CN113547855A - Photothermal sensitive microcapsule and preparation method and application thereof - Google Patents

Photothermal sensitive microcapsule and preparation method and application thereof Download PDF

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CN113547855A
CN113547855A CN202010340286.3A CN202010340286A CN113547855A CN 113547855 A CN113547855 A CN 113547855A CN 202010340286 A CN202010340286 A CN 202010340286A CN 113547855 A CN113547855 A CN 113547855A
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methyl
fluoran
compound
anilino
microcapsule
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肖时卓
周树云
陈萍
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Technical Institute of Physics and Chemistry of CAS
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Technical Institute of Physics and Chemistry of CAS
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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
    • B41M5/28—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using thermochromic compounds or layers containing liquid crystals, microcapsules, bleachable dyes or heat- decomposable compounds, e.g. gas- liberating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • 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
    • B41M5/333—Colour developing components therefor, e.g. acidic 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
    • B41M5/3331—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
    • B41M5/333—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
    • 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
    • B41M5/3338—Inorganic 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
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/41—Base layers supports or substrates
    • 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
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/46—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography characterised by the light-to-heat converting means; characterised by the heat or radiation filtering or absorbing means or layers
    • B41M5/465—Infrared radiation-absorbing materials, e.g. dyes, metals, silicates, C black
    • 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
    • B41M2205/32—Thermal receivers
    • 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
    • B41M2205/36—Backcoats; Back layers

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

Abstract

The invention discloses a photothermal sensing microcapsule which is characterized by comprising a capsule wall and a capsule core, wherein the capsule core comprises a dye precursor and an infrared light absorber. When the photo-thermal sensitive microcapsule is used for recording graphic and text information, the graphic and text information can be recorded in a non-contact color development mode of infrared light exposure, so that the problems of probe abrasion and aging and the like caused by contact color development of thermal probe printing are fundamentally solved; or the color can be developed by adopting a thermal probe printing mode, the direct color development is realized by one-time printing, and the two-step color development of firstly exposing and then heating development is eliminated. The invention also discloses a preparation method and application of the photothermal sensitive microcapsule.

Description

Photothermal sensitive microcapsule and preparation method and application thereof
Technical Field
The invention relates to the field of microcapsule preparation. More particularly, relates to a photothermal sensing microcapsule and a preparation method and application thereof.
Background
Silver salt information recording materials are highly effective optical information recording materials, and are one of the main types of video films. However, silver salt recording materials have the problems of noble metal pollution, complex preparation process, complex development operation and the like, and with the development of information technology, a recording material which is dry-processed, environment-friendly and simple in production and use is urgently needed. Thermal recording materials based on a thermal color development reaction of a leuco dye and a color developer that develops the color of the leuco dye are widely accepted and used.
Chinese patent CN1843767A discloses a microcapsule-based thermal recording material, which is composed of a support, a thermal imaging layer, an interlayer and a protective layer, etc. on the support, the thermal imaging layer is the most important factor for the thermal recording material to form images, and the technical characteristic is that the thermal imaging layer contains dye precursor microcapsules and color developing agent microcapsules, the structural design can improve the storage stability and the image quality, the microcapsules do not contain photoinitiator and photo-crosslinking components, do not have photosensitivity, and the information recording mode is thermal probe impression or printing contact color development, and there are inherent problems of contact color development such as probe adhesion, aging, abrasion, etc.
Chinese patent CN1731276A discloses a photothermal sensing microcapsule and a photothermal sensing recording material containing the photothermal sensing microcapsule, which is technically characterized in that the core of the photothermal sensing microcapsule comprises a dye precursor, a photoinitiator, a photopolymerization or photocrosslinking component and the like, the polymerization reaction is carried out after the selective radiation exposure to form a solid solution, the color development of the dye precursor and a color developing agent in the subsequent heating process is prevented, and a non-exposure area generates a colored substance due to the fact that the color developing agent permeates into the capsule wall and reacts with the dye precursor in the heating process. However, the development of the photothermal sensing microcapsule comprises two steps of selective exposure and heating development, which is slightly more complicated than the direct development of the common printing of the thermal sensing microcapsule.
Chinese patent CN1386095A discloses an imaging medium containing heat-developable photosensitive microcapsules, which is technically characterized in that a dye precursor microcapsule and a color-developing agent coating are positioned between two supports, and photosensitive substances sensitive to different wavelengths of light are respectively contained in different photosensitive microcapsules to ensure hardening when exposed to different wavelengths of light, so that different colors can be respectively formed after heating to form a color image. However, the formation of the recording material with the double support makes the production process complicated, and thus, it cannot be simply formed by one-step coating, and it is a two-step color development process of first exposure and then heating for development, which is somewhat complicated.
Disclosure of Invention
In view of the above disadvantages, a first object of the present invention is to provide a photothermographic microcapsule. When the photo-thermal sensitive microcapsule is used for recording graphic and text information, the graphic and text information can be recorded in a non-contact color development mode of infrared light exposure, so that the problems of probe abrasion and aging and the like caused by contact color development of thermal probe printing are fundamentally solved; or the color can be developed by adopting a thermal probe printing mode, the direct color development is realized by one-time printing, and the two-step color development of firstly exposing and then heating development is eliminated.
The second purpose of the invention is to provide a preparation method of the photothermal sensing microcapsule.
It is a third object of the present invention to provide a photothermographic recording material.
The fourth purpose of the invention is to provide an application of the photothermal sensing microcapsule.
In order to achieve the first purpose, the invention adopts the following technical scheme:
a photothermographic microcapsule comprising a wall and a core, said core comprising a dye precursor, an infrared light absorber.
Further, the dye precursor is an electron-donating leuco dye precursor, has a property of color development by donating electrons or receiving protons such as acid, and particularly has a partial skeleton such as lactone, lactam, sultone, spiropyran, ester, amide, or the like, and when it is brought into contact with an electron-accepting compound, that is, a color-developing agent, it is preferable that the partial skeleton is a colorless compound in which the ring is opened or cleaved.
Further, the dye precursor is selected from one or more of triphenylmethane phthalide compound, triarylmethane compound, fluorane compound, phenothiazine compound, thiafluorane compound, xanthene compound, indolphthalein (indopthalyl) compound, spiropyran (spiropyran) compound, azaphthalide compound, methine compound, rhodamine anilino lactam compound, rhodamine lactam compound, quinazoline compound, diaza xanthene compound and dilactone compound.
Further, the dye precursor is selected from the group consisting of 2-anilino-3-methyl-6-diethylaminofluoran, 2-anilino-3-methyl-6- (di-N-butylamino) fluoran, 2-anilino-3-methyl-6- (di-N-pentylamino) fluoran, 2-anilino-3-methyl-6- (N-N-propyl-N-methylamino) fluoran, 2-anilino-3-methyl-6- (N-isopropyl-N-methylamino) fluoran, 2-anilino-3-methyl-6- (N-isobutyl-N-methylamino) fluoran, 2-anilino-3-methyl-6- (N-N-pentyl-N- Methylamino) fluoran, 2-anilino-3-methyl-6- (N-sec-butyl-N-ethylamino) fluoran, 2-anilino-3-methyl-6- (N-N-pentyl-N-ethylamino) fluoran, 2-anilino-3-methyl-6- (N-isopentyl-N-ethylamino) fluoran, 2-anilino-3-methyl-6- (N-cyclohexyl-N-methylamino) fluoran, 2-anilino-3-methyl-6- (N-ethyl-p-toluylamino) fluoran, 2-anilino-3-methyl-6- (N-methyl-p-toluylamino) fluoran, 2-methyl-6- (N-ethyl-p-toluylamino) fluoran, 2-methyl-6- (N-N-methyl-p-toluylamino) fluoran, a, 2- (m-trichloromethylanilino) -3-methyl-6-diethylaminofluoran, 2- (m-trifluoromethylanilino) -3-methyl-6- (N-cyclohexyl-N-methylamino) fluoran, 2- (2, 4-dimethylanilino) -3-methyl-6-diethylaminofluoran, 2- (N-ethyl-p-toluylamino) -3-methyl-6- (N-ethylanilino) fluoran, 2- (N-methyl-p-toluylamino) -3-methyl-6- (N-propyl-p-toluylamino) fluoran, and a pharmaceutically acceptable salt thereof, 2-anilino-6- (N-N-hexyl-N-ethylamino) fluoran, 2- (o-chloroanilino) -6-diethylaminofluoran, 2- (o-bromoanilino) -6-diethylaminofluoran, 2- (o-chloroanilino) -6-dibutylaminofluoran, 2- (o-fluoroanilino) -6-dibutylaminofluoran, 2- (m-trifluoromethylanilino) -6-diethylaminofluoran, 2- (p-acetylanilino) -6- (N-N-pentyl-N-N-butylamino) fluoran, 2-benzylamino-6- (N-ethyl-p-toluylamino) fluoran, 2-benzylamino-6- (N-methyl-2, 4-dimethylanilino) fluorane, 2-benzylamino-6- (N-ethyl-2, 4-dimethylanilino) fluorane, 2-dibenzylamino-6- (N-methyl-p-toluylamino) fluorane, 2-dibenzylamino-6- (N-ethyl-p-toluylamino) fluorane, 2- (di-p-methylbenzylamino) -6- (N-ethyl-p-toluylamino) fluorane, 2- (. alpha. -phenylethylamino) -6- (N-ethyl-p-toluylamino) fluorane, 2-methylamino-6- (N-methylanilino) fluorane, 2-methylamino-6- (N-ethylanilino) fluorane, 2-benzylamino-6- (N-ethyl-p-toluylamino) fluorane, 2-methylamino-6- (N-methylanilino) fluorane, and a method for producing a compound, 2-methylamino-6- (N-propylanilino) fluoran, 2-ethylamino-6- (N-methyl-p-toluylamino) fluoran, 2-methylamino-6- (N-methyl-2, 4-dimethylanilino) fluoran, 2-ethylamino-6- (N-methyl-2, 4-dimethylanilino) fluoran, 2-dimethylamino-6- (N-methylanilino) fluoran, 2-dimethylamino-6- (N-ethylanilino) fluoran, 2-diethylamino-6- (N-methyl-p-toluidino) fluoran, benzoleuco methylene blue, 2- [3, 6-bis (diethylamino) -6- (o-chloroanilino) xanthenebenzoic acid lactam Amines, 2- [3, 6-bis (diethylamino) ] -9- (o-chloroanilino) xanthene benzoic acid lactam, 3-bis (p-dimethylaminophenyl) phthalide, 3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3-bis (p-dimethylaminophenyl) -6-diethylaminophthalide, 3-bis (p-dimethylaminophenyl) -6-chlorophthalide, 3-bis (p-dibutylaminophenyl) phthalide, 3- (2-methoxy-4-dimethylaminophenyl) -3- (2-hydroxy-4, 5-dichlorophenyl) phthalide, 3- (2-hydroxy-4-dimethylaminophenyl) -3- (2-methoxy-5-chlorophenyl) phthalide 3- (2-hydroxy-4-dimethoxyaminophenyl) -3- (2-methoxy-5-chlorophenyl) phthalide, 3- (2-hydroxy-4-dimethoxyaminophenyl) -3- (2-methoxy-5-nitrophenyl) phthalide, 3- (2-hydroxy-4-diethylaminophenyl) -3- (2-methoxy-5-methylphenyl) phthalide, 3, 6-bis (dimethylamino) fluorenylspiro (9,3 ') -6' -dimethylaminobenzthalide, 6 '-chloro-8' -methoxy-benzindolinospyran, 6 '-bromo-2' -methoxybenzindolinospyran.
The infrared light absorber is a photo-thermal conversion reagent, can absorb the light energy of infrared light and convert the light energy into heat energy, and is a compound which enables the photo-thermal sensitive microcapsule to be sensitive to the infrared light. Further, the absorption wavelength range of the infrared absorbent is 750-1100 nm; preferably 750-850 nm.
Further, the infrared light absorber is selected from one or more of carbon black, azo dyes, triarylamine dyes, cyanine dyes, indocyanine dyes and phthalocyanine dyes.
Further, the infrared light absorber is selected from one or more of benzindole series cyanine dyes and partial cyanine dyes. The absorption wavelength range is 750-850 nm. Exemplary may be commercial NK-2014 or NK-2268 from Japan, as well as other companies' congeners.
Further, the caplet further comprises a solvent.
Further, the solvent is selected from a high boiling point solvent or a low boiling point solvent.
Further, the high boiling point solvent is selected from one or more of tributyl phosphate, ditolyl phosphate, tricresyl phosphate, trioctyl phosphate, dioctyl phthalate, dibutyl phthalate, alkyl biphenyl or alkyl naphthalene. Such as isopropylnaphthalene, beta-methylnaphthalene.
Further, the low-boiling point solvent is selected from one or more of ethyl acetate, butyl acetate and cyclohexanone.
Further, the mass ratio of the infrared absorbent to the dye precursor is 1: 0.1-1: 50, preferably 1: 0.5-1: 40, and more preferably 1: 1-1: 10, and at this time, the problem that microcapsules synthesized in other proportions have poor infrared color development effect due to insufficient amount of infrared dye or have poor capsule stability due to defects on capsule walls caused by interfacial polycondensation reaction due to excessive amount of infrared dye can be solved.
Furthermore, the particle size of the photo-thermal microcapsule is 0.1-2.0 μm.
Further, the material of the capsule wall is polyurea or polyurethane.
Further, the material of the capsule wall is obtained by reacting a polyfunctional isocyanate compound with the wall-forming material B.
Further, the multifunctional isocyanate compound is one or more selected from toluene diisocyanate, diphenylmethane-4, 4 diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and D-110N.
The wall-forming material B is a known compound which can react with the wall-forming material A to form polyurethane or polyurea. Furthermore, the wall forming material B is selected from one or more of polyamine, polyalcohol or deionized water, the reaction of the material for preparing the capsule wall is mild and easy to control, and the prepared capsule has greatly improved stability and long shelf life.
In order to achieve the second purpose, the invention adopts the following technical scheme:
a preparation method of the photothermal sensing microcapsule comprises the following steps:
dissolving a dye precursor and an infrared absorber in a solvent, adding a polyfunctional group isocyanate compound, and uniformly mixing to obtain an oil phase;
preparing water solution of water-soluble resin to obtain water phase;
adding the oil phase into the water phase under high-speed shearing and stirring, and emulsifying to obtain an emulsion;
under the conditions of stirring and heating, adding a wall forming material B into the emulsion, and detecting the isocyanate peak of a polyfunctional isocyanate compound in the reaction liquid by infrared spectroscopy until the isocyanate peak disappears to obtain the photo-thermo-sensitive microcapsule suspension; and drying the photo-thermal sensitive microcapsule suspension in vacuum at normal temperature to obtain the photo-thermal sensitive microcapsule.
In the preparation method, the water phase is used as a protective colloid to prevent the oil phase from agglomerating after forming small liquid drops in the shearing process. In the photothermographic microcapsule prepared, the composition of the aqueous phase is absent.
Further, in the aqueous phase, the concentration of the aqueous solution of the water-soluble resin is 3-10 wt%, preferably 3-8 wt%.
Further, the water-soluble resin is selected from one or more of polyvinyl alcohol, polyvinylpyrrolidone, a copolymer of N-vinylpyrrolidone and vinyl acetate (VA resin for short), a copolymer of N-vinylpyrrolidone and (meth) acrylate, a copolymer of N-vinylpyrrolidone and (meth) acrylamide, a copolymer of N-vinylpyrrolidone and styrene, gelatin and a cellulose derivative.
Further, the cellulose derivative is selected from one of cellulose nitrate, cellulose acetate butyrate, cellulose xanthate, methyl cellulose, carboxymethyl cellulose, ethyl cellulose, hydroxyethyl cellulose, cyanoethyl cellulose, hydroxypropyl cellulose and hydroxypropyl methyl cellulose.
Further, the emulsifying time is 10-30 minutes.
Further, the heating temperature is 50-80 ℃.
Further, the manner of adding the wall-forming material B to the emulsion is dropwise or rapid addition, and for the uniformity of capsule formation, the manner of adding the wall-forming material B to the emulsion in a uniform dropwise manner is preferable.
The average grain diameter of the prepared photothermal sensitive microcapsule is 0.1-2.0 μm by the preparation method. The information recording material containing the photo-thermal sensitive microcapsules does not need a thermal probe to print and image, and the imaging precision is not controlled by the diameter of the thermal probe and is mainly determined by the average particle size of the photo-thermal sensitive microcapsules, so that the imaging precision of the photo-thermal sensitive microcapsule imaging material obtained by the preparation method can reach micron or even submicron level.
In order to achieve the third object, the invention provides the following technical solutions:
a photothermographic recording material includes a support, and a photosensitive imaging layer on the support. The photosensitive imaging layer comprises the photothermographic microcapsules and developer as described above for the first object.
The color developing agent can be nano solid particles or microcapsules or a mixture of the nano solid particles and the microcapsules. The color-developing agent of the present invention is a compound which is an electron-accepting compound and which changes the color of a dye precursor by contacting the dye precursor, and examples thereof include, but are not particularly limited to, phenol compounds, organic acids or metal salts thereof, and acidic substances such as hydroxybenzoates.
Specific examples of the developer include bisphenol compounds such as 2, 2-bis (4 '-hydroxyphenyl) propane (common name: bisphenol a), 2-bis (4' -hydroxyphenyl) pentane, 2-bis (4 '-hydroxy-3', 5 '-dichlorophenyl) propane, 1-bis (4' -hydroxyphenyl) cyclohexane, 2-bis (4 '-hydroxyphenyl) hexane, 1-bis (4' -hydroxyphenyl) propane, 1-bis (4 '-hydroxyphenyl) butane, 1-bis (4' -hydroxyphenyl) pentane, 1-bis (4 '-hydroxyphenyl) hexane, 1-bis (4' -hydroxyphenyl) heptane, 1, 1-bis (4 '-hydroxyphenyl) octane, 1-bis (4' -hydroxyphenyl) -2-methyl-pentane, 1-bis (4 '-hydroxyphenyl) -2-ethyl-hexane, 1-bis (4' -hydroxyphenyl) dodecane, 1, 4-bis (p-hydroxyphenyl cumyl) benzene, 1, 3-bis (p-hydroxyphenyl cumyl) benzene, bis (p-hydroxyphenyl) sulfone, bis (3-allyl-4-hydroxyphenyl) sulfone, benzyl bis (p-hydroxyphenyl) acetate, etc.; salicylic acid derivatives such as 3, 5-di- α -methylbenzylsalicylic acid, 3, 5-di-t-butylsalicylic acid, 3- α -dimethylbenzylsalicylic acid, 4- (. beta. -p-methoxyphenoxyethoxy) salicylic acid, and the like, and polyvalent metal salts thereof, particularly preferably zinc salts, aluminum salts; hydroxybenzoic acid esters such as benzyl paraben, 2-ethylhexyl paraben, β -resorcinolic acid- (2-phenoxyethyl) ester, etc.; phenols such as p-phenylphenol, 3, 5-diphenylphenol, cumylphenol, 4-hydroxy-4 '-isopropoxy-diphenylsulfone (common name D-8), 4-hydroxy-4' -phenoxy-diphenylsulfone and the like.
The color developing agent nano solid particles can be obtained by ball milling, sanding and other modes, and the average particle size is 0.1-1.0 mu m, preferably 0.3-0.8 mu m.
The developer microcapsule of the present invention can be prepared by any of the conventionally known chemical methods, such as interfacial polymerization, in-situ polymerization, complex coacervation, and phase separation, preferably by interfacial polymerization. The light-heat sensitive microcapsule can also be prepared by the preparation method of the light-heat sensitive microcapsule. The average particle size of the developer microcapsules is 0.1-2.0 μm.
The photothermographic recording material of the present invention comprises a support, which may be transparent, and examples thereof include polyester films such as polyethylene terephthalate and polybutylene terephthalate, cellulose triacetate films, and polymer films such as polyolefin films such as polypropylene and polyethylene. The support may be opaque, and examples thereof include a paper base and an aluminum plate base. The photosensitive imaging layer coating liquid is composed of a photothermal sensitive microcapsule suspension and a color developing agent suspension, and the volume ratio is 5: 1-1: 5. The coating method is a known coating method, and is not limited, for example, knife coating, dip coating, extrusion coating, and the like.
In order to achieve the fourth object, the present invention provides the following technical solutions:
use of the photothermographic microcapsules according to the first object above for the recording of graphic information.
Furthermore, the image and text information can be recorded by a non-contact color development mode of infrared light exposure or the color is developed by adopting a mode of thermal probe printing, and the color is directly developed by printing once.
The invention has the following beneficial effects:
in the photo-thermal sensitive microcapsule provided by the invention, the infrared light absorber and the dye precursor are used as capsule cores, so that the prepared photo-thermal sensitive microcapsule has infrared photosensitivity and heat sensitivity, and can be well applied to recording of image-text information. The quality ratio of the infrared absorbent to the dye precursor in the microcapsule is further controlled, so that the microcapsule has good infrared light developing and developing effect and structural stability.
According to the preparation method of the photo-thermal sensitive microcapsule provided by the invention, the preparation conditions are mild, and the prepared microcapsule has high stability and long shelf life.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 shows an infrared absorption curve of a photo and thermal sensitive microcapsule prepared in example 1, the lower curve in the figure being an infrared absorption spectrum of a reactant at the initial stage of a reaction; the upper curve is the infrared absorption spectrum of the reaction product after the reaction is finished.
Fig. 2 shows a scanning electron microscope image of the photothermographic microcapsule prepared in example 1.
Fig. 3 shows a thermogravimetric curve of the photo and thermal sensitive microcapsule prepared in example 1.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. Similar parts in the figures are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Examples 1 to 10
The raw materials of the photo and thermal microcapsules of examples 1 to 10 are shown in table 1, and the preparation method of the photo and thermal microcapsules includes the steps of:
(1) preparing an oil phase: weighing 5g of dye precursor, 0.5g of infrared absorber and 50g of ethyl acetate, heating and refluxing together to dissolve the dye precursor and the infrared absorber, adding the wall forming material A, and stirring uniformly to obtain an oil phase;
(2) preparation of an aqueous phase: preparing 100g of water-soluble resin 5 wt% aqueous solution to obtain a water phase;
(3) synthesizing the photo-thermal microcapsules: pouring the oil phase into the water phase under high-speed shearing and stirring, emulsifying for 10 minutes, transferring into a heating device, and dropwise adding a wall material B under stirring and heating conditions until the isocyanate peak of the wall material A in the reaction liquid disappears by infrared spectrum detection. The average particle diameter of the obtained photothermal sensitive microcapsule is 0.3-1.0 μm.
Wherein, the infrared absorption curve of the photo-thermal sensitive microcapsule prepared in example 1 is shown in fig. 1: the lower curve in the figure is the infrared absorption spectrum of the reactant at the initial stage of the reaction; the upper curve is the infrared absorption spectrum of the reaction product after the reaction is finished.
The scanning electron micrograph of the photo and thermal sensitive microcapsule prepared in example 1 is shown in fig. 2.
The thermal weight loss curve of the photo and thermal sensitive microcapsule prepared in example 1 is shown in fig. 3.
Table 1 composition of raw materials for each example
Figure BDA0002468312180000061
Example 11
In example 1, the oil phase was poured into the water phase to emulsify for 20 minutes, and the rest was not changed to prepare a photothermographic microcapsule. The average grain diameter of the prepared photothermal sensitive microcapsule is 0.3 mu m.
Example 12
In example 1, the oil phase was poured into the water phase to emulsify for 30 minutes, and the rest was not changed to prepare a photothermographic microcapsule. The average grain diameter of the prepared photo-thermal sensitive microcapsule is 0.1 mu m.
Example 13
In example 1, a photo-thermal sensitive microcapsule was prepared by preparing a 10% aqueous solution of a water-soluble resin to obtain a water phase and leaving the remainder unchanged. The average grain diameter of the prepared photothermal sensitive microcapsule is 1.8 mu m.
Example 14
In example 1, the ethyl acetate in the oil phase preparation was changed to β -methylnaphthalene, and the remainder was unchanged, to prepare a photothermographic microcapsule. The average grain diameter of the prepared photo-thermal sensitive microcapsule is 2.0 mu m.
Example 15
In example 1, the amount of the infrared light absorber was changed to 5g, and the rest was unchanged, to prepare a photo and thermal sensitive microcapsule. The average grain diameter of the prepared photothermal sensitive microcapsule is 0.9 mu m.
Example 16
In example 1, the amount of the infrared light absorber was changed to 0.1g, and the rest was unchanged, to prepare a photo and thermal sensitive microcapsule. The average grain diameter of the prepared photothermal sensitive microcapsule is 0.4 mu m.
Comparative example 1
In example 1, microcapsules were prepared without adding the infrared absorber and without changing the rest. The average particle size of the obtained microcapsules was 0.5 um.
Comparative example 2
In example 1, microcapsules were prepared by replacing the amount of the infrared absorber with 0.08g, and leaving the rest unchanged. The average particle size of the obtained microcapsules was 0.3 μm.
Comparative example 3
In example 1, a photo-thermal sensitive microcapsule was prepared by preparing a 15% aqueous solution of a water-soluble resin to obtain a water phase and leaving the remainder unchanged. The average grain diameter of the prepared photothermal sensitive microcapsule is 2.5 mu m.
The microcapsule suspensions obtained in examples 1 to 16 and comparative examples 1 to 3 were mixed with developer D-8In a volume ratio of 1:1, obtaining a photosensitive imaging layer coating liquid, uniformly coating the coating liquid on a PET (polyethylene terephthalate) film by using a wire rod, drying for 2min at 60 ℃ to obtain a photothermal response microcapsule precoating plate, and measuring the dry film weight of the precoating plate to be 3.0g/m2. The photosensitive property is that the pre-coated plate is exposed by a 808nm laser with the model of MDL-III-808-5W, and the image density value of the exposed area is measured by an Alice densitometer, and the specific process is as follows: in the exposure area, the infrared dye in the photo-thermal response microcapsule absorbs 830nm infrared laser to generate heat, so that the permeability of the capsule wall is increased, meanwhile, the generated heat also melts the color developing agent outside the capsule, and the color developing agent permeates into the capsule to develop the color of the dye precursor; the non-exposed areas have no color change. Then measuring the image density OD of the exposure area by an Alice densitometermaxSubtracting the image density OD of the non-exposed area0Obtaining the image density difference value delta OD after sensitizationLight-sensitiveAs shown in table 2. The heat-sensitive property is measured by heating for 1min with a hot plate and measuring the OD of the coating with an Alice spectrodensitometermaxValue, subtracting the image density value OD of the coating before heating0Obtaining the difference value Delta OD of the image density after heat sensingHeat-sensitive。
TABLE 2 difference in image density (Δ OD) of the coatings of the examples
Figure BDA0002468312180000071
Figure BDA0002468312180000081
Testing the thermal stability performance:
further, in examples 1 to 13, a color development stability test was conducted by baking at 50 ℃ for 1 to 3 days. The photothermal response microcapsule precoated plate is obtained by the method, the precoated plate is placed in a constant temperature oven at 50 ℃ and is respectively placed for 1 day, 2 days and 3 days, the photothermal response microcapsule precoated plate is exposed by a 808nm laser after being taken out, and the image density difference is measured by the method, and the result is shown in table 3. Color development stability experiments further prove that the photo-thermal sensitive microcapsule prepared by the method has good thermal stability, and the photo-sensitive color development performance is basically unchanged after being baked for 3 days at 50 ℃ and stored for three months at normal temperature.
TABLE 3 photothermal response microcapsule Pre-coated plate color development stability test
Figure BDA0002468312180000082
Figure BDA0002468312180000091
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.

Claims (10)

1. A photothermographic microcapsule comprising a wall and a core, wherein the core comprises a dye precursor and an infrared absorber.
2. The photothermographic microcapsule according to claim 1 wherein said dye precursor is a leuco dye precursor;
preferably, the dye precursor is selected from one or more of triphenylmethane phthalide compound, triarylmethane compound, fluorane compound, phenothiazine compound, sulfo-fluorane compound, xanthene compound, indole phthalide compound, spiropyran compound, aza phthalide compound, methine compound, rhodamine anilino lactam compound, rhodamine lactam compound, quinazoline compound, diaza xanthene compound and dilactone compound;
more preferably, the dye precursor is selected from the group consisting of 2-anilino-3-methyl-6-diethylaminofluoran, 2-anilino-3-methyl-6- (di-N-butylamino) fluoran, 2-anilino-3-methyl-6- (di-N-pentylamino) fluoran, 2-anilino-3-methyl-6- (N-N-propyl-N-methylamino) fluoran, 2-anilino-3-methyl-6- (N-isopropyl-N-methylamino) fluoran, 2-anilino-3-methyl-6- (N-isobutyl-N-methylamino) fluoran, 2-anilino-3-methyl-6- (N-N-pentyl-N-methylamino) fluoran Arylamino) fluoran, 2-anilino-3-methyl-6- (N-sec-butyl-N-ethylamino) fluoran, 2-anilino-3-methyl-6- (N-N-pentyl-N-ethylamino) fluoran, 2-anilino-3-methyl-6- (N-isopentyl-N-ethylamino) fluoran, 2-anilino-3-methyl-6- (N-cyclohexyl-N-methylamino) fluoran, 2-anilino-3-methyl-6- (N-ethyl-p-toluylamino) fluoran, 2-anilino-3-methyl-6- (N-methyl-p-toluylamino) fluoran, 2-methyl-ethyl-6- (N-methyl-p-toluylamino) fluoran, and a pharmaceutically acceptable salt thereof, 2- (m-trichloromethylanilino) -3-methyl-6-diethylaminofluoran, 2- (m-trifluoromethylanilino) -3-methyl-6- (N-cyclohexyl-N-methylamino) fluoran, 2- (2, 4-dimethylanilino) -3-methyl-6-diethylaminofluoran, 2- (N-ethyl-p-toluylamino) -3-methyl-6- (N-ethylanilino) fluoran, 2- (N-methyl-p-toluylamino) -3-methyl-6- (N-propyl-p-toluylamino) fluoran, and a pharmaceutically acceptable salt thereof, 2-anilino-6- (N-N-hexyl-N-ethylamino) fluoran, 2- (o-chloroanilino) -6-diethylaminofluoran, 2- (o-bromoanilino) -6-diethylaminofluoran, 2- (o-chloroanilino) -6-dibutylaminofluoran, 2- (o-fluoroanilino) -6-dibutylaminofluoran, 2- (m-trifluoromethylanilino) -6-diethylaminofluoran, 2- (p-acetylanilino) -6- (N-N-pentyl-N-N-butylamino) fluoran, 2-benzylamino-6- (N-ethyl-p-toluylamino) fluoran, 2-benzylamino-6- (N-methyl-2, 4-dimethylanilino) fluorane, 2-benzylamino-6- (N-ethyl-2, 4-dimethylanilino) fluorane, 2-dibenzylamino-6- (N-methyl-p-toluylamino) fluorane, 2-dibenzylamino-6- (N-ethyl-p-toluylamino) fluorane, 2- (di-p-methylbenzylamino) -6- (N-ethyl-p-toluylamino) fluorane, 2- (. alpha. -phenylethylamino) -6- (N-ethyl-p-toluylamino) fluorane, 2-methylamino-6- (N-methylanilino) fluorane, 2-methylamino-6- (N-ethylanilino) fluorane, 2-benzylamino-6- (N-ethyl-p-toluylamino) fluorane, 2-methylamino-6- (N-methylanilino) fluorane, and a method for producing a compound, 2-methylamino-6- (N-propylanilino) fluoran, 2-ethylamino-6- (N-methyl-p-toluylamino) fluoran, 2-methylamino-6- (N-methyl-2, 4-dimethylanilino) fluoran, 2-ethylamino-6- (N-methyl-2, 4-dimethylanilino) fluoran, 2-dimethylamino-6- (N-methylanilino) fluoran, 2-dimethylamino-6- (N-ethylanilino) fluoran, 2-diethylamino-6- (N-methyl-p-toluidino) fluoran, benzoleuco methylene blue, 2- [3, 6-bis (diethylamino) -6- (o-chloroanilino) xanthenebenzoic acid lactam Amines, 2- [3, 6-bis (diethylamino) ] -9- (o-chloroanilino) xanthene benzoic acid lactam, 3-bis (p-dimethylaminophenyl) phthalide, 3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3-bis (p-dimethylaminophenyl) -6-diethylaminophthalide, 3-bis (p-dimethylaminophenyl) -6-chlorophthalide, 3-bis (p-dibutylaminophenyl) phthalide, 3- (2-methoxy-4-dimethylaminophenyl) -3- (2-hydroxy-4, 5-dichlorophenyl) phthalide, 3- (2-hydroxy-4-dimethylaminophenyl) -3- (2-methoxy-5-chlorophenyl) phthalide 3- (2-hydroxy-4-dimethoxyaminophenyl) -3- (2-methoxy-5-chlorophenyl) phthalide, 3- (2-hydroxy-4-dimethoxyaminophenyl) -3- (2-methoxy-5-nitrophenyl) phthalide, 3- (2-hydroxy-4-diethylaminophenyl) -3- (2-methoxy-5-methylphenyl) phthalide, 3, 6-bis (dimethylamino) fluorenylspiro (9,3 ') -6' -dimethylaminobenzthalide, 6 '-chloro-8' -methoxy-benzindolinospyran, 6 '-bromo-2' -methoxybenzindolinospyran.
3. The photo-thermal microcapsule according to claim 1, wherein the infrared light absorber has an absorption wavelength ranging from 750 to 1100 nm; preferably 750-850 nm;
preferably, the infrared light absorber is selected from one or more of carbon black, azo dyes, triarylamine dyes, cyanine dyes, indocyanine dyes and phthalocyanine dyes;
more preferably, the infrared light absorber is selected from one or more of benzindole cyanine dyes and merocyanine dyes.
4. The photothermographic microcapsule according to claim 1 wherein said core further comprises a solvent; preferably, the solvent is selected from a high boiling point solvent or a low boiling point solvent;
preferably, the high-boiling point solvent is selected from one or more of tributyl phosphate, ditolyl phosphate, tricresyl phosphate, trioctyl phosphate, dioctyl phthalate, dibutyl phthalate, alkyl biphenyl or alkyl naphthalene;
preferably, the low-boiling point solvent is selected from one or more of ethyl acetate, butyl acetate and cyclohexanone.
5. The photo-thermal microcapsule according to claim 1, wherein the mass ratio of the infrared light absorber to the dye precursor is 1: 0.1-1: 50, preferably 1: 0.5-1: 40, more preferably 1: 1-1: 10;
preferably, the particle size of the photo-thermal microcapsule is 0.1-2.0 μm.
6. The photothermographic microcapsule according to claim 1, wherein the material of said wall is polyurea or polyurethane;
preferably, the material of the capsule wall is obtained by reacting a polyfunctional isocyanate compound with the wall-forming material B;
preferably, the multifunctional isocyanate compound is selected from one or more of toluene diisocyanate, diphenylmethane-4, 4 diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and D-110N;
preferably, the wall forming material B is selected from one or more of polyamine, polyalcohol or deionized water.
7. The method for preparing a photothermographic microcapsule according to any of claims 1-6 comprising the steps of:
dissolving a dye precursor and an infrared absorber in a solvent, adding a polyfunctional group isocyanate compound, and uniformly mixing to obtain an oil phase;
preparing water solution of water-soluble resin to obtain water phase;
adding the oil phase into the water phase under high-speed shearing and stirring, and emulsifying to obtain an emulsion;
under the conditions of stirring and heating, adding a wall forming material B into the emulsion, and detecting the isocyanate peak of a polyfunctional isocyanate compound in the reaction liquid by infrared spectroscopy until the isocyanate peak disappears to obtain the photo-thermo-sensitive microcapsule suspension; and drying the photo-thermal sensitive microcapsule suspension in vacuum at normal temperature to obtain the photo-thermal sensitive microcapsule.
8. The preparation method according to claim 7, wherein the concentration of the aqueous solution of the water-soluble resin in the aqueous phase is 3 to 10 wt%;
preferably, the water-soluble resin is selected from one or more of polyvinyl alcohol, polyvinylpyrrolidone, copolymer of N-vinyl pyrrolidone and vinyl acetate, copolymer of N-vinyl pyrrolidone and (methyl) acrylate, copolymer of N-vinyl pyrrolidone and (methyl) acrylamide, copolymer of N-vinyl pyrrolidone and styrene, gelatin and cellulose derivative;
preferably, the cellulose derivative is selected from one of cellulose nitrate, cellulose acetate butyrate, cellulose xanthate, methyl cellulose, carboxymethyl cellulose, ethyl cellulose, hydroxyethyl cellulose, cyanoethyl cellulose, hydroxypropyl cellulose and hydroxypropyl methyl cellulose;
preferably, the emulsifying time is 10-30 minutes;
preferably, the heating temperature is 50-80 ℃.
9. A photothermographic recording material comprising a support, and a photosensitive imaging layer disposed on the support, the photosensitive imaging layer comprising the photothermographic microcapsules of any of claims 1-6 and a developer in the form of nano-solid particles, microcapsules, or a mixture thereof;
preferably, the particle size of the photo-thermal sensitive microcapsule and the color developing agent microcapsule is preferably 0.1-2.0 μm, and the particle size of the color developing agent nano solid particle is preferably 0.3-0.8 μm.
10. Use of the photothermographic microcapsules according to any one of claims 1 to 6 for the recording of graphic information.
CN202010340286.3A 2020-04-26 2020-04-26 Photothermal sensitive microcapsule and preparation method and application thereof Pending CN113547855A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0414509A2 (en) * 1989-08-24 1991-02-27 Appleton Papers Inc. Heat sensitive record material
JP2000079766A (en) * 1998-07-03 2000-03-21 Oji Paper Co Ltd Thermosensitive recording material
CN1386095A (en) * 2000-06-01 2002-12-18 希毕克斯幻像有限公司 Imaging media containing heat developable photosensitive microcapsule
CN1644393A (en) * 2004-01-23 2005-07-27 富士胶片株式会社 Lithographic printing plate precursor and lithographic printing method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0414509A2 (en) * 1989-08-24 1991-02-27 Appleton Papers Inc. Heat sensitive record material
JP2000079766A (en) * 1998-07-03 2000-03-21 Oji Paper Co Ltd Thermosensitive recording material
CN1386095A (en) * 2000-06-01 2002-12-18 希毕克斯幻像有限公司 Imaging media containing heat developable photosensitive microcapsule
CN1644393A (en) * 2004-01-23 2005-07-27 富士胶片株式会社 Lithographic printing plate precursor and lithographic printing method

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