色性能と白紙部の耐熱変色性の両方の性能が良好であることを要するものと考えられる。
　そこで、本発明は、過酷な環境下であっても、発色性能と白紙部の耐熱変色性が共に優れ、その結果バーコード読み取り適性が良好である感熱記録体を提供することを目的とする。 As described above, it is considered that in order to have good barcode readability, both the color development performance and the heat discoloration resistance of the white paper portion need to be good.
Accordingly, an object of the present invention is to provide a heat-sensitive recording material that is excellent in both the color development performance and the heat discoloration property of the white paper portion even under a harsh environment, and as a result, has good barcode readability.
　本発明者らは鋭意検討の結果、感熱記録層に特定の２種類の顕色剤を含有させることにより上記課題を解決できることを見出し、本発明を完成するに至った。
　すなわち、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と電子受容性顕色剤とを含有する感熱記録層を設けた感熱記録体であって、該感熱記録層が、電子受容性顕色剤として(i)下記化学式（化１）
Figure JPOXMLDOC01-appb-C000003
 で表されるスルホン酸系化合物並びに(ii)４－ヒドロキシ－４’－アリルオキシジフェニルスルホン及び下記一般式（化２）
Figure JPOXMLDOC01-appb-C000004
 で表されるウレアウレタン系化合物から成る群から選択される少なくとも１種を含有することを特徴とする感熱記録体である。 As a result of intensive studies, the present inventors have found that the above-described problems can be solved by including two specific types of color developers in the heat-sensitive recording layer, and have completed the present invention.
That is, the present invention is a heat-sensitive recording material provided with a heat-sensitive recording layer containing a colorless or light-colored electron-donating leuco dye and an electron-accepting developer on a support, and the heat-sensitive recording layer comprises an electron As a receptive developer (i) the following chemical formula
Figure JPOXMLDOC01-appb-C000003
 (Ii) 4-hydroxy-4′-allyloxydiphenyl sulfone and the following general formula (Formula 2)
Figure JPOXMLDOC01-appb-C000004
 A heat-sensitive recording material comprising at least one selected from the group consisting of urea urethane compounds represented by the formula:
　本発明によれば、過酷な環境下であっても、発色性能と白紙部の耐熱変色性が共に優れ、その結果バーコード読み取り適性が良好である感熱記録体を提供することが可能である。
　さらに、感熱記録体上に保護層を設けることにより、耐水性、画像部の耐可塑剤性、白紙部の耐熱変色性が特に優れると共に、発色性能が良好な感熱記録体を提供することが可能である。 According to the present invention, it is possible to provide a heat-sensitive recording material that is excellent in both color development performance and heat discoloration resistance of a white paper portion even under a harsh environment, and as a result, has good barcode readability.
Furthermore, by providing a protective layer on the heat-sensitive recording material, it is possible to provide a heat-sensitive recording material that is particularly excellent in water resistance, plasticizer resistance in the image area, and heat discoloration resistance in the white paper area, and also has good color development performance. It is.
　以下、本発明の実施の形態について詳細に説明する。
　本発明の感熱記録体の感熱記録層は、顕色剤として(i)下記化学式（化１）
Figure JPOXMLDOC01-appb-C000005
 で表されるスルホン酸系化合物、並びに(ii)４－ヒドロキシ－４’－アリルオキシジフェニルスルホン及び下記一般式（化２）
Figure JPOXMLDOC01-appb-C000006
 で表されるウレアウレタン系化合物から成る群から選択される少なくとも１種を含有する。 Hereinafter, embodiments of the present invention will be described in detail.
The heat-sensitive recording layer of the heat-sensitive recording material of the present invention comprises (i) the following chemical formula (Formula 1) as a developer.
Figure JPOXMLDOC01-appb-C000005
 And (ii) 4-hydroxy-4′-allyloxydiphenyl sulfone represented by the following general formula (Formula 2):
Figure JPOXMLDOC01-appb-C000006
 Containing at least one selected from the group consisting of urea urethane compounds represented by the formula:
　本発明の感熱記録層は、顕色剤として、上記化学式（化１）で表されるスルホン酸系化合物とそれに相互作用する構造を有するもう一つの顕色剤を併用するため、下記のような効果があると考えられる。
　すなわち、本発明の感熱記録層が顕色剤として上記化学式（化１）で表されるスルホン酸系化合物及び４－ヒドロキシ－４’－アリルオキシジフェニルスルホンを含有すると、感熱記録層中に加熱溶融時および融解時の挙動が類似している２種類のスルホン酸系化合物が共存するため、顕色剤とロイコ染料との反応生成物である電子移動錯体の安定性が高くなり、発色性能と白紙部の耐熱変色性が共に優れ、バーコード読み取り適性が良好である感熱記録体が得られるものと推測される。
　一方、本発明の感熱記録層が顕色剤として上記化学式（化１）で表されるスルホン酸系化合物及び上記一般式（化２）で表されるウレタンウレア系化合物を含有すると、感熱記録層中に２種類のウレア結合を持つ化合物が共存するため、いずれか一方のみを含有した時よりもロイコ染料との反応効率が高まり、電子移動錯体が生成しやすくなると共に逆反応が起こりにくくなるため、発色性能と白紙部の耐熱変色性が共に優れ、バーコード読み取り適性が良好である感熱記録体が得られるものと推測される。
　さらに、感熱記録体上に保護層を設けた場合、すなわち、サーマルヘッドなどから与えられた熱エネルギーの一部を保護層が吸収してしまい、熱エネルギーが少ない場合においても、顕色剤とロイコ染料との反応生成物である電子移動錯体の安定性が十分に高くなるため、発色感度が低下せず、得られる感熱記録体のバーコード読み取り適性が良好であると推測される。 Since the heat-sensitive recording layer of the present invention uses, as a developer, the sulfonic acid compound represented by the above chemical formula (Chemical Formula 1) and another developer having a structure that interacts therewith, the following It is considered effective.
That is, when the heat-sensitive recording layer of the present invention contains a sulfonic acid compound represented by the above chemical formula (Formula 1) and 4-hydroxy-4′-allyloxydiphenyl sulfone as a developer, the heat-sensitive recording layer is heated and melted. Since two types of sulfonic acid compounds with similar behavior at the time of melting and melting coexist, the stability of the electron transfer complex, which is the reaction product of the developer and leuco dye, increases, and the color development performance and white paper It is presumed that a heat-sensitive recording material having both excellent heat discoloration resistance and good bar code readability can be obtained.
On the other hand, when the heat-sensitive recording layer of the present invention contains a sulfonic acid compound represented by the above chemical formula (Chemical Formula 1) and a urethane urea compound represented by the above General Formula (Chemical Formula 2) as a developer, the heat-sensitive recording layer. Since compounds with two types of urea bonds coexist in them, the reaction efficiency with leuco dyes is higher than when only one of them is contained, and it becomes easier to generate an electron transfer complex and the reverse reaction is less likely to occur. Therefore, it is presumed that a heat-sensitive recording material is obtained that has both excellent color development performance and heat discoloration resistance of the white paper portion, and good barcode readability.
Further, when a protective layer is provided on the thermal recording material, that is, when the protective layer absorbs part of the thermal energy given from the thermal head or the like and the thermal energy is low, the developer and leuco It is presumed that the stability of the electron transfer complex, which is a reaction product with the dye, is sufficiently high so that the color development sensitivity does not decrease and the bar code reading suitability of the resulting thermal recording material is good.
　このウレアウレタン系化合物は、具体的には下式（化３）～（化５）で表される３種類であり、これらは単独又は２種類以上混合して用いてもよい These urea urethane compounds are specifically three types represented by the following formulas (Chemical Formula 3) to (Chemical Formula 5), and these may be used alone or in combination of two or more.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　本発明においては、上記化合物以外の顕色剤を併用してもよい。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）、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、株式会社エーピーアイコーポレーション製商品名ＪＫＹ－２１４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、株式会社エーピーアイコーポレーション製商品名ＪＫＹ－２２４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）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）製商品名ＮＫＫ－３９５、Ｄ－１００として入手可能である。この他、特開平１０－２５８５７７号公報記載の高級脂肪酸金属複塩や多価ヒドロキシ芳香族化合物などの金属キレート型発色成分を含有することもできる。 In the present invention, a developer other than the above compounds may be used in combination. For example, activated acid clay, attapulgite, colloidal silica, inorganic acid substances such as aluminum silicate, 4,4′-isopropylidenediphenol, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy) Phenyl) -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 Nyl-4′-benzyloxyphenylsulfone, 3,4-dihydroxyphenyl-4′-methylphenylsulfone, 1- [4- (4-hydroxyphenylsulfonyl) phenoxy] -4- [4- (4-isopropoxyphenyl) Sulfonyl) phenoxy] butane, a phenol condensation composition described in JP-A No. 2003-154760, an aminobenzenesulfonamide derivative described in JP-A No. 8-59603, bis (4-hydroxyphenylthioethoxy) methane, 1,5- Di (4-hydroxyphenylthio) -3-oxapentane, butyl bis (p-hydroxyphenyl) acetate, methyl bis (p-hydroxyphenyl) acetate, 1,1-bis (4-hydroxyphenyl) -1-phenylethane 1,4-bis [α-methyl-α- (4′-hydroxy Enyl) 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), phenolic compounds such as diphenylsulfone bridged compounds described in WO97 / 16420, WO02 / 081229 or JP2002-301873 And 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- [ -(P-Tolylsulfonyl) propyloxy] salicylic acid, 5- [p- (2-p-methoxyphenoxyethoxy) cumyl] salicylic acid aromatic carboxylic acid, and zinc, magnesium, aluminum, calcium of these aromatic carboxylic acids And salts with polyvalent metal salts such as titanium, manganese, tin, nickel, and the like, as well as antipyrine complexes of zinc thiocyanate, and complex zinc salts of terephthalaldehyde acid with other aromatic carboxylic acids. These 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 JKY-214 manufactured by API Corporation. The phenol condensation composition described in JP-A No. 2003-154760 is available, for example, under the trade name JKY-224 manufactured by API Corporation, and is a diphenylsulfone cross-linking compound described in International Publication WO 97/16420. Is available under the trade name D-90 manufactured by Nippon Soda Co., Ltd. The compounds described in WO 02/081229 and the like are available as trade names NKK-395 and D-100 manufactured by Nippon Soda Co., Ltd. In addition, a metal chelate color-developing component such as a higher fatty acid metal double salt and a polyvalent hydroxyaromatic compound described in JP-A-10-258577 can also be contained.
　本発明では、上記化学式（化１）で表されるスルホン酸系化合物１重量部に対し、４－ヒドロキシ－４’－アリルオキシジフェニルスルホン又は上記一般式（化２）で表されるウレアウレタン系化合物を０．０１～１０．０重量部の割合で使用することが好ましく、０．１～５．０重量部の割合で使用することがより好ましい。上記化学式（化１）で表されるスルホン酸系化合物１重量部に対し４－ヒドロキシ－４’－アリルオキシジフェニルスルホン又は上記一般式（化２）で表されるウレアウレタン系化合物が０．０１重量部未満であると、得られる感熱記録体の発色性能が低下する傾向がみられる。一方、１０．０重量部を超えると、白紙部の耐熱変色性が十分でないことがある。
　本発明の感熱記録層が、上記化学式（化１）で表されるスルホン酸系化合物、４－ヒドロキシ－４’－アリルオキシジフェニルスルホン又は上記一般式（化２）で表されるウレアウレタン系化合物以外の顕色剤を含有する場合、上記化学式（化１）で表されるスルホン酸系化合物、４－ヒドロキシ－４’－アリルオキシジフェニルスルホン及び上記一般式（化２）で表されるウレアウレタン系化合物を合計した含有量は、該感熱記録層中に含有させる全顕色剤（上記化学式（化１）で表されるスルホン酸系化合物、４－ヒドロキシ－４’－アリルオキシジフェニルスルホン及び上記一般式（化２）で表されるウレアウレタン系化合物を含む）の好ましくは５０重量％以上であり、より好ましくは９０重量％以上である。 In the present invention, 4-hydroxy-4′-allyloxydiphenyl sulfone or the urea urethane type represented by the general formula (Chemical Formula 2) is used per 1 part by weight of the sulfonic acid type compound represented by the chemical formula (Chemical Formula 1). The compound is preferably used in a proportion of 0.01 to 10.0 parts by weight, more preferably 0.1 to 5.0 parts by weight. 4-hydroxy-4'-allyloxydiphenyl sulfone or urea urethane compound represented by the above general formula (Chemical Formula 2) is 0.01% per 1 part by weight of the sulfonic acid type compound represented by the chemical formula (Chemical Formula 1). If the amount is less than parts by weight, the color development performance of the resulting heat-sensitive recording material tends to deteriorate. On the other hand, if it exceeds 10.0 parts by weight, the heat discoloration of the white paper part may not be sufficient.
The heat-sensitive recording layer of the present invention comprises a sulfonic acid compound represented by the above chemical formula (Chemical Formula 1), 4-hydroxy-4′-allyloxydiphenyl sulfone, or a urea urethane compound represented by the above General Formula (Chemical Formula 2) When a developer other than the above is contained, the sulfonic acid compound represented by the above chemical formula (Chemical Formula 1), 4-hydroxy-4′-allyloxydiphenyl sulfone, and the urea urethane represented by the above general formula (Chemical Formula 2) The total content of the series compounds is the total developer contained in the thermosensitive recording layer (the sulfonic acid series compound represented by the above chemical formula (Chemical Formula 1), 4-hydroxy-4′-allyloxydiphenylsulfone and the above Preferably it is 50 weight% or more of the urethane urethane type compound represented by General formula (Formula 2), More preferably, it is 90 weight% or more.
　次に、本発明の感熱記録体の感熱記録層で使用されるその他の材料を例示するが、バインダー、架橋剤、顔料などは、上記課題に対する所望の効果を阻害しない範囲で、必要に応じて設けられた保護層等の各塗工層にも使用することが可能である。 Next, other materials used in the heat-sensitive recording layer of the heat-sensitive recording material of the present invention are exemplified, but binders, cross-linking agents, pigments, and the like may be used as necessary as long as they do not hinder the desired effects on the above-described problems. It can also be used for each coating layer such as a provided protective layer.
　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、フルオレン系化合物、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, any known leuco dyes in the field of conventional pressure-sensitive or thermal recording paper can be used, and are not particularly limited, but include triphenylmethane compounds, fluoran compounds, fluorenes. Of these, divinyl compounds and divinyl compounds are preferred. Specific examples of typical colorless or light-colored dyes (dye precursors) are shown below. 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 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－７－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 <Fluoran 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-chlorofluorane, 3-diethylamino-6-methyl-7- (m-trifluoromethylanilino) fluorane, 3-diethylamino-6-methyl-7- (o-chloroanilino) fluorane, 3- Diethylamino-6-methyl-7- (p-chloroanilino) fluorane, 3-diethylamino-6-methyl-7- (o-fluoroanilino) fluorane, 3-diethylamino-6-methyl-7- (m-methylanilino) fluorane 3-diethylamino-6-methyl-7-n-octylanilinofluorane, 3-di Tylamino-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-ethoxy Ethyl-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-anilinofluorane, 3-dibutylamino-6-methyl-7- (o, p-dimethylanilino) fluorane, 3-dibutylamino-6-methyl-7- ( o-chloroanilino) fluorane, 3-dibutylamino-6-methyl-7- (p-chloroanilino) fluorane, 3-dibutylamino-6-methyl-7- (o-fluoroanilino) fluorane, 3-dibutylamino-6 -Methyl-7- (m-trifluoromethylanilino) fluorane, 3-dibutylamino- 6-methyl-7-chlorofluorane, 3-dibutylamino-6-ethoxyethyl-7-anilinofluorane, 3-dibutylamino-6-chloro-7-anilinofluorane, 3-dibutylamino-6- Methyl-7-p-methylanilinofluorane, 3-dibutylamino-7- (o-chloroanilino) fluorane, 3-dibutylamino-7- (o-fluoroanilino) fluorane, 3-di-n-pentylamino -6-methyl-7-anilinofluorane, 3-di-n-pentylamino-6-methyl-7- (p-chloroanilino) fluorane, 3-di-n-pentylamino-7- (m-trifluoro Methylanilino) fluorane, 3-di-n-pentylamino-6-chloro-7-anilinofluorane, 3-di-n-pentylamino-7- (p-chloro) Nilino) fluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3- (N-methyl-N-propylamino) -6-methyl -7-anilinofluorane, 3- (N-methyl-N-cyclohexylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N-cyclohexylamino) -6-methyl-7 -Anilinofluorane, 3- (N-ethyl-N-xylamino) -6-methyl-7- (p-chloroanilino) fluorane, 3- (N-ethyl-p-toludino) -6-methyl-7-ani Linofluorane, 3- (N-ethyl-N-isoamylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N-isoamylamino) -6-chloro-7-a Linofluorane, 3- (N-ethyl-N-tetrahydrofurfurylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N-isobutylamino) -6-methyl-7-anilinofluor Oran, 3- (N-ethyl-N-ethoxypropylamino) -6-methyl-7-anilinofluorane, 3-cyclohexylamino-6-chlorofluorane, 2- (4-oxahexyl) -3-dimethyl Amino-6-methyl-7-anilinofluorane, 2- (4-oxahexyl) -3-diethylamino-6-methyl-7-anilinofluorane, 2- (4-oxahexyl) -3-dipropyl Amino-6-methyl-7-anilinofluorane, 2-methyl-6-p- (p-dimethylaminophenyl) aminoanilinofluorane, 2-methoxy-6-p -(P-dimethylaminophenyl) aminoanilinofluorane, 2-chloro-3-methyl-6-p- (p-phenylaminophenyl) aminoanilinofluorane, 2-chloro-6-p- (p- Dimethylaminophenyl) aminoanilinofluorane, 2-nitro-6-p- (p-diethylaminophenyl) aminoanilinofluorane, 2-amino-6-p- (p-diethylaminophenyl) aminoanilinofluorane, 2-diethylamino-6-p- (p-diethylaminophenyl) aminoanilinofluorane, 2-phenyl-6-methyl-6-p- (p-phenylaminophenyl) aminoanilinofluorane, 2-benzyl-6 -P- (p-phenylaminophenyl) aminoanilinofluorane, 2-hydroxy-6-p- (p-phenylamino) Nophenyl) aminoanilinofluorane, 3-methyl-6-p- (p-dimethylaminophenyl) aminoanilinofluorane, 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 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- Yl] -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) fluorane-γ- (3′-nitro) anilinolactam, 3,6 -Bis (diethylamino) fluorane-γ- (4'-nitro) anilinolactam, 1,1-bis- [2 ', 2', 2 ", 2" -tetrakis- (p-dimethylamino) Enyl) -ethenyl] -2,2-dinitrileethane, 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
　本発明で使用する増感剤としては、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－ビス－（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、ｏ－トルエンスルホンアミド、ｐ－トルエンスルホンアミドなどを例示することができる。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 used in the present invention, a conventionally known sensitizer can be used. Such sensitizers include fatty acid amides such as stearamide and palmitic acid amide, ethylene bisamide, montanic acid wax, polyethylene wax, 1,2-bis- (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-me Tylphenoxymethyl) biphenyl, 4,4′-ethylenedioxy-bis-benzoic acid dibenzyl ester, dibenzoyloxymethane, 1,2-di (3-methylphenoxy) ethylene, bis [2- (4-methoxy- Phenoxy) ethyl] ether, methyl p-nitrobenzoate, phenyl p-toluenesulfonate, o-toluenesulfonamide, p-toluenesulfonamide and the like. These sensitizers may be used alone or in combination of two or more.
　本発明で使用する顔料としては、カオリン、焼成カオリン、炭酸カルシウム、酸化アルミニウム、酸化チタン、炭酸マグネシウム、珪酸アルミニウム、珪酸マグネシウム、珪酸カルシウム、水酸化アルミニウム、シリカ等が挙げられ、要求品質に応じて併用することもできる。 Examples of the pigment used in the present invention include kaolin, calcined kaolin, calcium carbonate, aluminum oxide, titanium oxide, magnesium carbonate, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, and silica, depending on the required quality. It can also be used together.
　本発明で使用する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、アセトアセチル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、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、シリコーン変性ポリビニルアルコール、その他の変性ポリビニルアルコール、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、スチレン－無水マレイン酸共重合体、スチレン－ブタジエン共重合体並びにエチルセルロース、アセチルセルロースのようなセルロース誘導体、カゼイン、アラビヤゴム、酸化澱粉、エーテル化澱粉、ジアルデヒド澱粉、エステル化澱粉、ポリ塩化ビニル、ポリ酢酸ビニル、ポリアクリルアミド、ポリアクリル酸エステル、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、ポリアミド樹脂、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。これらの高分子物質は水、アルコール、ケトン類、エステル類、炭化水素などの溶剤に溶かして使用するほか、水又は他の媒体中に乳化又はペースト状に分散した状態で使用し、要求品質に応じて併用することもできる。 The binder used in the present invention includes fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, acetoacetylated polyvinyl alcohol, carboxy-modified polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, butyral-modified polyvinyl alcohol, and olefin-modified. Polyvinyl alcohol, nitrile modified polyvinyl alcohol, pyrrolidone modified polyvinyl alcohol, silicone modified polyvinyl alcohol, other modified polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, styrene-maleic anhydride copolymer, styrene-butadiene copolymer and Cell like ethyl cellulose, acetyl cellulose Derivatives, casein, arabic gum, oxidized starch, etherified starch, dialdehyde starch, esterified starch, polyvinyl chloride, polyvinyl acetate, polyacrylamide, polyacrylic ester, polyvinyl butyral, polystyrose and copolymers thereof And polyamide resin, silicone resin, petroleum resin, terpene resin, ketone resin, coumarone resin, and the like. These polymer substances are used by dissolving in water, alcohol, ketones, esters, hydrocarbons and other solvents, and are used in the form of emulsification or paste dispersion in water or other media. It can also be used in combination.
　本発明で使用する架橋剤としては、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、塩化アンモニウムなどを例示することができる。 Examples of the crosslinking agent used in the present invention include glyoxal, methylol melamine, melamine formaldehyde resin, melamine urea resin, polyamine epichlorohydrin resin, polyamide epichlorohydrin resin, potassium persulfate, ammonium persulfate, sodium persulfate, chloride chloride Examples include ferric iron, magnesium chloride, borax, boric acid, alum, ammonium chloride and the like.
　本発明で使用する滑剤としては、ステアリン酸亜鉛、ステアリン酸カルシウム等の脂肪酸金属塩、ワックス類、シリコーン樹脂類などが挙げられる。 Examples of the lubricant used in the present invention include fatty acid metal salts such as zinc stearate and calcium stearate, waxes, silicone resins and the like.
　本発明においては、上記課題に対する所望の効果を阻害しない範囲で、画像部の耐油性等を向上させる安定剤として、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）ブタン等を添加することもできる。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、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-tert-butyl-3-methylphenol), 2 as a stabilizer that improves the oil resistance and the like of the image area as long as the desired effect on the above-described problems is not impaired. 2,2'-di-t-butyl-5,5'-dimethyl-4,4'-sulfonyldiphenol, 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane, 1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane and the like can also be added. In addition, benzophenone and triazole ultraviolet absorbers, dispersants, antifoaming agents, antioxidants, fluorescent dyes, and the like can be used.
　本発明の感熱記録層に使用するロイコ染料、顕色剤、増感剤、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、ロイコ染料１重量部に対して顕色剤０．５～１０重量部、増感剤０．１～１０重量部、顔料０．５～２０重量部、安定化剤０．０１～１０重量部、その他の成分０．０１～１０重量部程度を使用する。バインダーは感熱記録層固形分中５～２５重量％程度が適当である。 The types and amounts of the leuco dye, developer, sensitizer, and other various components used in the heat-sensitive recording layer of the present invention are determined according to the required performance and recording suitability, and are not particularly limited. Usually, 0.5 to 10 parts by weight of developer, 0.1 to 10 parts by weight of sensitizer, 0.5 to 20 parts by weight of pigment, and 0.01 to 10 parts by weight of stabilizer for 1 part by weight of leuco dye. Parts and other components of about 0.01 to 10 parts by weight. The binder is suitably about 5 to 25% by weight in the solid content of the heat-sensitive recording layer.
　本発明において、ロイコ染料、顕色剤並びに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、バインダー及び目的に応じて各種の添加材料を加えて塗工液とする。この塗工液に用いる溶媒としては水あるいはアルコール等を用いることができ、その固形分は２０～４０重量％程度である。 In the present invention, the leuco dye, the developer, and the material to be added as necessary are finely divided to a particle size of several microns or less by a pulverizer such as a ball mill, an attritor, or a sand glider, or a suitable emulsifying device, Depending on the purpose, various additive materials are added to obtain a coating solution. As the solvent used in the coating solution, water or alcohol can be used, and its solid content is about 20 to 40% by weight.
　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ることもできる。
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。
　本発明において、保護層中の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重量部程度である。 In the heat-sensitive recording material of the present invention, a protective layer can be further provided on the heat-sensitive recording layer.
The protective layer is mainly composed of a pigment and a resin, and binders, pigments, crosslinking agents and the like exemplified as materials that can be used for the heat-sensitive recording layer can be used.
In the present invention, the content of the pigment and binder in the protective layer is about 30 to 300 parts by weight in solid content of the binder with respect to 100 parts by weight of the pigment.
　本発明の感熱記録体は、支持体上に感熱記録層を有するが、支持体と感熱記録層の間に下塗り層を設けることができる。
　この下塗り層は、主としてバインダーと顔料とから成る。
　下塗り層に用いるバインダーとしては、一般的に使用されている水溶性高分子あるいは疎水性高分子のエマルジョン等が適宜使用可能である。具体例としては、ポリビニルアルコール、ポリビニルアセタール、ヒドロキシエチルセルロース、メチルセルロース、カルボキシメチルセルロース、等のセルロース誘導体、デンプンとその誘導体、ポリアクリル酸ソーダ、ポリビニルピロリドン、アクリル酸アミド／アクリル酸エステル共重合体、アクリル酸アミド／アクリル酸エステル／メタクリル酸共重合体、スチレン／無水マレイン酸共重合体アルカリ塩、イソブチレン／無水マレイン酸共重合体アルカリ塩、ポリアクリルアミド、アルギン酸ソーダ、ゼラチン、カゼイン等の水溶性高分子、ポリ酢酸ビニル、ポリウレタン、スチレン／ブタジエン共重合体、ポリアクリル酸、ポリアクリル酸エステル、塩化ビニル／酢酸ビニル共重合体、ポリブチルメタクリレート、エチレン／酢酸ビニル共重合体、スチレン／ブタジエン／アクリル系共重合体等の疎水性高分子のエマルジョンを用いることができる。これらのバインダーは１種又は２種以上用いてもよい。 The heat-sensitive recording material of the present invention has a heat-sensitive recording layer on a support, but an undercoat layer can be provided between the support and the heat-sensitive recording layer.
This undercoat layer mainly comprises a binder and a pigment.
As the binder used for the undercoat layer, a commonly used water-soluble polymer or hydrophobic polymer emulsion or the like can be appropriately used. Specific examples include cellulose derivatives such as polyvinyl alcohol, polyvinyl acetal, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, starch and derivatives thereof, polysodium acrylate, polyvinyl pyrrolidone, acrylate / acrylate copolymers, acrylic acid Water-soluble polymers such as amide / acrylic acid ester / methacrylic acid copolymer, styrene / maleic anhydride copolymer alkali salt, isobutylene / maleic anhydride copolymer alkali salt, polyacrylamide, sodium alginate, gelatin, casein, Polyvinyl acetate, polyurethane, styrene / butadiene copolymer, polyacrylic acid, polyacrylate ester, vinyl chloride / vinyl acetate copolymer, polybutyl methacrylate, ethylene / acetic acid Cycloalkenyl copolymer, can be used styrene / butadiene / emulsion of a hydrophobic polymer such as an acrylic copolymer. These binders may be used alone or in combination of two or more.
　下塗り層に用いる顔料としては、従来一般的に使用されている公知の顔料、具体例としては炭酸カルシウム、シリカ、酸化亜鉛、酸化チタン、水酸化アルミニウム、水酸化マグネシウム、焼成カオリン、クレー、タルク等の無機顔料などを使用することができる。これらの顔料は１種又は２種以上用いてもよい。
　下塗り層中の顔料は、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。
　下塗り層の塗工液には必要に応じて、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。 As the pigment used in the undercoat layer, known pigments generally used conventionally, specific examples include calcium carbonate, silica, zinc oxide, titanium oxide, aluminum hydroxide, magnesium hydroxide, calcined kaolin, clay, talc, etc. Inorganic pigments can be used. These pigments may be used alone or in combination of two or more.
The pigment in the undercoat layer is usually 50 to 95 parts by weight, preferably 70 to 90 parts by weight with respect to 100 parts by weight of the total solid content.
Various additives such as a dispersant, a plasticizer, a pH adjuster, an antifoaming agent, a water retention agent, an antiseptic, a coloring dye, and an ultraviolet ray inhibitor may be appropriately blended in the undercoat layer coating liquid as necessary. Good.
　本発明において、感熱記録層及び感熱記録層以外の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布することができる。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。
　感熱記録層及び感熱記録層以外の塗工層の塗工量は、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、感熱記録層の一般的な塗工量は固形分で２～１２ｇ／ｍ２程度である。
　また、各層の塗工後にスーパーカレンダー掛けなど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必要適宜付加することができる。 In the present invention, the means for coating the heat-sensitive recording layer and the coating layer other than the heat-sensitive recording layer is not particularly limited, and can be applied according to a well-known conventional technique. 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 vent blade coater, a bevel blade coater, a roll coater, and a curtain coater is appropriately selected and used.
The coating amount of the coating layer other than the heat-sensitive recording layer and 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 of the heat-sensitive recording layer is solid. It is about 2 to 12 g / m 2 per minute.
Further, various known techniques in the heat-sensitive recording material field can be added as appropriate, such as applying a smoothing process such as supercalendering after coating each 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。各種分散液、あるいは塗工液を以下のように調製した In the following, the present invention is illustrated by examples, but is not intended to limit the present invention. In Examples and Comparative Examples, “parts” represents “parts by weight” and “%” represents “% by weight” unless otherwise specified. Various dispersions or coating solutions were prepared as follows.
［実施例１］
　下記配合からなる配合物を攪拌分散して、下塗り層塗工液を調製した。
＜下塗り層塗工液＞
　焼成カオリン（ＢＡＳＦ社製、商品名：アンシレックス９０）
　　　　　　　　　　　　　　　　　　　　　　　　　　　　１００．０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、商品名：
　ＳＴ５５２６、固形分４８％）　　　　　　　　　　　　　　１０．０部
　水　　　　　　　　　　　　　　　　　　　　　　　　　　　５０．０部
　次いで、下塗り層塗工液を支持体（坪量４７ｇ／ｍ２の上質紙）の片面に、固形分で塗工量１０．０ｇ／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。 [Example 1]
A composition comprising the following composition was stirred and dispersed to prepare an undercoat layer coating solution.
<Undercoat layer coating solution>
Baked kaolin (trade name: Ansilex 90, manufactured by BASF)
100.0 parts Styrene-butadiene copolymer latex (manufactured by Zeon Corporation, trade name:
ST5526, solid content 48%) 10.0 parts water 50.0 parts Next, the coating amount of the undercoat layer coating solution is 10.0 g in solid content on one side of the support (basis weight 47 g / m 2 fine paper). After coating by the vent blade method so as to be / m 2 , drying was performed to obtain an undercoat layer coated paper.
　下記配合の第一顕色剤分散液１～２（Ａ１液～Ａ２液）、第二顕色剤分散液１～２（Ｂ１液～Ｂ２液）、ロイコ染料分散液（Ｃ液）および増感剤分散液（Ｄ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。 First developer dispersions 1 to 2 (A1 liquid to A2 liquid), second developer dispersions 1 to 2 (B1 liquid to B2 liquid), leuco dye dispersion liquid (C liquid) and sensitization of the following composition The agent dispersion liquid (liquid D) was separately wet-ground with a sand grinder until the average particle size became 0.5 microns.
第一顕色剤分散液１（Ａ１液）
　化学式（化１）で表されるスルホン酸系化合物（ＢＡＳＦ社製、商品名：
　ＤＰ２０１）　　　　　　　　　　　　　　　　　　　　　　　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、商品名：ＰＶＡ
　１１７、固形分１０％）　　　　　　　　　　　　　　　　　　５．０部
　水　　　　　　　　　　　　　　　　　　　　　　　　　　　　１．５部
第一顕色剤分散液２（Ａ２液）
　ジフェニルスルホン架橋型化合物（日本曹達社製、商品名：Ｄ９０）
　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　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、商品名：ＰＶＡ
　１１７、固形分１０％）　　　　　　　　　　　　　　　　　　５．０部
　水　　　　　　　　　　　　　　　　　　　　　　　　　　　　１．５部 First developer dispersion 1 (A1 liquid)
A sulfonic acid compound represented by the chemical formula (Chemical Formula 1) (manufactured by BASF, trade name:
DP201) 6.0 parts Completely saponified polyvinyl alcohol aqueous solution (Kuraray Co., Ltd., trade name: PVA)
117, solid content 10%) 5.0 parts water 1.5 parts first developer dispersion 2 (liquid A2)
Diphenylsulfone cross-linking compound (Nippon Soda Co., Ltd., trade name: D90)
6.0 parts Completely saponified polyvinyl alcohol aqueous solution (Kuraray Co., Ltd., trade name: PVA)
117, solid content 10%) 5.0 parts water 1.5 parts
第二顕色剤分散液１（Ｂ１液）
　４－ヒドロキシ－４'－アリルオキシジフェニルスルホン（日華化学社製、
　　商品名：ＢＰＳ－ＭＡＥ）　　　　　　　　　　　　　　　　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、商品名：ＰＶＡ
　１１７、固形分１０％）　　　　　　　　　　　　　　　　　　５．０部
　水　　　　　　　　　　　　　　　　　　　　　　　　　　　　１．５部
第二顕色剤分散液２（Ｂ２液）
　化学式（化３）で表されるウレタンウレア系化合物（ケミプロ化成社製、
　　商品名：ＵＵ）　　　　　　　　　　　　　　　　　　　　　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、商品名：ＰＶＡ
　１１７、固形分１０％）　　　　　　　　　　　　　　　　　　５．０部
　水　　　　　　　　　　　　　　　　　　　　　　　　　　　　１．５部 Second developer dispersion 1 (B1 solution)
4-hydroxy-4′-allyloxydiphenyl sulfone (manufactured by Nikka Chemical Co., Ltd.)
Product name: BPS-MAE) 6.0 parts Completely saponified polyvinyl alcohol aqueous solution (Kuraray Co., Ltd., product name: PVA)
117, solid content 10%) 5.0 parts water 1.5 parts second developer dispersion 2 (B2 liquid)
Urethane urea compound represented by the chemical formula (Chemical Formula 3) (Chemipro Kasei Co., Ltd.,
Product name: UU) 6.0 parts Completely saponified polyvinyl alcohol aqueous solution (Kuraray Co., Ltd., product name: PVA)
117, solid content 10%) 5.0 parts water 1.5 parts
ロイコ染料分散液（Ｃ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、商品名：ＯＤＢ－２）　　　　　　　　　　　　　　　　　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、商品名：ＰＶＡ
　１１７、固形分１０％）　　　　　　　　　　　　　　　　　　５．０部
　水　　　　　　　　　　　　　　　　　　　　　　　　　　　　１．５部
増感剤分散液（Ｄ液）
　１，２－ビス－（３－メチルフェノキシ）エタン（三光社製、商品名：
　ＫＳ２３２）　　　　　　　　　　　　　　　　　　　　　　　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、商品名：ＰＶＡ
　１１７、固形分１０％）　　　　　　　　　　　　　　　　　　５．０部
　水　　　　　　　　　　　　　　　　　　　　　　　　　　　　１．５部 Leuco dye dispersion (liquid C)
3-dibutylamino-6-methyl-7-anilinofluorane (manufactured by Yamamoto Kasei Co., Ltd., trade name: ODB-2) 6.0 parts fully saponified polyvinyl alcohol aqueous solution (manufactured by Kuraray Co., Ltd., trade name: PVA)
117, solid content 10%) 5.0 parts water 1.5 parts sensitizer dispersion (liquid D)
1,2-bis- (3-methylphenoxy) ethane (manufactured by Sanko Co., Ltd., trade name:
KS232) 6.0 parts Completely saponified polyvinyl alcohol aqueous solution (Kuraray Co., Ltd., trade name: PVA)
117, solid content 10%) 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塗工液１を調製した。
＜感熱記録層塗工液１＞
　第一顕色剤分散液１（Ａ１液）　　　　　　　　　　　　　　１８．０部
　第二顕色剤分散液１（Ｂ１液）　　　　　　　　　　　　　　１８．０部
　ロイコ染料分散液（Ｃ液）　　　　　　　　　　　　　　　　１８．０部
　増感剤分散液（Ｄ液）　　　　　　　　　　　　　　　　　　３６．０部
　シリカ分散液（水澤化学社製、商品名：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（クラレ社製、商品名：ＰＶＡ
　１１７、固形分１０％）　　　　　　　　　　　　　　　　　２５．０部
　次いで、感熱記録層塗工液１を前記下塗り層塗工紙の下塗り層上に、固形分で塗工量６．０ｇ／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体を作製した。 Next, each dispersion was mixed at the following ratio to prepare a thermal recording layer coating solution 1.
<Thermosensitive recording layer coating solution 1>
1st developer dispersion 1 (A1 liquid) 18.0 parts 2nd developer dispersion 1 (B1 liquid) 18.0 parts Leuco dye dispersion (liquid C) 18.0 parts Sensitizer dispersion ( Liquid D) 36.0 parts Silica dispersion (manufactured by Mizusawa Chemical Co., Ltd., trade name: Mizukasil P-537, solid content 25%) 17.5 parts Complete saponified polyvinyl alcohol aqueous solution (Kuraray Co., Ltd., trade name: PVA)
117, solid content 10%) 25.0 parts Next, heat-sensitive recording layer coating solution 1 is applied onto the undercoat layer of the undercoat layer-coated paper so that the solid coating amount is 6.0 g / m 2. After coating by the blade method, drying was performed, and processing was performed with a super calender so that the smoothness became 500 to 1000 seconds, thereby producing a heat-sensitive recording material.
［実施例２］
　増感剤分散液（Ｄ液）中の１，２－ビス－（３－メチルフェノキシ）エタン（三光社製、商品名：ＫＳ２３２）６．０部をステアリン酸アマイド／パルチミン酸アマイド混合物（混合比率：７／３、日本化成社製、商品名：ＡＰ－１）６．０部に代えた以外は、実施例１と同様にして感熱記録体を作製した。
［実施例３］
　ロイコ染料分散液（Ｃ液）中の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、商品名：ＯＤＢ－２）６．０部を３－ジ－ｎ－ペンチルアミノ－６－メチル－７－アニリノフルオラン（山田化学社製、商品名：ＢＬＡＣＫ３０５）６．０部に代えた以外は、実施例１と同様にして感熱記録体を作製した。 [Example 2]
6.0 parts of 1,2-bis- (3-methylphenoxy) ethane (manufactured by Sanko Co., Ltd., trade name: KS232) in the sensitizer dispersion (liquid D) was mixed with stearic acid amide / paltimic acid amide mixture (mixing ratio). : 7/3, Nippon Kasei Co., Ltd., trade name: AP-1) A heat-sensitive recording material was produced in the same manner as in Example 1 except that 6.0 parts were used.
[Example 3]
6.0 parts of 3-dibutylamino-6-methyl-7-anilinofluorane (manufactured by Yamamoto Kasei Co., Ltd., trade name: ODB-2) in the leuco dye dispersion (liquid C) was mixed with 3-di-n-pentyl. A thermosensitive recording material was produced in the same manner as in Example 1 except that 6.0 parts of amino-6-methyl-7-anilinofluorane (trade name: BLACK305, manufactured by Yamada Chemical Co., Ltd.) was used.
［実施例４］
　感熱記録層塗工液１中のシリカ分散液の配合量を１７．５部から７．５部に代えて感熱記録層塗工液２とし、感熱記録層塗工液２を前記下塗り層塗工紙の下塗り層上に、固形分で塗工量６．０ｇ／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、下記割合からなる配合物を混合して保護層塗工液を調製した。
＜保護層塗工液＞
　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：ＫＬ
　３１８、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：ＷＳ４０
　３０、固形分２５％）　　　　　　　　　　　　　　　　　　　４．０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
　次いで、保護層塗工液を前記感熱記録層塗工紙の感熱記録層上に、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、感熱記録体を作製した。 [Example 4]
The amount of silica dispersion in the heat-sensitive recording layer coating liquid 1 is changed from 17.5 parts to 7.5 parts to obtain a heat-sensitive recording layer coating liquid 2, and the heat-sensitive recording layer coating liquid 2 is applied to the undercoat layer coating. On the undercoat layer of paper, after coating by the rod blade method so that the coating amount is 6.0 g / m 2 in terms of solid content, drying is performed so that the smoothness becomes 500 to 1000 seconds with a super calendar. The heat-sensitive recording layer coated paper was produced by processing.
Subsequently, the mixture which consists of the following ratio was mixed and the protective layer coating liquid was prepared.
<Protective layer coating solution>
Aluminum hydroxide dispersion (manufactured by Martinsberg,
Product name: Martyfin OL, solid content 50%) 9.0 parts Carboxy-modified polyvinyl alcohol aqueous solution (manufactured by Kuraray Co., Ltd., product name: KL)
318, solid content 10%) 30.0 parts Polyamide epichlorohydrin resin (manufactured by Seiko PMC, trade name: WS40)
30, solid content 25%) 4.0 parts Zinc stearate (manufactured by Chukyo Yushi Co., Ltd., trade name: Hydrin Z-7-30,
(Solid content: 30%) 2.0 parts Next, the protective layer coating liquid was applied onto the heat-sensitive recording layer of the heat-sensitive recording layer-coated paper so that the coating amount was 3.0 g / m 2 in terms of solid content. After coating by the method, drying was performed to produce a heat-sensitive recording material.
［実施例５］
　増感剤分散液（Ｄ液）中の１，２－ビス－（３－メチルフェノキシ）エタン（三光社製、商品名：ＫＳ２３２）６．０部をステアリン酸アマイド／パルチミン酸アマイド混合物（混合比率：７／３、日本化成社製、商品名：ＡＰ－１）６．０部に代えた以外は、実施例４と同様にして感熱記録体を作製した。
［実施例６］
　ロイコ染料分散液（Ｃ液）中の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、商品名：ＯＤＢ－２）６．０部を３－ジ－ｎ－ペンチルアミノ－６－メチル－７－アニリノフルオラン（山田化学社製、商品名：ＢＬＡＣＫ３０５）６．０部に代えた以外は、実施例４と同様にして感熱記録体を作製した。 [Example 5]
6.0 parts of 1,2-bis- (3-methylphenoxy) ethane (manufactured by Sanko Co., Ltd., trade name: KS232) in the sensitizer dispersion (liquid D) was mixed with stearic acid amide / paltimic acid amide mixture (mixing ratio). : 7/3, manufactured by Nippon Kasei Co., Ltd., trade name: AP-1) A heat-sensitive recording material was produced in the same manner as in Example 4 except that 6.0 parts was used.
[Example 6]
6.0 parts of 3-dibutylamino-6-methyl-7-anilinofluorane (manufactured by Yamamoto Kasei Co., Ltd., trade name: ODB-2) in the leuco dye dispersion (liquid C) was mixed with 3-di-n-pentyl. A thermosensitive recording material was produced in the same manner as in Example 4 except that 6.0 parts of amino-6-methyl-7-anilinofluorane (trade name: BLACK305, manufactured by Yamada Chemical Co., Ltd.) was used.
［実施例７］
　感熱記録層塗工液１の第二顕色剤分散液１（Ｂ１液）を第二顕色剤分散液２（Ｂ２液）に代えて感熱記録層塗工液３とし、感熱記録層塗工液１を感熱記録層塗工液３に代えて実施例１と同様にして感熱記録体を作製した。
［実施例８］
　増感剤分散液（Ｄ液）中の１，２－ビス－（３－メチルフェノキシ）エタン（三光社製、商品名：ＫＳ２３２）６．０部をステアリン酸アマイド／パルチミン酸アマイド混合物（混合比率：７／３、日本化成社製、商品名：ＡＰ－１）６．０部に代えた以外は、実施例７と同様にして感熱記録体を作製した。
［実施例９］
　ロイコ染料分散液（Ｃ液）中の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、商品名：ＯＤＢ－２）６．０部を３－ジ－ｎ－ペンチルアミノ－６－メチル－７－アニリノフルオラン（山田化学社製、商品名：ＢＬＡＣＫ３０５）６．０部に代えた以外は、実施例７と同様にして感熱記録体を作製した。 [Example 7]
The second developer dispersion liquid 1 (B1 liquid) of the heat-sensitive recording layer coating liquid 1 is replaced with the second developer dispersion liquid 2 (B2 liquid) to form a heat-sensitive recording layer coating liquid 3, and the heat-sensitive recording layer coating is performed. A heat-sensitive recording material was produced in the same manner as in Example 1 except that the liquid 1 was replaced with the heat-sensitive recording layer coating liquid 3.
[Example 8]
6.0 parts of 1,2-bis- (3-methylphenoxy) ethane (manufactured by Sanko Co., Ltd., trade name: KS232) in the sensitizer dispersion (liquid D) was mixed with stearic acid amide / paltimic acid amide mixture (mixing ratio). : 7/3, manufactured by Nippon Kasei Co., Ltd., trade name: AP-1) A heat-sensitive recording material was produced in the same manner as in Example 7 except that 6.0 parts were used.
[Example 9]
6.0 parts of 3-dibutylamino-6-methyl-7-anilinofluorane (manufactured by Yamamoto Kasei Co., Ltd., trade name: ODB-2) in the leuco dye dispersion (liquid C) was mixed with 3-di-n-pentyl. A thermosensitive recording material was produced in the same manner as in Example 7 except that 6.0 parts of amino-6-methyl-7-anilinofluorane (trade name: BLACK305, manufactured by Yamada Chemical Co., Ltd.) was used.
［実施例１０］
　感熱記録層塗工液２の第二顕色剤分散液１（Ｂ１液）を第二顕色剤分散液２（Ｂ２液）に代えて感熱記録層塗工液４とし、感熱記録層塗工液４を前記下塗り層塗工紙の下塗り層上に、固形分で塗工量６．０ｇ／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得た。
　次いで、保護層塗工液を前記感熱記録層塗工紙の感熱記録層上に、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、感熱記録体を作製した。
［実施例１１］
　増感剤分散液（Ｄ液）中の１，２－ビス－（３－メチルフェノキシ）エタン（三光社製、商品名：ＫＳ２３２）６．０部をステアリン酸アマイド／パルチミン酸アマイド混合物（混合比率：７／３、日本化成社製、商品名：ＡＰ－１）６．０部に代えた以外は、実施例１０と同様にして感熱記録体を作製した。
［実施例１２］
　ロイコ染料分散液（Ｃ液）中の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、商品名：ＯＤＢ－２）６．０部を３－ジ－ｎ－ペンチルアミノ－６－メチル－７－アニリノフルオラン（山田化学社製、商品名：ＢＬＡＣＫ３０５）６．０部に代えた以外は、実施例１０と同様にして感熱記録体を作製した。 [Example 10]
The second developer dispersion liquid 1 (B1 liquid) of the heat-sensitive recording layer coating liquid 2 is replaced with the second developer dispersion liquid 2 (B2 liquid) to obtain a heat-sensitive recording layer coating liquid 4, and the heat-sensitive recording layer coating is applied. The liquid 4 was applied on the undercoat layer of the undercoat layer coated paper by the rod blade method so that the coating amount was 6.0 g / m 2 as a solid content, and then dried, and the smoothness was measured with a super calendar. The heat-sensitive recording layer-coated paper was obtained by processing for 500 to 1000 seconds.
Next, the protective layer coating solution is applied onto the heat-sensitive recording layer of the heat-sensitive recording layer-coated paper by the rod blade method so that the coating amount is 3.0 g / m 2 in solids, and then dried. A heat-sensitive recording material was produced.
[Example 11]
6.0 parts of 1,2-bis- (3-methylphenoxy) ethane (manufactured by Sanko Co., Ltd., trade name: KS232) in the sensitizer dispersion (liquid D) was mixed with stearic acid amide / paltimic acid amide mixture (mixing ratio). : 7/3, manufactured by Nippon Kasei Co., Ltd., trade name: AP-1) A heat-sensitive recording material was produced in the same manner as in Example 10 except that 6.0 parts were used.
[Example 12]
6.0 parts of 3-dibutylamino-6-methyl-7-anilinofluorane (manufactured by Yamamoto Kasei Co., Ltd., trade name: ODB-2) in the leuco dye dispersion (liquid C) was mixed with 3-di-n-pentyl. A thermosensitive recording material was produced in the same manner as in Example 10, except that 6.0 parts of amino-6-methyl-7-anilinofluorane (trade name: BLACK305, manufactured by Yamada Chemical Co., Ltd.) were used.
［比較例１］
　感熱記録層塗工液１中の第一顕色剤分散液１（Ａ１液）を３６．０部、第二顕色剤分散液１（Ｂ１液）を０部とした以外は、実施例１と同様にして感熱記録体を作製した。
［比較例２］
　感熱記録層塗工液１中の第一顕色剤分散液１（Ａ１液）を０部、第二顕色剤分散液１（Ｂ１液）を３６．０部とした以外は、実施例１と同様にして感熱記録体を作製した。
［比較例３］
　感熱記録層塗工液３中の第一顕色剤分散液１（Ａ１液）を０部、第二顕色剤分散液２（Ｂ２液）を３６．０部とした以外は、実施例７と同様にして感熱記録体を作製した。
［比較例４］
　感熱記録層塗工液１の第一顕色剤分散液１（Ａ１液）を第一顕色剤分散液２（Ａ２液）に代えて感熱記録層塗工液５とし、感熱記録層塗工液１を感熱記録層塗工液５に代えて実施例１と同様にして感熱記録体を作製した。
［比較例５］
　感熱記録層塗工液３の第一顕色剤分散液１（Ａ１液）を第一顕色剤分散液２（Ａ２液）に代えて感熱記録層塗工液６とし、感熱記録層塗工液３を感熱記録層塗工液６に代えて実施例７と同様にして感熱記録体を作製した。 [Comparative Example 1]
Example 1 except that 36.0 parts of the first developer dispersion 1 (A1 liquid) and 0 parts of the second developer dispersion 1 (B1 liquid) in the thermosensitive recording layer coating liquid 1 were used. A thermosensitive recording material was produced in the same manner as described above.
[Comparative Example 2]
Example 1 except that 0 parts of the first developer dispersion 1 (A1 liquid) and 36.0 parts of the second developer dispersion 1 (B1 liquid) in the thermosensitive recording layer coating liquid 1 were used. A thermosensitive recording material was produced in the same manner as described above.
[Comparative Example 3]
Example 7 except that 0 parts of the first developer dispersion 1 (A1 liquid) and 36.0 parts of the second developer dispersion 2 (B2 liquid) in the thermosensitive recording layer coating liquid 3 were used. A thermosensitive recording material was produced in the same manner as described above.
[Comparative Example 4]
The first developer dispersion liquid 1 (A1 liquid) of the heat-sensitive recording layer coating liquid 1 is replaced with the first developer dispersion liquid 2 (A2 liquid) to obtain a heat-sensitive recording layer coating liquid 5, and the heat-sensitive recording layer coating is applied. A heat-sensitive recording material was produced in the same manner as in Example 1 except that the liquid 1 was replaced with the heat-sensitive recording layer coating liquid 5.
[Comparative Example 5]
The first developer dispersion liquid 1 (A1 liquid) of the heat-sensitive recording layer coating liquid 3 is replaced with the first developer dispersion liquid 2 (A2 liquid) to obtain a heat-sensitive recording layer coating liquid 6, and the heat-sensitive recording layer coating is applied. A heat-sensitive recording material was produced in the same manner as in Example 7 except that the liquid 3 was replaced with the heat-sensitive recording layer coating liquid 6.
　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 following evaluation was performed about the produced thermosensitive recording material.
<Coloring performance (print density)>
The produced thermal recording medium is a checkered pattern using a TH-PMD manufactured by Okura Electric Co., Ltd. (with thermal recording paper printing tester and Kyocera thermal head installed) with an applied energy of 0.35 mJ / dot and a printing speed of 50 mm / sec. Is printed. The printing density of the printing part was measured with a Macbeth densitometer (RD-914, using an amber filter) to evaluate the color development performance.
＜白紙部の耐熱変色性＞
　作製した感熱記録体について、８０℃の環境下で２４時間処理した後、２３℃、５０％ＲＨ環境下に３時間静置した。
　非印字部（白紙部）の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、処理前後の値の差から地色発色値を算出し、非印字部（白紙部）の耐熱性を下記の基準で評価した。
　地色発色値＝（処理後の非印字部の濃度）－（処理前の非印字部の濃度）
　優：地色発色値が０．１未満
　良：地色発色値が０．１以上０．３未満
　可：地色発色値が０．３以上０．５未満
　不可：地色発色値が０．５以上 <Heat-resistant discoloration of blank paper>
The produced thermal recording material was treated in an environment at 80 ° C. for 24 hours, and then allowed to stand in an environment at 23 ° C. and 50% RH for 3 hours.
Measure the density of the non-printing area (blank area) with a Macbeth densitometer (RD-914, using amber filter), calculate the ground color value from the difference between before and after processing, and heat resistance of the non-printing area (blank area) Sex was evaluated according to the following criteria.
Ground color development value = (density of non-printed area after processing)-(density of non-printed area before processing)
Excellent: Ground color development value is less than 0.1 Good: Ground color development value is 0.1 or more and less than 0.3 Possible: Ground color development value is 0.3 or more and less than 0.5 Impossibility: Ground color development value is 0.00. 5 or more
＜バーコード読み取り適性＞
　作製した感熱記録体について、８０℃の環境下で２４時間処理した後、２３℃、５０％ＲＨ環境下に３時間静置した。
　ゼブラ社製ラベルプリンタ１４０ＸｉIIIを用い、印字レベル＋１０、印字速度１５．２ｃｍ／秒（６インチ／秒）でバーコード（ＣＯＤＥ３９）を印字した後、印字されたバーコードをバーコード検証機（Ｈｏｎｅｙｗｅｌｌ社製、ＱＣＰＣ６００、光源６４０ｎｍ）で評価した。評価結果をＡＮＳＩ規格のシンボルグレードで記した。
　シンボルグレード：バーコードをバーと垂直方向に１０分割して、各箇所１回ずつ読み取り試験を実施し、その平均値を（優）Ａ、Ｂ、Ｃ、Ｄ、Ｆ（劣）の５段階評価で表す。 <Bar code reading aptitude>
The produced thermal recording material was treated in an environment at 80 ° C. for 24 hours, and then allowed to stand in an environment at 23 ° C. and 50% RH for 3 hours.
After printing a barcode (CODE39) at a printing level of +10 and a printing speed of 15.2 cm / second (6 inches / second) using a label printer 140XiIII manufactured by Zebra, the printed barcode is converted into a barcode verification machine (Honeywell) Manufactured, QCPC600, light source 640 nm). The evaluation results are shown in ANSI standard symbol grades.
Symbol grade: Bar code is divided into 10 in the vertical direction with the bar, and a reading test is performed once for each location. The average value is (excellent) A, B, C, D, F (poor) Represented by
　評価結果を表１に示す。
Figure JPOXMLDOC01-appb-T000010
 　表１から、感熱記録層に顕色剤として本願発明の２種類の顕色剤を含有させた場合には、発色性能と白紙部の耐熱変色性が共に優れ、バーコード読み取り適性が良好であることがわかる。 The evaluation results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000010
 From Table 1, when the two types of developer of the present invention are contained as a developer in the heat-sensitive recording layer, both the color development performance and the heat discoloration property of the white paper portion are excellent, and the barcode readability is good. I understand that.

Claims (1)

  1. 支持体上に無色ないし淡色の電子供与性ロイコ染料と電子受容性顕色剤とを含有する感熱記録層を設けた感熱記録体であって、該感熱記録層が、電子受容性顕色剤として
    (i)下記化学式（化１）
    Figure JPOXMLDOC01-appb-C000001
     で表されるスルホン酸系化合物、並びに
    (ii)４－ヒドロキシ－４’－アリルオキシジフェニルスルホン及び下記一般式（化２）
    Figure JPOXMLDOC01-appb-C000002
     で表されるウレアウレタン系化合物から成る群から選択される少なくとも１種を含有することを特徴とする感熱記録体。     A heat-sensitive recording material provided with a heat-sensitive recording layer containing a colorless or light-colored electron-donating leuco dye and an electron-accepting developer on a support, wherein the heat-sensitive recording layer is used as an electron-accepting developer.
    (i) The following chemical formula (Formula 1)
    Figure JPOXMLDOC01-appb-C000001
     A sulfonic acid compound represented by:
    (ii) 4-hydroxy-4′-allyloxydiphenyl sulfone and the following general formula (Formula 2)
    Figure JPOXMLDOC01-appb-C000002
     A heat-sensitive recording material comprising at least one selected from the group consisting of urea urethane compounds represented by:
PCT/JP2013/082451 2012-12-18 2013-12-03 Thermal recording body WO2014097881A1 (en)

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JP2012-275299 2012-12-18
JP2012275299A JP2016028847A (en) 2012-12-18 2012-12-18 Thermosensitive recording medium
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JP2013117692A JP2016028848A (en) 2013-06-04 2013-06-04 Thermosensitive recording medium

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JP2020152667A (en) * 2019-03-19 2020-09-24 三光株式会社 N,n'-diarylurea derivative and production method thereof, and thermal recording material using the same

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JP2002160462A (en) * 2000-11-29 2002-06-04 Oji Paper Co Ltd Heat-sensitive recording medium
JP2003291542A (en) * 2002-04-05 2003-10-15 Oji Paper Co Ltd Heat-sensitive recording paper
JP2007030371A (en) * 2005-07-27 2007-02-08 Nicca Chemical Co Ltd Thermal recording material
JP2012224001A (en) * 2011-04-20 2012-11-15 Oji Paper Co Ltd Method for producing heat-sensitive recording medium

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Publication number Priority date Publication date Assignee Title
JP2002160462A (en) * 2000-11-29 2002-06-04 Oji Paper Co Ltd Heat-sensitive recording medium
JP2003291542A (en) * 2002-04-05 2003-10-15 Oji Paper Co Ltd Heat-sensitive recording paper
JP2007030371A (en) * 2005-07-27 2007-02-08 Nicca Chemical Co Ltd Thermal recording material
JP2012224001A (en) * 2011-04-20 2012-11-15 Oji Paper Co Ltd Method for producing heat-sensitive recording medium

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020152667A (en) * 2019-03-19 2020-09-24 三光株式会社 N,n'-diarylurea derivative and production method thereof, and thermal recording material using the same

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