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
  • B41M5/28—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using thermochromic compounds or layers containing liquid crystals, microcapsules, bleachable dyes or heat- decomposable compounds, e.g. gas- liberating
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
  • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
  • B41M5/323—Organic colour formers, e.g. leuco dyes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
  • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
  • B41M5/337—Additives; Binders

Definitions

• the present invention relates to a heat-sensitive recording material utilizing a color reaction between a dye precursor and a developer, and more specifically, a portion colored by thermal energy from a thermal head, a thermal stamp, or the like is in a yellow hue range.
• the present invention relates to a heat-sensitive recording material having high recording density and light-resistant storage stability of a recording portion and good heat-resistant background fogging.
• a heat-sensitive recording material that uses a reaction between a dye precursor and a developer and reacts both substances with thermal energy to obtain a recorded image is well known.
• Such a heat-sensitive recording material is relatively inexpensive, and the recording device is compact and easy to maintain, so that it is used not only as a recording medium for facsimiles and printers but also in a wide range of fields.
• the main object of the present invention is to provide a heat-sensitive recording material having a high recording density in the yellow hue region and excellent in light-resistant storage stability and heat-resistant background fogging of the recording portion.
• the present inventors have used a dye precursor represented by the following general formula (1) and a phenol compound represented by the following general formula (2) in the heat-sensitive recording layer. It came to solve the said problem. That is, the present invention relates to the following thermal recording material.
• thermosensitive recording medium comprising a thermosensitive recording layer containing a dye precursor and a developer on one surface of a support, wherein the thermosensitive recording layer is represented by the following general formula (1) And a phenolic compound represented by the following general formula (2).
• R 1 and R 2 may be the same or different and each represents a hydrogen atom or a branched alkoxy group which may having a carbon number 1 - 8, R 3 is a C1- 4 represents an alkyl group which may be branched.
• R 4 represents a saturated or unsaturated alkylene group that may be substituted, a saturated or unsaturated alkylidene group that may be substituted, or a cycloalkylene group that may be substituted
• R 5 and R 6 May be the same or different and each represents a hydrogen atom, a halogen atom, a saturated or unsaturated alkyl group which may be substituted, or a saturated or unsaturated alkoxyl group which may be substituted.
• the dye precursor represented by the general formula (1) is 4- [2- (2-butoxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethylbenzenamine, 4- [ 2- (2-pentyloxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethylbenzenamine, 4- [2- (2-hexyloxyphenyl) -6-phenyl-4-pyridinyl] -N , N-dimethylbenzenamine, 4- [2- [2- (ethoxyphenyl] -6-phenyl-4-pyridinyl] -N, N-dimethylbenzenamine, 4- [2- (2-octyloxyphenyl)- 6-phenyl-4-pyridinyl] -N, N-dimethylbenzenamine, 4- (2,6-diphenyl-4-pyridinyl) -N, N-dimethylbenzenamine, 4- [2,6-bis (2 Butoxy
• Item 3 The phenol compound represented by the general formula (2) is 2,2′-methylenebis (4-methyl-6-tert-butylphenol) and 2,2′-methylenebis (4-ethyl-6-tert- Item 3.
• the thermal recording material according to Item 1 or 2 which is at least one member selected from the group consisting of (butylphenol).
• Item 4 The heat-sensitive recording material according to any one of Items 1 to 3, wherein an average particle size of the phenol compound represented by the general formula (2) is 0.4 to 2.0 ⁇ m.
• Item 5 The heat-sensitive recording material according to any one of Items 1 to 4, wherein the support has a metallic luster.
• Item 6 The thermal recording material according to Item 5, wherein the dynamic color density obtained by printing the thermal recording material with a thermal head with an applied energy of 0.97 mJ / dot is 1.00 or more.
• Item 7 The heat-sensitive recording material according to Item 5 or 6, wherein the support has a metallic luster on the surface of a substrate having no metallic luster.
• the heat-sensitive recording material of the present invention has a high recording density in the yellow hue region, and is excellent in light-resistant storage stability and heat-resistant background fogging of the recording area. Further, when the support has a metallic luster, the heat-sensitive recording material of the present invention has an effect that the color-development image has a metallic luster and exhibits a vivid golden metallic tone in addition to the above effects.
• the heat-sensitive recording layer in the present invention contains a dye precursor represented by the general formula (1), a developer, and a phenol compound represented by the general formula (2). Thereby, yellow coloring is exhibited, and the storage stability and heat resistant background fogging property of the recording portion are excellent in the yellow hue range.
• the dye precursor represented by the general formula (1) is 4- [2- (2-butoxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethylbenzenamine, 4- [2- (2 -Pentyloxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethylbenzenamine, 4- [2- (2-hexyloxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethyl Benzeneamine, 4- [2- [2- (ethoxyphenyl] -6-phenyl-4-pyridinyl] -N, N-dimethylbenzenamine, 4- [2- (2-octyloxyphenyl) -6-phenyl- 4-pyridinyl] -N, N-dimethylbenzenamine, 4- (2,6-diphenyl-4-pyridinyl) -N, N-dimethylbenzenamine, 4- [2,6-bis (2-but
• R 1 or R 2 in the general formula (1) is an alkoxy group having 4 to 8 carbon atoms. Is preferably represented. Further, from the viewpoint of improving the recording density, it is preferable that either R 1 or R 2 represents a hydrogen atom. From the viewpoint of increasing the recording density, it is preferable to exclude the case where R 1 and R 2 are hydrogen atoms at the same time in the general formula (1).
• the form of the dye precursor contained in the heat-sensitive recording layer is not particularly limited.
• the dye precursor is used in the form of solid fine particles, a polyvalent isocyanate compound is used as a solvent, and the dye precursor is a solute.
• examples include use in the form of composite fine particles obtained by polymerizing a polyisocyanate compound after emulsifying and dispersing a solution-like composition contained in water, or use in the form of microcapsules encapsulated in microcapsules. And can be appropriately selected and used so as to obtain desired quality.
• water is used as a dispersion medium and pulverized by various wet pulverizers such as a sand grinder, an attritor, a ball mill, a cobo mill, and the like.
• water-soluble polymer compounds such as alcohol, modified polyvinyl alcohols such as sulfone-modified polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, styrene-maleic anhydride copolymer salts, and derivatives thereof, surfactants, It can be dispersed in a dispersion medium together with a foaming agent to form a dispersion, and this dispersion can be used for the preparation of a thermal recording layer coating liquid.
• modified polyvinyl alcohols such as sulfone-modified polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, styrene-maleic anhydride copolymer salts, and derivatives thereof
• surfactants It can be dispersed in a dispersion medium together with a foaming agent to form a dispersion, and this dispersion can be used for the preparation of a thermal recording layer coating liquid.
• phenol compound represented by the general formula (2) examples include, for example, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert).
• -Butylphenol 2,2'-ethylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4 , 6-di-tert-butylphenol), 2,2′-ethylidenebis (4-methyl-6-tert-butylphenol), 2,2′-ethylidenebis (4-ethyl-6-tert-butylphenol), 2, 2 ′-(2,2′-propylidene) bis (4,6-di-tert-butylphenol), 2,2′-methylenebis (4-me Carboxymethyl -6-tert-butylphenol), 2,2'-methylenebis (6-tert-butylphenol)
• the content ratio of the phenol compound represented by the general formula (2) is not particularly limited, but is about 1 to 500 parts by mass, preferably about 10 to 200 parts by mass with respect to 100 parts by mass of the dye precursor. is there.
• the average particle size of the phenolic compound represented by the general formula (2) is preferably in the range of 0.4 to 2.0 ⁇ m, from the viewpoint of improving the recording density and the light resistance storage stability, and 0.4 to 1.5 ⁇ m. More preferably, it is the range.
• an average particle diameter is a volume average particle diameter by a laser diffraction method.
• examples of the storage stability improver include 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane, 1,1,3-tris (2-methyl-4- Hydroxy-5-tert-butylphenyl) butane, 1,1-bis (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 4,4 ′-[1,4-phenylenebis (1-methyl) Ethylidene)] bisphenol and phenol compounds such as 4,4 ′-[1,3-phenylenebis (1-methylethylidene)] bisphenol, 4-benzyloxyphenyl-4 ′-(2-methyl-2,3-epoxy Propyloxy) phenylsulfone, 4- (2-methyl-1,2-epoxyethyl) diphenylsulfone, and 4- (2-ethyl-1,2-epoxy) At least one selected from epoxy compounds such as ethyl) diphenylsulfone and
• the color developer in the present invention is selected from those having the property of being liquefied or dissolved by an increase in temperature, and the property of causing color development upon contact with the dye precursor.
• Specific examples of the developer include organic acidic substances such as phenol compounds, aromatic carboxylic acids, or polyvalent metal salts of these compounds.
• the developer may be usually present in the composite fine particles or in the microcapsules, or may be present in the state of solid dispersed fine particles.
• the content ratio of the developer is preferably about 30 to 2000 parts by mass, more preferably about 50 to 250 parts by mass with respect to 100 parts by mass of the dye precursor.
• the composite fine particles can be prepared by a method similar to the method of preparing the composite fine particles containing the dye precursor.
• developer examples include, for example, 4-tert-butylphenol, 4-acetylphenol, 4-tert-octylphenol, 4,4′-sec-butylidene diphenol, 4-phenylphenol, 4,4′-dihydroxy Diphenylmethane, 4,4′-isopropylidene diphenol, 4,4′-dihydroxydiphenyl ether, 4,4′-cyclohexylidene diphenol, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4 -Hydroxyphenyl) -1-phenylethane, 4,4'-dihydroxydiphenyl sulfide, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 4,4'-dihydroxydiphenylsulfone, 2,4 ' -Dihydroxydiphenylsulfone, 4-hydro Si-4′-isopropoxydiphenylsulfone, 4-hydroxy-4′-n-propyl
• a sensitizer can be further contained in order to improve the recording sensitivity.
• compounds conventionally known as sensitizers for thermal recording materials can be used.
• parabenzylbiphenyl, dibenzyl terephthalate, phenyl 1-hydroxy-2-naphthoate, dibenzyl oxalate Di-o-chlorobenzyl adipate, 1,2-diphenoxyethane, 1,2-di (3-methylphenoxy) ethane, di-p-methylbenzyl oxalate, di-p-chlorobenzyl oxalate, , 2-bis (3,4-dimethylphenyl) ethane, 1,3-bis (2-naphthoxy) propane, metaterphenyl, diphenyl, benzophenone, and the like.
• Auxiliaries such as developer, preservability improver, and sensitizer used in the heat-sensitive recording layer are dispersed in water in the same manner as when the dye precursor is used in the form of solid dispersed fine particles. What is necessary is just to mix with this in the case of preparation of the coating liquid.
• these adjuvants can be dissolved in a solvent and emulsified in water using a water-soluble polymer compound as an emulsifier.
• the preservability improver and the sensitizer may be contained in the composite fine particles containing the dye precursor.
• a fine pigment having a high whiteness and an average particle size of 10 ⁇ m or less can be contained in the heat-sensitive recording layer.
• inorganic carbonates such as calcium carbonate, magnesium carbonate, kaolin, clay, talc, calcined clay, silica, diatomaceous earth, synthetic aluminum silicate, zinc oxide, titanium oxide, aluminum hydroxide, barium sulfate, surface treated calcium carbonate and silica
• organic pigments such as urea-formalin resin, styrene-methacrylic acid copolymer resin, and polystyrene resin can be used.
• an adhesive is used, and if necessary, a crosslinking agent, waxes, metal soaps, colored dyes, colored pigments, fluorescent dyes, and the like can be used.
• the adhesive include polyvinyl alcohol and derivatives thereof, starch and derivatives thereof, cellulose derivatives such as hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, and ethylcellulose, sodium polyacrylate, polyvinylpyrrolidone, and acrylamide-acrylate.
• Water-soluble polymer materials such as polymers, acrylamide-acrylic acid ester-methacrylic acid ester copolymers, styrene-maleic anhydride copolymers, isobutylene-maleic anhydride copolymers, casein, gelatin and derivatives thereof, Polyvinyl acetate, polyurethane, polyacrylic acid, polyacrylic acid ester, vinyl chloride-vinyl acetate copolymer, polybutyl methacrylate, ethylene-vinyl acetate Emulsion coalescence such as styrene - butadiene copolymer, styrene - butadiene - can be given latex water-insoluble polymer such as an acrylic copolymer.
• a crosslinking agent for curing the adhesive can be contained in the thermosensitive recording layer.
• aldehyde compounds such as glyoxal, polyamine compounds such as polyethyleneimine, epoxy compounds, polyamide resins, melamine resins, glyoxylate, dimethylol urea compounds, aziridine compounds, blocked isocyanate compounds, and ammonium persulfate, second chloride
• the total solid content of the heat-sensitive recording layer contains at least one cross-linking agent selected from iron and inorganic compounds such as magnesium chloride, sodium tetraborate and potassium tetraborate, or boric acid, boric acid triesters, boron-based polymers and hydrazide compounds. It is preferably used in the range of about 1 to 10 parts by mass with respect to 100 parts by mass.
• waxes such as paraffin wax, carnauba wax, microcrystalline wax, polyolefin wax, and polyethylene wax
• higher fatty acid amides such as stearamide and ethylenebisstearic amide, And higher fatty acid esters and derivatives thereof.
• the metal soap added to the heat-sensitive recording layer examples include higher fatty acid polyvalent metal salts such as zinc stearate, aluminum stearate, calcium stearate, and zinc oleate.
• the heat-sensitive recording material of the present invention is used as a two-color heat-sensitive recording material, it is possible to include a colored dye or a pigment having a color tone complementary to the low-temperature color tone in the heat-sensitive recording layer. It is preferably used for adjusting the color tone of the front and rear multicolor thermosensitive recording materials.
• various auxiliary agents such as an oil repellent, an antifoaming agent and a viscosity modifier can be further added to the heat-sensitive recording layer as long as the effects of the present invention are not impaired.
• microcapsules encapsulating an ultraviolet absorber or solid dispersed fine particles of the ultraviolet absorber can be added to greatly improve the light resistance.
• the ultraviolet absorber include salicylic acid-based ultraviolet absorbers such as phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octyloxy Benzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2- Examples thereof include benzophenone-based ultraviolet absorbers such as hydroxy-4-methoxy-5sulfobenzophenone.
• salicylic acid-based ultraviolet absorbers such as phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octyloxy
• the heat-sensitive recording layer in the present invention is a dispersion in which, for example, water is used as a dispersion medium, and a specific dye precursor, a developer, a specific phenol compound, if necessary, a preservability improver, a sensitizer, etc. are dispersed together or separately.
• a coating solution for a heat-sensitive recording layer prepared by mixing and stirring a pigment, an adhesive, a crosslinking agent, other auxiliaries and the like, if necessary, using a solution, preferably in a dry weight of 2 to 12 g / m 2. It is formed by applying and drying on a support so as to be about 2 to 8 g / m 2 .
• the type, shape, dimensions and the like of the support in the present invention are not particularly limited.
• high-quality paper acidic paper, neutral paper
• medium-quality paper coated paper, art paper, cast-coated paper, glassine paper, resin
• various transparent supports can be appropriately selected and used.
• the support in the present invention may have a metallic luster on at least one surface.
• the support of the heat-sensitive recording medium has a metallic luster, so that in the yellow colored hue range, the recording density is high, the recording area has excellent light-resistant storage and heat-resistant background fogging, and the colored image has a metallic luster.
• a support having a metallic luster for example, a support having a metallic luster such as a metal plate, a metal foil, or a metal film itself, high-quality paper (acidic paper, neutral paper), medium-quality paper, coated paper, art paper , Supports coated with metallic luster on substrates that do not have metallic luster, such as cast coated paper, glassine paper, paperboard, cardboard, resin laminated paper, polyolefin synthetic paper, synthetic fiber paper, nonwoven fabric, synthetic resin film, etc. .
• the substrate may be transparent, translucent, or opaque. Among these, since a specular gloss can be obtained visually, a support provided with a metallic gloss on a film or synthetic paper is preferable.
• a method for imparting a metallic luster to the surface of a substrate there are a method of plating, a method of bonding a metal foil such as an aluminum foil, and a method of bonding a paper or film having a metal vapor-deposited layer. Furthermore, there is a method in which a metal vapor deposition film such as aluminum or silver is directly provided on the substrate. In this case, a smooth resin layer is preliminarily provided on the surface of the substrate, and a direct vapor deposition method in which a metal vapor is deposited thereon to form a metal layer, and a metal vapor deposition layer previously provided on the film is coated with an adhesive. There is a method in which the film is peeled off and transferred to a substrate.
• a method of providing a metallic luster layer by printing or coating on a substrate there is also a method of providing a metallic luster layer by printing or coating on a substrate.
• a metallic glossy surface using a metal ink obtained by mixing a metal powder such as aluminum powder or an aluminum paste in which aluminum powder is dispersed in a solvent with a vehicle.
• a metal powder such as aluminum powder or an aluminum paste in which aluminum powder is dispersed in a solvent with a vehicle.
• mica powder such as aluminum powder or an aluminum paste in which aluminum powder is dispersed in a solvent with a vehicle.
• mica powder but mica or ink using inorganic pearl pigment such as pigment obtained by coating mica with titanium oxide.
• thermosensitive recording layer provided with a support having a metallic luster has the thermosensitive recording layer formed on the support and covers part or all of the metallic luster of the support as viewed from the recording surface side.
• the heat-sensitive recording layer may be formed on the side having the metallic luster of the support, and for example, if it is a support having a metallic luster that can be visually confirmed through the substrate like a transparent substrate, You may form in the other side of the surface which has a metallic luster of a support body.
• an undercoat layer can be provided between the support and the heat-sensitive recording layer, it is preferable that the undercoat layer does not mask the metallic luster of the support.
• thermosensitive recording medium comprising a support having a metallic luster
• the dye precursor in the thermosensitive recording layer develops a yellowish color tone, but since the colored image has a metallic luster when viewed from the recording surface side, it is vividly visible. It can exhibit a golden metal tone.
• the dye precursor present in the form of fine particles in the heat-sensitive recording layer and the developer that develops the color of the dye precursor by reacting with heating is once melted by the applied energy of a thermal head and solidified again.
• the irregular reflection in the heat-sensitive recording layer is reduced and a golden metal tone can be obtained through the heat-sensitive recording layer.
• the heat-sensitive recording layer covers the metallic luster of the support, but since the color image exhibits a golden metal tone, the degree to which the thermo-sensitive recording layer conceals the metallic luster of the support is limited.
• it is not particularly limited, and it may be a mat-like plain paper like when viewed from the recording surface side, or may be such that the metallic luster can be visually confirmed through the heat-sensitive recording layer.
• the dynamic color density obtained by printing the thermal recording material with a thermal head such as a printer with an applied energy of 0.97 mJ / dot is 1.00 or more.
• the load on the printer can be reduced, the contrast can be increased, and the color density can be increased to obtain a sufficient golden metal tone.
• the upper limit of the dynamic color density is not particularly limited, but if it exceeds 2.0, the color developability is saturated.
• the dynamic color density is the Y (yellow) density of the recording portion.
• the yellow color is suppressed and the heat resistant background fogging property is excellent in a high temperature atmosphere.
• the content of the dye precursor represented by the general formula (1) may be less than usual, preferably 1.3 g / m 2 or less, more preferably 1.1 g / m 2 or less. Can do.
• an undercoat layer can be provided between the support and the heat-sensitive recording layer as necessary. Thereby, the recording sensitivity can be further increased.
• the undercoat layer supports an undercoat layer coating solution containing an oil-absorbing pigment having an oil absorption of 70 ml / 100 g or more, particularly about 80 to 150 ml / 100 g, at least one of organic hollow particles and thermally expandable particles, and a binder. It is formed by applying and drying on top.
• the oil absorption is a value determined according to the method described in JIS K 5101.
• a pigment having a high porosity such as silica or calcined kaolin
• the coating amount of the undercoat layer coating solution is preferably about 3 to 20 g / m 2 by dry weight, and more preferably about 4 to 12 g / m 2 .
• the binder in the undercoat layer can be appropriately selected from those that can be used in the heat-sensitive recording layer.
• these binders starch-vinyl acetate graft copolymer, polyvinyl alcohol, styrene-butadiene latex and the like are preferable from the viewpoint of improving barrier properties.
• a protective layer containing a known water-soluble polymer material and pigment, which has been conventionally used in thermal recording materials, can be provided on the thermal recording layer.
• the water-soluble polymer material and the pigment materials exemplified in the above-mentioned heat-sensitive recording layer can be used.
• the light resistance can be greatly improved by containing the microcapsules encapsulating the ultraviolet absorber or the solid dispersed fine particles of the ultraviolet absorber in the protective layer.
• microcapsules having a wall film made of polyurethane-polyurea resin or aminoaldehyde resin are excellent in heat resistance, and are therefore added to the thermal recording layer or protective layer for the purpose of preventing sticking to the thermal head.
• the protective layer By including a pigment in the protective layer, it is possible to prevent debris adhesion and sticking to the thermal head.
• a pigment As the oil absorption amount of the pigment, it is preferable to use a pigment of 50 ml / 100 g or more.
• the pigment content is preferably an amount that does not decrease the recording density, that is, 50% by mass or less of the total solid content of the protective layer.
• the protective layer is, for example, a coating solution for the protective layer prepared by mixing and stirring an adhesive, a pigment, if necessary, a crosslinking agent, other auxiliary agents, etc., using water as a dispersion medium, and the coating amount is preferably 0 by dry weight. It is formed by applying and drying on the heat-sensitive recording layer so as to be about 1 to 15 g / m 2 , more preferably about 0.5 to 8 g / m 2 .
• a resin layer cured with an electron beam or ultraviolet light can be provided on the heat-sensitive recording layer or the protective layer.
• resins that can be cured with an electron beam are described in Japanese Patent Application Laid-Open No. 58-177392, Japanese Patent Application Laid-Open No. 58-177392, and the like.
• auxiliary agents such as a non-electron beam curable resin, a pigment, an antifoaming agent, a leveling agent, a lubricant, a surfactant, and a plasticizer can be appropriately added.
• pigments such as calcium carbonate and aluminum hydroxide, and lubricants such as waxes and silicon to prevent sticking to the thermal head.
• an adhesive paper, a re-moistened adhesive paper, and a delayed tack paper can be obtained by applying a coating process with a pressure-sensitive adhesive, a re-humidified adhesive, a delayed tack type pressure-sensitive adhesive, or the like on the back surface.
• a function as a thermal transfer paper, an ink jet paper, a carbonless paper, an electrostatic recording paper, or a zeography paper can be added to form a recording paper capable of double-sided recording.
• a double-sided thermal recording material can also be used.
• the heat-sensitive recording layer is applied using a heat-sensitive recording layer coating solution containing a dye precursor and a developer, and the protective layer is applied layer by layer using a protective layer coating solution containing a water-soluble polymer material.
• a heat-sensitive recording layer coating solution containing a dye precursor and a developer
• the protective layer is applied layer by layer using a protective layer coating solution containing a water-soluble polymer material.
• it may be formed by drying, or simultaneous multi-layer coating in which two or more layers are simultaneously coated may be performed.
• the simultaneous multilayer coating is a method in which two or more layers are coated at the same time, and includes a method in which the upper layer is coated without drying after the lower layer is coated.
• each layer on the support examples include air knife method, blade method, gravure method, roll coater method, spray method, dipping method, bar method, curtain method, slot die method, slide die method, and extrusion method. Any known coating method such as the above may be used.
• a back layer can be provided for suppressing permeation of oil and plasticizer from the back surface of the heat-sensitive recording material, or for curling control and antistatic.
• the heat-sensitive recording surface may be applied to either a metal roll or an elastic roll of the calendar.
• blend with a dye precursor, a color developer, a phenol compound, a preservability improving agent, and a protective layer uses laser diffraction type particle size distribution analyzer SALD-2200 (made by Shimadzu Corporation). Then, the volume average particle diameter was measured.
• Example 1 Preparation of liquid A (dye precursor dispersion) 4- [2- (2-octyloxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethylbenzenamine 40 parts, polyvinyl alcohol (degree of polymerization 500)
• the composition comprising 40 parts of a 10% aqueous solution having a saponification degree of 88% and 20 parts of water is adjusted to an average particle diameter of 0.7 ⁇ m using a vertical sand mill (a sand grinder manufactured by IMEX Co., Ltd.). After being pulverized and dispersed, a dye precursor dispersion was obtained.
• liquid B developer dispersion
• developer dispersion From 40 parts of 4-hydroxy-4'-isopropoxydiphenylsulfone, 40 parts of 10% aqueous solution of polyvinyl alcohol (polymerization degree 500, saponification degree 88%), and water 20 parts
• the resulting composition was pulverized and dispersed using an ultraviscomil so that the average particle size was 1.5 ⁇ m to obtain a developer dispersion.
• liquid C (phenol compound dispersion) 40 parts of 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 40 parts of 10% aqueous solution of polyvinyl alcohol (polymerization degree 500, saponification degree 88%), And the composition which consists of 20 parts of water was grind
• liquid D (kaolin dispersion) Kaolin (trade name: UW-90 (registered trademark), manufactured by BASF) 80 parts, 40% aqueous solution of sodium polyacrylate (trade name: Aron T-50, Toagosei ( A composition comprising 1 part) and 53 parts of water was pulverized and dispersed using a sand mill until the volume average particle diameter was 1.6 ⁇ m to obtain a kaolin dispersion.
• Kaolin trade name: UW-90 (registered trademark), manufactured by BASF
• 40% aqueous solution of sodium polyacrylate (trade name: Aron T-50, Toagosei ( A composition comprising 1 part) and 53 parts of water was pulverized and dispersed using a sand mill until the volume average particle diameter was 1.6 ⁇ m to obtain a kaolin dispersion.
• acetoacetyl-modified polyvinyl alcohol (trade name: Gohsenx (registered trademark) Z-200, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., degree of polymerization: about 1000, degree of saponification: about 98 parts by weight of 15% aqueous solution of 98 mol%), paraffin wax (trade name: Hydrin P-7, manufactured by Chukyo Yushi Co., Ltd., solid content concentration 30%), 7.5 parts, 5% aqueous surfactant solution (trade name: SN wet OT-70, manufactured by San Nopco Co., Ltd.) 5 parts, Glyoxal (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., solid content concentration 40%) 0.3 part, and a composition comprising 12.5 parts of water, The mixture was stirred to obtain a protective layer coating solution.
• acetoacetyl-modified polyvinyl alcohol (trade name: Gohsenx (registered trademark) Z-200, manufactured by
• thermosensitive recording material After drying the coating solution for the thermosensitive recording layer and the coating solution for the protective layer on one side of a synthetic paper (trade name: FPG-80, manufactured by YUPO Corporation, thickness: 80 ⁇ m), respectively.
• the coating amount after coating was applied with a Mayer bar so that the coating amount after drying was 6 g / m 2 and 3 g / m 2 , dried, and then subjected to supercalendering to obtain a heat-sensitive recording material.
• Example 2 In the preparation of the liquid C of Example 1, 2,2′-methylenebis (4-methyl-6-tert-butylphenol) was used instead of 2,2′-methylenebis (4-ethyl-6-tert-butylphenol). A heat-sensitive recording material was obtained in the same manner as in Example 1 except that.
• Example 3 In the preparation of the liquid C of Example 1, the average particle diameter of 2,2′-methylenebis (4-ethyl-6-tert-butylphenol) was changed to 2.0 ⁇ m, and pulverized and dispersed to 1.5 ⁇ m. Except for the above, a heat-sensitive recording material was obtained in the same manner as in Example 1.
• Example 4 In the preparation of the liquid C of Example 1, the average particle diameter of 2,2′-methylenebis (4-ethyl-6-tert-butylphenol) was pulverized and dispersed so as to be 0.5 ⁇ m instead of 2.0 ⁇ m. Except for this, a heat-sensitive recording material was obtained in the same manner as in Example 1.
• Example 5 Instead of 4- [2- (2-octyloxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethylbenzenamine in the preparation of solution A in Example 1, 4- [2- (2 A thermosensitive recording material was obtained in the same manner as in Example 1 except that -butoxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethylbenzenamine was used.
• Example 6 In the production of the heat-sensitive recording material of Example 1, aluminum vapor-deposited paper (trade name: Almic T, manufactured by Toppan Label Co., Ltd., thickness 50 ⁇ m) was used instead of synthetic paper, and heat-sensitive on the surface provided with the aluminum vapor-deposited layer. A heat-sensitive recording material was obtained in the same manner as in Example 1 except that the recording layer coating solution and the protective layer coating solution were applied.
• Almic T manufactured by Toppan Label Co., Ltd., thickness 50 ⁇ m
• Example 7 In the preparation of solution C in Example 6, 2,2′-methylenebis (4-methyl-6-tert-butylphenol) was used instead of 2,2′-methylenebis (4-ethyl-6-tert-butylphenol). A heat-sensitive recording material was obtained in the same manner as in Example 6 except that.
• Example 8 In the preparation of the liquid C of Example 6, the average particle diameter of 2,2′-methylenebis (4-ethyl-6-tert-butylphenol) was changed to 2.0 ⁇ m, and pulverized and dispersed to 1.5 ⁇ m. Except for the above, a heat-sensitive recording material was obtained in the same manner as in Example 6.
• Example 9 In the preparation of the liquid C of Example 6, 2,2′-methylenebis (4-ethyl-6-tert-butylphenol) was pulverized and dispersed so that the average particle diameter was 0.5 ⁇ m instead of 2.0 ⁇ m. Except for this, a heat-sensitive recording material was obtained in the same manner as in Example 6.
• Example 10 instead of 4- [2- (2-octyloxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethylbenzenamine in the preparation of solution A in Example 6, 4- [2- (2 A heat-sensitive recording material was obtained in the same manner as in Example 6 except that -butoxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethylbenzenamine was used.
• Comparative Example 8 A heat-sensitive recording material was obtained in the same manner as in Example 6 except that 11 parts of liquid C was not used in the preparation of the heat-sensitive recording layer coating liquid of Example 6.
• thermosensitive recording material thus obtained was evaluated as follows. The results were as shown in Tables 1 and 2.
• the unrecorded portion (background portion) of the thermal recording material is treated at 60 ° C. for 24 hours, the unrecorded portion Y (yellow) is measured using an x-rite spectral densitometer (trade name: x-rite 528, using color measurement). Concentration was measured.
• the density of the background portion after the treatment is preferably 0.10 or less, but is preferably 0.25 or less when the support has a metallic luster.
• the heat-sensitive recording material having high recording density and light-resistant storage stability of the recording portion and good heat-resistant background fogging property is used for a gold voucher, ticket, ticket, bag, label, coupon utilizing a clear yellow hue. It can be expected to be put to practical use in applications such as tickets.
• the heat-sensitive recording material of the present invention provides a color image having a color tone different from the color tone of the dye precursor contained in the heat-sensitive recording layer. It is possible to record variable information that takes advantage of the vivid golden metal color tone, such as various tickets such as gold vouchers, coupons, receipts, labels, bags, sample books, price tags, packing tags, direct mail, It is suitably used for displays such as message cards, advertisements, signboards, packaging and packaging materials, and for applications such as substituting gold leaf.

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• 2016
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