WO2003031195A1 - Materiau d'enregistrement thermique - Google Patents

Materiau d'enregistrement thermique Download PDF

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Publication number
WO2003031195A1
WO2003031195A1 PCT/JP2001/008592 JP0108592W WO03031195A1 WO 2003031195 A1 WO2003031195 A1 WO 2003031195A1 JP 0108592 W JP0108592 W JP 0108592W WO 03031195 A1 WO03031195 A1 WO 03031195A1
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Prior art keywords
group
heat
general formula
dispersion
recording material
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PCT/JP2001/008592
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English (en)
Japanese (ja)
Inventor
Shoji Hizatate
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Mitsubishi Paper Mills Limited
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Application filed by Mitsubishi Paper Mills Limited filed Critical Mitsubishi Paper Mills Limited
Priority to DE10197272.5T priority Critical patent/DE10197272B4/de
Priority to PCT/JP2001/008592 priority patent/WO2003031195A1/fr
Priority to US10/490,434 priority patent/US7071144B2/en
Publication of WO2003031195A1 publication Critical patent/WO2003031195A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/337—Additives; Binders
    • B41M5/3375—Non-macromolecular compounds
    • 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
    • B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
    • B41M5/3275—Fluoran compounds
    • 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
    • B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
    • B41M5/3336—Sulfur compounds, e.g. sulfones, sulfides, sulfonamides

Definitions

  • the present invention relates to a heat-sensitive recording material, which is particularly excellent in thermal responsiveness and image storability, and has a small amount of scum adhered to a thermal head of a heat-sensitive printer. As a result, printing trouble occurs even in long-distance printing. No heat-sensitive recording material. Background art
  • the heat-sensitive recording material is generally composed of a heat-sensitive material mainly composed of an electron-donating, usually colorless or pale-colored dye precursor on a support, and an electron-accepting developer, which reacts when heated to form a dye precursor.
  • a recording layer is provided, and when heated with a thermal head, hot pen, laser light, etc., the dye precursor and the electron-accepting color developer react instantaneously to obtain a recorded image.
  • thermosensitive recording materials can be recorded with relatively simple equipment, and have the advantages of easy maintenance, no noise, and other advantages.Measurement recorders, facsimile machines, printers, computer terminals It is used in a wide range of fields, such as vending machines for labels, labels, and ticketes.
  • heat-sensitive recording materials have been used in financial-related recording paper, such as receipts for gas, water, and electricity bills, financial institution ATM usage statements, and various receipts.
  • thermal recording materials are not expected to expand in a wide variety of ways.
  • the amount of scum adhered to the thermal head is small. It is becoming.
  • thermal recording material used for the above-mentioned financial-related recording paper becomes unclear due to the adhesion of scum to the thermal head even when long-distance printing is continued.
  • the above-mentioned portable printer using the meter reading paper is even more difficult because it is difficult to carry out maintenance work such as cleaning of the thermal head on the road.
  • Sensitives have the function of dissolving or encapsulating nearby dye precursors and electron-accepting developers when they are melted by the transferred thermal energy, thereby accelerating the color-forming reaction. Also, increasing the compatibility with an electron-accepting color developer is one means for increasing the sensitivity of a heat-sensitive recording material.
  • waxes are disclosed in JP-A-48-192331, naphthol derivatives are disclosed in JP-A-57-64593, and JP-A-60-56 is disclosed.
  • No. 588 discloses an example in which diphenoxetanes are added.
  • the addition of these sensitizers is accompanied by an increase in the amount of heat-fusible substances, and it is extremely difficult to reduce the amount of scum adhered to the thermal head.
  • An object of the present invention is to provide a heat-sensitive recording material which has basic characteristics such as high thermal response and color density, excellent image storability, and the amount of scum adhered to a thermal head of a thermal printer. To provide a heat-sensitive recording material having a small amount of heat.
  • the present invention provides a heat-sensitive recording layer having a heat-sensitive recording layer containing an electron-donating, usually colorless or pale-colored dye precursor, and an electron-accepting color developer that develops the dye precursor in response to heating.
  • the heat-sensitive recording layer containing an electron-donating, usually colorless or pale-colored dye precursor, and an electron-accepting color developer that develops the dye precursor in response to heating.
  • R 1 and R 2 may be the same or different, and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group or an arylslephonyl group;
  • n an integer of 1 to 3
  • n an integer from 0 to 2)
  • A represents an alkyl group, an alkenyl group or an alkylamino group
  • R 3 and R 4 may be the same or different, and each represents a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, or an aryl group. Represents a group
  • R 5 and R 6 may be the same or different, and represent an alkyl group having 1 to 5 carbon atoms, a cyclohexyl group or an aryl group,
  • R 7 represents a hydrogen atom, a methyl group, a trifluoromethyl group or a halogen atom
  • R 8 represents a hydrogen atom, a methyl group or a halogen atom
  • the gist of the present invention is a heat-sensitive recording material characterized in that:
  • the heat-sensitive recording layer is composed of ethylene daricol dimethacrylyl ether, 2-benzyloxynaphthalene, bis (4-methylbenzinole) oxalate, 1,2-bis (phenoxymethyl) benzene, p It can contain at least one other sensitizer selected from —acetotoluidine and 4— (4-methylphenoxy) biphenyl.
  • the amide derivative represented by the general formula (2) in the heat-sensitive recording layer ethylene glycol dimethatryl ether, 2-benzyloxynaphthalene, bis-oxalate (4 Weight ratio of other sensitizers selected from 1,2-bis (phenoxymethyl) benzene, p-acetotoluidine and 4- (4-methinolephenoxy) biphenyl (compound (2) and other sensitizers) Agent) is preferably in the range of 1/2 to 5: 1.
  • the heat-sensitive recording layer comprises:
  • R 9 , R 1G and R 11 may be the same or different and each represents a hydrogen atom, an alkyl group, an alkyl group, an aryl group, an aralkyl group, an alkali metal, an alkaline earth metal, or a transition. Stands for metal or amine,
  • Any two groups selected from R 9 , R 1G and R 11 may be linked to each other to form a ring
  • the heat-sensitive recording layer comprises:
  • R 15 represents a cyclohexyl group, a fuel group or a tert-butyl group
  • R 16 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cyclohexyl group, a phenyl group or a tert-butynole group.
  • R 13 represents a covalent bond or an alkylene group having 1 to 3 carbon atoms
  • R 14 may contain a compound represented by a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a group represented by R 12 ⁇ .
  • the heat-sensitive recording layer comprises:
  • R 17 is a covalent bond, a C 8 anoalkylene group or
  • R 20 represents a 2,2,6,6-tetramethyl-14-piperidyl group or a 1,2,2,6,6-pentamethyl_4-piperidyl group
  • R 18 and R 19 may be the same or different and represent a 2,2,6,6-tetramethyl-4-piperidyl group or a 1,2,2,6,6-pentamethyl-4-piperidyl group. Can be contained.
  • the diphenylsulfone derivative represented by the general formula (1) is preferably 4,4′-dihydroxydiphenylsulfone.
  • an electron-accepting head coloring agent which forms a part of the heat-sensitive recording layer and forms a dye precursor includes:
  • the diphenyl sulfone derivative represented by the following formula is used.
  • R 1 and R 2 may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an arkeel group, an aralkyl group, an aryl group or an arylsulfonyl group.
  • examples of the halogen atom include chlorine, bromine, iodine, and fluorine.
  • examples of the alkyl group include a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, a linear or branched pentyl. And the like.
  • Examples of the alkenyl group include a butyl group and an aryl group
  • examples of the aralkyl group include a benzyl group and a phenethyl group.
  • Examples of the aryl group include a phenyl group, a naphthyl group, and a 4-methylphenyl group.
  • Examples of the arylsulfonyl group include a phenylsulfol group, a 4-methylphenylsulfonyl group, and a 2-methylphenylsolenoyl group. And so on.
  • diphenylsulfone derivatives can be used alone or as a mixture of two or more, if necessary.
  • the amide derivative represented by the general formula (2) and the fluorane derivative represented by the general formula (3) are added to the thermosensitive recording layer together with the diphenylsulfone derivative represented by the general formula (1).
  • the weight ratio of the diphenyl sulfone derivative represented by the general formula (1) to the amide derivative represented by the general formula (2) is 2Z
  • l to l2 higher thermal responsiveness is exhibited, and the amount of scum adhered to the thermal head of the thermal printer is small, and as a result, there is no printing failure even in long-distance printing. It can be used as recording material.
  • the amide derivative contained in the heat-sensitive recording layer plays a role as a sensitizer, and its chemical formula is represented by the general formula (2)
  • a in the general formula (2) represents an alkyl group, an alkenyl group or an alkylamino group
  • examples of the alkyl group include long-chain alkyl groups having 12 to 22 carbon atoms.
  • examples of the alkenyl group include a long-chain alkenyl group having 12 to 22 carbon atoms.
  • examples of the alkylamino group include an amino group substituted with the above alkynole group.
  • the alkyl group or the alkylamino group may have a substituent such as an alkenyl group, an aryl group, an alkoxy group, a halogen atom, a hydroxyl group, an acyl group, an acyloxy group, and an acylamino group.
  • R 3 and R 4 may be the same or different and each represents a hydrogen atom, an alkyl group, a hydroxyalkyl group, an alkenyl group, an aralkyl group or an aryl group.
  • Groups. Examples of the above-mentioned hydroxyalkyl group include those in which the above-mentioned alkyl group is substituted with a hydroxyl group.
  • Examples of the alkenyl group include a vinyl group, an aryl group, an oleyl group, and a cis-13-docosel group.
  • Examples of the aralkyl group include a benzyl group and a phenethyl group.
  • Examples of the aryl group include a phenyl group, a 4-methylphenyl group, and a naphthyl group.
  • the alkyl group or aryl group may have a substituent such as an acyl group, an acyloxy group, or an acylamino group.
  • Examples of the compound represented by the general formula (2) include lauric amide, palmitic amide, stearic amide, behenic amide, eric acid amide, N-panolemicyl palmitic acid amide, N-stearyl stearic acid amide, N-stearyl—12-hydroxystearic acid amide, N-oley ⁇ / — 12-hydroxyhydroxystearic acid amide, N-methylol stearic acid amide, N-methylol Behenic acid amide, methylenebisstearic acid amide, methylenebislauric acid amide, methylenebis (12-hydroxystearic acid amide), ethylenebiscapric acid amide, ethylenebislauric acid amide, ethylenebisstearic acid amide Amide, ethylenebisisostearic acid amide, ethylenebis (12-hydroxystearic acid Amide), ethylenebisbehenic acid amide, hexamethylenebisstearic acid amide, hexamethylenebisste
  • amide derivatives represented by the general formula (2) palmitic acid amide, stearic acid amide, behenic acid amide, ⁇ -methylol stearic acid amide, Tylene bisstearic acid amide is preferably used because of its excellent heat responsiveness.
  • the electron-donating usually colorless to light-colored dye precursor constituting a part of the heat-sensitive recording layer includes:
  • a fluoran derivative represented by the following formula is used.
  • R 5 and R 6 may be the same or different and each represents an alkyl group having 1 to 5 carbon atoms, a cyclohexyl group, an aryl group (such as a phenyl group), and R 7 is hydrogen.
  • R 7 represents an atom, methyl group, trifluoromethyl group or a halogen atom (chlorine, bromine, iodine, fluorine), and R 8 is a hydrogen atom, a methyl group or a halogen atom
  • Examples of the compound represented by the general formula (3) include 3-dibutylamino-7- (2-chloroanilino) fluoran, 3-ethylethylamino-7- (2-chloroaylino) fluoran, and 3-ethylamino-6 —Methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, 3-dipentylamino-6-methyl-7-anilinofluoran, 3- (N-ethyl-N— Tolyl) amino 6-methinole 7-anilinofluoran, 3- (N-ethyl-1N-trinole) amino-6-methyl-1 7- (4-toluidino) fluoran, 3-piperidino_6-methylinole 7-a Nilinofluoran, 3—Jetylamino-7— (4-12 Trois Nilino) Fluoran, 3— (N—Methyl-1-N—
  • 3-dibutylamino-6-methyl-7-anilinofluoran 3-getylamino-6-methyl-7- ⁇ -linofunoleolane, 3- (N-ethyl) 1-N-isoamyl) amino-6-methyl-1 7-anilinov 4 ⁇ orane, 3- (N-methyl-N-cyclohexinole) amino-6-methylenol 7-anilinofluoran, 3-dibutylamino-7 (2-chloroayurino) Fluorane and 3-dipentylamine 6-methyl-7- ⁇ -linolefluoran are preferably used.
  • the weight ratio (compound (1) / compound (2)) of the diphenylsulfone derivative represented by the general formula (1) to the amide derivative represented by the general formula (2) is 2 A range of 1 to 12 is preferred. If the proportion of the diphenyl sulfone derivative represented by the general formula (1) exceeds the above range, good thermal responsiveness cannot be obtained. The concentration decreases.
  • the heat-sensitive recording layer may be provided, if necessary, with ethylene glycol dimetha tolyl ether, 2-benzyloxynaphthalene, bis (4-methylinobenzyl) oxalate, 1,2-bis (phenoxy).
  • thermosensitive recording material having even higher thermal responsiveness can be obtained. The reason is considered to be that these compounds further improve the compatibility between the dye precursor and the electron-accepting developer.
  • the amide derivative represented by the general formula (2) ethylene glycol dimetha tolyl ether, 2-benzyloxynaphthalene, bis (4-methylbenzinole) oxalate, 1,2-bis (phenoxymethyl)
  • the weight ratio (compound (2) and other sensitizers) to other sensitizers selected from benzene and 4- (4-methylphenoxy) biphenyl is preferably in the range of 1: 2 to 5: 1.
  • the heat-sensitive recording layer may have the general formula (4)
  • the storage stability of the image area with respect to temperature is further improved, and a heat-sensitive recording material having excellent thermal response can be obtained.
  • R 9 , R 10 and R 11 may be the same or different, and each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkali metal, an alkaline earth metal, Represents a transition metal or an amine, and examples of the alkyl group include a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, and a linear or branched pentyl group.
  • the alkenyl group include a vinyl group, an aryl group, and an oleyl group.
  • Examples of the aryl group include a phenyl group, a naphthyl group, a 4-tert-butylphenylamine, and a 4,6-di-tert- group. Butylphenyl group, 4-chlorophenyl group, 4-benzyloxyphenyl group, 3,5-di-tert-butyl-4-hydroxyphenyl group and the like. Benzyl group, phenethyl group and the like.
  • Examples of the alkali metal include Li, Na, and K.
  • Examples of the alkaline earth metal include ⁇ a and Ca.
  • Examples of the transition metal include Zn, Fe, and the like.
  • Examples of the amine include a substituted ammonium group such as an ammonium group or an alkyl-substituted ammonium group.
  • esterhenol phosphate derivative represented by the general formula (4) examples include trifenyl phosphate, dipheninolephosphate, bis (4-tert-butynolephenine) phosphate, and bis (4,6-di-tert-butynolephene).
  • 2,2′-methylenebis (4,6-di-tert-butylpheninole) phosphate and 2,2′-methylenebis (4,6-di A sodium salt of (i-tert-butynolefenisole) phosphate is preferably used.
  • the phosphoric ester derivative represented by the general formula (4) is preferably contained in an amount of 1 to 30% by weight, more preferably 3 to 10% by weight, based on the electron-accepting developer. preferable.
  • the effect of improving the image storability is small. It inhibits the contact between the reactive dye precursor and the electron-accepting developer, and tends to cause a decrease in thermal responsiveness.
  • R 15 represents a cyclohexyl group, a phenyl group or a tert-butyl group
  • R 16 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cyclohexyl group, a phenyl group or a tert-butyl group.
  • R 13 represents a covalent bond or an alkylene group having 1 to 3 carbon atoms
  • R 14 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a group represented by R 12 ), whereby the storage stability of the image area with respect to temperature can be improved. An improved thermosensitive recording material can be obtained.
  • the alkyl group having 1 to 8 carbon atoms as R 16 is preferably a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group.
  • the alkylene group having 1 to 3 carbon atoms as R 13 is preferably a methylene group, an ethylene group, or a propylene group
  • the alkyl group having 1 to 8 carbon atoms as R 14 is a methyl group
  • Examples of the hindered phenol compound represented by the general formula (5) include 1,1,2,2-tetrakis (5-cyclohexyl-14-hydroxy-2-methylphenole) ethane and 1,1 , 2,2-Tetrakis (3-phenyl-hydroxy-4,4-hydroxyphenyl) ethane, 1,1,2,2-Tetrakis (3-tert-butyl-14-hydroxyphenyl) ethane, 1,1, 3-tris (3-cyclohexyl 4-hydroxy benzoyl) butane, 1,1,3-tris (5-cyclohexynole 4-hydr) 1,2,3-methylhexyl-2-butane, 1,1,3-tris (3-cyclohexyl-4-hydroxy-5-methynolephenyl) butane, 1,1,3-tris (3- 4-phenol-1-butane, 1,1,3-tris (5-phenyl-4-hydroxy-2-methylphenyl) butane, 1,1,3-tris (3-tert-buty
  • the hindered fuanol derivative represented by the general formula (5) is preferably contained in an amount of 1 to 30% by weight, more preferably 3 to 10% by weight, based on the electron-accepting developer.
  • hindered phenol derivative represented by the general formula (5) is less than 1% by weight of the electron-accepting developer, the effect on the improvement of image preservability is small. Inhibits contact between the dye precursor and the electron-accepting developer, It tends to cause a decrease in responsiveness.
  • the heat-sensitive recording layer may optionally contain a general formula
  • R 17 is a covalent bond, an alkylene group having 1 to 8 carbon atoms or
  • R 20 represents a 2,2,6,6-tetramethyl-1-piperidyl group or a 1,2,2,6,6-pentamethyl-4-piperidyl group
  • R 18 and R 19 may be the same or different and each represents a 2,2,6,6-tetramethyl-14-piperidyl group or 1,2,2,6,6-pentamethyl- 4- represents a piperidyl group ⁇
  • a heat-sensitive recording material having improved storage stability of an image portion with respect to temperature can be obtained.
  • Examples of the hindered amine derivative represented by the general formula (7) include bis (2,2,6,6,1-tetramethyl-14-piperidyl) sebacate, and bis (2,2,6,6) succinate. , —Tetramethyl-1-4-piperidyl) ester, butane-1 1,2,3,4-tetracarboxylic acid-tetrakis (1,2,2,6,6-pentamethinole (4-piberidi / le)) ester, butane-1 1,2,3,4-tetranorenoleic acid monotetrax (2,2,6,6-tetramethyl (4-piberidyl)) ester, etc., and the compound represented by the general formula (7)
  • the compounds are not limited to these, and these compounds can be used alone or in combination of two or more as necessary.
  • 1,2,3,4-Tetrakisolenoic acid-tetrakis (1,2,2,6,6-pentamethyl (4-piberidyl)) ester and butane mono 1,2,3,4-tetracarboxylic acid tetrakis (2 2,2,6,6-tetramethyl (4-piperidyl)) ester is particularly preferable because it has a large effect of improving the heat-resistant storage stability of the color image area.
  • the hinderdamine derivative represented by the general formula (7) is preferably contained in an amount of 1 to 30% by weight, more preferably 3 to 10% by weight, based on the electron-accepting developer.
  • the hinderdamine derivative represented by the general formula (7) is less than 1% by weight based on the electron-accepting developer, the effect of improving the image storability is small. It hinders contact between the dye precursor and the electron-accepting color developer and tends to cause a decrease in thermal responsiveness.
  • the heat-sensitive recording material of the present invention comprises, as essential components, an electron-donating, usually colorless or pale-colored dye precursor, an electron-accepting color developer, and an amide derivative as a photosensitive agent, and after dispersing them in a binder.
  • the dye precursor and the electron-accepting developer instantly react with each other by applying a thermal recording layer by applying it on a support and heating it with a thermal head, hot pen, laser light, etc. Is what you get.
  • a pigment, a binder, an antioxidant, an anti-sticking agent and the like are added to the heat-sensitive recording layer as needed.
  • the heat-sensitive recording layer contains the fluoran derivative represented by the general formula (3) as a dye precursor, but the general formula (3) is not impaired in the effect of the present invention.
  • a dye precursor other than the compound represented by the formula (1) can be used together with the dye precursor represented by the general formula (3), which is an essential component.
  • these dye precursors those commonly used in heat-sensitive recording materials and pressure-sensitive recording materials can be used, but are not limited thereto.
  • Examples of the dye precursor other than the compound represented by the general formula (3) are as follows. That is,
  • Triaryl methane compound 3,3-bis (p-dimethylaminophenyl) -16-dimethylaminophthalide (crystal violet lactone), 3,3-bis (p-dimethylaminophenol) Enyl) phthalide, 3- (p-dimethylaminophenyl) -3- (1,2-dimethylindole-3-yl) phthalide, 3- (p 3-Dimethylaminophenyl) 3- (2-methylindole-3-yl) phthalide, 3- (p-dimethylaminophenyl) 1-3- (2-phenylindole-3-yl) phthalide , 3,3-bis (1,2-dimethylindole-3-yl) -1-5-dimethylaminophthalide, 3,3-bis (1,2-dimethylindone-l-yl) -1 6- Dimethylaminophthalide, 3,3-bis (9-ethylcarbazole-13-yl) 15-Dimethyl
  • thiazine-based compounds such as benzoinoleurocomethylene methylene, p-nitrobenzoinoleurocomethylene methylene
  • dye precursors other than the compound represented by the general formula (3). These dye precursors can be used alone or as a mixture of two or more, if necessary.
  • the heat-sensitive recording layer is mainly used for coloring the dye precursor.
  • an electron accepting color developer other than the compound represented by the general formula (1) is used as long as the effects of the present invention are not impaired. You can also.
  • these electron-accepting color developers acidic substances commonly used for heat-sensitive recording materials and pressure-sensitive recording materials are used, but are not limited thereto. Examples of these electron-accepting color developing agents include phenol derivatives, aromatic carboxylic acid derivatives, N, N 7 -diarylthiourea derivatives, arylsulfonylurea derivatives, and polyvalent metal salts such as a dumbbell salt of an organic compound.
  • Examples of electron-accepting developers other than the compound represented by the above general formula (1) include 4-hydroxy-4'-isopropoxydiphenylsulfone and 4-hydroxy-14'-benzyloxydiphenyl. Sulfone, 4-hydroxy-4'-propoxydiphenolenoleshon, 4-hydroxy-4'-benzenesolephoninole 1,2,4-bis ( ⁇ -hydroxypheninole) propane, 1,1-bis (p-hydroxypheninole) pentane, 1-bis (p-hydroxypheninole) 1,1-bis (p-hydroxyphenyl) hexane, 1,1-bis (p-hydroxyphenyl) cyclohexane, 2,2-bis (p-hydroxy) (Shifen-2-ole) propane, 2,2-bis (p-hydroxyphenyl) hexane, 1,1-bis (p-hydroxyphenyl) 1-2-ethynolehexane, 2,2-bis (3-chloro) Mouth 4-Hydroxyphenyl
  • a compound represented by the general formula (2) and, if necessary, other heat-fusible compounds as a heat-fusible sensitizer in the heat-sensitive recording layer can be contained within a range that does not impair the effect of the above.
  • the other heat-fusible compound preferably has a melting point of 60 to 180 ° C, more preferably a melting point of 80 to 140 ° C.
  • heat-fusible compounds include synthetic waxes such as paraffin wax, microcrystalline wax, polyethylene wax, and carnauba wax, and natural waxes, bis (4-methoxyphenyl) ether, 2,2 ' —Ethyl compounds such as bis (4-methoxyphenoxy) getyl ether, 1,2-bis (3-methynolef enoxy) ethane, naphthyl ether derivatives, anthryl ether derivatives, aliphatic ethers, dipheninole adipate, Estenole compounds such as dibenzyl oxalate, di (4-chlorobenzyl) oxalate, diphenyl carbonate, dimethyl terephthalate, dibenzyl terephthalate, phenyl benzenesulfonate, 4-acetylacetophenone, m-terpheninole, 4 1 Benzinolebiphenyl, 4 1 Known heat-fusible compounds such as
  • pigments used in the heat-sensitive recording layer include kieselguhr, talc, kaolin, calcined kaolin, calcium carbonate, magnesium carbonate, titanium oxide, zinc oxide, silicon oxide, aluminum hydroxide, and urea.
  • Inorganic and organic pigments such as formalin resin.
  • the binder used in the heat-sensitive recording layer Te is, starches, human de Loki Chez chill cellulose, methyl Se Honoré loin, carboxymethyl sheet cellulose, gelatin, casein, polyvinyl - alcohol, denatured polyvinyl alkenyl alcohol, sodium polyacrylate, acrylic acid Ami de / / acrylic acid ester le co Water solubility of polymers, terpolymers of acrylamide / acrylic acid ester / methacrylic acid, alkali salts of styrene / maleic anhydride copolymer, and salts of ethylene Z maleic anhydride copolymer Binders, polyacetate butyl, polyurethane, polyacrylate, styrene-butadiene copolymer, atarilonitrile / butadiene copolymer, methyl acrylate / butadiene copolymer, ethylene z-butyl acetate copo
  • additives include higher fatty acid metal salts such as zinc stearate and calcium stearate, paraffin, paraffin oxide, polyethylene, polyethylene oxide, stearic acid amide, custard for the purpose of preventing abrasion of the heating print head or preventing stating.
  • Waxes such as wax, dispersants such as sodium octylsulfosuccinate, ultraviolet absorbers such as benzophenone and benzotriazole, surfactants and fluorescent dyes can be added as necessary. In monkey.
  • paper is mainly used.1
  • Non-woven fabric, plastic film, synthetic paper, metal foil, etc., or a composite sheet combining these can be used as necessary.
  • a single-layer or multiple-layer overcoat layer is provided to protect the heat-sensitive recording layer, and a single-layer or multiple layers of an undercoat layer made of pigment or resin are provided between the heat-sensitive recording layer and the support.
  • Various known techniques in the production of heat-sensitive recording materials can be used.
  • the coating amount of the heat-sensitive recording layer is determined by the amount of dye precursor and an electron accepting color developing agent is a color-forming component, usually, the coating weight of the dye precursor is 0. 1 ⁇ 1. O g / m 2 Appropriate.
  • the amount of the electron-accepting developer is usually preferably in the range of 5 to 500% by weight, particularly preferably in the range of 20 to 400% by weight, based on the dye precursor.
  • Dispersions A to S were prepared by the following method.
  • 4,4'-Dihydroxydiphenephone 200 g was dispersed in a mixture of 200 g of a 10% aqueous solution of a sulfonated polybutyl alcohol and 600 g of water, and the average particle size was 1.0 with a bead mill. / Xm to obtain a dispersion A.
  • 4-Hydroxy-1 4'-isopropoxydiphenylenolesnorefone 200 g was dispersed in a mixture of 200% aqueous 10% sulfone group-modified polyvinyl alcohol and 600 g of water, and the average particle size was 1. The mixture was pulverized to 0 ⁇ to obtain a dispersion ⁇ .
  • the mixture was pulverized with a single mill to an average particle size of 1.0 / 1 m to obtain a dispersion D.
  • Dispersion E 100 g of stearic acid amide was dispersed in a mixture of 100 g of a 10% aqueous solution of sulfonated polyvinyl alcohol and 800 g of water, and crushed with a bead mill until the average particle size became 5.0 / m. Dispersion E was obtained.
  • ⁇ Dispersion F> Disperse 200 g of 2-benzyl / reoxynaphthalene in a mixture of 200 g of 10% sulfonate-modified polybutyl alcohol aqueous solution and 600 g of water, and pulverize with a bead mill until the average particle size becomes 1.0 / xm. A dispersion F was obtained.
  • ethylene glycol dimethatryl ether is dispersed in a mixture of 200 g of an aqueous solution of 10% sulfonated polybutyl alcohol and 600 g of water, and ground with a bead mill until the average particle size becomes 1.0 / m.
  • a dispersion G was obtained.
  • 200 g of p-acetotoluidine is dispersed in a mixture of 200 g of a 10% sulfonate-modified aqueous polyvinyl alcohol solution and 600 g of water, and the mixture is ground by a bead mill until the average particle size becomes 1.0 ⁇ , and dispersed. Liquid J was obtained.
  • Table 1 shows the types, compound names, concentrations and particle sizes of the main components of the dispersions A to S.
  • Dispersion I Sensitive 1,2 _bis (phenoxymethinole) benzene 20 1.0 Dispersion J ⁇ Sensitive p-acetotoluidine 20 1.0 Dispersion K ⁇ Sensitive 41- (4-methylphenoxy) bihue 20 1.0 Dispersion L L Sensitizer 4-Acetinolebiphenyl 20 1.0 Dispersion M ⁇ , ⁇ Narenos 4- ⁇ tert-Noah / Lenoenole;
  • Dispersion Q Developer 2,4'-Dihydroxydiphenylenolesnorephone 20 1.0
  • the dispersions prepared above and other dispersions and aqueous solutions were mixed in the proportions shown below, water was added so that the coating solution concentration was 15%, and the mixture was sufficiently stirred to prepare a heat-sensitive coating solution. .
  • a coating solution having the following composition was applied to a high-quality paper having a basis weight of 40 g / m 2 so that the solid content was 9 g / m 2 , and dried to prepare a heat-sensitive coated paper.
  • the thermal coating liquid prepared in (1) is coated on the thermal coating paper prepared in (2) so that the solid content becomes 4 g / m 2, and dried to obtain a thermal recording material. Produced.
  • a heat-sensitive recording material was obtained in the same manner as in Example 1 except that the addition ratio of the dispersion E in Example 1 was changed from 60 parts to 120 parts.
  • a heat-sensitive recording material was obtained in the same manner as in Example 1 except that the addition ratio of the dispersion E in Example 1 was changed from 60 parts to 240 parts.
  • Dispersion E of Example 1 was changed from 60 parts to 100 parts, and Dispersion F was obtained in the same manner as in Example 1 except that 50 parts of was added.
  • a heat-sensitive recording material was obtained in the same manner as in Example 1 except that the addition ratio of the dispersion E in Example 1 was changed from 60 parts to 100 parts, and that 50 parts of the dispersion G was added.
  • a heat-sensitive recording material was obtained in the same manner as in Example 1 except that the addition ratio of the dispersion E in Example 1 was changed from 60 parts to 100 parts, and that the dispersion H was added to 50 parts. .
  • a heat-sensitive recording material was obtained in the same manner as in Example 1, except that the addition ratio of the dispersion E in Example 1 was changed from 60 parts to 100 parts, and 50 parts of the dispersion I was added.
  • a heat-sensitive recording material was obtained in the same manner as in Example 1, except that the addition ratio of the dispersion E in Example 1 was changed from 60 parts to 100 parts, and 50 parts of the dispersion J was added.
  • a heat-sensitive recording material was obtained in the same manner as in Example 1 except that the addition ratio of the dispersion E in Example 1 was changed from 60 parts to 100 parts, and the dispersion K was added to 50 parts. .
  • a heat-sensitive recording material was obtained in the same manner as in Example 1, except that 70 parts of Dispersion F was added in the preparation of the coating solution for forming a heat-sensitive recording layer in Example 1.
  • a heat-sensitive recording material was obtained in the same manner as in Example 1 except that the addition ratio of the dispersion E in Example 1 was changed from 60 parts to 80 parts, and the dispersion F was added with 60 parts of kneaded.
  • a heat-sensitive recording material was obtained in the same manner as in Example 1 except that the addition ratio of the dispersion E in Example 1 was changed from 60 parts to 160 parts, and that 20 parts of the dispersion F was added.
  • a heat-sensitive recording material was obtained in the same manner as in Example 1 except that the addition ratio of the dispersion E in Example 1 was changed from 60 parts to 180 parts, and that the dispersion F was added with 10 parts of kneading. .
  • Example 14 A heat-sensitive recording material was obtained in the same manner as in Example 1 except that the addition ratio of the dispersion E in Example 1 was changed from 60 parts to 200 parts, and the dispersion J was added with 50 parts of kneaded. .
  • a heat-sensitive recording material was obtained in the same manner as in Example 1 except that the addition ratio of the dispersion E in Example 1 was changed from 60 parts to 100 parts, and 100 parts of the dispersion J was added. .
  • the heat sensitivity was the same as in Example 1 except that the addition ratio of the dispersion E in Example 1 was changed from 60 parts to 100 parts, and 50 parts of the dispersion F and 3 parts of the dispersion M were added. The recording material was obtained.
  • Example 2 In the same manner as in Example 1 except that the addition ratio of the dispersion E in Example 1 was changed from 60 parts to 100 parts, and 50 parts of the dispersion F and 3 parts of the dispersion N were added. Thus, a heat-sensitive recording material was obtained.
  • the heat sensitivity was the same as in Example 1 except that the addition ratio of the dispersion E in Example 1 was changed from 60 parts to 100 parts, and 50 parts of the dispersion F and 3 parts of the dispersion O were added.
  • the recording material was obtained.
  • Example 1 was repeated except that the addition ratio of the dispersion E was changed from 60 parts to 100 parts, and that 50 parts of the dispersion F, 3 parts of the dispersion M, and 3 parts of the dispersion N were added.
  • a heat-sensitive recording material was obtained in the same manner as in Example 1.
  • Example 1 was repeated except that the addition ratio of the dispersion E was changed from 60 parts to 100 parts, and that 50 parts of the dispersion F, 3 parts of the dispersion M, and 3 parts of the dispersion O were added.
  • a heat-sensitive recording material was obtained in the same manner as in Example 1.
  • Example 1 was repeated except that the addition ratio of dispersion E was changed from 60 parts to 100 parts, and dispersion F was 50 parts, dispersion N was 3 parts, and dispersion O was 3 parts.
  • a heat-sensitive recording material was obtained in the same manner as in Example 1.
  • a heat-sensitive recording material was obtained in the same manner as in Example 4 except that the addition ratio of the dispersion A in Example 4 was changed from 60 parts to 50 parts, and that 10 parts of the dispersion Q was added.
  • a heat-sensitive recording material was obtained in the same manner as in Example 5, except that the addition ratio of the dispersion C in Example 5 was changed from 30 parts to 20 parts, and that 10 parts of the dispersion R was added.
  • thermosensitive recording material was obtained in the same manner as in Example 7, except that Dispersion C in Example 7 was replaced with Dispersion S.
  • a heat-sensitive recording material was obtained in the same manner as in Example 1 except that the addition ratio of the dispersion E in Example 1 was changed from 60 parts to 40 parts.
  • a heat-sensitive recording material was obtained in the same manner as in Example 1, except that the addition ratio of the dispersion E in Example 1 was changed from 60 parts to 300 parts.
  • a heat-sensitive recording material was obtained in the same manner as in Example 1, except that Dispersion E of Example 1 was replaced with Dispersion F.
  • thermosensitive recording material was obtained in the same manner as in Example 1, except that Dispersion E of Example 1 was replaced with Dispersion G.
  • thermosensitive recording material was obtained in the same manner as in Example 1, except that Dispersion E of Example 1 was replaced with Dispersion H.
  • a heat-sensitive recording material was obtained in the same manner as in Example 1, except that Dispersion E of Example 1 was replaced with Dispersion I.
  • Example 2 The heat sensitivity was the same as in Example 1 except that Dispersion E of Example 1 was replaced with Dispersion J. A recording material was obtained.
  • a heat-sensitive recording material was obtained in the same manner as in Example 1 except that Dispersion E of Example 1 was replaced with Dispersion K.
  • a heat-sensitive recording material was obtained in the same manner as in Example 1, except that Dispersion E of Example 1 was replaced with Dispersion L.
  • thermosensitive recording material was obtained in the same manner as in Example 2 except that Dispersion A of Example 1 was replaced with Dispersion B.
  • a heat-sensitive recording material was obtained in the same manner as in Example 2 except that Dispersion C of Example 1 was replaced with Dispersion D.
  • thermosensitive recording material was obtained in the same manner as in Example 4, except that Dispersion C of Example 1 was replaced with Dispersion D.
  • a heat-sensitive recording material was obtained in the same manner as in Example 4 except that Dispersion A of Example 4 was replaced with Dispersion B.
  • a heat-sensitive recording material was obtained in the same manner as in Example 5, except that Dispersion A in Example 5 was replaced with Dispersion B.
  • thermosensitive recording material was obtained in the same manner as in Example 6, except that Dispersion A in Example 6 was replaced with Dispersion B.
  • thermosensitive recording material was obtained in the same manner as in Example 7, except that Dispersion A of Example 7 was replaced with Dispersion B.
  • thermosensitive recording material was obtained in the same manner as in Example 8, except that Dispersion A of Example 8 was replaced with Dispersion B.
  • a heat-sensitive recording material was obtained in the same manner as in Example 9, except that Dispersion A in Example 9 was replaced with Dispersion B.
  • the heat-sensitive recording materials prepared in the above Examples and Comparative Examples were calendered so that the Beck smoothness of the heat-sensitive coated surface was 400 to 500 seconds, and the following evaluation was performed. Tables 6 and 7 show the results of the evaluation.
  • the evaluation method is as follows.
  • a printing test was performed using an Okura Electric Facsimile Tester TH-PMD. Using a thermal head with a dot density of 8 dots / mm and a head resistance of 185 ⁇ , a head voltage of 12 V and a pulse width of 1. Oms ec are used for printing, and the color density is determined by Macbeth RD-918. It was measured with a reflection densitometer. Table 1 shows the evaluation results. Practical density of 1.05 or higher at 1.0 ms e c is required.
  • thermosensitive recording material printed at 1.0 ms ec and the unprinted background after being stored at 60 ° C for 24 hours was used to evaluate the thermal response characteristics. It was measured with a type 18 reflection densitometer. Table 1 shows the evaluation results.
  • thermosensitive recording material was used.
  • the thermal recording materials of Examples 1 to 24 were compared with the thermal recording materials of Comparative Examples 1 to 18. Excellent in properties. That is, the thermal responsiveness and the heat resistance of the image portion are 1.10 to 1.38 and 0.98 to 1.32 in the example, respectively, whereas the thermal response and the heat resistance of the image portion are 0.98 to 1.32 in the comparative example. 25 and 0.73 to 1.09 The example is superior to the comparative example. Furthermore, when comparing the adhesion of scum, in the examples, all the ranks were 3 or higher (mostly ranks 4 or 5) and the scum adhesion was small. There is a lot of sticking and it is not practical.
  • the heat-sensitive recording materials of the examples were highly evaluated in all of the thermal responsiveness, the heat resistance, and the anti-scum adhesion property, and were highly practical.
  • the heat-sensitive recording materials of Examples 16 to 23 had good property balance and high overall evaluation.
  • the heat-sensitive recording material of the present invention containing a specific diphenylsulfone derivative, a specific amide derivative and a specific fluoran derivative as essential components in the heat-sensitive recording layer, It is excellent in responsiveness and image storability, and the amount of scum adhered to the thermal head of the thermal printer is small. As a result, printing trouble does not occur even in long-distance printing.
  • a specific ester / resin phosphate derivative, a hindered phenol / resin derivative, a specific hindered amine derivative, etc. in the heat-sensitive recording layer, the balance between the thermal responsiveness and the storage characteristics of the image area is further improved. And a heat-sensitive recording material can be obtained.

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

Abstract

L'invention porte sur un matériau d'enregistrement thermique ayant une excellente stabilité au stockage et une excellente sensibilité à la chaleur dans des zones d'images et ayant une teneur réduite en dépôts sur la tête de l'imprimante thermique. Le matériau d'enregistrement thermique possède notamment une couche d'enregistrement thermique contenant à la fois un précurseur de colorant donneur d'électrons qui est incolore et de couleur pâle dans des conditions ordinaires et un développeur accepteur d'électrons qui réagit à la chaleur avec le précurseur de colorant lors du développement d'une couleur. Cette couche d'enregistrement thermique se caractérise en ce qu'elle contient un dérivé de sulfone diphényle spécifique, un dérivé d'amide spécifique et un dérivé fluorane spécifique, le rapport pondéral dérivé de sulfone diphényle/dérivé d'amide étant compris entre 2/1 et 1/2.
PCT/JP2001/008592 2000-08-09 2001-09-28 Materiau d'enregistrement thermique WO2003031195A1 (fr)

Priority Applications (3)

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DE10197272.5T DE10197272B4 (de) 2001-09-28 2001-09-28 Thermisches Aufzeichnungsmaterial
PCT/JP2001/008592 WO2003031195A1 (fr) 2001-09-28 2001-09-28 Materiau d'enregistrement thermique
US10/490,434 US7071144B2 (en) 2000-08-09 2001-09-28 Thermal recording material

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7674527B2 (en) * 2003-09-19 2010-03-09 Dai Nippon Printing Co., Ltd. Coated paper

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JPS57212096A (en) * 1981-06-25 1982-12-27 Honshu Paper Co Ltd Heat-sensitive recording material
JPS60219086A (ja) * 1984-04-16 1985-11-01 Adeka Argus Chem Co Ltd 感熱記録体
JPH06312580A (ja) * 1993-03-04 1994-11-08 New Oji Paper Co Ltd 感熱記録体
JP2000247035A (ja) * 1999-03-02 2000-09-12 Oji Paper Co Ltd 感熱記録体
EP1092552A1 (fr) * 1999-03-05 2001-04-18 Nippon Paper Industries Co., Ltd. Materiau d'enregistrement thermique
JP2001080216A (ja) * 1999-09-14 2001-03-27 Nicca Chemical Co Ltd 感熱記録材料
JP2001080218A (ja) * 1999-09-14 2001-03-27 Nicca Chemical Co Ltd 感熱記録材料
JP2001113832A (ja) * 1999-10-15 2001-04-24 Nippon Kayaku Co Ltd 感熱記録材料
JP2001205941A (ja) * 2000-01-25 2001-07-31 Mitsubishi Paper Mills Ltd 感熱記録材料
JP2001232947A (ja) * 2000-02-25 2001-08-28 Nippon Paper Industries Co Ltd 感熱記録シート
JP2001239761A (ja) * 2000-03-01 2001-09-04 Oji Paper Co Ltd 感熱記録体

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Publication number Priority date Publication date Assignee Title
US7674527B2 (en) * 2003-09-19 2010-03-09 Dai Nippon Printing Co., Ltd. Coated paper

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