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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
  • B41M2205/04—Direct thermal recording [DTR]
• • 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
  • B41M5/323—Organic colour formers, e.g. leuco dyes
  • B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
• • 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
  • B41M5/337—Additives; Binders
  • B41M5/3375—Non-macromolecular compounds

Definitions

• the present invention relates to a heat-sensitive recording material utilizing color development by a reaction between a color-developing dye and a color developer.
• a leuco dye and a color developer such as a phenolic compound are separately dispersed in the form of fine particles, and then the two are mixed, and a binder, a sensitizer, a filler, a lubricant, etc. are added to the mixture.
• the coating liquid obtained by adding the additive is applied to paper, film, synthetic paper, etc., and one or both of the leuco dye and the color developer are melted and contacted by heating to develop a color. Get a record.
• a thermal printer or the like with a built-in thermal head is used to develop the color of such a heat-sensitive recording material.
• this heat-sensitive recording method is (1) no noise during recording, (2) no need for development and fixing, (3) maintenance-free, and (4) machine comparison. Due to its low cost, it is widely used in facsimiles, computer outputs, printers such as calculators, recorders for medical measurement, automatic ticket vending machines, heat-sensitive recording labels, and the like.
• Patent Document 3 a heat-sensitive recording material using a specific color-developing compound, which has excellent water resistance of the printed portion and whose background exhibits high stability against heat, has been disclosed (Patent Document 3).
• the plasticizer resistance of is not sufficient.
• a chromogenic compound exhibiting high storage stability with respect to a plasticizer a diphenyl sulfone crosslinked compound (Patent Document 4) and a urea urethane compound (Patent Document 5) have been proposed, but the thermal responsiveness is low. There was a problem.
• a heat-sensitive recording material having improved storage stability of a printed portion by using a specific color-developing compound and a urea urethane compound in combination has been disclosed.
• a specific color-developing compound and a urea urethane compound in combination has been disclosed.
• a high humidity environment is disclosed. Since the background fog that occurs when stored underneath is remarkable, it has been an issue to achieve both thermal responsiveness and storage stability of the printed portion and the background.
• the present invention provides a recording material or a recording sheet using a non-phenolic compound as a color developer, which has excellent water resistance of a printed portion and good heat resistance of a background portion, as opposed to such a conventional technique.
• a non-phenolic compound as a color developer
• the present inventor has excellent water resistance in the printed portion of the heat-sensitive recording material using the compound represented by the following general formula (1) as the color-developing compound.
• the present invention has been completed by newly discovering that the background portion has excellent heat resistance.
• R 1 to R 10 are independently hydrogen atom, halogen atom, nitro group, amino group, alkyl group, hydroxy group, alkoxy group, aryloxy group, alkylcarbonyloxy group and arylcarbonyloxy group, respectively. , Alkylcarbonylamino group, arylcarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, monoalkylamino group, dialkylamino group, or arylamino group.
• a heat-sensitive recording material wherein the compound represented by the general formula (1) is a compound represented by the following formula (2).
• the present invention it is possible to provide a heat-sensitive recording material in which the printed portion has excellent color development and water resistance and the background portion has excellent heat resistance.
• the present invention relates to a thermal recording material containing the compound represented by the above general formula (1) as a color-developing compound, a thermal recording layer containing the same, and a thermal recording paper.
• examples of the halogen atom in R 1 to R 10 of the general formula (1) include a fluorine atom, a chlorine atom or a bromine atom, and a fluorine atom or a chlorine atom is preferable.
• examples of the alkyl group in R 1 to R 10 of the general formula (1) include a linear, branched or cyclic alkyl group, and among them, a linear or branched alkyl group is used.
• a linear alkyl group is more preferred.
• the range of the number of carbon atoms is usually C1 to C12, preferably C1 to C8, more preferably C1 to C6, and even more preferably C1 to C4.
• linear chains such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl.
• examples of the alkoxy group in R 1 to R 10 of the general formula (1) include a linear, branched or cyclic alkoxy group, and among them, a linear or branched alkoxy group is used. Preferred, linear alkoxy groups are more preferred.
• the range of the number of carbon atoms is usually C1 to C12, preferably C1 to C8, more preferably C1 to C6, and even more preferably C1 to C4.
• linear alkoxy groups such as methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexyloxy, n-heptoxy, n-octyloxy, n-nonyloxy and n-decyloxy; iso.
• the aryloxy group in R 1 to R 10 of the general formula (1) is preferably a C6 to C12 aryloxy group, and specific examples thereof include phenoxy, naphthyloxy, biphenyloxy and the like. Will be.
• examples of the alkylcarbonyloxy group in R 1 to R 10 of the general formula (1) include a linear, branched chain or cyclic alkylcarbonyloxy group.
• C1 to C10 alkylcarbonyloxy groups are preferable. Specific examples thereof include methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, n-butylcarbonyloxy, n-pentylcarbonyloxy, n-hexylcarbonyloxy, n-heptylcarbonyloxy, n-octylcarbonyloxy, and the like.
• Linear alkylcarbonyloxy groups such as n-nonylcarbonyloxy, n-decylcarbonyloxy; isopropylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, t-butylcarbonyloxy, isoamylcarbonyloxy, t-amylcarbonyloxy , Isohexylcarbonyloxy, t-hexylcarbonyloxy, isoheptylcarbonyloxy, t-heptylcarbonyloxy, isooctylcarbonyloxy, t-octylcarbonyloxy, 2-ethylhexylcarbonyloxy, isononylcarbonyloxy, isodecylcarbonyloxy, etc.
• Alkylcarbonyloxy group of branched chain preferably C3 to C10; cyclic (preferably C3 to C7) alkyl such as cyclopropylcarbonyloxy, cyclobutylcarbonyloxy, cyclopentylcarbonyloxy, cyclohexylcarbonyloxy, cycloheptylcarbonyloxy and the like.
• alkyl such as cyclopropylcarbonyloxy, cyclobutylcarbonyloxy, cyclopentylcarbonyloxy, cyclohexylcarbonyloxy, cycloheptylcarbonyloxy and the like.
• Examples include carbonyloxy groups. Of these, a linear or branched alkylcarbonyloxy group is preferable, and a linear alkylcarbonyloxy group is more preferable.
• the arylcarbonyloxy group in R 1 to R 10 of the general formula (1) is preferably C6-C12 arylcarbonyloxy group, and specific examples thereof are phenylcarbonyloxy and naphthylcarbonyl. Oxy, biphenylcarbonyloxy and the like can be mentioned.
• examples of the alkylcarbonylamino group in R 1 to R 10 of the general formula (1) include a linear, branched or cyclic alkylcarbonylamino group. Of these, C1 to C10 alkylcarbonylamino groups are preferable. Specific examples thereof include methylcarbonylamino, ethylcarbonylamino, n-propylcarbonylamino, n-butylcarbonylamino, n-pentylcarbonylamino, n-hexylcarbonylamino, n-heptylcarbonylamino, and n-octylcarbonylamino.
• Linear alkylcarbonylamino groups such as n-nonylcarbonylamino, n-decylcarbonylamino; isopropylcarbonylamino, isobutylcarbonylamino, sec-butylcarbonylamino, t-butylcarbonylamino, isoamylcarbonylamino, t-amylcarbonylamino , Isohexylcarbonylamino, t-hexylcarbonylamino, isoheptylcarbonylamino, t-heptylcarbonylamino, isooctylcarbonylamino, t-octylcarbonylamino, 2-ethylhexylcarbonylamino, isononylcarbonylamino, isodecylcarbonylamino, etc.
• Alkylcarbonylamino group of branched chain preferably C3 to C10; cyclic (preferably C3 to C7) alkyl such as cyclopropylcarbonylamino, cyclobutylcarbonylamino, cyclopentylcarbonylamino, cyclohexylcarbonylamino, cycloheptylcarbonylamino and the like.
• Carbonylamino groups, etc. may be mentioned. Of these, a linear or branched alkylcarbonylamino group is preferable, and a linear alkylcarbonylamino group is more preferable.
• the arylcarbonylamino group in R1 to R10 of the general formula ( 1 ) is preferably a C6-C12 arylcarbonylamino group. Specific examples thereof include phenylcarbonylamino, naphthylcarbonylamino, biphenylcarbonylamino and the like.
• examples of the alkylsulfonylamino group in R 1 to R 10 of the general formula (1) include a linear, branched or cyclic alkylsulfonylamino group. Of these, C1 to C10 alkylsulfonylamino groups are preferred.
• Specific examples thereof include methylsulfonylamino, ethylsulfonylamino, n-propylsulfonylamino, n-butylsulfonylamino, n-pentylsulfonylamino, n-hexylsulfonylamino, n-heptylsulfonylamino, n-octylsulfonylamino, and the like.
• Linear alkylsulfonylamino groups such as n-nonylsulfonylamino, n-decylsulfonylamino; isopropylsulfonylamino, isobutylsulfonylamino, sec-butylsulfonylamino, t-butylsulfonylamino, isoamylsulfonylamino, t-amylsulfonylamino, Isohexylsulfonylamino, t-hexylsulfonylamino, isoheptylsulfonylamino, t-heptylsulfonylamino, isooctylsulfonylamino, t-octylsulfonylamino, 2-ethylhexylsulfonylamino, isononyls
• Alkylsulfonylamino groups of branched chains preferably C3 to C10); cyclic (preferably C3 to C7) alkylsulfonyls such as cyclopropylsulfonylamino, cyclobutylsulfonylamino, cyclopentylsulfonylamino, cyclohexylsulfonylamino, cycloheptylsulfonylamino.
• Amino groups, etc. may be mentioned. Of these, a linear or branched alkylsulfonylamino group is preferable, and a linear alkylsulfonylamino group is more preferable.
• the arylsulfonylamino group in R1 to R10 of the general formula ( 1 ) is preferably a C6-C12 arylsulfonylamino group. Specific examples thereof include phenylsulfonylamino, toluenesulfonylamino, naphthylsulfonylamino, biphenylsulfonylamino and the like.
• examples of the monoalkylamino group in R 1 to R 10 of the formula (1) include a linear, branched chain or cyclic monoalkylamino group.
• mono-C1 to C10 alkylamino groups are preferable. Specific examples thereof include methylamino, ethylamino, n-propylamino, n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamino and the like.
• Linear monoalkylamino groups areopropylamino, isobutylamino, sec-butylamino, t-butylamino, isoamylamino, t-amylamino, isohexylamino, t-hexylamino, isoheptylamino, t-heptylamino, Monoalkylamino groups of branched chains (preferably C3-C10) such as isooctylamino, t-octylamino, 2-ethylhexylamino, isononylamino, isodecylamino; cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexyl Cyclic (preferably C3 to C7) monoalkylamino groups such as amino and cycloheptylamino, and the like can be mentioned. Of these, a linear or branched monoalkyla
• examples of the dialkylamino group in R 1 to R 10 of the general formula (1) include a linear, branched chain or cyclic dialkylamino group.
• di-C1 to C10 alkylamino groups are preferable. Specific examples thereof include dimethylamino, diethylamino, di-n-propylamino, di-n-butylamino, di-n-pentylamino, di-n-hexylamino, di-n-heptylamino, and di-n-.
• Linear dialkylamino groups such as octylamino, di-n-nonylamino, di-n-decylamino; diisopropylamino, diisobutylamino, di-sec-butylamino, di-t-butylamino, diisoamylamino, di-t- Amylamino, diisohexylamino, dit-hexylamino, diisoheptylamino, dit-heptylamino, diisooctylamino, dit-octylamino, di- (2-ethylhexyl) amino, diisononylamino, Dialkylamino group of branched chain such as diisodecylamino (preferably having two branched chains of C3 to C10); cyclic (dicyclopropylamino, dicyclobutylamino, dicyclopentylamino, dicycl
• examples of the arylamino group in R 1 to R 10 of the general formula (1) include a monoarylamino group or a diarylamino group. Of these, mono-C6 to C12 arylamino groups are preferable. Specific examples thereof include phenylamino (anilino), naphthylamino, biphenylamino and the like. Similarly, examples of the arylamino group include diC6 to C12 arylamino groups. Specific examples thereof include diphenylamino, dinaphthylamino, and di (biphenyl) amino.
• the compound represented by the general formula (1) is preferably the compound of the general formula (2).
• R 1 to R 3 in the above general formula (2) are preferably an alkyl group or a hydrogen atom, more preferably a linear C1 to C4 alkyl group or a hydrogen atom, and particularly preferably a methyl group or a hydrogen atom.
• examples of the substitution position of the substituent represented by the following general formula (3) include the ortho position, the meta position, and the para position, and the para position or the meta position is preferable.
• the compound of the above general formula (1) of the present invention can be obtained, for example, by a known synthetic method described in European Journal of Medicinal Chemistry (2017), 125, 856-880 (Non-Patent Document 1). [Manufacturing process]
• R 1 to R 10 have the same meanings as described above.
• the compound of the above general formula [1-2] can be produced by reacting the compound of the general formula [1-1] with a phenyl isocyanate compound in the presence or absence of a base.
• the solvent used in this reaction is not particularly limited as long as it does not affect the reaction, and is, for example, an amide compound such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.
• Halogenized hydrocarbon compounds such as methylene chloride and chloroform; Aromatic hydrocarbon compounds such as benzene, toluene and xylene; Ether compounds such as dioxane, tetrahydrofuran, anisole, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and diethylene glycol diethyl ether; Nitrile compounds such as acetonitrile; ketone compounds such as acetone and 2-butanone; ester compounds such as ethyl acetate and butyl acetate; sulfone compounds such as sulfolane; sulfoxide compounds such as dimethyl sulfoxide, water and the like, which are mixed You may use it.
• Aromatic hydrocarbon compounds such as benzene, toluene and xylene
• Ether compounds such as dioxane, tetrahydrofuran, anisole, ethylene glycol dimethyl ether, di
• the amount of the phenyl isocyanate compound used in this reaction is usually 0.1 to 50 times mol, preferably 0.5 to 3 times mol, with respect to the compound of the general formula [1-1].
• Bases optionally used in this reaction include inorganic bases such as, for example, sodium hydroxide, potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, potassium hydrogencarbonate, potassium carbonate, and cesium carbonate; organics such as triethylamine and diisopropylethylamine. Examples include bases. The amount of these bases used is 0.1 to 50 times mol, preferably 0.5 to 5 times mol, with respect to the compound of the general formula [1-1].
• the reaction temperature of this reaction is usually ⁇ 78 to 120 ° C., preferably ⁇ 10 to 80 ° C.
• the reaction may be carried out for 10 minutes to 24 hours.
• the compound of the general formula [1-2] is reacted with phosphorus oxychloride, thionyl chloride, chlorsulfonic acid, oxalyl chloride and the like in the presence or absence of a base. It can be produced by a method of producing a sulfonic acid chloride, which is subsequently reacted with a phenol compound, or a method of directly reacting with a phenol compound by dehydration condensation.
• the solvent used in this reaction is not particularly limited as long as it does not affect the reaction, and is, for example, an amide compound such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone; Halogenated hydrocarbon compounds such as methylene chloride and chloroform; aromatic hydrocarbon compounds such as benzene, toluene and xylene; ether compounds such as dioxane, tetrahydrofuran, anisole, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and diethylene glycol diethyl ether; acetonitrile Nitrile compounds such as; ketone compounds such as acetone and 2-butanone; ester compounds such as ethyl acetate and butyl acetate; sulfone compounds such as sulfolane; You may.
• an amide compound such as N, N-dimethylformamide, N, N-d
• the amount of the phenol compound used in this reaction is 0.1 to 50 times mol, preferably 0.7 to 3 times mol, with respect to the compound of the general formula [1-2], and the reaction temperature is usually. It is ⁇ 78 to 100 ° C., preferably ⁇ 20 to 80 ° C.
• the reaction time may be 10 minutes to 24 hours.
• the color-developing compound is usually 1 to 50% by mass, preferably 5 to 30% by mass
• the compound represented by the above general formula (1) is usually 1 to 70% by mass, preferably 1 to 70% by mass. 10 to 50% by mass, sensitizer 1 to 80% by mass, storage improver usually 0 to 30% by mass, binder usually 1 to 90% by mass, filler usually 0 to 80% by mass, etc.
• the lubricant, the surfactant, the defoaming agent, and the ultraviolet absorber are each used in an arbitrary ratio, for example, usually 0 to 30% by mass (mass% is the mass ratio of each component in the heat-sensitive color-developing layer).
• the compound represented by the formula (1) in terms of the mass ratio of each compound is usually 0.5 to 20 times, more preferably 1 to 1 to the color-developing compound 1. Each is used in the range of 5 times the mass ratio.
• a color-developing compound, a sensitizer or other additives known by itself other than the above-mentioned components may be used in combination.
• the color-developing compound used in the present invention is not particularly limited as long as it is generally used for pressure-sensitive recording paper or heat-sensitive recording paper.
• Examples of the color-developing compound used include, for example, a fluorine-based compound, a triarylmethane-based compound, a spiro-based compound, a diphenylmethane-based compound, a thiazine-based compound, a lactam-based compound, and a fluorene-based compound, and a fluorine-based compound is preferable.
• fluorin-based compound examples include, for example, 3-diethylamino-6-methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, 3- (N-methyl-N-).
• triarylmethane compound examples include 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (also known as crystal violet lactone or CVL) and 3,3-bis (p-dimethyl).
• spiro-based compound examples include, for example, 3-methylspirodinaphthopyrane, 3-ethylspirodinaphthopyrane, 3,3'-dichlorospiridinaftpyran, 3-benzylspirodinaftpyran, and 3-propylspirobenzo.
• Piran 3-methylnaphtho- (3-methoxybenzo) spiropiran, 1,3,3-trimethyl-6-nitro-8'-methoxyspiro (indrin-2,2'-benzopyran), etc .
• diphenylmethane compounds For example, N-halophenyl-leucoauramine, 4,4-bis-dimethylaminophenylbenzhydrylbenzyl ether, N-2,4,5-trichlorophenylleucooramine, etc .
• Specific examples of thiazine compounds include.
• benzoyl leucomethylene blue p-nitrobenzoyl leucomethylene blue, etc .
• lactam compounds include, for example, Rhodamine B anilinolactam, Rhodamine B-p-chloroanilinolactam, etc .
• fluorene-based compounds include, for example.
• the color-developing compound that can be used in combination with the present invention is not particularly limited, but may be any compound generally used for pressure-sensitive recording papers and heat-sensitive recording papers, for example, ⁇ -naphthol, ⁇ -naphthol, and p-octylphenol.
• waxes include wood wax, carnauba wax, shelac, paraffin, montan wax, paraffin oxide, polyethylene wax, polyethylene oxide and the like; and higher fatty acids include, for example, stearic acid and behenic acid.
• higher fatty acid amides include stearic acid amides, oleic acid amides, N-methylstearic acid amides, erucic acid amides, methylolbechenic acid amides, methylene bisstearic acid amides, ethylene bisstearic acid amides, and the like; higher fatty acids.
• anilide examples include stearate anilide, linoleic acid anilide and the like;
• examples of the naphthalene derivative include 1-benzyloxynaphthalene, 2-benzyloxynaphthalene, 1-hydroxynaphthoic acid phenyl ester, 2,6-diisopropylnaphthalene and the like.
• examples of the aromatic ether include 1,2-diphenoxyetane, 1,4-diphenoxybutane, 1,2-bis (3-methylphenoxy) ethane, 1,2-bis (4-methoxyphenoxy).
• Ester 1,2-bis (3,4-dimethylphenyl) ester, 1-phenoxy-2- (4-chlorophenoxy) ester, 1-phenoxy-2- (4-methoxyphenoxy) ester, 1,2- Examples thereof include diphenoxymethylbenzene, diphenylglycol and the like; examples of the aromatic carboxylic acid derivative include p-hydroxybenzoic acid benzyl ester, p-benzyloxybenzoic acid benzyl ester, terephthalic acid dibenzyl ester and the like; aromatics.
• Examples of the sulfonic acid ester derivative include p-toluenesulfonic acid phenyl ester, phenylmethicylene sulfonate, 4-methylphenylmethicylene sulfonate, 4-tolylmethylene sulfonate and the like;
• examples of the carbonic acid or oxalic acid diester derivative include. Examples thereof include diphenyl carbonate, dibenzyl oxalate ester, di (4-chlorobenzyl) oxalate ester, di (4-methylbenzyl) oxalate ester; and examples of the biphenyl derivative include p-benzylbiphenyl and p-allyl.
• the storage stability improving agent used in the present invention include, for example, 2,2'-methylenebis (4-methyl-6-t-butylphenol) and 2,2'-methylenebis (4-ethyl-6-t-butylphenol). ), 2,2'-Etilidenebis (4,6-di-t-butylphenol), 4,4'-thiobis (2-methyl-6-t-butylphenol), 4,4'-butylidenebis (6-t-) Butyl-m-cresol), 1- [ ⁇ -methyl- ⁇ - (4'-hydroxyphenyl) ethyl] -4- [ ⁇ ', ⁇ '-bis (4'-hydroxyphenyl) ethyl] benzene, 1,1 , 3-Tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane, 1,1,3-Tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, Tris (2,6) -Dimethyl-4-t-butylphenol
• binder used in the present invention include, for example, methyl cellulose, methoxy cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, cellulose, polyvinyl alcohol (PVA), carboxyl group modified polyvinyl alcohol, sulfonic acid group modified polyvinyl alcohol, and the like.
• Water-soluble polymers such as alkali salts of maleic acid copolymers; or (meth) acrylic acid ester copolymers, styrene / (meth) acrylic acid ester copolymers, polyurethanes, polyester-based polyurethanes, polyether-based polyurethanes, Polyvinyl acetate, ethylene / vinyl acetate copolymer, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, polyvinylidene chloride, polystyrene, styrene / butadiene (SB) copolymer, carboxylated styrene / butadiene (SB) Polymers, styrene / butadiene / acrylic acid-based copolymers, acrylonitrile / butadiene (NB) copolymers, carboxylated acrylonitrile / butadiene (NB) copolymers, colloidal silica and
• filler used in the present invention examples include calcium carbonate, magnesium carbonate, magnesium oxide, silica, white carbon, talc, clay, alumina, magnesium hydroxide, aluminum hydroxide, aluminum oxide, barium sulfate, and polystyrene resin. , Urea-formalin resin and the like.
• additives other than the above can be used, for example, higher fatty acid metal salts such as zinc stearate and calcium stearate for the purpose of preventing thermal head wear and sticking; antioxidant or antiaging.
• higher fatty acid metal salts such as zinc stearate and calcium stearate for the purpose of preventing thermal head wear and sticking
• antioxidant or antiaging examples thereof include a phenol derivative for imparting an effect, an ultraviolet absorber such as a benzophenone-based compound and a benzotriazole-based compound; or various surfactants and antifoaming agents.
• Dispersers such as ball mills, attritors, sand mills, etc., which are the color-developing compounds used in the present invention and the compounds represented by the above general formula (1), are separately combined with a binder or other additives as necessary.
• the dispersion is mixed to prepare a heat-sensitive recording material coating liquid, and paper (plain paper, High-quality paper, coated paper, etc. can be used), applied on a support such as plastic sheet, synthetic paper, etc. with a bar coater, blade coater, etc. so that the dry mass is usually 1 to 20 g / m 2 , and dried to record heat.
• a layer is formed to make a thermal recording sheet.
• an intermediate layer may be provided between the heat-sensitive recording layer and the support, or an overcoat layer (protective layer) may be provided on the heat-sensitive recording layer.
• the intermediate layer and the overcoat layer (protective layer) are pulverized and dispersed as necessary in the same manner as in the preparation of the heat-sensitive recording material coating liquid, for example, together with the above-mentioned binder or other additives if necessary, and are intermediate. It can be formed by preparing a coating liquid for a layer or a coating liquid for an overcoat layer (protective layer), applying the coating liquid so that the mass at the time of drying is usually about 0.1 to 10 g / m 2 , and drying. ..
• part is a mass part
• % in the description of the solution is mass%.
• Example 1 Preparation of heat-sensitive recording material A multi-bead shocker (model: PV1001 (S)) manufactured by Yasui Kikai Co., Ltd. with the following composition of compound number 2 shown in Table 1 obtained in Synthesis Example 1 was used. The solution was prepared by grinding and dispersing for 1 hour.
• a mixture having the following composition is crushed and dispersed by a laser diffraction / scattering particle size distribution measuring device LA-950 (HORIBA, Ltd.) so that the median particle size is 1 ⁇ m using a sand grinder, and a dispersion liquid of a color-developing compound [ B] was prepared.
• each liquid obtained above and the following chemicals were mixed with the following composition to prepare a thermal recording material coating liquid, and the mass at the time of drying was 5 g / m 2 on high-quality paper having a basis weight of 50 g / m 2 . It was applied and dried so as to form a heat-sensitive recording layer.
• a protective layer coating liquid having the following composition was applied onto the heat-sensitive recording layer so that the mass at the time of drying was 2 g / m 2 , and dried to prepare a thermal recording paper with a protective layer.
• Example 1 A mixture having the following composition was crushed and dispersed by a laser diffraction / scattering particle size distribution measuring device LA-950 (HORIBA, Ltd.) so that the median particle size was 1 ⁇ m using a sand grinder to prepare the [C] solution.
• liquid [C] was used instead of liquid [A] and mixed at the following composition ratio to prepare a heat-sensitive recording material coating liquid.
• a comparative thermal recording paper with a protective layer was obtained in the same manner as in Example 1.
• Example 1 The thermal recording papers obtained in Example 1 and Comparative Example 1 were printed using a thermal printer (TH-M2 / PP) manufactured by Okura Engineering Co., Ltd. with a pulse width of 1.2 msec, and the sample was printed at 25 ° C. for 24 hours. It was immersed in water.
• the colors were measured under the conditions of Illuminant C as the light source, ANSI A as the density standard, and a viewing angle of 2 degrees. The results are shown in Table 2 below. It can be seen that the higher the residual rate, the better the water resistance.
• Residual rate (%) (Macbeth reflection density of the color-developing part of the sample after the test) / (Macbeth reflection density of the color-developing part of the sample before the test) ⁇ 100 (I)
• Example 1 using the compound of the present invention as a color-developing compound remains as compared with Comparative Example 1 using bisphenol S, which is a color-developing compound described in Patent Document 2.
• the rate is high, and it can be said that the present invention is superior in water resistance to the color-developing portion as compared with the prior art.
• Example 1 using the color-developing compound of the present invention has a small change in ISO whiteness before and after the heat resistance test, and therefore has the color-developing property described in Patent Document 2. It can be seen that the heat resistance of the skin is superior to that of Comparative Example 1 using the compound bisphenol S.

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• Heat Sensitive Colour Forming Recording (AREA)

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• 2021
  • 2021-08-27 JP JP2022545727A patent/JP7655667B2/ja active Active
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