CN111483250A - Thermosensitive microcapsule color developing material and preparation method thereof - Google Patents
Thermosensitive microcapsule color developing material and preparation method thereof Download PDFInfo
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- CN111483250A CN111483250A CN202010317450.9A CN202010317450A CN111483250A CN 111483250 A CN111483250 A CN 111483250A CN 202010317450 A CN202010317450 A CN 202010317450A CN 111483250 A CN111483250 A CN 111483250A
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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
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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
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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
- B41M5/333—Colour developing components therefor, e.g. acidic compounds
- B41M5/3333—Non-macromolecular compounds
- B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
- B41M5/3336—Sulfur compounds, e.g. sulfones, sulfides, sulfonamides
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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
- B41M5/337—Additives; Binders
- B41M5/3372—Macromolecular compounds
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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
- B41M5/337—Additives; Binders
- B41M5/3375—Non-macromolecular compounds
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- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention discloses a heat-sensitive microcapsule chromogenic material, which specifically comprises the following components: dye precursor microcapsules, a developer, a surfactant and polyvinyl alcohol; the dye precursor microcapsule comprises a capsule wall and a capsule core wrapped by the capsule wall, wherein the capsule wall is polyurea or polyurethane, and the capsule core comprises a dye precursor and a solvent; the dye precursors include S205, ODB-2, GN-2 and RED-3, and the solvents include ethyl acetoacetate and ethyl acetate. The novel dye precursor is adopted and matched with the color developing agent, so that the color developing density can be improved, the printed black has a pure effect, and the black can be used as a medical recording material.
Description
Technical Field
The invention relates to the technical field of information recording materials, in particular to a thermosensitive microcapsule material and a preparation method thereof.
Background
Information recording and reproduction materials are an essential tool in human study, life and work. With the rapid development of information technology, information in the form of pictures, characters and the like needs to be recorded, stored or reproduced, and people put higher demands on information recording and reproducing materials. The current information recording and reproducing materials mainly include two major types, namely silver salt information recording materials and thermosensitive information recording materials.
Among them, silver salt information recording material is a high-efficiency optical information recording material, which integrates receiving, storing and reproducing of optical information, and is widely used in the fields of science and technology, military, medical treatment, human daily life and the like. However, silver salt recording materials use noble metal silver as a raw material, and the preparation process is complex and the environmental pollution is serious; and when in use, the ink needs to be subjected to multiple links such as light, development, fixation, drying and the like, has harsh technical conditions and high cost, and is difficult to adapt to the requirements of social development.
The thermosensitive information recording material reproduces information by a dry technology, does not need development, can use common paper as a support, has simple processing technology, is easy to obtain high-density images, has simple processing equipment, low price and no noise in the recording process, and has development advantages. Especially, the heat-sensitive microcapsule material can improve the information recording resolution by controlling the particle size distribution of the microcapsule, has the advantages of convenient and quick development, high resolution, low pollution and the like, becomes a novel carrier for information recording and image reproduction, and has huge application potential and market in the information field.
The heat-sensitive microcapsule material is characterized in that a dye precursor is formed into a microcapsule, the microcapsule wall adopts polyurethane, and the interior does not contain an initiator and a monomer which can generate a photo-hardening reaction. Then, the dye microcapsule is formed into a coating layer of the information recording material with a corresponding solid dispersion developer and other additives. The selective heating of the imaging layer by a thermal print head with certain geometric dimensions is used, and the permeability of the microcapsule wall is adjusted by the change of temperature to obtain images. After the temperature is lowered, the microcapsule wall is re-hardened and no longer has permeability, thereby fixing the image, improving the image stability, and being a pure thermosensitive recording material.
The existing thermosensitive microcapsule material achieves the color development effect through the interaction of a dye precursor and a color developing agent, but the color development effect achieved by the currently adopted dye precursor and the color developing agent cannot meet the use requirement of a medical recording material, and the specific expression is that when a black image is printed, the color density is low, and the printed image shows red under illumination, so that the application in the field of medical recording is influenced.
Therefore, it is an urgent need to solve the problems of the art to provide a heat-sensitive microcapsule material with high color density and a preparation method thereof.
Disclosure of Invention
In view of the above, the present invention provides a thermosensitive microcapsule material and a preparation method thereof, wherein a novel dye precursor is adopted to be matched with a color developing agent to improve the color density, so that the color density can reach 3.31 under the detection condition of 150 ℃, and the printed black material has an excellent black effect and can be used as a medical recording material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a heat-sensitive microcapsule chromogenic material comprises the following components in parts by weight: 20-70 parts of dye precursor microcapsules, 10-60 parts of color developing agent, 5-15 parts of surfactant and 0.1-5 parts of polyvinyl alcohol; the dye precursor microcapsule comprises a capsule wall and a capsule core wrapped by the capsule wall, wherein the capsule wall is polyurea or polyurethane, and the capsule core comprises a dye precursor and a solvent; the dye precursor comprises S205, ODB-2, GN-2 and RED-3, and the solvent comprises cyclohexanone and ethyl acetate.
The beneficial effects of the preferred technical scheme are as follows: the solvent selected by the invention is prepared by mixing cyclohexanone and ethyl acetate, wherein the cyclohexanone does not react with the dye, the solubility of the cyclohexanone to the dye is high, and the solvent is matched with the ethyl acetate to accelerate the dissolving speed.
Preferably, the capsule core comprises the following components in percentage by weight: 10-40% of dye precursor and 60-90% of solvent.
Preferably, the dye precursor comprises the following components in parts by weight: 40-70 parts of S205, 10-20 parts of ODB-2, 5-20 parts of RED-3 and 5-10 parts of GN-2.
The beneficial effects of the preferred technical scheme are as follows: the dye precursor is added with S205, so that the RED is not deviated under the sunlight when printing the high-density black, and the use amount of RED-3 and GN-2 can be reduced. Wherein S205 is a dye produced by Shouguangfukang pharmaceutical Co., Ltd; ODB-2 is a dye produced by Shouguang Fukang pharmaceutical Co.Ltd; GN-2 is a dye produced by Tokyo Kaisha, Japan; RED-3 is a dye produced by Tokyo Kabushiki Kaisha, Japan.
Preferably, the solvent comprises the following components in percentage by weight: 80-99% of ethyl acetate and 1% -20% of cyclohexanone.
The beneficial effects of the preferred technical scheme are as follows: according to the invention, the amount of ethyl acetate is adjusted by cyclohexanone, so that the amount of ethyl acetate is reasonable, microcapsules which cannot be formed due to too much ethyl acetate are avoided, and microcapsules which are not easy to disperse due to too little ethyl acetate are avoided.
A preparation method of a photosensitive microcapsule chromogenic material is characterized by comprising the following steps:
s1 preparation of dye precursor microcapsules
S11, weighing a dye precursor, cyclohexanone and ethyl acetate according to the thermosensitive microcapsule chromogenic material, mixing and stirring, and heating for dissolving to obtain a dye mixture;
s12, cooling the dye mixture, adding xylylene diisocyanate, and stirring to obtain an oil phase mixture;
s13, adding a surfactant into the polyvinyl alcohol aqueous solution, and stirring to obtain an aqueous phase mixture;
s14, slowly adding the oil phase mixture into the water phase mixture, and stirring to obtain an oil emulsion dispersion;
s15, adding deionized water and tetraethylenepentamine into the oil emulsion dispersion liquid, and then reacting under the stirring condition to obtain a dye precursor microcapsule;
s2 preparation of developer solution
S21, adding a surfactant and a color developing agent into the polyvinyl alcohol aqueous solution, and uniformly stirring to obtain a mixed solution;
s22, grinding the mixed solution to obtain a color developing agent solution;
s3, mixing the dye precursor capsule with the developer solution to obtain mixed color developing solution; and extruding and coating the mixed color developing solution to obtain the heat-sensitive microcapsule color developing material.
Preferably, step S1 specifically includes the following steps: step S11, heating to 70-90 ℃;
cooling to 15-30 ℃ in the step S12, wherein the mass ratio of the dye mixture to the xylylene diisocyanate is (3-20): 1, the rotation speed of the stirring is 300-1200rpm, and the time is 1-5 min.
Preferably, in step S13, the concentration of the aqueous polyvinyl alcohol solution is 2 to 10%, the alcoholysis degree is 88%, the average polymerization degree is 2245, and the mass ratio of the aqueous polyvinyl alcohol solution to the surfactant is (100 to 400): 1, the surfactant comprises OP-10, Tween-80, betaine or Tween-60, and the stirring speed is 200-1000rpm and the time is 30-60 min;
in step S14, the volume ratio of the oil phase to the water phase is 1 (1-4), the stirring speed is 6000-12000rpm, the stirring time is 5-20min, and the average particle size of the oil emulsion dispersion is 0.2-0.8 μm.
Preferably, the mass ratio of the oil emulsion dispersion, the deionized water and the tetraethylenepentamine in the step S15 is (0.3-1): 1: (0.01-0.1), the stirring speed is 200-1000rpm, the reaction temperature is 50-70 ℃, the reaction time is 2-7h, and the average particle size of the dye precursor microcapsule is 0.2-0.8 μm.
Wherein the xylylene diisocyanate is D-110N produced by Tokyo chemical company of Japan; OP-10 is a product produced by Fuyu fine chemical industry Co., Ltd.
The beneficial effects of the preferred technical scheme are as follows: under the reaction temperature, the stirring speed and the raw material consumption disclosed by the invention, the dye precursor microcapsule is easier to form and is not easy to agglomerate and break.
Preferably, in step S21, the polyvinyl alcohol aqueous solution has a concentration of 2 to 10%, an alcoholysis degree of 88%, and an average polymerization degree of 2245, and the developer solution is prepared from the following components in percentage by mass: 80-95% of polyvinyl alcohol aqueous solution, 3-10% of surfactant and 5-10% of color developing agent, wherein the stirring speed is 200-500rpm, and the time is 30-60 min; grinding to a particle size of 0.2-0.8 μm in step S22.
Wherein the surfactant can be Bs12 surfactant, and the Bs12 surfactant is dodecyl dimethyl betaine SX-BS12H of Shanghai Shengxuan Biotech Co., Ltd; the color developing agent adopts D-8 color developing agent, and the D-8 color developing agent is 2, 4-diphenylsulfuryl phenol produced by Shouguang Fukang pharmaceutical Co.
The beneficial effects of the preferred technical scheme are as follows: the color density and transparency of the final product can be improved by the above raw material amount, stirring speed and time.
Preferably, step S3 is specifically: respectively weighing 20-70% of dye precursor microcapsule, 10-50% of developer solution and 5-15% of polyvinyl alcohol aqueous solution by mass percent; stirring the polyvinyl alcohol aqueous solution with the concentration of 2-10%, the alcoholysis degree of 88% and the average polymerization degree of 2245 at the rotation speed of 200-1000rpm for 60-120min to obtain a mixed color developing solution, and extruding and coating to obtain the thermosensitive microcapsule color developing material
The beneficial effects of the preferred technical scheme are as follows: under the raw material dosage and reaction conditions disclosed by the invention, the prepared thermosensitive microcapsule chromogenic material has higher color density and higher transparency.
Preferably, the extrusion coating is performed by using a slide head.
Wherein, the coating can be more uniform by adopting the slide head, the operation is easier than that of using color developing agent microcapsules by using color developing agent dispersion liquid, and the color development efficiency is higher.
According to the technical scheme, compared with the prior art, the invention discloses a thermosensitive microcapsule material and a preparation method thereof, and the thermosensitive microcapsule material has the following beneficial effects:
(1) the specific solvent is matched with the fuel on the premise, and is matched with the color developing agent, so that the color density of color development can be improved, the printed black effect is excellent, and the black ink can be used as a medical recording material;
(2) the preparation method disclosed by the invention is simple to operate and is beneficial to industrial popularization.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention discloses a heat-sensitive microcapsule chromogenic material, which specifically comprises the following components in percentage by weight: 20-70 parts of dye precursor microcapsules, 10-60 parts of color developing agent, 5-15 parts of surfactant and 0.1-5 parts of polyvinyl alcohol; the dye precursor microcapsule comprises a capsule wall and a capsule core wrapped by the capsule wall, wherein the capsule wall is polyurea or polyurethane, and the capsule core comprises a dye precursor and a solvent; dye precursors include S205, ODB-2, GN-2, and RED-3; the solvent comprises cyclohexanone and ethyl acetate.
Wherein, the capsule core comprises the following components in percentage by weight: 10-40% of dye precursor and 60-90% of solvent.
The dye precursor comprises the following components in parts by weight: 40-70 parts of S205, 10-20 parts of ODB-2, 5-20 parts of RED-3 and 5-10 parts of GN-2.
The solvent comprises the following components in percentage by weight: 80-99% of ethyl acetate and 1% -20% of cyclohexanone.
The invention also provides a preparation method of the photosensitive microcapsule chromogenic material, which comprises the following steps:
s1 preparation of dye precursor microcapsules
S11, weighing a dye precursor, cyclohexanone and ethyl acetate according to the thermosensitive microcapsule chromogenic material, mixing and stirring, and heating to 70-90 ℃ for dissolution to obtain a dye mixture;
s12, cooling the dye mixture to 15-30 ℃, adding xylylene diisocyanate, and stirring to obtain an oil phase mixture; the mass ratio of the dye mixture to the xylylene diisocyanate is (3-20): 1, stirring at the rotating speed of 300-1200rpm for 1-5 min;
s13, adding a surfactant into the polyvinyl alcohol aqueous solution, and stirring to obtain an aqueous phase mixture; wherein the concentration of the polyvinyl alcohol aqueous solution is 2-10%, the alcoholysis degree is 88%, the average polymerization degree is 2245, and the mass ratio of the polyvinyl alcohol aqueous solution to the surfactant is (100-400): 1, the surfactant comprises OP-10, Tween-80, betaine or Tween-60, the stirring speed is 200-1000rpm, and the stirring time is 30-60 min;
s14, slowly adding the oil phase mixture into the water phase mixture, and stirring to obtain an oil emulsion dispersion; the volume ratio of the oil phase to the water phase is 1 (1-4), the stirring speed is 6000-12000rpm, the time is 5-20min, and the average particle size of the oil emulsion dispersion is 0.2-0.8 μm;
s15, adding deionized water and tetraethylenepentamine into the oil emulsion dispersion liquid, and then reacting under the stirring condition to obtain a dye precursor microcapsule; the mass ratio of the oil emulsion dispersion liquid to the deionized water to the tetraethylenepentamine is (0.3-1) and is (1): (0.01-0.1), the stirring speed is 200-1000rpm, the reaction temperature is 50-70 ℃, the reaction time is 2-7h, and the average particle size of the dye precursor microcapsule is 0.2-0.8 μm.
S2 preparation of developer solution
S21, adding a surfactant and a color developing agent into the polyvinyl alcohol aqueous solution, and uniformly stirring to obtain a mixed solution; the concentration of the polyvinyl alcohol aqueous solution is 2-10%, the alcoholysis degree is 88%, the average polymerization degree is 2245, and the color developing agent solution is prepared from the following components in percentage by mass: 80-95% of polyvinyl alcohol aqueous solution, 3-10% of surfactant and 5-10% of color developing agent, wherein the stirring speed is 200-500rpm, and the stirring time is 30-60 min;
s22, enabling the mixed solution to have a particle size of 0.2-0.8 mu m to obtain a color developing agent solution;
s3, respectively weighing 20-70% by mass of dye precursor microcapsules, 10-50% by mass of developer solution and 5-15% by mass of polyvinyl alcohol aqueous solution; stirring the polyvinyl alcohol aqueous solution with the concentration of 2-10%, the alcoholysis degree of 88% and the average polymerization degree of 2245 at the rotating speed of 200-1000rpm for 60-120min to obtain a mixed color developing solution, and carrying out extrusion coating to obtain the heat-sensitive microcapsule color developing material.
Example 1
The preparation method of the dye precursor microcapsule A specifically comprises the following steps:
15g of S205, 5g of ODB-2, 10g of RED-3, 5g of GN-2, 2g of ethyl acetoacetate and 160g of ethyl acetate were added to a 300ml beaker, stirred, heated to dissolve, and when cooled to room temperature, 80g of D110-N was added and stirred to obtain an oil phase mixture.
In a 1000ml vessel, 400g of an aqueous polyvinyl alcohol solution having a concentration of 5%, a degree of alcoholysis of 88% and an average degree of polymerization of 2245 was charged, and 40g of OP10 was added and stirred to obtain an aqueous phase.
Slowly adding the oil phase mixture into the water phase solution, and dispersing at 6000rpm for 15min with high speed shearing stirring to obtain oil emulsion dispersion with average particle diameter of 0.8 μm. 400g of a polyvinyl alcohol aqueous solution having a concentration of 3%, an alcoholysis degree of 88% and an average polymerization degree of 2245 and 6g of tetraethylenepentamine were added to the oil emulsion dispersion, and then reacted at 50 ℃ for 4 hours with a stirring speed of 500rpm to obtain a dye precursor microcapsule A having an average particle size of 0.8. mu.m.
Example 2
The preparation method of the dye precursor microcapsule B specifically comprises the following steps:
16g of S205, 4g of ODB-2, 10g of RED-3, 5g of GN-2, 4g of ethyl acetoacetate and 130g of ethyl acetate were added to a 300ml beaker, stirred, heated to dissolve, and when cooled to room temperature, 80g of D110-N was added and stirred to obtain an oil phase mixture.
In a 1000ml vessel, 400g of an aqueous polyvinyl alcohol solution having a concentration of 5%, a degree of alcoholysis of 88% and an average degree of polymerization of 2245 was charged, and 40g of OP10 was added and stirred to obtain an aqueous phase.
Slowly adding the oil phase mixture into the water phase solution, and dispersing at 6000rpm for 15min with high speed shearing stirring to obtain oil emulsion dispersion with average particle diameter of 0.8 μm. 400g of a 3% polyvinyl alcohol aqueous solution having an alcoholysis degree of 88% and an average polymerization degree of 2245 and 6g of tetraethylenepentamine were added to the oil emulsion dispersion, and then reacted at 50 ℃ for 4 hours with a stirring speed of 500rpm to obtain a dye precursor microcapsule B having an average particle size of 0.8. mu.m.
Example 3
The preparation method of the dye precursor microcapsule C specifically comprises the following steps:
20g of S205, 5g of ODB-2, 7g of RED-3, 3g of GN-2, 4g of ethyl acetoacetate and 130g of ethyl acetate were added to a 300ml beaker, stirred, heated to dissolve, and when cooled to room temperature, 80g of D110-N was added and stirred to obtain an oil phase mixture.
In a 1000ml vessel, 400g of an aqueous polyvinyl alcohol solution having a concentration of 5%, a degree of alcoholysis of 88% and an average degree of polymerization of 2245 was charged, and 40g of OP10 was added and stirred to obtain an aqueous phase.
Slowly adding the oil phase mixture into the water phase solution, and dispersing at 6000rpm for 15min with high speed shearing stirring to obtain oil emulsion dispersion with average particle diameter of 0.8 μm. 400g of a 3% polyvinyl alcohol aqueous solution having an alcoholysis degree of 88% and an average polymerization degree of 2245 and 6g of tetraethylenepentamine were added to the oil emulsion dispersion, and then reacted at 50 ℃ for 4 hours with a stirring speed of 500rpm to obtain a dye precursor microcapsule B having an average particle size of 0.8. mu.m.
Example 4
The preparation method of the dye precursor microcapsule D specifically comprises the following steps:
17g of S205, 3g of ODB-2, 5g of RED-3, 3g of GN-2, 2g of ethyl acetoacetate and 160g of ethyl acetate were added to a 300ml beaker, stirred, heated to dissolve, and when cooled to room temperature, 80g of D110-N was added and stirred to obtain an oil phase mixture.
In a 1000ml vessel, 400g of an aqueous polyvinyl alcohol solution having a concentration of 5%, a degree of alcoholysis of 88% and an average degree of polymerization of 2245 was charged, and 40g of OP10 was added and stirred to obtain an aqueous phase.
The oil phase mixture obtained above was slowly added to the aqueous phase solution, and dispersed for 15min at 12000rpm with high-speed shear stirring to obtain an oil emulsion dispersion having an average particle size of 0.25 μm. 400g of a 3% polyvinyl alcohol aqueous solution having an alcoholysis degree of 88% and an average polymerization degree of 2245 and 7g of tetraethylenepentamine were added to the oil emulsion dispersion, and then reacted at 50 ℃ for 4 hours with a stirring speed of 500rpm to obtain a dye precursor microcapsule C having an average particle size of 0.25. mu.m.
Example 5
The preparation method of the dye precursor microcapsule E specifically comprises the following steps:
16g of S205, 4g of ODB-2, 8g of RED-3, 1g of GN-2, 2g of ethyl acetoacetate and 160g of ethyl acetate were added to a 300ml beaker, stirred, heated to dissolve, and when cooled to room temperature, 80g of D110-N was added and stirred to obtain an oil phase mixture.
In a 1000ml vessel, 400g of an aqueous polyvinyl alcohol solution having a concentration of 5%, a degree of alcoholysis of 88% and an average degree of polymerization of 2245 was added, and 20g of OP10 was added and stirred to obtain an aqueous phase.
Slowly adding the obtained oil phase mixture into the water phase solution, and dispersing at 10000rpm for 15min by high speed shearing stirring to obtain oil emulsion dispersion with average particle diameter of 0.35 μm. 400g of a 3% polyvinyl alcohol aqueous solution having an alcoholysis degree of 88% and an average polymerization degree of 2245 and 7g of tetraethylenepentamine were added to the oil emulsion dispersion, and then reacted at 50 ℃ for 4 hours with a stirring speed of 500rpm to obtain a dye precursor microcapsule D having an average particle size of 0.35. mu.m.
Example 6
The preparation method of the developer dispersion liquid E specifically comprises the following steps:
500g of a polyvinyl alcohol aqueous solution having a concentration of 2%, a degree of alcoholysis of 88% and an average degree of polymerization of 2245 was put into a 1000ml beaker, 30ml of BS12 surfactant was added, 25g of D-8 was added, 500rpm was stirred uniformly, and then it was ground to 0.5. mu.m, to obtain a developer dispersion E having an average particle diameter of 0.5. mu.m.
Example 7
The preparation method of the developer dispersion liquid F specifically comprises the following steps:
500g of a polyvinyl alcohol aqueous solution having a concentration of 2%, a degree of alcoholysis of 88% and an average degree of polymerization of 3300 was put into a 1000ml beaker, 30ml of BS12 surfactant was added, 25g of D-8 was added, 500rpm was uniformly stirred, and then it was ground to 0.5. mu.m, to obtain a developer dispersion F having an average particle diameter of 0.5. mu.m.
Example 8
The preparation method of the developer dispersion liquid G specifically comprises the following steps:
500G of a polyvinyl alcohol aqueous solution having a concentration of 2%, a degree of alcoholysis of 88% and an average degree of polymerization of 3400 was put into a 1000ml beaker, 30ml of BS12 surfactant was added, 25G of D-8 was added, 500rpm was uniformly stirred, and then it was ground to 0.3 μm to obtain a developer dispersion G having an average particle diameter of 0.3 μm.
Example 9
The preparation method of the developer dispersion liquid H specifically comprises the following steps:
500g of a polyvinyl alcohol aqueous solution having a concentration of 2%, a degree of alcoholysis of 88% and an average degree of polymerization of 3500 was put into a 1000ml beaker, 30ml of BS12 surfactant was added, 25g of D-8 was added, 500rpm was uniformly stirred, and then it was ground to 0.8. mu.m, to obtain a developer dispersion H having an average particle diameter of 0.8. mu.m.
Example 10
A preparation method of a heat-sensitive microcapsule chromogenic material specifically comprises the following steps:
(1) preparation of Mixed color developing solution
The dye precursor microcapsules prepared above and the developer dispersion were uniformly mixed in a stirred vessel according to the amounts given in table 1 below, and a polyvinyl alcohol aqueous solution having a concentration of 2%, an alcoholysis degree of 88%, and an average polymerization degree of 3500 was added to obtain a color-developing layer coating solution
TABLE 1
(2) Coating of
And (3) coating the mixed color developing solution in an extrusion coating mode, coating according to the coating weight of 140 g/square meter, and fully drying to obtain the sample film coated with the heat-sensitive microcapsule color developing material.
The color density of the sample film was measured, and the results are shown in table 2 below. Wherein, the instrument for testing color density: X-RITE341C (manufactured by AICOLOUR COLOUR TECHNOLOGY CO., LTD.), temperature developing instrument: the flat press (Jiangtuan printing equipment, Inc. in Guangzhou city) is prepared by pressing and ironing 3S at a corresponding temperature when coating is carried out, and then carrying out color density test. Comparative example was taken with Fuji medical X-ray film.
The values of a and b developed at 150 ℃ were measured, and the results are shown in Table 3.
Wherein, the value of a and b is measured by an X-RITECI 7600; temperature color development instrument: a flat press (Jiangchuan printing equipment, Inc., Guangzhou city); detection standard a: 0 to-3; b: < -4 >; the method comprises the following steps: and (3) coating the mixed color developing solution in an extrusion coating mode, coating according to the coating weight of 140 g/square meter, and performing testing after pressing for 3 seconds at corresponding temperature.
TABLE 2
| Sample number | 90℃ | 100℃ | 110℃ | 120℃ | 130℃ | 140℃ | 150℃ |
| 1 | 0.18 | 0.23 | 0.38 | 1.25 | 1.79 | 2.56 | 2.89 |
| 2 | 0.20 | 0.24 | 0.42 | 1.33 | 2.28 | 3.01 | 3.30 |
| 3 | 0.21 | 0.24 | 0.43 | 1.34 | 2.26 | 3.02 | 3.31 |
| 4 | 0.17 | 0.22 | 0.35 | 1.01 | 1.56 | 2.30 | 2.65 |
| 5 | 0.16 | 0.20 | 0.31 | 0.95 | 1.55 | 2.01 | 2.59 |
| Comparative example | 0.19 | 0.22 | 0.36 | 1.26 | 1.83 | 2.62 | 2.92 |
TABLE 3
| Sample number | a | b |
| 1 | -3.8 | -6.0 |
| 2 | -3.2 | -5.5 |
| 3 | -0.7 | -4.3 |
| 4 | 2.2 | -1.0 |
| 5 | -4.0 | 2.1 |
| Comparative example | -0.8 | -4.5 |
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The heat-sensitive microcapsule chromogenic material is characterized by comprising the following components in parts by weight: 20-70 parts of dye precursor microcapsules, 10-60 parts of color developing agent, 5-15 parts of surfactant and 0.1-5 parts of polyvinyl alcohol; the dye precursor microcapsule comprises a capsule wall and a capsule core wrapped by the capsule wall, wherein the capsule wall is polyurea or polyurethane, and the capsule core comprises a dye precursor and a solvent; the dye precursors include S205, ODB-2, GN-2 and RED-3; the solvent comprises cyclohexanone and ethyl acetate.
2. The heat-sensitive microcapsule chromogenic material according to claim 1, wherein said core comprises the following components in percentage by weight: 10-40% of dye precursor and 60-90% of solvent.
3. The heat-sensitive microcapsule coloring material according to claim 1 or 2, wherein the dye precursor comprises the following components in parts by weight: 40-70 parts of S205, 10-20 parts of ODB-2, 5-20 parts of RED-3 and 5-10 parts of GN-2.
4. The heat-sensitive microcapsule coloring material of claim 1, wherein the solvent comprises the following components in percentage by weight: 80-99% of ethyl acetate and 1% -20% of cyclohexanone.
5. A preparation method of a photosensitive microcapsule chromogenic material is characterized by comprising the following steps:
s1 preparation of dye precursor microcapsules
S11 weighing a dye precursor, cyclohexanone and ethyl acetate according to the heat-sensitive microcapsule chromogenic material of any one of claims 1 to 4, mixing and stirring, and heating for dissolving to obtain a dye mixture;
s12, cooling the dye mixture, adding xylylene diisocyanate, and stirring to obtain an oil phase mixture;
s13, adding a surfactant into the polyvinyl alcohol aqueous solution, and stirring to obtain an aqueous phase mixture;
s14, slowly adding the oil phase mixture into the water phase mixture, and stirring to obtain an oil emulsion dispersion;
s15, adding deionized water and tetraethylenepentamine into the oil emulsion dispersion liquid, and then reacting under the stirring condition to obtain a dye precursor microcapsule;
s2 preparation of developer solution
S21, adding a surfactant and a color developing agent into the polyvinyl alcohol aqueous solution, and uniformly stirring to obtain a mixed solution;
s22, grinding the mixed solution to obtain a color developing agent solution;
s3, mixing the dye precursor capsule with the developer solution to obtain mixed color developing solution; and extruding and coating the mixed color developing solution to obtain the heat-sensitive microcapsule color developing material.
6. The method for preparing a heat-sensitive microcapsule chromogenic material according to claim 5, wherein the step S1 specifically comprises the following steps: step S11, heating to 70-90 ℃;
cooling to 15-30 ℃ in the step S12, wherein the mass ratio of the dye mixture to the xylylene diisocyanate is (3-20): 1, the rotating speed of the stirring is 300-1200rpm, and the time is 1-5 min.
7. The method for preparing a heat-sensitive microcapsule coloring material according to claim 6, wherein in step S13, the concentration of the aqueous solution of polyvinyl alcohol is 2-10%, the alcoholysis degree is 88%, the average polymerization degree is 2245, and the mass ratio of the aqueous solution of polyvinyl alcohol to the surfactant is (100-400): 1, the surfactant comprises OP-10, Tween-80, betaine or Tween-60, and the stirring speed is 200-1000rpm and the time is 30-60 min;
in step S14, the volume ratio of the oil phase to the water phase is 1 (1-4), the stirring speed is 6000-12000rpm, the time is 5-20min, and the average particle size of the oil emulsion dispersion is 0.2-0.8 μm.
8. The preparation method of the heat-sensitive microcapsule chromogenic material as claimed in claim 6, wherein the mass ratio of the oil emulsion dispersion, the deionized water and the tetraethylenepentamine in step S15 is (0.3-1): 1: (0.01-0.1), the stirring speed is 200-1000rpm, the reaction temperature is 50-70 ℃, the reaction time is 2-7h, and the average particle size of the dye precursor microcapsule is 0.2-0.8 μm.
9. The method for preparing a heat-sensitive microcapsule color developing material according to claim 5, wherein in step S21, the concentration of the polyvinyl alcohol aqueous solution is 2-10%, the alcoholysis degree is 88%, and the average polymerization degree is 2245, and the color developing agent solution is prepared from the following components in percentage by mass: 80-95% of polyvinyl alcohol aqueous solution, 3-10% of surfactant and 5-10% of color developing agent, wherein the stirring speed is 200-500rpm, and the stirring time is 30-60 min; in step S22, the particles are ground to a particle size of 0.2-0.8 μm.
10. The method for preparing a heat-sensitive microcapsule chromogenic material according to claim 5, wherein step S3 specifically comprises: respectively weighing 20-70% by mass of dye precursor microcapsules, 10-50% by mass of color developing agent solution and 5-15% by mass of polyvinyl alcohol aqueous solution; and stirring the polyvinyl alcohol aqueous solution with the concentration of 2-10%, the alcoholysis degree of 88% and the average polymerization degree of 2245 at the rotating speed of 200-1000rpm for 60-120min to obtain a mixed color developing solution, and extruding and coating to obtain the heat-sensitive microcapsule color developing material.
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Application publication date: 20200804 |