CN114058204B - Fluorine-containing thermosensitive dye microcapsule, preparation method thereof and film - Google Patents

Fluorine-containing thermosensitive dye microcapsule, preparation method thereof and film Download PDF

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CN114058204B
CN114058204B CN202210041835.6A CN202210041835A CN114058204B CN 114058204 B CN114058204 B CN 114058204B CN 202210041835 A CN202210041835 A CN 202210041835A CN 114058204 B CN114058204 B CN 114058204B
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emulsion
film
fluorine
microcapsule
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CN114058204A (en
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宋拥军
伍锡焱
赵政
宋恺明
陆晓东
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Huqiu Image New Material Technology Suzhou Co ltd
Huqiu Image Suzhou Co ltd
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Huqiu Image New Material Technology Suzhou Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/41—Organic pigments; Organic dyes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • 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
    • 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
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/423—Intermediate, backcoat, or covering layers characterised by non-macromolecular compounds, e.g. waxes
    • 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
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/426—Intermediate, backcoat, or covering layers characterised by inorganic compounds, e.g. metals, metal salts, metal complexes
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • 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
    • 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
    • B41M2205/38—Intermediate layers; Layers between substrate and imaging layer
    • 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
    • B41M2205/40—Cover layers; Layers separated from substrate by imaging layer; Protective layers; Layers applied before imaging
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2413/00—Characterised by the use of rubbers containing carboxyl groups
    • C08J2413/02—Latex
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate

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  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)

Abstract

The invention provides a fluorine-containing thermosensitive dye microcapsule, a preparation method thereof and a film, wherein the microcapsule comprises a capsule wall and a capsule core emulsion; the capsule core emulsion comprises phthalide heat-sensitive dye, higher fatty alcohol and emulsifier in a molar ratio of (2-2.5) - (2.5-3.0) - (0.25-0.3). The fluorine-containing thermosensitive dye microcapsule provided by the invention is applied to a film, and the film has good antistatic property, waterproof effect, ultraviolet resistance, weather resistance, high surface resistance and scratch resistance. Meanwhile, in the aspect of development, the exposure area is found to have higher image density and low RMS granularity, and the defects of poor image quality, high film storage difficulty, environmental pollution of the film and the like of the traditional silver halide photosensitive imaging film can be overcome. The capsule has important application in medical imaging, and is suitable for recording and storing medical diagnosis digital images.

Description

Fluorine-containing thermosensitive dye microcapsule, preparation method thereof and film
Technical Field
The invention belongs to the technical field of medical treatment, and particularly relates to a fluorine-containing thermosensitive dye microcapsule, a preparation method thereof and a film.
Background
The thermosensitive recording material is generally composed of a medium such as a thermosensitive dye and a developer, and when the temperature reaches a certain range, a color development reaction occurs between the two. The pattern is displayed by controlling the color development area, but the early thermal film has considerable defects, such as low resolution of the printed pattern, unobvious color contrast, difficult film preservation and the like. With the development of technology, the discovery of microencapsulation technology and thermal chemistry has expanded the potential applications of heat sensitive materials.
The microcapsule technology (Microencapsulation) is a technology of wrapping trace substances in a polymer film, and is a micro-packaging technology for storing solid, liquid and gas. The microcapsule consists of two parts of a core material and a wall material, wherein the core material can be an oil-soluble compound, a water-soluble compound or a mixture, and the state of the core material can be powder, solid, liquid or gas; the wall material is generally natural polymer, semi-synthetic polymer and synthetic polymer material. It can be applied to thermosensitive printing surface to encapsulate developer, dye, pigment, solvent, inorganic colloid, etc. At present, wall materials adopted by the thermosensitive dye microcapsule mainly comprise urea resin, melamine-formaldehyde resin and the like. The developing effect of the film prepared by the microcapsule prepared by the wall material needs to be improved.
Disclosure of Invention
In view of the above, the present invention aims to provide a fluorine-containing heat-sensitive dye microcapsule, a preparation method and an application thereof, wherein the RMS granularity of the film is small.
The invention provides a fluorine-containing thermosensitive dye microcapsule, which comprises a capsule wall and a capsule core emulsion;
the capsule wall is a polymer with a structure shown in a formula I:
Figure 204170DEST_PATH_IMAGE001
formula I
The R is selected from-CH2(CH2NHCH2)mCH2-, m is 1 to 5;
the Rf is selected from C1-C5 fluoroalkyl or-PhC (CH)3)2Ph-；
The R is1Is selected from-Ph (CH)2)nPh-and n are 1-4;
the value of x is 1-3; the value of y is 1-3;
the capsule core emulsion comprises the following components in a molar ratio of (2-2.5): (2.5-3.0): (0.25-0.3) phthalide heat-sensitive dye, higher fatty alcohol and emulsifier.
In the present invention, R may be selected from-CH2CH2NHCH2CH2NHCH2CH2NHCH2CH2-、-CH2CH2NHCH2CH2-、-CH2CH2NHCH2CH2NHCH2CH2-or-CH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NHCH2CH2-；
Said Rf is selected from-PhC (CH)3)2Ph-、-CF2CF2CF2CF2-、-CH2CF2CF2CH2-、-CF2CF2CF2-or-CF2-；
The R is1Is selected from-PhCH2Ph-or-PhCH2CH2Ph-。
In the invention, the phthalide thermosensitive dye is selected from model ODB-1 and/or ODB-2;
the higher fatty alcohol is selected from one or more of dodecanol, tetradecanol and hexadecanol;
the emulsifier is selected from styrene-maleic anhydride copolymer.
The invention provides a preparation method of the fluorine-containing thermosensitive dye microcapsule in the technical scheme, which comprises the following steps:
mixing fluorinated diisocyanate, non-fluorinated diisocyanate, phthalide thermosensitive dye, higher fatty alcohol and emulsifier, adding the mixture into water and protective colloid, and stirring to obtain oil-water emulsion; then dropwise adding a polyamine aqueous solution under the stirring condition, and carrying out interface reaction to obtain the fluorine-containing thermosensitive dye microcapsule;
the polyamine is selected from pentaethylenehexamine, tetraethylenepentamine, triethylenetetramine or diethylenetriamine.
In the present invention, the protective layer is made of a protective layer emulsion; the protective layer emulsion comprises inorganic filler, an ultraviolet absorbent, a lubricant and an adhesive; the mass ratio of the inorganic filler to the ultraviolet absorbent to the lubricant to the adhesive is (10-5): (0.05-0.1): (0.3-0.05): 30, of a nitrogen-containing gas;
the back layer is prepared by coating back layer emulsion; the back layer emulsion comprises the following components in percentage by mass (1-100): (1-50): (0.1-0.05) a mixture of an inorganic filler, a binder and an ultraviolet absorber.
In the invention, the thickness of the thermosensitive imaging layer is 30-45 μm, and the thickness of the back layer is 10-15 μm; the thickness of the protective layer is 15 to 25 μm.
The invention provides a fluorine-containing thermosensitive dye microcapsule, which comprises a capsule wall and a capsule core emulsion; the capsule wall is a polymer with a structure shown in a formula I; the capsule core emulsion comprises the following components in a molar ratio of (2-2.5): (2.5-3.0): (0.25-0.3) phthalide heat-sensitive dye, higher fatty alcohol and emulsifier. The fluorine-containing thermosensitive dye microcapsule provided by the invention is applied to a film, and the film has good antistatic property, waterproof effect, ultraviolet resistance, weather resistance, high surface resistance and scratch resistance. Meanwhile, in the aspect of development, the exposure area is found to have higher image density and low RMS granularity, and the defects of poor image quality, high film storage difficulty, environmental pollution of the film and the like of the traditional silver halide photosensitive imaging film can be overcome. The capsule has important application in medical imaging, and is suitable for recording and storing medical diagnosis digital images.
Drawings
Fig. 1 is a schematic structural diagram of a capsule provided by the present invention.
Detailed Description
The invention provides a fluorine-containing thermosensitive dye microcapsule, which comprises a capsule wall and a capsule core emulsion;
the capsule wall is a polymer with a structure shown in a formula I:
Figure 515065DEST_PATH_IMAGE001
formula I
The R is selected from-CH2(CH2NHCH2)mCH2-, m is 1 to 5;
the Rf is selected from C1-C5 fluoroalkyl or-PhC (CH)3)2Ph-；
The R is1Is selected from-Ph (CH)2)nPh-and n are 1-4;
the value of x is 1-3; the value of y is 1-3;
the capsule core emulsion comprises the following components in a molar ratio of (2-2.5): (2.5-3.0): (0.25-0.3) phthalide heat-sensitive dye, higher fatty alcohol and emulsifier.
In the present invention, R may be selected from-CH2CH2NHCH2CH2NHCH2CH2NHCH2CH2-、-CH2CH2NHCH2CH2-、-CH2CH2NHCH2CH2NHCH2CH2-or-CH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NHCH2CH2-；
Said Rf is selected from-PhC (CH)3)2Ph-、-CF2CF2CF2CF2-、-CH2CF2CF2CH2-、-CF2CF2CF2-or-CF2-；
The R is1Is selected from-PhCH2Ph-or-PhCH2CH2Ph-。
The capsule core emulsion comprises the following components in a molar ratio of (2-2.5): (2.5-3.0): (0.25-0.3) phthalide heat-sensitive dye, higher fatty alcohol and emulsifier. In the invention, the phthalide thermosensitive dye is selected from 2-phenylamino-3-methyl-6-diethylfluorane and/or 2-phenylamino-3-methyl-6-dibutylaminofluorane; the higher fatty alcohol is selected from one or more of dodecanol, tetradecanol and hexadecanol; the emulsifier is selected from styrene-maleic anhydride copolymer.
In the invention, the preparation method of the fluorine-containing thermosensitive dye microcapsule comprises the following steps:
mixing fluorinated diisocyanate, non-fluorinated diisocyanate, phthalide thermosensitive dye, higher fatty alcohol and emulsifier, adding the mixture into water and protective colloid, and stirring to obtain oil-water emulsion; then dropwise adding a polyamine aqueous solution under the stirring condition, and carrying out interface reaction to obtain the fluorine-containing thermosensitive dye microcapsule;
the polyamine is selected from pentaethylenehexamine, tetraethylenepentamine, triethylenetetramine or diethylenetriamine.
In the present invention, the protective colloid is preferably polyvinyl alcohol 224 or polyvinyl alcohol 217; the protective colloid can prevent the emulsified microemulsion particles from adhering and agglomerating.
In the present invention, the fluorine-containing isocyanate and the non-fluorinated diisocyanate and the polyamine are prepared by the following interfacial reaction route:
Figure 939968DEST_PATH_IMAGE002
。
in the invention, the molar ratio of the fluorine-containing diisocyanate to the non-fluorinated diisocyanate to the polyamine monomer is 1-3: 1.6. In the examples, the ratio of fluorinated diisocyanate to non-fluorinated diisocyanate was 1: 3. The use amount of the non-fluorinated diisocyanate is large, so that the problems that the fluorine-containing polyurea is easy to crystallize to cause high gray level and the like are solved while the performance is ensured, and the production cost is reduced.
Mixing the fluorine-containing diisocyanate and the non-fluorinated diisocyanate, adding a capsule core material, and forming microcapsule emulsion under the shearing action of a high-speed shearing machine, wherein the rotating speed of the high-speed shearing machine is 10000 r/min-12000 r/min; the shearing time is 10 min; after microcapsule emulsion is formed, slowly dripping aqueous solution of polyamine to generate functional group reaction; the stirring speed of mechanical stirring during interfacial polymerization is 600 r/min-700 r/min; the temperature of the interfacial polymerization was: 60-70 ℃; the reaction time of the interfacial polymerization is 3.5-4.5 h, preferably 4 h.
In the present invention, the protective colloid is selected from PVA solutions; the PVA solution is selected from PVA224 or PVA 217; the PVA solution accounts for 3.5-4.5% by mass.
The average particle size of the fluorine-containing thermosensitive dye microcapsule is less than 5 microns, and preferably less than 2 microns. The smaller particle size is beneficial to improving the influence density and reducing the gray level, but the solution with too small particle size is agglomerated, so that the prepared film has 'dead spots'.
In the invention, the aqueous solution of the polyamine is preferably dropwise added under the stirring condition of 550-650 rpm.
The invention adopts fluorine-containing isocyanate and non-fluorinated isocyanate to be combined for use, and the capsule core material is coated in the polyurea microcapsule by an interfacial polymerization technology; the film prepared by the fluorine-containing polyurea microcapsule material has good antistatic property, waterproof effect, ultraviolet resistance and weather resistance, and meanwhile, in the aspect of development, the invention discovers that an exposure area has higher image density and low RMS granularity, and can solve the defects of poor image quality, high film storage difficulty, non-environmental-friendly film and the like of the traditional silver halide photosensitive imaging film; in addition, the non-fluorinated isocyanate material is doped for use, so that the problems of easy crystallization, high gray level and the like of the fluorine-containing polyurea are solved, and the production cost is reduced.
The invention provides a film containing a heat-sensitive microcapsule chromogenic material, which comprises a heat-sensitive imaging layer, a protective layer, a substrate and a back layer which are sequentially arranged;
the thermosensitive imaging layer is prepared by coating a thermosensitive imaging layer coating liquid; the coating liquid of the thermal sensitive imaging layer comprises filler, a color developing agent, a polyvinyl alcohol aqueous solution, a dispersing agent and the fluorine-containing thermal sensitive dye microcapsule or the fluorine-containing thermal sensitive dye microcapsule prepared by the preparation method of the technical scheme.
The mass ratio of the fluorine-containing heat-sensitive dye microcapsule to the color developing agent to the filler to the polyvinyl alcohol aqueous solution to the dispersing agent is (l-2): (0.1-0.2): (0.5-1): (0.08-0.14): (0.1-0.2). In the present invention, the filler is selected from one or more of calcium carbonate, high-fineness polyethylene powder and urea-formaldehyde resin powder; preferably calcium carbonate; the calcium carbonate has low cost, good dispersibility in emulsion and difficult agglomeration.
The color developing agent is selected from one or more of bisphenol A, bisphenol S, p-hydroxybenzoic acid and 2, 4-dihydroxybenzoic acid; the dispersing agent is selected from the following components in a mass ratio of 80-90: sodium alginate and nano TiO of 12A mixture of (a); the polyvinyl alcohol in the polyvinyl alcohol aqueous solution is selected from PVA224 or PVA 217; the mass concentration of the polyvinyl alcohol aqueous solution is 3.5-4.5%; in the specific example, the PVA224 is used as an aqueous solution of polyvinyl alcohol, and the mass percentage is 4.5%. Sodium alginate and a small amount of nano TiO2The compound is beneficial to the dispersion of microcapsules, color developing agents and the like, and the formed emulsion has good stability.
In the present invention, the protective layer is made of a protective layer emulsion; the protective layer emulsion comprises inorganic filler, an ultraviolet absorbent, a lubricant and an adhesive; the mass ratio of the inorganic filler to the ultraviolet absorbent to the lubricant to the adhesive is (10-5): (0.05-0.1): (0.3-0.05): 30.
the inorganic filler is selected from one or more of calcium carbonate, silica and alumina. The lubricant is selected from one or more of higher fatty acid metal salt, polyolefin fine particle with low molecular weight, higher fatty acid amide and the like; the adhesive is selected from one or more of polyvinyl alcohol, polyvinyl acetate, polyvinyl acetal and a-cyanoacrylate. The ultraviolet absorbent is prepared from (1-1.5) the following components in percentage by mass: (0.4-0.6) a mixture of a phenyl compound, inorganic nano zinc oxide and UV-292; the phenyl compound is selected from one or more of 1, 4-dihydroxy benzophenone, phenyl o-hydroxybenzoate, 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane and 2-hydroxy-4-n-octoxy benzophenone. According to the invention, the phenyl compound, the inorganic nano zinc oxide and the UV-292 are compounded, so that on one hand, the addition of the organic antioxidant can be reduced, and the cost is saved; on the other hand, the synergistic effect between the antioxidant and the phenyl compound is fully exerted, the film is prevented from generating yellow change, and the storage time of the film is prolonged.
In the present invention, the substrate is selected from PET supports.
In the present invention, the backing layer is made by emulsion coating of a backing layer; the back layer emulsion comprises the following components in percentage by mass (1-100): (1-50): (0.1 to 0.05) a mixture of an inorganic filler, a binder and an ultraviolet absorber; the mass of the inorganic filler, the adhesive and the ultraviolet absorber is preferably (15-30): 50: (0.1 to 0.05); the inorganic filler is selected from one or more of calcium carbonate, silica and alumina; the binder is selected from one or more of PVA, carboxylic styrene-butadiene latex, acrylic resin and cellulose derivatives. The ultraviolet absorber in the back layer and the ultraviolet absorber in the protective layer are in the same range, and the specific types can be different.
In the invention, the thickness of the thermosensitive imaging layer is 30-45 μm, and the thickness of the back layer is 10-15 μm; the thickness of the protective layer is 15 to 25 μm. The coating weight of the thermosensitive imaging layer, the back layer and the protective layer is preferably 80-90 mL/m2、20~25 mL/m2And 15 to 25 mL/m2. In a specific embodiment, the coating amounts of the thermosensitive imaging layer, the back layer and the protective layer are respectively 80 mL/m2、20 mL/m2And 15 mL/m2。
In order to further illustrate the present invention, the following examples are provided to describe a fluorine-containing heat-sensitive dye microcapsule, a method for preparing the same, and a film in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) Preparing microcapsules: adding 2, 2-bis (4-isocyanatophenyl) hexafluoropropane (0.03 mol, 11.58 g) and xylene diisocyanate (0.01 mol, 2.5 g) into a 500ml flask provided with a mechanical stirrer, a reflux condenser, a temperature probe and a dropping funnel, stirring and mixing, adding a thermosensitive dye ODB-214 g, tetradecanol 14g and styrene maleic anhydride copolymer 2g, stirring and dissolving; after the dissolution, 200ml of deionized water and 40ml of an aqueous PVA224 solution (mass fraction: 4.5%) were added, and the mixture was vigorously stirred at 10000r/min for 10min using a high-speed shearing machine to obtain an o/w emulsion.
Then an aqueous solution (100ml) of tetraethylenepentamine (0.016mol, 5.94g) was slowly added to the o/w emulsion. The procedure was carried out at room temperature, with stirring at 600r/min by means of a stirrer. After the dropwise addition, the temperature is raised to 65 ℃ and the mixture is continuously stirred for 4 hours to obtain the fluorine-containing heat-sensitive microcapsule emulsion.
(2) Preparing an imaging layer emulsion: 100ml of PVA224 aqueous solution (4.5 mass percent) was added to a 250ml flask equipped with a mechanical stirrer, a reflux condenser, a temperature probe and a dropping funnel, 12g of 2, 4-dihydroxybenzoic acid was added, 10g of a dispersant (9.8 g of sodium alginate, 0.2g of nano-titanium dioxide) was added thereto, and stirring was carried out for 30 minutes to form an emulsion. In another 500ml flask equipped with a mechanical stirrer, reflux condenser, temperature probe and dropping funnel, 100g of the fluorine-containing microcapsule emulsion and 50g of calcium carbonate were added, stirred, and the emulsion was added dropwise with stirring for about 30min to disperse it uniformly for further use.
(3) Preparing a back coating and protective layer emulsion:
preparing protective layer emulsion: 100g of carboxylic styrene-butadiene latex is added into a 250ml flask with a mechanical stirrer, 30g of calcium carbonate and 0.1g of ultraviolet absorbent (0.04 g of phenyl ortho-hydroxybenzoate, 0.04g of inorganic nano zinc oxide and UV-2920.02 g) are added under stirring, and stirring is carried out for 30min to form uniformly dispersed emulsion for later use.
Preparation of back coating emulsion: adding 90g of polyvinyl alcohol adhesive into a 250ml flask with a mechanical stirrer, adding 30g of calcium carbonate powder, 0.9g of zinc stearate and 0.1g of ultraviolet absorbent under stirring, and stirring for 30min to form uniformly dispersed emulsion for later use.
(4) Film coating:
step four: the coating is carried out by a portable extrusion coating method. According to the coating weight of the thermosensitive imaging layer and the protective layer, respectively 80 ml/m2、15 ml/m2Coating on a PET support, coating the other side of the PET support with a backing layer of 20ml/m2And fully drying to obtain the sample film coated with the heat-sensitive microcapsule chromogenic material.
Example 2:
(1) preparing microcapsules: adding 2, 2-bis (4-isocyanatophenyl) hexafluoropropane (0.02 mol, 7.72 g) and xylene diisocyanate (0.02 mol, 5.0 g) into a 500ml flask provided with a mechanical stirrer, a reflux condenser, a temperature probe and a dropping funnel, stirring and mixing, adding a thermosensitive dye ODB-214 g, tetradecanol 14g and styrene maleic anhydride copolymer 2g, stirring and dissolving; after the mixture is cleared, 200ml of deionized water and 40ml of PVA224 aqueous solution (mass fraction: 4.5%) are added, and the mixture is stirred vigorously at a speed of 10000r/min for 10min by using a high-speed shearing machine to obtain an o/w emulsion.
Then an aqueous solution (100ml) of tetraethylenepentamine (0.016mol, 5.94g) was slowly added to the o/w emulsion. The procedure was carried out at room temperature, with stirring at 600r/min by means of a stirrer. After the dropwise addition, the temperature is raised to 65 ℃ and the mixture is continuously stirred for 4 hours to obtain the fluorine-containing heat-sensitive microcapsule emulsion.
(2) Preparing an imaging layer emulsion: 100ml of PVA224 aqueous solution (4.5 mass percent) was added to a 250ml flask equipped with a mechanical stirrer, a reflux condenser, a temperature probe and a dropping funnel, 12g of 2, 4-dihydroxybenzoic acid was added, 10g of a dispersant (9.8 g of sodium alginate, 0.2g of nano-titanium dioxide) was added thereto, and stirring was carried out for 30 minutes to form an emulsion. In another 500ml flask equipped with a mechanical stirrer, reflux condenser, temperature probe and dropping funnel, 100g of the fluorine-containing microcapsule emulsion and 50g of calcium carbonate were added, stirred, and the emulsion was added dropwise with stirring for about 30min to disperse it uniformly for further use.
(3) Preparing a back coating and protective layer emulsion:
preparing protective layer emulsion: 100g of carboxylic styrene-butadiene latex is added into a 250ml flask with a mechanical stirrer, 30g of calcium carbonate and 0.1g of ultraviolet absorbent (0.04 g of phenyl ortho-hydroxybenzoate, 0.04g of inorganic nano zinc oxide and UV-2920.02 g) are added under stirring, and stirring is carried out for 30min to form uniformly dispersed emulsion for later use.
Preparation of back coating emulsion: adding 90g of polyvinyl alcohol adhesive into a 250ml flask with a mechanical stirrer, adding 30g of calcium carbonate powder, 0.9g of zinc stearate and 0.1g of ultraviolet absorbent (0.04 g of phenyl ortho-hydroxybenzoate, 0.04g of inorganic nano zinc oxide and UV-2920.02 g) under stirring, and stirring for 30min to form uniformly dispersed emulsion for later use.
(4) Film coating:
step four: the coating is carried out by a portable extrusion coating method. According to the coating weight of the thermosensitive imaging layer and the protective layer, respectively 80 ml/m2、15 ml/m2Coating on a PET support, coating the other side of the PET support with a backing layer of 20ml/m2And fully drying to obtain the sample film coated with the heat-sensitive microcapsule chromogenic material.
Example 3:
(1) preparing microcapsules: adding 2, 2-bis (4-isocyanatophenyl) hexafluoropropane (0.01 mol, 3.86 g) and xylene diisocyanate (0.03 mol, 7.5 g) into a 500ml flask provided with a mechanical stirrer, a reflux condenser, a temperature probe and a dropping funnel, stirring and mixing, adding a thermosensitive dye ODB-214 g, tetradecanol 14g and styrene maleic anhydride copolymer 2g, stirring and dissolving; after the dissolution, 200ml of deionized water and 40ml of an aqueous PVA224 solution (mass fraction: 4.5%) were added, and the mixture was vigorously stirred at 10000r/min for 10min using a high-speed shearing machine to obtain an o/w emulsion.
Then an aqueous solution (100ml) of tetraethylenepentamine (0.016mol, 5.94g) was slowly added to the o/w emulsion. The procedure was carried out at room temperature, with stirring at 600r/min by means of a stirrer. After the dropwise addition, the temperature is raised to 65 ℃ and the mixture is continuously stirred for 4 hours to obtain the fluorine-containing heat-sensitive microcapsule emulsion.
(2) Preparing an imaging layer emulsion: 100ml of PVA224 aqueous solution (4.5 mass percent) was added to a 250ml flask equipped with a mechanical stirrer, a reflux condenser, a temperature probe and a dropping funnel, 12g of 2, 4-dihydroxybenzoic acid was added, 10g of a dispersant (9.8 g of sodium alginate, 0.2g of nano-titanium dioxide) was added thereto, and stirring was carried out for 30 minutes to form an emulsion. In another 500ml flask equipped with a mechanical stirrer, reflux condenser, temperature probe and dropping funnel, 100g of the fluorine-containing microcapsule emulsion and 50g of calcium carbonate were added, stirred, and the emulsion was added dropwise with stirring for about 30min to disperse it uniformly for further use.
(3) Preparing a back coating and protective layer emulsion:
preparing protective layer emulsion: 100g of carboxylic styrene-butadiene latex is added into a 250ml flask with a mechanical stirrer, 30g of calcium carbonate and 0.1g of ultraviolet absorbent (0.04 g of phenyl ortho-hydroxybenzoate, 0.04g of inorganic nano zinc oxide and UV-2920.02 g) are added under stirring, and stirring is carried out for 30min to form uniformly dispersed emulsion for later use.
Preparation of back coating emulsion: adding 90g of polyvinyl alcohol adhesive into a 250ml flask with a mechanical stirrer, adding 30g of calcium carbonate powder, 0.9g of zinc stearate and 0.1g of ultraviolet absorbent under stirring, and stirring for 30min to form uniformly dispersed emulsion for later use.
(4) Film coating:
step four: the coating is carried out by a portable extrusion coating method. According to the coating weight of the thermosensitive imaging layer and the protective layer, respectively 80 ml/m2、15 ml/m2Coating on a PET support, coating the other side of the PET support with a backing layer of 20ml/m2And fully drying to obtain the sample film coated with the heat-sensitive microcapsule chromogenic material.
Comparative example 1:
(1) preparing microcapsules: in a 500ml flask provided with a mechanical stirrer, a reflux condenser, a temperature probe and a dropping funnel, xylene alkyl diisocyanate (0.04 mol, 10 g) is stirred and mixed, thermal dye ODB-214 g, tetradecanol 14g and styrene maleic anhydride copolymer 2g are added, stirred and dissolved; after the dissolution, 200ml of deionized water and 40ml of an aqueous PVA224 solution (mass fraction: 4.5%) were added, and the mixture was vigorously stirred at 10000r/min for 10min using a high-speed shearing machine to obtain an o/w emulsion.
Then an aqueous solution (100ml) of tetraethylenepentamine (0.016mol, 5.94g) was slowly added to the o/w emulsion. The procedure was carried out at room temperature, with stirring at 600r/min by means of a stirrer. After the dropwise addition, the temperature is raised to 65 ℃ and the mixture is continuously stirred for 4 hours to obtain the fluorine-containing heat-sensitive microcapsule emulsion.
(2) Preparing an imaging layer emulsion: 100ml of PVA224 aqueous solution (4.5 mass percent) was added to a 250ml flask equipped with a mechanical stirrer, a reflux condenser, a temperature probe and a dropping funnel, 12g of 2, 4-dihydroxybenzoic acid was added, 10g of a dispersant (9.8 g of sodium alginate, 0.2g of nano-titanium dioxide) was added thereto, and stirring was carried out for 30 minutes to form an emulsion. In another 500ml flask equipped with a mechanical stirrer, reflux condenser, temperature probe and dropping funnel, 100g of the fluorine-containing microcapsule emulsion and 50g of calcium carbonate were added, stirred, and the emulsion was added dropwise with stirring for about 30min to disperse it uniformly for further use.
(3) Preparing a back coating and protective layer emulsion:
preparing protective layer emulsion: 100g of carboxylic styrene-butadiene latex is added into a 250ml flask with a mechanical stirrer, 30g of calcium carbonate and 0.1g of ultraviolet absorbent (0.04 g of phenyl ortho-hydroxybenzoate, 0.04g of inorganic nano zinc oxide and UV-2920.02 g) are added under stirring, and stirring is carried out for 30min to form uniformly dispersed emulsion for later use.
Preparation of back coating emulsion: adding 90g of polyvinyl alcohol adhesive into a 250ml flask with a mechanical stirrer, adding 30g of calcium carbonate powder, 0.9g of zinc stearate and 0.1g of ultraviolet absorbent under stirring, and stirring for 30min to form uniformly dispersed emulsion for later use.
(4) Film coating:
step four: the coating is carried out by a portable extrusion coating method. According to the coating weight of the thermosensitive imaging layer and the protective layer, respectively 80 ml/m2、15 ml/m2Coating on a PET support, coating the other side of the PET support with a backing layer of 20ml/m2And fully drying to obtain the sample film coated with the heat-sensitive microcapsule chromogenic material.
Example 4
(1) Preparing microcapsules: adding 2, 2-bis (4-isocyanatophenyl) hexafluoropropane (0.02 mol, 7.72 g) and xylene diisocyanate (0.02 mol, 5.0 g) into a 500ml flask provided with a mechanical stirrer, a reflux condenser, a temperature probe and a dropping funnel, stirring and mixing, adding a thermosensitive dye ODB-214 g, tetradecanol 14g and styrene maleic anhydride copolymer 2g, stirring and dissolving; after the dissolution, 200ml of deionized water and 40ml of an aqueous PVA224 solution (mass fraction: 4.5%) were added, and the mixture was vigorously stirred at 10000r/min for 10min using a high-speed shearing machine to obtain an o/w emulsion.
Then an aqueous solution (100ml) of tetraethylenepentamine (0.016mol, 5.94g) was slowly added to the o/w emulsion. The procedure was carried out at room temperature, with stirring at 600r/min by means of a stirrer. After the dropwise addition, the temperature is raised to 65 ℃ and the mixture is continuously stirred for 4 hours to obtain the fluorine-containing heat-sensitive microcapsule emulsion.
(2) Preparing an imaging layer emulsion: 100ml of PVA224 aqueous solution (4.5 mass percent) was added to a 250ml flask equipped with a mechanical stirrer, a reflux condenser, a temperature probe and a dropping funnel, 12g of 2, 4-dihydroxybenzoic acid was added, 5g of a dispersant (4.9 g of sodium alginate, 0.1g of nano-titanium dioxide) was added thereto, and stirring was carried out for 30 minutes to form an emulsion. In another 500ml flask equipped with a mechanical stirrer, reflux condenser, temperature probe and dropping funnel, 100g of the fluorine-containing microcapsule emulsion and 50g of calcium carbonate were added, stirred, and the emulsion was added dropwise with stirring for about 30min to disperse it uniformly for further use.
(3) Preparing a back coating and protective layer emulsion:
preparing protective layer emulsion: 100g of carboxylic styrene-butadiene latex is added into a 250ml flask with a mechanical stirrer, 30g of calcium carbonate and 0.1g of ultraviolet absorbent (0.04 g of phenyl ortho-hydroxybenzoate, 0.04g of inorganic nano zinc oxide and UV-2920.02 g) are added under stirring, and stirring is carried out for 30min to form uniformly dispersed emulsion for later use.
Preparation of back coating emulsion: adding 90g of polyvinyl alcohol adhesive into a 250ml flask with a mechanical stirrer, adding 30g of calcium carbonate powder, 0.9g of zinc stearate and 0.1g of ultraviolet absorbent under stirring, and stirring for 30min to form uniformly dispersed emulsion for later use.
(4) Film coating:
step four: the coating is carried out by a portable extrusion coating method. According to the coating weight of the thermosensitive imaging layer and the protective layer, respectively 80 ml/m2、15 ml/m2Coating on a PET support, coating the other side of the PET support with a backing layer of 20ml/m2And fully drying to obtain the sample film coated with the heat-sensitive microcapsule chromogenic material.
Comparative example 2
(1) Preparing microcapsules: adding 2, 2-bis (4-isocyanatophenyl) hexafluoropropane (0.02 mol, 7.72 g) and xylene diisocyanate (0.02 mol, 5.0 g) into a 500ml flask provided with a mechanical stirrer, a reflux condenser, a temperature probe and a dropping funnel, stirring and mixing, adding a thermosensitive dye ODB-214 g, tetradecanol 14g and styrene maleic anhydride copolymer 2g, stirring and dissolving; after the dissolution, 200ml of deionized water and 40ml of an aqueous PVA224 solution (mass fraction: 4.5%) were added, and the mixture was vigorously stirred at 10000r/min for 10min using a high-speed shearing machine to obtain an o/w emulsion.
Then an aqueous solution (100ml) of tetraethylenepentamine (0.016mol, 5.94g) was slowly added to the o/w emulsion. The procedure was carried out at room temperature, with stirring at 600r/min by means of a stirrer. After the dropwise addition, the temperature is raised to 65 ℃ and the mixture is continuously stirred for 4 hours to obtain the fluorine-containing heat-sensitive microcapsule emulsion.
(2) Preparing an imaging layer emulsion: 100ml of an aqueous PVA224 solution (4.5% by mass) was placed in a 250ml flask equipped with a mechanical stirrer, reflux condenser, temperature probe and dropping funnel, and 12g of 2, 4-dihydroxybenzoic acid was added thereto and stirred for 30 minutes to form an emulsion. In another 500ml flask equipped with a mechanical stirrer, reflux condenser, temperature probe and dropping funnel, 100g of the fluorine-containing microcapsule emulsion and 50g of calcium carbonate were added, stirred, and the emulsion was added dropwise with stirring for about 30min to disperse it uniformly for further use.
(3) Preparing a back coating and protective layer emulsion:
preparing protective layer emulsion: 100g of carboxylic styrene-butadiene latex is added into a 250ml flask with a mechanical stirrer, 30g of calcium carbonate and 0.1g of ultraviolet absorbent (0.04 g of phenyl ortho-hydroxybenzoate, 0.04g of inorganic nano zinc oxide and UV-2920.02 g) are added under stirring, and stirring is carried out for 30min to form uniformly dispersed emulsion for later use.
Preparation of back coating emulsion: adding 90g of polyvinyl alcohol adhesive into a 250ml flask with a mechanical stirrer, adding 30g of calcium carbonate powder, 0.9g of zinc stearate and 0.1g of ultraviolet absorbent under stirring, and stirring for 30min to form uniformly dispersed emulsion for later use.
(4) Film coating:
step four: the coating is carried out by a portable extrusion coating method. Thermal imagingThe coating weight of the layer and the protective layer is respectively 80 ml/m2、15 ml/m2Coating on a PET support, coating the other side of the PET support with a backing layer of 20ml/m2And fully drying to obtain the sample film coated with the heat-sensitive microcapsule chromogenic material.
Example 5
(1) Preparing microcapsules: adding 2, 2-bis (4-isocyanatophenyl) hexafluoropropane (0.02 mol, 7.72 g) and xylene diisocyanate (0.02 mol, 5.0 g) into a 500ml flask provided with a mechanical stirrer, a reflux condenser, a temperature probe and a dropping funnel, stirring and mixing, adding a thermosensitive dye ODB-214 g, tetradecanol 14g and styrene maleic anhydride copolymer 2g, stirring and dissolving; after the dissolution, 200ml of deionized water and 40ml of an aqueous PVA224 solution (mass fraction: 4.5%) were added, and the mixture was vigorously stirred at 10000r/min for 10min using a high-speed shearing machine to obtain an o/w emulsion.
Then an aqueous solution (100ml) of tetraethylenepentamine (0.016mol, 5.94g) was slowly added to the o/w emulsion. The procedure was carried out at room temperature, with stirring at 600r/min by means of a stirrer. After the dropwise addition, the temperature is raised to 65 ℃ and the mixture is continuously stirred for 4 hours to obtain the fluorine-containing heat-sensitive microcapsule emulsion.
(2) Preparing an imaging layer emulsion: 100ml of PVA224 aqueous solution (4.5 mass percent) was added to a 250ml flask equipped with a mechanical stirrer, a reflux condenser, a temperature probe and a dropping funnel, 12g of 2, 4-dihydroxybenzoic acid was added, 10g of a dispersant (9.8 g of sodium alginate, 0.2g of nano-titanium dioxide) was added thereto, and stirring was carried out for 30 minutes to form an emulsion. In another 500ml flask equipped with a mechanical stirrer, reflux condenser, temperature probe and dropping funnel, 100g of the fluorine-containing microcapsule emulsion and 50g of calcium carbonate were added, stirred, and the emulsion was added dropwise with stirring for about 30min to disperse it uniformly for further use.
(3) Preparing a back coating and protective layer emulsion:
preparing protective layer emulsion: 100g of carboxylated styrene-butadiene latex was added to a 250ml flask equipped with a mechanical stirrer, and 30g of calcium carbonate and 0.1g of ultraviolet absorber (o-nitroaniline (UV-P)) were added under stirring and stirred for 30min to form a uniformly dispersed emulsion for use.
Preparation of back coating emulsion: in a 250ml flask equipped with a mechanical stirrer, 90g of polyvinyl alcohol adhesive was added, and 30g of calcium carbonate powder, 0.9g of zinc stearate, and 0.1g of ultraviolet absorber (o-nitroaniline (UV-P)) were added under stirring, and stirred for 30min to form a uniformly dispersed emulsion for later use.
(4) Film coating:
step four: the coating is carried out by a portable extrusion coating method. According to the coating weight of the thermosensitive imaging layer and the protective layer, respectively 80 ml/m2、15 ml/m2Coating on a PET support, coating the other side of the PET support with a backing layer of 20ml/m2And fully drying to obtain the sample film coated with the heat-sensitive microcapsule color developing material.
Comparative example 3
(1) Preparing microcapsules: adding 2, 2-bis (4-isocyanatophenyl) hexafluoropropane (0.02 mol, 7.72 g) and xylene diisocyanate (0.02 mol, 5.0 g) into a 500ml flask provided with a mechanical stirrer, a reflux condenser, a temperature probe and a dropping funnel, stirring and mixing, adding a thermosensitive dye ODB-214 g, tetradecanol 14g and styrene maleic anhydride copolymer 2g, stirring and dissolving; after the mixture is cleared, 200ml of deionized water and 40ml of PVA224 aqueous solution (mass fraction: 4.5%) are added, and the mixture is stirred vigorously at a speed of 10000r/min for 10min by using a high-speed shearing machine to obtain an o/w emulsion.
Then an aqueous solution (100ml) of tetraethylenepentamine (0.016mol, 5.94g) was slowly added to the o/w emulsion. The procedure was carried out at room temperature, with stirring at 600r/min by means of a stirrer. After the dropwise addition, the temperature is raised to 65 ℃ and the mixture is continuously stirred for 4 hours to obtain the fluorine-containing heat-sensitive microcapsule emulsion.
(2) Preparing an imaging layer emulsion: 100ml of PVA224 aqueous solution (4.5 mass percent) was added to a 250ml flask equipped with a mechanical stirrer, a reflux condenser, a temperature probe and a dropping funnel, 12g of 2, 4-dihydroxybenzoic acid was added, 10g of a dispersant (9.8 g of sodium alginate, 0.2g of nano-titanium dioxide) was added thereto, and stirring was carried out for 30 minutes to form an emulsion. In another 500ml flask equipped with a mechanical stirrer, reflux condenser, temperature probe and dropping funnel, 100g of the fluorine-containing microcapsule emulsion and 50g of calcium carbonate were added, stirred, and the emulsion was added dropwise with stirring for about 30min to disperse it uniformly for further use.
(3) Preparation of back coating and protective layer emulsion:
preparing protective layer emulsion: 100g of carboxylic styrene-butadiene latex was added to a 250ml flask equipped with a mechanical stirrer, 30g of calcium carbonate was added with stirring, and stirred for 30min to form a uniformly dispersed emulsion for use.
Preparation of back coating emulsion: adding 90g of polyvinyl alcohol adhesive into a 250ml flask provided with a mechanical stirrer, adding 30g of calcium carbonate powder and 0.9g of zinc stearate under stirring, and stirring for 30min to form uniformly dispersed emulsion for later use.
(4) Film coating:
step four: the coating is carried out by a portable extrusion coating method. According to the coating weight of the thermosensitive imaging layer and the protective layer, respectively 80 ml/m2、15 ml/m2Coating on a PET support, coating the other side of the PET support with a backing layer of 20ml/m2And fully drying to obtain the sample film coated with the heat-sensitive microcapsule color developing material.
The invention adopts the following method to test the performance of the fluorine-containing thermo-sensitive film:
1. the method for testing the image density of the film comprises the following steps:
the invention adopts infrared laser with the wavelength of about 820nm to carry out exposure experiment on the film example. Through the exposure of infrared laser, the capsule wall of the microcapsule of the exposed part is cracked and dissolved to a certain extent due to the rise of temperature, and the dye precursor is contacted with a color developing agent to generate color developing reaction; in the non-exposed region, no color reaction occurs, and color contrast is formed. The control of the laser is realized through software and programs, and the pattern of the medical image is formed. And (3) carrying out density detection on the image formed after thermal development by using an X-Rite504 type spectrodensitometer to obtain a change rule of the image along with different proportions of the microcapsule wall material.
Table 1 raw material amount and image density test result of film
Figure 285499DEST_PATH_IMAGE003
As can be seen from table 1: the introduction of the fluorine-containing diisocyanate monomer as a capsule wall material of the microcapsule can increase the image density of the film and improve the development effect.
2. The method for testing the ultraviolet resistance and the weather resistance of the film comprises the following steps: the thermo-sensitive films of examples 1 to 5 and comparative example 3 were aged in an aging oven and the films were tested for image density and fog at various times, and the results are shown in Table 2:
TABLE 2 variation in image Density of films at different exposure times after Heat fixing
Figure 639120DEST_PATH_IMAGE004
As can be seen from table 2: the introduction of the fluorine-containing microcapsule material enhances the stability and the oxidation resistance of the film and enhances the storage resistance of the film. After the film with the fluorine-containing unit is placed for a certain time, the image density of an exposure area of the film is not changed greatly, the aging and yellowing phenomena of the film are obviously reduced, and the obvious fog phenomenon is not generated. In addition, compared with the common ultraviolet absorbent, the compounded ultraviolet absorbent has better anti-yellowing effect.
3. RMS granularity test
The granularity characterizes the fluctuation of the spatial density in the developed imaging layer, and in this case can be used to measure the distribution of the heat-sensitive microcapsules, the smaller the value, the more uniform the distribution of the microcapsules on the film, and the standard deviation σ(D)To indicate that the film granularity is a value of 1000 σ(D)This value is called RMS granularity. The specific test method is as follows
Figure 437312DEST_PATH_IMAGE005
In the formula: diLayer density at layer i;
Figure 964108DEST_PATH_IMAGE006
the average density of the image layer is shown;
n is the number of measurement points;
RMS granularity tests were performed on examples 1-6 and comparative examples 1-2, and the test results were as follows:
TABLE 3 film RMS granularity test results
Figure 164145DEST_PATH_IMAGE007
After sodium alginate is added as a dispersing agent, the RMS granularity of the film is effectively improved, and the product quality is greatly improved.
4. The antistatic performance test method of the film comprises the following steps: the films of examples 1 to 3 and comparative example 1 were measured for surface resistance by a micro surface resistance meter.
5. The waterproof effect test method of the film comprises the following steps: and completely immersing the test sample in deionized water, observing the transparent and whitish state of the surface after soaking for 5 hours at room temperature, taking out the test sample, and strongly rubbing the surface for 10 times by using fingers to test the waterproof degree of the protective layer.
And (3) judging standard:
a: the coating is transparent, the surface of the coating is smooth and is not erased to drop substances, and the water resistance is excellent;
b: the coating is slightly whitish, the surface of the coating is smooth/is not erased to drop substances, and the water resistance is good;
c: whitish, the surface of the coating is dissolved and easily rubbed off and dropped, and the water resistance is poor.
6. The method for testing the scratch resistance of the film comprises the following steps: the films of examples 1 to 3 and comparative example 1 were placed under 0000# steel wool of 500g load, rubbed back and forth 40 times, the wear-resistant grade of the matting agent coating film was judged according to the number of scratches after rubbing, the number of scratches was one grade between 0 and 5, the number of scratches was two grades between 6 and 10, the number of scratches was three grades between 11 and 15, the number of scratches was four grades between 16 and 20, the number of scratches was five grades between 21 and 25, the number of scratches was six grades between 26 and 30, and the remainder was seven grades.
The results of the above-mentioned anti-sticking property, anti-static property, water-proof effect, and scratch resistance are shown in Table 4:
table 4 film performance test results
Figure 688667DEST_PATH_IMAGE008
According to the test results in table 4, it can be known that the thermal sensitive film prepared from the fluorine-containing microcapsule has good anti-sticking property, anti-static property, waterproof effect, scratch resistance and mechanical property due to the change of the microstructure.
From the above embodiments, the present invention provides a fluorine-containing thermosensitive dye microcapsule, comprising a capsule wall and a capsule core emulsion; the capsule wall is a polymer with a structure shown in a formula I; the capsule core emulsion comprises the following components in a molar ratio of (2-2.5): (2.5-3.0): (0.25-0.3) phthalide heat-sensitive dye, higher fatty alcohol and emulsifier. The fluorine-containing thermosensitive dye microcapsule provided by the invention is applied to a film, and the film has good antistatic property, waterproof effect, ultraviolet resistance, weather resistance, high surface resistance and scratch resistance. Meanwhile, in the aspect of development, the exposure area is found to have higher image density and low RMS granularity (2-3), and the defects of poor image quality, high film storage difficulty, environmental pollution of the film and the like of the traditional silver halide photosensitive imaging film can be overcome. The capsule has important application in medical imaging, and is suitable for recording and storing medical diagnosis digital images.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (5)

1. A fluorine-containing thermosensitive dye microcapsule comprises a capsule wall and a capsule core emulsion;
the capsule wall is a polymer with a structure shown in a formula I:
Figure DEST_PATH_IMAGE002
formula I
The R is selected from-CH2CH2NHCH2CH2NHCH2CH2NHCH2CH2-、-CH2CH2NHCH2CH2-、-CH2CH2NHCH2CH2NHCH2CH2-or-CH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NHCH2CH2-；
Said Rf is selected from-PhC (CF)3)2Ph-；
The R is1Is selected from-PhCH2Ph-or-PhCH2CH2Ph-；
The value of x is 1-3; the value of y is 1-3;
the capsule core emulsion comprises the following components in a molar ratio of (2-2.5): (2.5-3.0): (0.25-0.3) phthalide heat-sensitive dye, higher fatty alcohol and emulsifier; the phthalide thermosensitive dye is selected from 2-phenylamino-3-methyl-6-diethylfluorane and/or 2-phenylamino-3-methyl-6-dibutylamino fluorane; the higher fatty alcohol is selected from one or more of dodecanol, tetradecanol and hexadecanol; the emulsifier is selected from styrene-maleic anhydride copolymer; the emulsifier accounts for 23-27% of the mass of the higher fatty alcohol;
the average particle size of the fluorine-containing thermosensitive dye microcapsule is 2-5 microns.
2. A method for preparing the fluorine-containing thermosensitive dye microcapsule according to claim 1, comprising the steps of:
mixing fluorinated diisocyanate, non-fluorinated diisocyanate, phthalide thermosensitive dye, higher fatty alcohol and emulsifier, adding the mixture into water and protective colloid, and stirring to obtain oil-water emulsion; then dropwise adding a polyamine aqueous solution under the stirring condition, and carrying out interface reaction to obtain the fluorine-containing thermosensitive dye microcapsule;
the fluorinated diisocyanate is 2, 2-bis (4-isocyanatophenyl) hexafluoropropane;
the polyamine is selected from pentaethylenehexamine, tetraethylenepentamine, triethylenetetramine or diethylenetriamine.
3. A film containing heat-sensitive microcapsule chromogenic material comprises a heat-sensitive imaging layer, a protective layer, a substrate and a back layer which are sequentially arranged;
the thermosensitive imaging layer is prepared by coating a thermosensitive imaging layer coating liquid; the heat-sensitive imaging layer coating liquid comprises a filler, a developer, a polyvinyl alcohol aqueous solution, a dispersing agent and the fluorine-containing heat-sensitive dye microcapsule of claim 1;
the dispersing agent is selected from the following components in a mass ratio of 80-90: sodium alginate and nano TiO of 12A mixture of (a).
4. A sheet according to claim 3, wherein the protective layer is made of a protective layer emulsion; the protective layer emulsion comprises inorganic filler, an ultraviolet absorbent, a lubricant and an adhesive; the mass ratio of the inorganic filler to the ultraviolet absorbent to the lubricant to the adhesive is (10-5): (0.05-0.1): (0.3-0.05): 30, of a nitrogen-containing gas; the ultraviolet absorbent is selected from the following components in mass ratio of (1-1.5) to (1-1.5): (0.4-0.6) a mixture of a phenyl compound, inorganic nano zinc oxide and UV-292; the phenyl compound is selected from one or more of 1, 4-dihydroxy benzophenone, phenyl o-hydroxybenzoate, 1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane and 2-hydroxy-4-n-octoxy benzophenone;
the back layer is prepared by coating back layer emulsion; the back layer emulsion comprises the following components in percentage by mass (1-100): (1-50): (0.1-0.05) a mixture of an inorganic filler, a binder and an ultraviolet absorber.
5. A film according to claim 3 wherein the thickness of the thermosensitive imaging layer is 30 to 45 μm and the thickness of the back layer is 10 to 15 μm; the thickness of the protective layer is 15 to 25 μm.
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