WO2005121072A1 - Hydroxyphenylhydroxy- alkilamides, compositions thermo-réversibles et matériaux thermiques réversibles pour impression qui les contiennent, et processus de développement et de réduction de la couleur avec le même extrait. - Google Patents

Hydroxyphenylhydroxy- alkilamides, compositions thermo-réversibles et matériaux thermiques réversibles pour impression qui les contiennent, et processus de développement et de réduction de la couleur avec le même extrait. Download PDF

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Publication number
WO2005121072A1
WO2005121072A1 PCT/JP2005/004974 JP2005004974W WO2005121072A1 WO 2005121072 A1 WO2005121072 A1 WO 2005121072A1 JP 2005004974 W JP2005004974 W JP 2005004974W WO 2005121072 A1 WO2005121072 A1 WO 2005121072A1
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Prior art keywords
color
electron
recording material
compound
reversible thermosensitive
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PCT/JP2005/004974
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English (en)
Japanese (ja)
Inventor
Seishi Izumi
Toshihide Kawasaki
Ryusuke Sakuma
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Kabushiki Kaisha Pilot Corporation
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Priority to JP2006514414A priority Critical patent/JP4813353B2/ja
Publication of WO2005121072A1 publication Critical patent/WO2005121072A1/fr

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    • 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
    • B41M5/305—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers with reversible electron-donor electron-acceptor compositions
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C235/16—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a six-membered aromatic ring

Definitions

  • the present invention relates to a novel hydroxyfluorohydroxyalkylamide compound which can be used for heat-sensitive recording (color development / decoloration / decolorization), a recording material reversible thermosensitive composition using the same, and a recording medium. It concerns the decoloring process.
  • thermal paper a paper coated with a fine powder of a leuco dye, bisphenol A, a sensitizer, a storage stabilizer and the like together with a binder is also known.
  • This thermal paper utilizes coloration by heat supplied from the head of a thermal printer (for example, see Patent Document 1).
  • thermochromic composition using a leuco dye, which is an electron-donating coloring compound, and a phenol, which is an electron-accepting compound, is described in Patent Document 2, for example. .
  • Patent Documents 3-5, etc. disclose reversible thermochromic compositions and compositions containing this composition in microcapsules, in which the color density is selected by component (b) and the coloration temperature is determined by component (c).
  • Patent Documents 6 to 9 disclose electric children.
  • a recording layer composed of an electron-accepting compound such as a color-forming compound, gallic acid or phloroglucinol and a binder such as cellulose acetate is provided on a substrate, an image is formed with heat, and an image is formed with water or water vapor.
  • An erasable reversible recording material is disclosed.
  • Patent Document 10 discloses a biphasic solution comprising a compound having a rataton ring as an electron-donating color conjugate and an alkylphenol which is liquid at room temperature as an electron-accepting conjugate.
  • the material described in this patent document is colorless and transparent when heated, and loses its fluidity when cooled to develop color.
  • it since there is no hysteresis, it is not possible to retain records, and there is room for improvement as a recording material.
  • Patent Literature 11 discloses a complex of gallic acid and 3-methoxypropylamine, which is an amphoteric conjugate having a functional group relating to color development or decoloration, crystal violet lactone and polybutyl alcohol binder.
  • Patent Document 16 discloses a heat-sensitive recording material comprising a compound having at least one of a phenolic hydroxyl group or a carboxyl group and having an amino group as a functional group, and a binder of talristal bioretactone and a methacrylic resin. ing.
  • thermosensitive recording materials are difficult to control the temperature of color development and decoloration due to competitive color development and decoloration, and have poor image contrast.
  • the material is degraded due to the decoloring, and the number of times of repeated use is reduced.
  • Patent Document 22 discloses an electron-donating color-forming compound, a phosphonic acid conjugate having a long-chain aliphatic hydrocarbon group, an aliphatic carboxylic acid compound, and a phenolic conjugate. Coloration and quenching by the combination of an electron-donating compound and an electron-donating color-forming compound. By controlling the heating and cooling of colors, recording materials can be easily made, and recording materials that stably maintain the colors at room temperature have been proposed. When the composition is heated to the color development temperature range, the two conjugates are melted and reacted to form a ring, thereby opening the color and forming a color. It is said that the state can be maintained.
  • the color forming body is formed. It is presumed that the color is separated from the color, and as a result, the color is erased. That is, in the relationship between the electron-donating color-forming compound and the electron-accepting compound, the compound is solidified while being kept in a reacted state, so that the color-developed state is maintained, It is stated that the receptive compound crystallizes and separates under thermal conditions, forming a single crystal and maintaining a bleached state.
  • Non-Patent Document 1 there is a problem that the decoloring speed takes a long time.
  • Patent Document 23 proposes a recording material capable of repeating printing and erasing in the same manner.By using a special phenolic conjugate as an electron-accepting conjugate, the erasing speed is improved, It is shown that the print image can be almost erased by heating within one second.
  • the storage stability of this material is not always sufficient at temperatures exceeding 30 ° C, so it is necessary to further improve the storage stability in practical use. desired.
  • Non-Patent Document 1 described above discloses, as a means for solving these problems (storage stability, erasing speed, or coloring / erasing density), hydrogen bonding in a molecule and acidity of an electron-accepting compound.
  • the hydrogen bonding property is effectively improved by introducing a hydrogen-bonding functional group into the long-chain alkyl group of the electron-accepting compound and introducing a methylene chain as a spacer.
  • Investigation results of materials that can be expressed and have good storage stability have been reported.
  • the storage stability is improved by using this electron-accepting conjugate, the introduction of a functional group and a spacer increases the melting point by about 20-50 ° C. as compared to before the introduction. .
  • This melting point is correlated with the color-forming temperature, that is, with the color-forming sensitivity, and as a result, the color-forming sensitivity tends to decrease.
  • the decrease in color sensitivity is due to the fact that fax, Or, in the case of a thermal head such as a thermal printer, it means that the color density becomes low, and it is difficult to use it as it is with existing hardware. As a result, issues remain, such as the need to use dedicated hardware or use other additives such as sensitizers to increase sensitivity.
  • Patent Document 1 Japanese Patent Publication No. 4-7600
  • Patent Document 2 US Pat. No. 3,560,229
  • Patent Document 3 Japanese Patent Publication No. 51-44706
  • Patent Document 4 Japanese Patent Publication No. 51 44707
  • Patent Document 5 Japanese Patent Publication No. 51-44708
  • Patent Document 6 JP-A-58-191190
  • Patent Document 7 JP-A-60-257289
  • Patent Document 8 Japanese Patent Publication No. Hei 4 30355
  • Patent Document 9 Japanese Patent Publication No. 4 30916
  • Patent Document 10 JP-A-63-315287
  • Patent Document 11 JP-A-5-254244
  • Patent Document 12 JP-A-5-262032
  • Patent Document 13 JP-A-6-48028
  • Patent Document 14 JP-A-2-188293
  • Patent Document 15 JP-A-2-188294
  • Patent Document 16 International Patent Publication No. WO90Z11898 pamphlet
  • Patent Document 17 JP-A-4-46986
  • Patent Document 18 JP-A-4-303680
  • Patent Document 19 JP-A-4-50289
  • Patent Document 20 JP-A-4-50290
  • Patent Document 21 JP-A-5-177931
  • Patent Document 22 Patent No. 2981558
  • Patent Document 23 Japanese Patent No. 3380277
  • Non-patent Document 1 Ricoh Technical Report 25, 6 (1999)
  • Non-Patent Document 2 Proceedings of the 3rd Technical Meeting of the Society of Electrophotography 1997, 10 (1997) Disclosure of Invention
  • An object of the present invention is to maintain color stability and erasability, and to have good storage stability against heat in a colored state without lowering the color sensitivity or high-speed erasability.
  • An object of the present invention is to provide an electron-accepting compound which can be applied to a reversible thermosensitive recording material, and to provide a reversible thermosensitive recording material using the same and a coloring / erasing process.
  • the hydroxyphenylhydroxyalkylamido conjugate according to the present invention is characterized by being represented by the following general formula (I).
  • n is an integer of 13 and A is a straight-chain hydroxyalkyl group having a hydroxyl group bonded to a carbon atom other than the terminal carbon.
  • the reversible thermosensitive composition according to the present invention comprises a hydroxyphenylhydroxyalkylamidide compound represented by the general formula (I) and an electron-donating color-forming compound. It is a feature.
  • the reversible thermosensitive recording material according to the present invention is a recording material comprising a hydroxyphenylhydroxyalkylamide conjugate represented by the general formula (I) and an electron donating coloration conjugate. It is characterized by comprising an element.
  • the color developing / erasing process comprises a recording element containing a hydroxyphenyl hydroxyalkylamide compound represented by the general formula (I) and an electron-donating color-forming compound.
  • the reversible thermosensitive recording material is heated to a color development temperature at which both the electron-accepting compound and the electron-donating color-forming compound melt, and then rapidly cooled to stably maintain a color-developed state.
  • the melting temperature is lower than the coloring temperature. It is characterized in that it is decolorized by heating to the decolorization temperature range where the reaction and the reverse reaction occur.
  • a reversible thermosensitive recording material having excellent color stability and erasability, color sensitivity, a balance between a color developing temperature and a color erasing temperature, and excellent storage stability against heat in a color developing state is realized.
  • a hydroxyphenylhydroxyalkylamide compound which is a possible electron accepting compound.
  • the hydroxyphenylhydroxyalkylamide compound is suitable for a reversible thermosensitive recording material, and can also realize a reversible thermosensitive composition, a reversible thermosensitive recording material, and a coloring / decoloring process having the above-mentioned characteristics. It is.
  • FIG. 1 is a conceptual diagram of coloring or decoloring in the reversible thermosensitive composition of the present invention.
  • FIG. 3 is a DSC chart of N- (4-hydroxyphenyl) -12-hydroxystearamide synthesized in Synthesis Example 1!
  • FIG. 4 IR ⁇ vector of N- (3-hydroxyphenyl) -12-hydroxystearamide synthesized in Synthesis Example 2.
  • FIG. 5 is a DSC chart of N- (3-hydroxyphenyl) -12-hydroxystearamide synthesized in Synthesis Example 2.
  • FIG. 7 is a DSC chart of N- (4-hydroxyphenyl) -12-hydroxypentadecaneamide synthesized in Synthesis Example 3.
  • the present inventor has found that a functional group capable of forming a hydrogen bond, specifically a hydroxyl group, is not bonded to a terminal carbon in an alkyl chain of an amide group-containing phenolic compound having a long-chain alkyl group.
  • the hydroxyphenylhydroxyalkylamido conjugate according to the present invention is represented by the following general formula (I).
  • n is an integer of 13 and A is a straight-chain hydroxyalkyl group having a hydroxyl group bonded to a carbon atom other than the terminal carbon.
  • This hydroxyphenylhydroxyalkylamide compound can be used as an electron-accepting compound that can be used in a heat-sensitive recording material in combination with an electron-donating color-forming compound. For this reason, the hydroxyphenylhydroxyalkylamide compound according to the present invention may be hereinafter referred to as an electron-accepting compound.
  • n and 1 are each independently an integer of 0 or more, and k represents an integer of 1 or more.
  • m + 1 When m + 1 increases, aggregation of alkyl chains tends to occur easily when used in a reversible thermosensitive recording material, and erasability tends to improve. Therefore, m + 1 is preferably 6 or more. More preferably, it is 11 or more. On the other hand, when the value of m + 1 decreases, the melting point of the compound tends to decrease and the color sensitivity tends to improve. Therefore, the value of m + 1 is preferably 22 or less.
  • k is preferably 1 or 2 from the viewpoint of the erasability of an image and the stability of coloring when used in a reversible thermosensitive recording material.
  • the compound represented by the general formula (I) can be synthesized by using an commonly known amide synthesis method. More specifically, an aminophenol having 13 hydroxyl groups and a hydroxyalkylcarboxylic acid having a hydroxyl group bonded to a carbon other than the terminal carbon are optionally combined with a solvent and Z or a catalyst in the presence of a solvent. It can be produced by heating to reflux.
  • a solvent and Z or a catalyst in the presence of a solvent. It can be produced by heating to reflux.
  • these electron accepting conjugates can be synthesized using general-purpose chemicals.
  • Whether or not the target compound has been obtained is determined by differential scanning calorimetry (hereinafter referred to as DSC). And IR absorption spectrum (hereinafter sometimes referred to as IR).
  • the reversible thermosensitive composition according to the present invention comprises the hydroxyphenylhydroxyalkylamide compound represented by the general formula (I) and an electron-donating color former. This composition shows a reversible color change by temperature control. This composition can also be used as an irreversible thermochromic composition.
  • FIG. 1 shows a conceptual diagram of color development or decoloration by a combination (that is, a mixture) of an electron-accepting compound and an electron-donating color-forming compound in the reversible thermosensitive composition according to the present invention. is there.
  • the decolored state A is a state in which the two conjugates have not reacted in the mixture.
  • the electron-accepting compound When this mixture is heated and reaches D (the temperature near or above D is called the color temperature range, which is the temperature near the melting point of the electron-accepting compound) via B and C, the electron-accepting compound is heated.
  • the product and the electron-donating color-forming compound react in a melt-mixed state and develop color.
  • the electron-accepting compound and the electron-donating color-forming compound are solidified in a reacted state, so that the path from the decolored state A to the colored state D is a different path.
  • the color development state is maintained at a low temperature, for example, at room temperature.
  • the electron accepting compound alone causes aggregation of the alkyl chain, and the electron donating color forming compound Is broken and the color is erased. Even if this is cooled to room temperature, it does not change to the color developing state E and is kept in the decoloring state A.
  • the use of the electron-accepting conjugate of the present invention can maintain any state of color development and decoloration at a low temperature.
  • the electron-accepting conjugate that can be used in the present invention is limited to those described in the general formula (I), but the electron-donating color compound combined therewith is not particularly limited.
  • an electron-donating color-forming compound is a colorless or pale-colored dye used as a pressure-sensitive thermosensitive dye, which is generally called a leuco dye, and includes triphenylmethanephthalide dyes, fluoran dyes, Drillphthalide dyes, spiropyran dyes, rhodamine lactam dyes, trifluorophenolic dyes, azaphthalide dyes, azomethine dyes, And phenothiazine dyes.
  • Specific examples of the electron-donating color-forming compound that can be used in the present invention will be shown below, but it should not be construed that the invention is limited thereto.
  • the electron accepting compound and the Z or electron donating compound may be used in combination of a plurality of types of compounds.
  • the reversible thermosensitive composition according to the present invention essentially comprises the hydroxyphenylhydroxyalkylamide compound and an electron-donating color-forming compound. These compounds can be blended in an optional ratio as required.
  • the amount of the electron-donating coloring compound is preferably 4 to 10 mol per 1 mol of the hydroxyalkylamide compound (electron-accepting compound). More preferably, it is 5-7 mol.
  • a stabilizer such as a stabilizer, a decolorization accelerator, and a sensitizer can be further included.
  • the reversible thermosensitive composition according to the present invention may further comprise a solvent or a vehicle for dissolving or dispersing the above components.
  • a solvent or a vehicle for dissolving or dispersing the above components When the above components are dissolved or dispersed in a solvent, the composition according to the present invention can be used as an ink, for example, a gel ink.
  • the pattern drawn by the ink can be colored or erased by temperature control.
  • the reversible thermosensitive recording material according to the present invention comprises a recording element containing the hydroxyphenol hydroxyalkylamide compound of the general formula (I) and an electron-donating color former. .
  • This recording element may include the reversible thermosensitive composition described above.
  • This recording material can be colored or discolored and decolored by controlling the temperature. Therefore, the reversible thermosensitive recording material according to the present invention can be said to be a reversible thermochromic recording material.
  • the reversible thermosensitive recording material according to the present invention can be a recording material of any shape as long as it has such a recording element.
  • a matrix polymer or a mixture in which an electron-accepting compound and an electron-donating color-forming compound are uniformly dispersed in a vehicle may be used as a single film, or may be coated on a support. It is possible to form a recording layer in the form of a film by forming a recording layer in the form of a film.
  • the recording material may be a recording element that has been formed, or a recording element in which an electron-accepting compound and an electron-donating color-forming compound are encapsulated in microcapsules.
  • a recording material is used, for example, as an electrostatic toner.
  • Such powders or microcapsules may contain the matrix polymer or may contain the various additives.
  • these powders or microcapsules can be encapsulated in microcapsules, if necessary, with further additives to form recording elements.
  • a material in which such a powder or a microcapsule is adhered or fixed on a support is also one of the reversible thermosensitive recording materials according to the present invention.
  • the electron accepting compound and the electron donating color forming compound which can be used in the present invention are described below.
  • the recording material can uniformly disperse or retain the electron-accepting compound, the electron-donating color-forming compound, and other additives as necessary, and It is not particularly limited as long as it does not inhibit the color development or decoloration of.
  • Such a matrix polymer include polychlorinated vinyl, vinyl chloride-vinylinoleate copolymer, cenorellose-based polymer, polystyrene, styrene-based copolymer, acrylic polymer, gen-based polymer, and the like.
  • examples include polyester, polyurethane, polycarbonate, and polybutyl alcohol.
  • the vehicle those generally used in the field of printing can be used.
  • the support may be transparent or translucent.
  • opaque polymer films or sheets, synthetic paper and processed paper, glass plates, metal plates, etc. are used, and the recording layer is provided directly on the support or the adhesion between the support and the recording layer is improved on the support.
  • an undercoat layer may be provided, and a recording layer may be provided thereon. It is also preferable to select such an undercoat layer that has an effect of imparting heat insulation and the like in addition to the improvement of adhesion.
  • a transparent protective layer may be provided on the surface of the recording material to prevent the recording layer from being contaminated by harmful gas or the like.
  • the protective layer can be formed by vapor deposition of an inorganic substance, coating with a polymer solution or the like, or can be formed by laminating a polymer film.
  • an intermediate layer such as an adhesive layer or an adhesive layer may be provided.
  • various additives such as a surfactant, an antistatic agent, a lubricant, an antioxidant, and an ultraviolet absorber may be added to the protective layer or the intermediate layer.
  • an ultraviolet absorbing layer made of an ultraviolet absorbing polymer may be provided as an intermediate layer.
  • Such an ultraviolet absorbing layer may be provided independently of the above-mentioned protective layer or intermediate layer, or may contain the above-mentioned additive at the same time.
  • a back coat layer may be provided.
  • the reversible thermosensitive recording material of the present invention can be used in the form of a layer on a support, it is possible to use an electron-accepting compound, an electron-donating compound and, if necessary, other additives.
  • the reversible thermosensitive recording material can be formed by applying a solution or dispersion containing the composition onto a support by various coating methods such as bar coating and spin coating.
  • the recording layer provided on the support surface preferably has a thickness of 1 ⁇ m to 30 ⁇ m when dried, and more preferably 2 m to 10 m.
  • the recording material of the present invention can be displayed by coloring the color with a heat-sensitive printer such as a fax or a thermal transfer printer, a heat roll, etc., and blowing hot air at a decoloring temperature, heating with a hot stamp, a heat roll, etc. Can be used to erase the color.
  • a heat-sensitive printer such as a fax or a thermal transfer printer, a heat roll, etc.
  • the reversible thermosensitive recording material of the present invention comprises a coloring agent alone in a recording layer or in a layer other than the recording layer, for example, a support, an undercoat layer, a protective layer, an adhesive or pressure-sensitive adhesive layer. From the color (X) to the color (Y) in which the color of the colorant alone and the color of the electron-donating color-forming compound in the colored state are mixed, or vice versa, from (Y) to (X) You can make a change.
  • the type and amount of the coloring agent that can be used here are arbitrary, but when they are present in the recording layer, the coloring reaction between the electron-accepting compound and the electron-donating color-forming compound should not be inhibited. Should be selected. If a colorant is present in the recording layer or in a layer other than the recording layer, it should be selected so that the change in color or change in contrast is appropriate.
  • the reversible thermosensitive recording material of the present invention is a recording material comprising the electron accepting compound of the above general formula (I) and the electron donating color forming compound in a predetermined character, figure or pattern on a support.
  • a recording layer can also be formed. That is, when the recording layer is heated to the color development temperature range, a part or the whole of the recording layer develops or discolors, thereby enabling recording or display. At this time, by forming a plurality of recording layers that develop or change colors into different colors in a pattern such as a stripe shape or a matrix shape, a plurality of colors can be developed.
  • the recording layer may be formed so as to cover the underlayer in a color-developed state. Therefore, when a predetermined character, figure or pattern is formed on the support in advance, and the recording layer is uniformly laminated on the predetermined character, figure, or pattern, the temperature control becomes difficult. Therefore, by coloring or decoloring the recording layer, part or all of the recording layer is colored or decolored or discolored, and part or all of the characters, figures or patterns on the support are concealed or transparent. Thus, reversible recording or display becomes possible. Also, predetermined characters, figures, and patterns can be formed on both the recording layer and the support and used in combination.
  • the recording material in the present invention is a term including a display material.
  • the color developing and erasing process according to the present invention is carried out at a temperature at which both the electron-donating color-forming compound and the electron-accepting compound in the reversible thermosensitive composition or the reversible thermosensitive recording material are melted by a suitable heat source.
  • a color is developed by heating and then rapidly cooled to maintain a stable color development state, and the color is decolorized by heating to a decoloring temperature range below the color development temperature where the melting reaction and the reverse reaction occur. It is.
  • Examples of the heat source include a thermal head, a laser beam, a hot roller, a hot stamp, hot air, high frequency heating, radiant heat from a heat transfer heater, a hot pen, a heated thermostatic oven, and infrared irradiation.
  • a thermal head, a laser beam, a heat sink, or the like is preferable.
  • the recording layer can be rapidly cooled by removing the heat source, and a colored state can be obtained. At that time, it is possible to cool sufficiently by keeping the surrounding environmental temperature at about room temperature.However, by performing the local heating in a short time, the temperature difference with the non-heated portion other than the heated portion is combined. As a result, rapid cooling can be ensured. More specifically, the color developing temperature in the color developing / erasing process of the present invention is 90 ° C. or higher, preferably 100-140 ° C.
  • thermosensitive recording material to change the reversible thermosensitive recording material from the color-developed state to the decolored state, for example,
  • thermosensitive recording material is reheated to a temperature at which both of its included components, the electron-donating color-forming compound and the electron-accepting compound, are melted, that is, the color-forming temperature or higher.
  • a method of performing temperature control for storing heat in a peripheral environment or a peripheral portion of a support or the like during reheating by the heat source and using the temperature is used.
  • the decoloring temperature is 60 to 130 ° C, preferably 80 to 120 ° C.
  • the cooling rate and the stamping energy are adjusted to change the material from the decolored state to the colored state.
  • the heating means used at this time can be used in common.
  • the development of the decolored state can be achieved by the same thermal control as that for obtaining the color-developed state, except that the temperature conditions described in (1) or (2) above are adjusted. Therefore, the heating means that can be used to obtain the color-developed state and the heating means that can be used to obtain the decolored state can be used for both by adjusting the energy applied to the recording material. It is.
  • thermosensitive recording material when used as a reversible thermosensitive recording material, it is widely used for facsimile and the like, and is applied to ordinary thermal printers and bar code printing. It can be colored by a thermal printer with a head or a heat roll.
  • the recording material is brought into contact with an electric heater and a hot plate heated to a coloring temperature, and then the supply of energy for heating is stopped, and the support and the like are heated. Then, it can be gradually cooled by a method such as cooling.
  • the color is erased by a method such as blowing hot air at an erasing temperature, heating with a hot stamp, a heat roll, a hot plate, or an on-surface heating element. be able to.
  • a recording material is applied to a film or paper by using a thermal printer having a thermal head, such as a thermal transfer printer, which is applied to a normal thermal printer or a bar code printing widely used for facsimile and the like.
  • a thermal printer having a thermal head such as a thermal transfer printer, which is applied to a normal thermal printer or a bar code printing widely used for facsimile and the like.
  • the energy that is applied to the recording material is the decolorizing temperature. After the adjustment, the color is erased by applying energy to the entire surface of the recording material.
  • the reversible thermosensitive recording material of the present invention can be applied to sheet-like materials or cards having a recording layer, and further to use as a toner or as an ink for writing, etc. It is also possible to appropriately combine two or more kinds.
  • Endothermic end temperature 156. 03 ° C
  • N- (4-Hydroxyphenyl) -12-hydroxypentadecaneamide was obtained in the same manner as in Synthesis Example 1 except that 12-hydroxystearic acid was changed to 12-hydroxypentadecanoic acid. Fusion The point was 151 ° C. The obtained IR ⁇ vector and DSC chart are shown in Figs. The measured values for these forces were as follows.
  • N- (4-hydroxyphenyl) 12-hydroxystearamide of Example 1 was changed to N- (4-hydroxyphenyl) -12-hydroxypentadecaneamide, and 140 ° C calorific heat was applied at 120 ° C.
  • the repetition of color development and color erasure was confirmed in the same manner as in Example 1 except that the color development and color erasure were performed, and it was confirmed that color development and color erasure could be repeated.
  • Styrene acrylic ester copolymer 20 parts by weight
  • N- (4-hydroxyphenyl) -12-hydroxystearamide 10 parts by weight
  • thermosensitive recording material The composition was heated and dissolved in 170 parts by weight of tetrahydrofuran (THF) to prepare a solution of a reversible thermosensitive recording material.
  • THF tetrahydrofuran
  • This solution was applied to a 100-m-thick white polyethylene terephthalate film (manufactured by Toray Industries, Inc.) using a wire bar, and then heated and dried at 100 ° C to obtain a 4-m-thick reversible film.
  • a recording layer made of a thermosensitive recording material was provided to produce a recording material. When this recording material was heated to 140 ° C and cooled to room temperature (20 ° C), a blue-violet color was formed.
  • This recording material was heated to 100 ° C for 1 second, cooled to room temperature, heated to 140 ° C, and then cooled to room temperature. As a result, reversal of color erasing and color development was possible.
  • the optical densities of the color-developed state and the decolored state were measured using a Macbeth densitometer RD-915 (trade name), and the OD values were 0.80 in the color-developed state and 0.07 in the decolored state. An excellent recording material was obtained.
  • Styrene acrylic ester copolymer (Hymer TB-1000F (trade name) manufactured by Sanyo Chemical Industries, Ltd.): 20 parts by weight
  • N- (4-hydroxyphenyl) -12-hydroxystearamide 10 parts by weight
  • This solution is applied to a 75 ⁇ m-thick white polyethylene terephthalate film using a wire bar, and then heated and dried at 100 ° C to form a 7-m-thick reversible thermosensitive recording material that also has power.
  • a recording material was prepared. The recording material was heated to 140 ° C. on a hot plate and cooled to room temperature. The recording material was heated at 110 ° C. for 1 second, cooled to room temperature, heated to 140 ° C., and then cooled to room temperature. As a result, decoloring and color development could be performed reversibly. At this time, the optical densities in the color-developed state and the decolored state were measured using a Macbeth densitometer RD-915 (trade name). Value, and an excellent recording material was obtained.
  • Example 4 was repeated except that N- (4-hydroxyphenyl) 12-hydroxystearamide was changed to 10 parts by weight of N- (4-hydroxyphenyl) -stearamide (melting point 133 ° C). Similarly, a recording material was prepared. When this recording material was heated to 140 ° C. and cooled to room temperature (20 ° C.), a blue-violet color developed. The operation of heating the recording material to 100 ° C, cooling to room temperature, heating to 140 ° C, and cooling to room temperature was repeated. As a result, decoloring and color development could be performed reversibly. The optical densities of the color-developed state and the decolored state at this time were measured using a Macbeth densitometer RD-915. The OD values were 0.65 in the color-developed state and 0.07 in the decolored state. It was confirmed that the recording material was inferior to the recording material of the present invention.
  • Example 4 and Comparative Example 1 were printed with a thermal head (printing energy 0.25 mj / dot), left in a constant temperature bath at 40 ° C for 24 hours, and the optical density before and after storage at this time was measured. The measurement was performed using a densitometer RD-915 (trade name) to evaluate the storage stability of the printed matter. Storage stability was calculated according to the following equation.
  • Print storage rate (%) ⁇ (OD value of printed matter after storage, base OD value after storage) / (OD value of printed matter before storage-base OD value before storage) ⁇ X 100 [Table 1]
  • a recording material was prepared.
  • the evaluation criteria of the storage stability were determined by the following criteria from the print preservation rate when stored at 40 ° C for 24 hours.
  • ⁇ More than 40% and 80% or less
  • Example 6 10 N-4- (Hydroxyphenyl) -12-hydroxystearamide was changed to the amide compound shown in Table 3, the compounding amount in the table was used, and color development and decoloration were confirmed by heating to each temperature and then cooling. A color development and decoloration test was performed in the same manner as in Example 5, except that the test was performed.
  • the amounts in the table are parts by weight based on 20 parts by weight of the styrene acrylic ester copolymer.
  • N4HP 12HSA N— (4-hydroxyphenyl) 12-hydroxystearamide * N3HP 12HSA: N— (3-hydroxyphenyl) 12-hydroxystearamide * N4HP 12HPA: N— (4-hydroxyphenyl) —12-Hydroxy dd pentadecaneamide
  • Example 5 The same procedure as in Example 5 was repeated except that the leuco dye was changed to the leuco dye shown in the table below.
  • Example 12 ⁇ 4 ⁇ 12 ⁇ 11.4 0DB 2.8 1.16 0.20
  • Example 13 ⁇ 4 ⁇ 12 ⁇ 11.2 Black15 3.0 0.06
  • Example 14 ⁇ 4 ⁇ 12 ⁇ 11.4 0DB-7 2.8 1.16 0.20
  • Example 15 ⁇ 4 ⁇ 12 ⁇ 11.2 PSD-150 3.0 0.06
  • Example 16 ⁇ 4 ⁇ 12 ⁇ 11.4 PSD-300A 2.8 1.16
  • Example 17 ⁇ 4 ⁇ 12 ⁇ 11.2 Black173 3.0 S-205 Fluoran leuco dye manufactured by Yamada Chemical Industry Co., Ltd.
  • ODB Fluoran-based leuco dye manufactured by Yamamoto-Daisei Co., Ltd.
  • Blackl5 Fluoran leuco dye, manufactured by Yamamoto Iidai Co., Ltd.
  • ODB-7 Fluoran leuco dye manufactured by Yamamoto Kasei Co., Ltd.
  • PSD-300A Fluoran leuco dye manufactured by Nippon Soda Co., Ltd.
  • Blackl73 Fluoran leuco dye manufactured by Yamamoto Kasei Co., Ltd.
  • a color development and decoloration test was performed in the same manner as in Example 5, except that the matrix polymer was changed to the matrix polymer shown in the table below.
  • Saturated polyester 1 Byron 240, manufactured by Toyobo Co., Ltd.
  • Saturated polyester 2 Byron GK-640, manufactured by Toyobo Co., Ltd.
  • Saturated copolymerized polyester urethane Byron UR-1400, manufactured by Toyobo Co., Ltd.
  • Polystyrene Hymer ST-120, manufactured by Sanyo Chemical Industries, Ltd.
  • the mixture was pulverized and dispersed for 90 minutes with a sand grinder (TSG-4H (trade name) manufactured by IMETUS Co., Ltd.) to obtain a reversible recording material dispersion having an average particle size of about 1 ⁇ m. .
  • TSG-4H sand grinder
  • This dispersion was applied to a 75 ⁇ m-thick white polyethylene terephthalate film using a wire bar, and then heated and dried at 80 ° C to form a thick reversible heat-sensitive recording material with a recording layer that also had the power. And a recording material was produced.
  • This recording material was printed using a commercially available FAX (UF-A6CL (trade name, manufactured by Matsushita Electric Industrial Co., Ltd.)) without passing through a film, and a deep blue color was formed.
  • the recording material was heated with a heat roller at 110 ° C for 1 second, cooled to room temperature, and the fax printing operation was repeated. could be done. At this time, the optical density in the color-developed state and the decolored state was measured using a Macbeth densitometer.
  • Styrene acrylic ester copolymer (Hymer TB-1000F (trade name) manufactured by Sanyo Chemical Industries, Ltd.): 20 parts by weight
  • N- (4-hydroxyphenyl) -12-hydroxystearamide 10 parts by weight
  • thermosensitive recording material Using a sample mill (SK-M3 (trade name), manufactured by Kyoritsu Riko Co., Ltd.), a powdery reversible thermosensitive recording material was obtained. This powder was confirmed for the repeatability of coloring and decoloring in the same manner as in Example 1, and showed the same behavior as in Example 1.
  • Powdered recording material of Example 32 15 parts by weight
  • the mixture containing the above components is pulverized and dispersed for 60 minutes by a sand grinder (TSG-4H (trade name) manufactured by IMETUS Co., Ltd.), and an aqueous dispersion of a reversible recording material having an average particle size of about 1 ⁇ m is obtained. Obtained. 15 parts by weight of this aqueous dispersion
  • Reversible recording is possible by mixing 6 parts by weight of a 5% aqueous solution of polybutyl alcohol (using Gohsenol GM-14 (trade name) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) as the polybutyl alcohol and mixing and stirring the composition.
  • a heat-sensitive ink capable of obtaining a clear image was obtained.
  • This solution was applied on an 80 ⁇ m polypropylene film (upo FPG80 (trade name) manufactured by Upo Corporation) using a painting brush to obtain a reversible recorded image.
  • upo FPG80 trade name
  • thermo ink After applying the above-mentioned thermal ink to a 75 ⁇ m-thick white polyethylene terephthalate film using a wire bar, it is heated and dried at 80 ° C. to form a recording layer made of a reversible thermosensitive recording material having a thickness.
  • a recording material was printed using a commercially available FAX (UF-A6CL (trade name, manufactured by Matsushita Electric Industrial Co., Ltd.)) without passing through a film, and a deep blue color was formed.
  • This recording material was heated with a heat roller at 120 ° C. for 1 second, cooled to room temperature, and the above-described fax printing operation was repeated.
  • the above results suggest that the coloring / decoloring mechanism of the reversible recording material of the present invention and the structure of the hydroxyphenylhydroxyalkylamide compound have the following relationship. are doing. Although the coloring temperature has a relationship with the melting point, it seems that the position of the long-chain alkyl group having a hydroxyl group having a hydrogen bonding function also has an effect.
  • N- (4-hydroxyphenyl) -12-hydroxypentadecaneamide has a melting point of N- (4-hydroxyphenyl)- It is about 10 ° C higher than 12-hydroxystearamide, but its coloring temperature as a recording material is about 10 ° C lower. This means that the position of the hydrogen bond from the amide group is the same for both, but the distance from the alkyl group end is shorter for N- (4-hydroxyphenyl) -12-hydroxypentadecaneamide. Since the steric hindrance has been reduced, the amide compound alone is considered to have a higher melting point.
  • N- (3-hydroxyphenyl) -12-hydroxystearamide has a higher acidity than N- (4 hydroxyphenyl) 12-hydroxystearamide.
  • the reversible thermosensitive recording material using the electron accepting compound according to the present invention is excellent in color stability and erasability, color development sensitivity, balance between color development temperature and color erasure temperature, and storage stability against heat in a color development state. I have. Therefore, it can be generally used as an erasable or rewritable recording material. In particular, since the balance between the coloring temperature and the erasing temperature is appropriate, the degree of freedom of hardware for forming or erasing images is increased. In addition, by achieving high levels of color sensitivity, erasability, and storage stability, it can be used for general-purpose thermal printers such as fax machines, and can be applied to various applications.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L’invention apporte de nouveaux hydroxyphénylhydroxy-alkylamides ; des compositions thermosensibles réversibles et des matériaux thermiques réversibles pour impression qui contiennent les amides et qui sont excellents pour la stabilité de développement de la couleur, le caractère effaçable, la sensibilité du développement de la couleur, l’équilibre entre la température de développement et d’effacement de la couleur et pour la stabilité de l’état de coloration en cours ; et un processus de développement et de réduction de la couleur grâce aux amides, plus spécifiquement les hydroxyphénylhydroxyalkylamides étant représentés par la formule générale (I) ; et des compositions thermosensibles réversibles et des matériaux thermiques réversibles pour impression contenant chacun un composé accepteur d’électron comme décrit plus haut et un composé donneur d’électron de formation de la couleur : (I) (où n est un nombre entier compris entre 1 et 3) ; et A est un hydroxyalkyl non ramifié ayant un groupe hydroxyl sur un atome de carbone qui n’est pas en bout de chaîne). Le matériau pour impression peut engendrer un développement ou un effacement de la couleur en contrôlant la température.
PCT/JP2005/004974 2004-03-22 2005-03-18 Hydroxyphenylhydroxy- alkilamides, compositions thermo-réversibles et matériaux thermiques réversibles pour impression qui les contiennent, et processus de développement et de réduction de la couleur avec le même extrait. WO2005121072A1 (fr)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
WO2020203603A1 (fr) * 2019-03-29 2020-10-08 パイロットインキ株式会社 Composition thermochromique réversible, pigment thermochromique réversible en microcapsule la comprenant, et instrument d'écriture l'utilisant

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JPS5163137A (fr) * 1974-10-03 1976-06-01 Roussel Uclaf
JPS63297357A (ja) * 1987-05-29 1988-12-05 Ono Pharmaceut Co Ltd 新規なアルキル硫酸エステル誘導体、それらの製造方法およびそれらを有効成分として含有する薬剤
JPH09216469A (ja) * 1996-02-14 1997-08-19 Fuji Photo Film Co Ltd 感熱記録材料
WO2004016213A2 (fr) * 2002-08-15 2004-02-26 The Research Foundation Of State University Of New York Bibliotheques combinatoires d'analogues autoinducteurs, d'agonistes et d'antagonistes autoinducteurs, et leurs procedes d'utilisation

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US2824883A (en) * 1953-10-07 1958-02-25 Miles Lab Amide synthesis using anion exchange resin catalysts

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Publication number Priority date Publication date Assignee Title
JPS5163137A (fr) * 1974-10-03 1976-06-01 Roussel Uclaf
JPS63297357A (ja) * 1987-05-29 1988-12-05 Ono Pharmaceut Co Ltd 新規なアルキル硫酸エステル誘導体、それらの製造方法およびそれらを有効成分として含有する薬剤
JPH09216469A (ja) * 1996-02-14 1997-08-19 Fuji Photo Film Co Ltd 感熱記録材料
WO2004016213A2 (fr) * 2002-08-15 2004-02-26 The Research Foundation Of State University Of New York Bibliotheques combinatoires d'analogues autoinducteurs, d'agonistes et d'antagonistes autoinducteurs, et leurs procedes d'utilisation

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020203603A1 (fr) * 2019-03-29 2020-10-08 パイロットインキ株式会社 Composition thermochromique réversible, pigment thermochromique réversible en microcapsule la comprenant, et instrument d'écriture l'utilisant
CN113646052A (zh) * 2019-03-29 2021-11-12 百乐墨水株式会社 可逆热变色性组合物、内包有该可逆热变色性组合物的可逆热变色性微胶囊颜料及使用了该可逆热变色性微胶囊颜料的书写工具
CN113646052B (zh) * 2019-03-29 2024-05-17 百乐墨水株式会社 可逆热变色性组合物、可逆热变色性微胶囊颜料及书写工具

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