CN107267046B - A kind of thermo-chromatic and preparation method thereof, application - Google Patents
A kind of thermo-chromatic and preparation method thereof, application Download PDFInfo
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- CN107267046B CN107267046B CN201710541348.5A CN201710541348A CN107267046B CN 107267046 B CN107267046 B CN 107267046B CN 201710541348 A CN201710541348 A CN 201710541348A CN 107267046 B CN107267046 B CN 107267046B
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/41—Base layers supports or substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/42—Intermediate, backcoat, or covering layers
- B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
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- 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
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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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
- C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
- B41M2205/32—Thermal receivers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
- B41M2205/36—Backcoats; Back layers
-
- 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
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- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- 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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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- C08K2201/00—Specific properties of additives
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
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Abstract
The present invention relates to medical film technical field, especially a kind of thermo-chromatic and preparation method thereof, application.The first aspect of the invention provides a kind of thermo-chromatic, successively includes from top to bottom, protective layer, thermographic layer, substrate layer, backing layer；The thermographic layer includes at least colour developing microcapsules, dye microcapsule, colour developing auxiliary agent, adhesive.The second aspect of the invention provides the preparation method of the thermo-chromatic, at least includes the following steps: thermographic layer, backing layer are respectively coated by coating technique on the two sides of substrate layer；Then protective layer is coated on to again the another side of thermographic layer, obtain thermo-chromatic after drying.The third aspect of the invention provides application of the thermo-chromatic in field of medical imaging.
Description
Technical field
The present invention relates to medical film technical field, especially a kind of thermo-chromatic and preparation method thereof, application.
Background technique
With the continuous development of Medical Imaging Technology, the demand of Medical film is gradually increased.From wet type Medical film to
Dry type Medical film and dry type medical digital film.Traditional wet Medical film refers mainly to light-sensitive silver halide Medical film, should
Class film is influenced vulnerable to outside environmental elements, blackening due to long oxidation, and it is big to save difficulty.The imaging process needs of film pass through
Developing fixing completes the process, and film generates waste liquid during developing fixing, pollutes environment.Dry type Medical film does not need picture then
Wet type Medical film is like that a kind of processing method by temperature-sensitive, laser or inkjet printing by development and fixing solution processing
The Medical film of novel digital imaging.Process environmental protection is convenient, imaging clearly.Currently, dry type Medical film is in medical shadow
As having become mainstream in record.
Dry type medical film structure is generally made of backing layer, bottom, film support, bottom, imaging layer and cuticular layer.
Dry type medical film is classified according to the difference of imaging mode, can be divided into laser printing dry type film, inkjet printing dry type film,
Thermal printing dry type film.Laser printing dry type film is a kind of photosensitive material medical adhesive to grow up with laser printer
The advantages of piece, the film is image stabilization, easy to process, but the film using coating material cost it is slightly higher, use scope by
To limitation, and that there are storage stabilities is poor；Inkjet printing dry type film is a kind of medical imaging film for inkjet printing,
Smooth performance and anti-static effect are poor when use；Thermal printing dry type film is a kind of medical film for thermal printing, one
As be imaged using organic heat susceptible coating, part film has that chip base and thermographic layer adhesive force are bad while smooth
Performance and anti-static effect are poor, cause to generate adhesion phenomenon in print procedure, it is poor to cross machine performance, it is therefore desirable to which the back side is coated
To improve smooth performance and anti-static function, higher cost.
In conclusion laser printing dry type film, inkjet printing dry type film and thermal printing dry type film polyester piece
There is smooth performance in the base back side and anti-static function is poor, and adhesion phenomenon is generated in print procedure, it is poor cross machine performance, therefore need
The back side is wanted to be coated to improve smooth performance and anti-static function, higher cost.Part thermal printing dry type film is used simultaneously
There are bad phenomenons with thermographic layer adhesive force for the bottom of polyester film base.
The protective film layer of thermo-chromatic is mainly the film layer of polyvinyl alcohol at present, and waterproofness is very poor, is easy dampness, is generated
Heat transfer is uneven, and skin friction resistance is big, influences the colour developing of imaging layer, the critical component of damage temperature sensitive imaging device when serious.
Thus, it is also very desirable to a kind of novel thermosensitive film is obtained by research and development, with to solve the above technical problems.
Summary of the invention
In order to solve the above-mentioned technical problem, the first aspect of the invention provides a kind of thermo-chromatic, from top to bottom according to
It is secondary to include, protective layer, thermographic layer, substrate layer, backing layer；
The thermographic layer includes at least colour developing microcapsules, dye microcapsule, colour developing auxiliary agent, adhesive.
As a preferred technical solution of the present invention, the protective layer includes at least in parts by weight
As a preferred technical solution of the present invention, the substrate layer is selected from: polyurethane resin, poly terephthalic acid second
It is diester resin, polystyrene resin, polyacrylate resin, polycarbonate resin, any one in superbrnaching end-hydroxy polyester
Kind or several mixing.
As a preferred technical solution of the present invention, it is former to include at least following preparation in parts by weight for the backing layer
Material:
As a preferred technical solution of the present invention, the matting agent is silane coupler modified silica solution.
As a preferred technical solution of the present invention, the crosslinking agent is melamine.
As a preferred technical solution of the present invention, the partial size of the color developer microcapsule is 0.1~1 micron.
As a preferred technical solution of the present invention, the partial size of the dye microcapsule is 0.1~1 micron.
The second aspect of the invention provides the preparation method of thermo-chromatic, at least includes the following steps:
Thermographic layer, backing layer are respectively coated by coating technique on the two sides of substrate layer；Then protective layer is applied again
Cloth obtains thermo-chromatic in the another side of thermographic layer after drying.
The third aspect of the invention provides application of the thermo-chromatic in field of medical imaging.
The above-mentioned of the application and other features, aspects and advantages are more readily understood with reference to following detailed description.
Specific embodiment
The detailed description for preferred implementation method of the invention below of participating in the election of and including embodiment this hair can be more easily to understand
Bright content.Unless otherwise defined, all technologies used herein and scientific term have common with fields of the present invention
The normally understood identical meaning of technical staff.When there is a conflict, the definition in this specification shall prevail.
As used herein term " by ... preparation " it is synonymous with "comprising".Term "comprising" used herein, " comprising ",
" having ", " containing " or its any other deformation, it is intended that cover non-exclusionism includes.For example, the combination comprising listed elements
Object, step, method, product or device are not necessarily limited to those elements, but may include not expressly listed other elements or
Such composition, step, method, product or the intrinsic element of device.
Conjunction " Consists of " excludes any element that do not point out, step or component.If in claim, this
Phrase will make claim closed, so that it is not included the material in addition to the material of those descriptions, but relative normal
Except rule impurity.When being rather than immediately following after theme in the clause that phrase " Consists of " appears in claim main body,
It is only limited to element described in the clause；Other elements are not excluded except the claim as a whole.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit
When the Range Representation that choosing value limits, this should be understood as specifically disclosing by any range limit or preferred value and any range
Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open
When range " 1 to 5 ", described range should be interpreted as including range " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise the range is intended to include its end
Value and all integers and score in the range.
Singular includes that plural number discusses object, unless the context clearly dictates otherwise." optional " or it is " any
It is a kind of " refer to that the item described thereafter or event may or may not occur, and the description include situation that event occurs and
The situation that event does not occur.
Approximate term in specification and claims is used to modify quantity, and it is specific to indicate that the present invention is not limited to this
Quantity further includes the acceptable modified part without will lead to the change of dependency basis this function close with the quantity.Phase
It answers, modifies a numerical value with " about ", " about " etc., mean that the present invention is not limited to the exact numericals.In some examples, approximate
Term likely corresponds to the precision of the instrument of measurement numerical value.In present specification and claims, range limits can be with
Combination and/or exchange, these ranges if not stated otherwise include all subranges contained therebetween.
In addition, indefinite article "an" before element of the present invention or component and "one" quantitative requirement to element or component
(i.e. frequency of occurrence) unrestriction.Therefore "one" or "an" should be read as including one or at least one, and odd number
The element or component of form also include plural form, unless the obvious purport of the quantity refers to singular.
" polymer " means polymerizable compound prepared by the monomer by the identical or different type of polymerization.Generic term
" polymer " includes term " homopolymer ", " copolymer ", " terpolymer " and " copolymer ".
In order to solve the above-mentioned technical problem, the first aspect of the invention provides a kind of thermo-chromatic, from top to bottom according to
It is secondary to include, protective layer, thermographic layer, substrate layer, backing layer；
The thermographic layer includes at least colour developing microcapsules, dye microcapsule, colour developing auxiliary agent, adhesive.
Protective layer
As a preferred technical solution of the present invention, the protective layer includes at least in parts by weight
In the application, the polyurethane adhesive can be commercially available acquisition, can also be obtained by self-control.
In the application, the polyurethane adhesive is commercially available acquisition, is purchased from Shanghai Shou Xing Industrial Co., Ltd..
In the application, the polyvinyl alcohol is vinal.
In the application, the nano silica is silica nanosphere.
In the application, the silica nanosphere is commercially available acquisition, is purchased from Nanjing Ji Cang nanosecond science and technology Co., Ltd.
In a preferred embodiment, the levelling agent is selected from: organic silicon modified by polyether levelling agent, fluorine richness poly- third
Any one in olefin(e) acid ester levelling agent.
In a preferred embodiment, the protective layer the preparation method comprises the following steps:
Deionized water, the levelling agent for weighing corresponding parts by weight are added in stirred tank after mixing these three raw materials, are mixed
It is slowly added to polyvinyl alcohol after stirring 10min, 10min is again stirring for, nano silica is then added into system, continue to stir
20min is mixed, polyurethane adhesive is then added, continues to stir 30min, obtains protective layer.
In a preferred embodiment, the protective layer with a thickness of 0.1~1 μm.
Thermographic layer
In the application, the thermographic layer includes at least colour developing microcapsules, dye microcapsule, colour developing auxiliary agent, adhesive.
As a preferred technical solution of the present invention, the colour developing microcapsules include colour developing cyst wall and colour developing capsule-core；Institute
The material for stating colour developing cyst wall is polyurethane；The colour developing capsule-core includes color developing agent and solvent.
What the color developing agent can be enumerated has: 4,4 '-isopropylidene xenols, 4,4 '-cyclohexylidene xenols, 1,1- are bis-
(4- hydroxy phenyl) ethane, 1,1- bis- (4- hydroxy phenyl) -1- diphenylphosphino ethanes, 4,4 '-dihydroxydiphenylsulisomers, 2,4 '-dihydroxy
Diphenyl sulphone (DPS), 4- hydroxyl -4 '-isopropoxy diphenyl sulphone (DPS), 3,3 '-diallyl -4,4 '-dihydroxydiphenylsulisomers, 2,2 '-bis- [4- (4-
Hydroxy phenyl) phenoxy group] Anaesthetie Ether, 4,4 '-bis- (4- methyl -3- carboxamideridyl phenyl) urides] diphenyl sulphone (DPS), N- pairs
Tosyl-N ' -3- (tolysulfonyl oxygroup) phenylurea, 3,3 '-bis- (tolysulfonyl carbamoylamino) diphenyl sulphone (DPS)s,
4-HBA benzyl ester, N, N '-two-m-chloro phenylthiourea, N- p-toluenesulfonyl-N '-phenylurea, 4-4 '-are bis- (to toluene
Sulfonamido formamido group) diphenyl-methane, 4- [2- (to methoxyphenoxy) ethyoxyl] zinc salicylate, [3- is (to toluene sulphur by 4-
Acyl group) propoxyl group] zinc salicylate, 5- [p- (2- is to methoxyphenoxy ethyoxyl) cumyl] zinc salicylate etc..
In a preferred embodiment, it is described colour developing microcapsules the preparation method is as follows:
(1) 10 grams of xylenylphosphates, 80 grams of ethyl acetate are added in 200 milliliters of reaction flasks, are added with stirring 30
Gram 4- hydroxyl -4'- isopropoxy diphenyl sulphone (DPS) dissolves by heating, it is to be cooled to room temperature when, add 20 grams of oil-soluble polymerization monomers
TDI, stirring, obtains color developing agent mixed solution.
(2) be added in round bottom container 400ml concentration be 4.5%, alcoholysis degree 88%, average degree of polymerization be 3450 it is poly-
Vinyl alcohol aqueous solution obtains water phase.
(3) color developing agent mixed solution is slowly added into water phase, is then dispersed under the speed of 15000r/min
15min obtains the newborn dispersion liquid of the oil that average grain diameter is 0.22um.Deionized water 100ml, tetrem is added into the newborn dispersion liquid of the oil
1 gram of five amine of alkene reacts 5 hours at 55 DEG C then with the mixing speed of 800r/min, and obtaining average grain diameter is 0.20 micron aobvious
Toner microcapsules.
As a preferred technical solution of the present invention, the partial size of the color developer microcapsule is 0.1~1 micron.
As a preferred technical solution of the present invention, the dye microcapsule includes dyestuff cyst wall and dyestuff capsule-core；Institute
The material for stating dyestuff cyst wall is polyurethane；The dyestuff capsule-core includes at least dyestuff former.
The specific example of the dyestuff former are as follows: 3- [2,2- bis- (1- Ethyl-2-Methyl indol-3-yl) vinyl] -3-
Bis- (p- the dimethylamino phenyl) -6- dimethylamino -2- benzos of (4- lignocaine-phenyl) -2- benzo (c) furanone, 3,3-
(c) furanone, 3- (4- lignocaine -2- aminomethyl phenyl) -3- (4- dimethylamino phenyl) -6- dimethylamino -2- benzo (c) furan
It mutters ketone, 3- Cyclohexylamino -6- chlorine fluorane (fluoran), 3- lignocaine -6- methyl -7- chlorine fluorane, lignocaine -6 3-,
8- dimethyl fluorane, 3- lignocaine -7- chlorine fluorane, 3- (N- ethyl-N- isopentyl) amino -6- methyl -7- anilino fluorane,
3- bis- (normal-butyl) amino -6- methyl -7- anilino fluorane, 3- bis- (n-pentyl) amino -6- methyl -7- anilino fluorane, 3-
(N- ethyl-para-totuidine base) -6- methyl -7- anilino fluorane, the chloro- 7- anilino fluorane of (normal-butyl) amino of 3- bis- -6-, 3-
Pyrrolidinyl -6- methyl -7- anilino fluorane, 3- piperidino -6- methyl -7- anilino fluorane, bis- [1- (the 4- methoxies of 3,3-
Base phenyl) Asia -1- (4- dimethylamino phenyl) second -2- base] -4,5,6,7- tetra- chloro- 2- benzo (c) furanones, 3- p- (p- two
Methylamino anilino-) anilino- -6- methyl -7- chlorine fluorane, p- (p-chloroaniline base) anilino- -6- methyl -7- chlorine fluorane of 3-,
3- [1,1- bis- (1- Ethyl-2-Methyl indol-3-yls)] p- lignocaine phenyl -2- benzo (c) furanone of -3-, 3,3- are bis-
(1- normal-butyl -2 methyl indole -3- base) -2- benzo (c) furanone, bis- (dimethylamino) fluorenes -9- spiral shells -3 '-(6 '-two of 3,6-
Methylamino) -2- benzo (c) furanone, bis- (4- lignocaine -2- ethoxyl phenenyl) -4- azepine -2- benzo (c) furans of 3,3-
Ketone etc..Dyestuff is not limited to those given above, and dyestuff can be used with combination of two or more.Although the measurement due to dyestuff is determined
It is different in the difference of the developer used, to its there is no limit.
In a preferred embodiment, the dye microcapsule the preparation method is as follows:
(1) ODB-2 (Shandong Rui Kang refines), the GN-2 (Tokyo chemical conversion) of 1 parts by weight, 1 weight of 5 parts by weight are weighed
The CK-16 (Wenzhou dragon victory) of part, the ethyl acetate of 30 parts by weight are added in dissolving pan, are stirred, and after heating for dissolving, are cooled to 50
DEG C when, be added 8 parts by weight polyurethane prepolymer and 5 parts by weight dicyclohexyl methyl hydride diisocyanate, stir evenly, obtain
To oily phase.
(2) polyurethane prepolymer the preparation method comprises the following steps:
In dry three-necked flask, the hydroxy-end capped hyper-branched polyester of 3 parts by weight is dissolved in 20ml acetone soln, is obtained
To hydroxy-end capped hyperbranched poly ester solution；The isoflurane chalcone diisocyanate of 10 parts by weight is dissolved in 50ml acetone soln, is obtained
To isoflurane chalcone diisocyanate solution；Under nitrogen protection, isoflurane chalcone diisocyanate solution is added dropwise to hydroxy-end capped
In hyperbranched poly ester solution, into mixed solution, the catalyst dibutyltin dilaurylate of 0.01 parts by weight is added, by reaction temperature
Degree is warming up to 85 DEG C, and reaction obtained polyurethane prepolymer after 2 hours.
(3) 1788 polyvinyl alcohol water solution of PVA that 100 parts by weight concentration are 6% is provided, water phase is obtained.
(4) above-mentioned oil is mutually slowly added into aqueous phase solution, while using high shear agitation with 5600 revs/min of speed
Degree dispersion 7 minutes obtains the oil-in-water dispersion emulsion that average grain diameter is 0.35um；Into scattered lotion be added 30 parts go from
Sub- water, 1.2 parts of tetraethylenepentamine are reacted 3 hours at 55 DEG C then under 600 revs/min of mixing speed, obtain average grain
The dye microcapsule of diameter 0.2um.
What the colour developing auxiliary agent can be enumerated has: neopelex.
What described adhesive can be enumerated has: it can be synthesis, be also possible to commercially available, what can be enumerated has: gelatin,
Polyurethane adhesive, animal glue etc., preferably gelatin.
In a preferred embodiment, the thermographic layer the preparation method comprises the following steps:
Temperature-sensitive microcapsules, color developer microcapsule, colour developing auxiliary agent, adhesive are added in three-necked flask, after mixing evenly,
Obtain thermographic layer.
In a preferred embodiment, the thermographic layer with a thickness of 5~20 μm.
Substrate layer
In a preferred embodiment, the substrate layer is selected from: polyurethane resin, polyethylene terephthalate tree
Rouge, polystyrene resin, polyacrylate resin, polycarbonate resin, in superbrnaching end-hydroxy polyester any one or it is several
The mixing of kind.
In a kind of optimal embodiment, the substrate layer is selected from: polyurethane resin and superbrnaching end-hydroxy polyester
Mixing, and the weight ratio between the polyurethane resin and superbrnaching end-hydroxy polyester is 5:1.
In a preferred embodiment, the substrate layer with a thickness of 100~200 μm.
Backing layer
As a preferred technical solution of the present invention, it is former to include at least following preparation in parts by weight for the backing layer
Material:
In the application, the polyurethane modified epoxy resin the preparation method is as follows:
(1) in dry three-necked flask, the hydroxy-end capped hyper-branched polyester of 3 parts by weight is dissolved in 20ml acetone soln
In, obtain hydroxy-end capped hyperbranched poly ester solution；The isoflurane chalcone diisocyanate of 10 parts by weight is dissolved in 50ml acetone soln
In, obtain isoflurane chalcone diisocyanate solution；Under nitrogen protection, isoflurane chalcone diisocyanate solution is added dropwise to hydroxyl
In terminated hyperbranched polyester liquid, into mixed solution, the catalyst dibutyltin dilaurylate of 0.01 parts by weight is added, it will be anti-
Temperature is answered to be warming up to 85 DEG C, reaction obtained polyurethane after 2 hours；
(2) it in the polyurethane that the step of 8 parts by weight of bisphenol A epoxy resin being added to 3 parts by weight (1) obtains, is warming up to
It 80 DEG C, reacts under nitrogen protection, reacts 2 hours, polyurethane modified epoxy resin can be obtained.
In the application, the matting agent is silica solution.
In a preferred embodiment, the silica solution is silane coupler modified silica solution.
What the silane coupling agent can be enumerated has: amino silicane coupling agent, epoxy silane coupling,
What the amino silicane coupling agent can be enumerated has: N- (2- aminoethyl) -3- aminopropyl trimethoxysilane, 3- ammonia
Propyl-triethoxysilicane, N- (2- aminoethyl) -3- aminopropyltriethoxy dimethoxysilane, N- (2- aminoethyl) -3- aminopropyl
Triethoxysilane and 3- aminopropyl trimethoxysilane etc..
What the epoxy silane coupling can be enumerated has: γ-glycidoxypropyltrime,hoxysilane, γ-ring
Oxygen propoxypropyl triethoxysilane, γ-glycidoxypropyl group tripropoxy silane, three fourth of γ-glycidoxypropyl group
Oxysilane, 3,4- epoxycyclohexylmethyl trimethoxy silane, 3,4- epoxycyclohexylmethyl triethoxysilane, β-
(3,4- expoxycyclohexyl) ethyl trimethoxy silane, β-(3,4- expoxycyclohexyl) ethyl triethoxysilane etc..
In a preferred embodiment, the silane coupler modified silica solution the preparation method comprises the following steps:
The silica solution (silica dioxide granule content is 20wt%, partial size 15nm) of 10 parts by weight is added to three-necked flask
In and be stirred；In room temperature and under continuing stirring condition, N- (2- aminoethyl) -3- aminopropyl trimethoxy of 3 parts by weight is taken
Silane is added drop-wise in silica solution, rate of addition 10ml/min；Then the pH value of glacial acetic acid regulation system is being selected to continue to 8
Stirring obtains silane coupler modified silica solution to 20h.
In a preferred embodiment, the silica solution is dodecyl sodium sulfate, silane coupling agent changes jointly
Property silica solution.
In a preferred embodiment, the common modified silicasol of the dodecyl sodium sulfate, silane coupling agent
The preparation method comprises the following steps:
The silica solution (silica dioxide granule content is 20wt%, partial size 15nm) of 10 parts by weight is added to three-necked flask
In and be stirred；In room temperature and under continuing stirring condition, N- (2- aminoethyl) -3- aminopropyl trimethoxy of 2 parts by weight is taken
Silane is added drop-wise in silica solution, rate of addition 10ml/min；Then the dodecyl sodium sulfonate of 2 parts by weight is added into system again
Sodium；Then the pH value of glacial acetic acid regulation system is being selected to continue stirring to 8 to 20h, 20h is stirred at room temperature, obtains dodecane
The common modified silicasol of base sodium sulfonate, silane coupling agent.
Crosslinking agent in the application is not particularly limited, preferably melamine, in chitosan any one or
Several mixing.
Antistatic agent in the application is not particularly limited, and can be resisted for Polymeric anti-static agent, cationic quiet
Electric agent, anionic antistatic agent, any one or a few the mixing in non-ionic antistatic agent.
One kind be preferably embodiment in, the backing layer the preparation method comprises the following steps:
After 10min first is mixed in deionized water and antistatic agent, polyurethane modified epoxy resin is then added, it will
Temperature is increased to 50 DEG C, stirs 30min, then adds crosslinking agent, be again stirring for 30min, be eventually adding matting agent, and back is made
Layer.
In a preferred embodiment, the backing layer of the substrate layer is 0.5~5 μm.
The second aspect of the invention provides the preparation method of thermo-chromatic, at least includes the following steps:
Thermographic layer, backing layer are respectively coated by coating technique on the two sides of substrate layer；Then protective layer is applied again
Cloth obtains thermo-chromatic in the another side of thermographic layer after drying.
The third aspect of the invention provides application of the thermo-chromatic in field of medical imaging.
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is only used
In the invention will be further described, it should not be understood as limiting the scope of the invention, professional and technical personnel in the field
The some nonessential modifications and adaptations made according to the content of aforementioned present invention, still fall within protection scope of the present invention.
In addition, if without other explanations, it is raw materials used to be all commercially available, it is purchased from traditional Chinese medicines chemical reagent.
Embodiment 1:
The present embodiment 1 provides a kind of thermo-chromatic, successively includes from top to bottom, protective layer, thermographic layer, substrate
Layer, backing layer；
The protective layer includes at least in parts by weight
The polyurethane adhesive is purchased from Shanghai Shou Xing Industrial Co., Ltd..
The polyvinyl alcohol is vinal, is purchased from Chongqing Ying Zhu building materials Co., Ltd.
The nano silica is purchased from Nanjing Ji Cang nanosecond science and technology Co., Ltd.
The levelling agent organic silicon modified by polyether levelling agent is purchased from crop field chemistry.
The protective layer the preparation method comprises the following steps:
Deionized water, the levelling agent for weighing corresponding parts by weight are added in stirred tank after mixing these three raw materials, are mixed
It is slowly added to polyvinyl alcohol after stirring 10min, 10min is again stirring for, nano silica is then added into system, continue to stir
20min is mixed, polyurethane adhesive is then added, continues to stir 30min, obtains protective layer.
The thermographic layer includes colour developing microcapsules, dye microcapsule, colour developing auxiliary agent, adhesive.
It is described colour developing microcapsules the preparation method is as follows:
(1) 10 grams of xylenylphosphates, 80 grams of ethyl acetate are added in 200 milliliters of reaction flasks, are added with stirring 30
Gram 4- hydroxyl -4'- isopropoxy diphenyl sulphone (DPS) dissolves by heating, it is to be cooled to room temperature when, add 20 grams of oil-soluble polymerization monomers
TDI, stirring, obtains color developing agent mixed solution.
(2) be added in round bottom container 400ml concentration be 4.5%, alcoholysis degree 88%, average degree of polymerization be 3450 it is poly-
Vinyl alcohol aqueous solution obtains water phase.
(3) color developing agent mixed solution is slowly added into water phase, is then dispersed under the speed of 15000r/min
15min obtains the newborn dispersion liquid of the oil that average grain diameter is 0.22um.Deionized water 100ml, tetrem is added into the newborn dispersion liquid of the oil
1 gram of five amine of alkene reacts 5 hours at 55 DEG C then with the mixing speed of 800r/min, and obtaining average grain diameter is 0.20 micron aobvious
Toner microcapsules.
The dye microcapsule the preparation method is as follows:
(1) ODB-2 (Shandong Rui Kang refines), the GN-2 (Tokyo chemical conversion) of 1 parts by weight, 1 weight of 5 parts by weight are weighed
The CK-16 (Wenzhou dragon victory) of part, the ethyl acetate of 30 parts by weight are added in dissolving pan, are stirred, and after heating for dissolving, are cooled to 50
DEG C when, be added 8 parts by weight polyurethane prepolymer and 5 parts by weight dicyclohexyl methyl hydride diisocyanate, stir evenly, obtain
To oily phase.
(2) polyurethane prepolymer the preparation method comprises the following steps:
In dry three-necked flask, the hydroxy-end capped hyper-branched polyester of 3 parts by weight is dissolved in 20ml acetone soln, is obtained
To hydroxy-end capped hyperbranched poly ester solution；The isoflurane chalcone diisocyanate of 10 parts by weight is dissolved in 50ml acetone soln, is obtained
To isoflurane chalcone diisocyanate solution；Under nitrogen protection, isoflurane chalcone diisocyanate solution is added dropwise to hydroxy-end capped
In hyperbranched poly ester solution, into mixed solution, the catalyst dibutyltin dilaurylate of 0.01 parts by weight is added, by reaction temperature
Degree is warming up to 85 DEG C, and reaction obtained polyurethane prepolymer after 2 hours.
(3) 1788 polyvinyl alcohol water solution of PVA that 100 parts by weight concentration are 6% is provided, water phase is obtained.
(4) above-mentioned oil is mutually slowly added into aqueous phase solution, while using high shear agitation with 5600 revs/min of speed
Degree dispersion 7 minutes obtains the oil-in-water dispersion emulsion that average grain diameter is 0.35um；Into scattered lotion be added 30 parts go from
Sub- water, 1.2 parts of tetraethylenepentamine are reacted 3 hours at 55 DEG C then under 600 revs/min of mixing speed, obtain average grain
The dye microcapsule of diameter 0.2um.
The colour developing auxiliary agent is neopelex；
Described adhesive is gelatin.
The preparation method of the thermographic layer is:
Temperature-sensitive microcapsules, color developer microcapsule, colour developing auxiliary agent, adhesive are added in three-necked flask, after mixing evenly,
Obtain thermographic layer.
The substrate layer is polyurethane resin.
The backing layer prepares raw material including at least following in parts by weight:
The polyurethane modified epoxy resin the preparation method is as follows:
(1) in dry three-necked flask, the hydroxy-end capped hyper-branched polyester of 3 parts by weight is dissolved in 20ml acetone soln
In, obtain hydroxy-end capped hyperbranched poly ester solution；The isoflurane chalcone diisocyanate of 10 parts by weight is dissolved in 50ml acetone soln
In, obtain isoflurane chalcone diisocyanate solution；Under nitrogen protection, isoflurane chalcone diisocyanate solution is added dropwise to hydroxyl
In terminated hyperbranched polyester liquid, into mixed solution, the catalyst dibutyltin dilaurylate of 0.01 parts by weight is added, it will be anti-
Temperature is answered to be warming up to 85 DEG C, reaction obtained polyurethane after 2 hours；
(2) it in the polyurethane that the step of 8 parts by weight of bisphenol A epoxy resin being added to 3 parts by weight (1) obtains, is warming up to
It 80 DEG C, reacts under nitrogen protection, reacts 2 hours, polyurethane modified epoxy resin can be obtained.
The matting agent is silica solution, is purchased from Zhejiang Province Yuda Chemical Co., Ltd.
The crosslinking agent is melamine.
The antistatic agent is glycerin monostearate.
The backing layer the preparation method comprises the following steps:
After 10min first is mixed in deionized water and antistatic agent, polyurethane modified epoxy resin is then added, it will
Temperature is increased to 50 DEG C, stirs 30min, then adds crosslinking agent, be again stirring for 30min, be eventually adding matting agent, and back is made
Layer.
The preparation method of thermo-chromatic, at least includes the following steps:
Thermographic layer, backing layer are respectively coated by coating machine on the two sides of substrate layer；Then protective layer is coated with again
In the another side of thermographic layer, through thermal finalization, winding obtains thermo-chromatic.
The protective layer with a thickness of 0.15 μm；The thermographic layer with a thickness of 5 μm；The substrate layer with a thickness of
180μm；The backing layer with a thickness of 0.5 μm
Embodiment 2:
The present embodiment 2 provides a kind of thermo-chromatic, successively includes from top to bottom, protective layer, thermographic layer, substrate
Layer, backing layer；
The protective layer includes at least in parts by weight
The polyurethane adhesive is purchased from Shanghai Shou Xing Industrial Co., Ltd..
The polyvinyl alcohol is vinal, is purchased from Chongqing Ying Zhu building materials Co., Ltd.
The nano silica is purchased from Nanjing Ji Cang nanosecond science and technology Co., Ltd.
The levelling agent organic silicon modified by polyether levelling agent is purchased from crop field chemistry.
The protective layer the preparation method comprises the following steps:
Deionized water, the levelling agent for weighing corresponding parts by weight are added in stirred tank after mixing these three raw materials, are mixed
It is slowly added to polyvinyl alcohol after stirring 10min, 10min is again stirring for, nano silica is then added into system, continue to stir
20min is mixed, polyurethane adhesive is then added, continues to stir 30min, obtains protective layer.
The thermographic layer includes colour developing microcapsules, dye microcapsule, colour developing auxiliary agent, adhesive.
It is described colour developing microcapsules the preparation method is as follows:
(1) 10 grams of xylenylphosphates, 80 grams of ethyl acetate are added in 200 milliliters of reaction flasks, are added with stirring 30
Gram 4- hydroxyl -4'- isopropoxy diphenyl sulphone (DPS) dissolves by heating, it is to be cooled to room temperature when, add 20 grams of oil-soluble polymerization monomers
TDI, stirring, obtains color developing agent mixed solution.
(2) be added in round bottom container 400ml concentration be 4.5%, alcoholysis degree 88%, average degree of polymerization be 3450 it is poly-
Vinyl alcohol aqueous solution obtains water phase.
(3) color developing agent mixed solution is slowly added into water phase, is then dispersed under the speed of 15000r/min
15min obtains the newborn dispersion liquid of the oil that average grain diameter is 0.22um.Deionized water 100ml, tetrem is added into the newborn dispersion liquid of the oil
1 gram of five amine of alkene reacts 5 hours at 55 DEG C then with the mixing speed of 800r/min, and obtaining average grain diameter is 0.20 micron aobvious
Toner microcapsules.
The dye microcapsule the preparation method is as follows:
(1) ODB-2 (Shandong Rui Kang refines), the GN-2 (Tokyo chemical conversion) of 1 parts by weight, 1 weight of 5 parts by weight are weighed
The CK-16 (Wenzhou dragon victory) of part, the ethyl acetate of 30 parts by weight are added in dissolving pan, are stirred, and after heating for dissolving, are cooled to 50
DEG C when, be added 8 parts by weight polyurethane prepolymer and 5 parts by weight dicyclohexyl methyl hydride diisocyanate, stir evenly, obtain
To oily phase.
(2) polyurethane prepolymer the preparation method comprises the following steps:
In dry three-necked flask, the hydroxy-end capped hyper-branched polyester of 3 parts by weight is dissolved in 20ml acetone soln, is obtained
To hydroxy-end capped hyperbranched poly ester solution；The isoflurane chalcone diisocyanate of 10 parts by weight is dissolved in 50ml acetone soln, is obtained
To isoflurane chalcone diisocyanate solution；Under nitrogen protection, isoflurane chalcone diisocyanate solution is added dropwise to hydroxy-end capped
In hyperbranched poly ester solution, into mixed solution, the catalyst dibutyltin dilaurylate of 0.01 parts by weight is added, by reaction temperature
Degree is warming up to 85 DEG C, and reaction obtained polyurethane prepolymer after 2 hours.
(3) 1788 polyvinyl alcohol water solution of PVA that 100 parts by weight concentration are 6% is provided, water phase is obtained.
(4) above-mentioned oil is mutually slowly added into aqueous phase solution, while using high shear agitation with 5600 revs/min of speed
Degree dispersion 7 minutes obtains the oil-in-water dispersion emulsion that average grain diameter is 0.35um；Into scattered lotion be added 30 parts go from
Sub- water, 1.2 parts of tetraethylenepentamine are reacted 3 hours at 55 DEG C then under 600 revs/min of mixing speed, obtain average grain
The dye microcapsule of diameter 0.2um.
The colour developing auxiliary agent is neopelex；
Described adhesive is gelatin.
The preparation method of the thermographic layer is:
Temperature-sensitive microcapsules, color developer microcapsule, colour developing auxiliary agent, adhesive are added in three-necked flask, after mixing evenly,
Obtain thermographic layer.
The substrate layer is polyurethane resin.
The backing layer prepares raw material including at least following in parts by weight:
The polyurethane modified epoxy resin the preparation method is as follows:
(1) in dry three-necked flask, the hydroxy-end capped hyper-branched polyester of 3 parts by weight is dissolved in 20ml acetone soln
In, obtain hydroxy-end capped hyperbranched poly ester solution；The isoflurane chalcone diisocyanate of 10 parts by weight is dissolved in 50ml acetone soln
In, obtain isoflurane chalcone diisocyanate solution；Under nitrogen protection, isoflurane chalcone diisocyanate solution is added dropwise to hydroxyl
In terminated hyperbranched polyester liquid, into mixed solution, the catalyst dibutyltin dilaurylate of 0.01 parts by weight is added, it will be anti-
Temperature is answered to be warming up to 85 DEG C, reaction obtained polyurethane after 2 hours；
(2) it in the polyurethane that the step of 8 parts by weight of bisphenol A epoxy resin being added to 3 parts by weight (1) obtains, is warming up to
It 80 DEG C, reacts under nitrogen protection, reacts 2 hours, polyurethane modified epoxy resin can be obtained.
The matting agent is silica solution, is purchased from Zhejiang Province Yuda Chemical Co., Ltd.
The crosslinking agent is melamine.
The antistatic agent is glycerin monostearate.
The backing layer the preparation method comprises the following steps:
After 10min first is mixed in deionized water and antistatic agent, polyurethane modified epoxy resin is then added, it will
Temperature is increased to 50 DEG C, stirs 30min, then adds crosslinking agent, be again stirring for 30min, be eventually adding matting agent, and back is made
Layer.
The preparation method of thermo-chromatic, at least includes the following steps:
Thermographic layer, backing layer are respectively coated by coating machine on the two sides of substrate layer；Then protective layer is coated with again
In the another side of thermographic layer, through thermal finalization, winding obtains thermo-chromatic.
The protective layer with a thickness of 0.15 μm；The thermographic layer with a thickness of 5 μm；The substrate layer with a thickness of
180μm；The backing layer with a thickness of 0.5 μm
Embodiment 3:
The present embodiment 3 provides a kind of thermo-chromatic, successively includes from top to bottom, protective layer, thermographic layer, substrate
Layer, backing layer；
The protective layer includes at least in parts by weight
The polyurethane adhesive is purchased from Shanghai Shou Xing Industrial Co., Ltd..
The polyvinyl alcohol is vinal, is purchased from Chongqing Ying Zhu building materials Co., Ltd.
The nano silica is purchased from Nanjing Ji Cang nanosecond science and technology Co., Ltd.
The levelling agent organic silicon modified by polyether levelling agent is purchased from crop field chemistry.
The protective layer the preparation method comprises the following steps:
Deionized water, the levelling agent for weighing corresponding parts by weight are added in stirred tank after mixing these three raw materials, are mixed
It is slowly added to polyvinyl alcohol after stirring 10min, 10min is again stirring for, nano silica is then added into system, continue to stir
20min is mixed, polyurethane adhesive is then added, continues to stir 30min, obtains protective layer.
The thermographic layer includes colour developing microcapsules, dye microcapsule, colour developing auxiliary agent, adhesive.
It is described colour developing microcapsules the preparation method is as follows:
(1) 10 grams of xylenylphosphates, 80 grams of ethyl acetate are added in 200 milliliters of reaction flasks, are added with stirring 30
Gram 4- hydroxyl -4'- isopropoxy diphenyl sulphone (DPS) dissolves by heating, it is to be cooled to room temperature when, add 20 grams of oil-soluble polymerization monomers
TDI, stirring, obtains color developing agent mixed solution.
(2) be added in round bottom container 400ml concentration be 4.5%, alcoholysis degree 88%, average degree of polymerization be 3450 it is poly-
Vinyl alcohol aqueous solution obtains water phase.
(3) color developing agent mixed solution is slowly added into water phase, is then dispersed under the speed of 15000r/min
15min obtains the newborn dispersion liquid of the oil that average grain diameter is 0.22um.Deionized water 100ml, tetrem is added into the newborn dispersion liquid of the oil
1 gram of five amine of alkene reacts 5 hours at 55 DEG C then with the mixing speed of 800r/min, and obtaining average grain diameter is 0.20 micron aobvious
Toner microcapsules.
The dye microcapsule the preparation method is as follows:
(1) ODB-2 (Shandong Rui Kang refines), the GN-2 (Tokyo chemical conversion) of 1 parts by weight, 1 weight of 5 parts by weight are weighed
The CK-16 (Wenzhou dragon victory) of part, the ethyl acetate of 30 parts by weight are added in dissolving pan, are stirred, and after heating for dissolving, are cooled to 50
DEG C when, be added 8 parts by weight polyurethane prepolymer and 5 parts by weight dicyclohexyl methyl hydride diisocyanate, stir evenly, obtain
To oily phase.
(2) polyurethane prepolymer the preparation method comprises the following steps:
In dry three-necked flask, the hydroxy-end capped hyper-branched polyester of 3 parts by weight is dissolved in 20ml acetone soln, is obtained
To hydroxy-end capped hyperbranched poly ester solution；The isoflurane chalcone diisocyanate of 10 parts by weight is dissolved in 50ml acetone soln, is obtained
To isoflurane chalcone diisocyanate solution；Under nitrogen protection, isoflurane chalcone diisocyanate solution is added dropwise to hydroxy-end capped
In hyperbranched poly ester solution, into mixed solution, the catalyst dibutyltin dilaurylate of 0.01 parts by weight is added, by reaction temperature
Degree is warming up to 85 DEG C, and reaction obtained polyurethane prepolymer after 2 hours.
(3) 1788 polyvinyl alcohol water solution of PVA that 100 parts by weight concentration are 6% is provided, water phase is obtained.
(4) above-mentioned oil is mutually slowly added into aqueous phase solution, while using high shear agitation with 5600 revs/min of speed
Degree dispersion 7 minutes obtains the oil-in-water dispersion emulsion that average grain diameter is 0.35um；Into scattered lotion be added 30 parts go from
Sub- water, 1.2 parts of tetraethylenepentamine are reacted 3 hours at 55 DEG C then under 600 revs/min of mixing speed, obtain average grain
The dye microcapsule of diameter 0.2um.
The colour developing auxiliary agent is neopelex；
Described adhesive is gelatin.
The preparation method of the thermographic layer is:
Temperature-sensitive microcapsules, color developer microcapsule, colour developing auxiliary agent, adhesive are added in three-necked flask, after mixing evenly,
Obtain thermographic layer.
The substrate layer is polyurethane resin.
The backing layer prepares raw material including at least following in parts by weight:
The polyurethane modified epoxy resin the preparation method is as follows:
(1) in dry three-necked flask, the hydroxy-end capped hyper-branched polyester of 3 parts by weight is dissolved in 20ml acetone soln
In, obtain hydroxy-end capped hyperbranched poly ester solution；The isoflurane chalcone diisocyanate of 10 parts by weight is dissolved in 50ml acetone soln
In, obtain isoflurane chalcone diisocyanate solution；Under nitrogen protection, isoflurane chalcone diisocyanate solution is added dropwise to hydroxyl
In terminated hyperbranched polyester liquid, into mixed solution, the catalyst dibutyltin dilaurylate of 0.01 parts by weight is added, it will be anti-
Temperature is answered to be warming up to 85 DEG C, reaction obtained polyurethane after 2 hours；
(2) it in the polyurethane that the step of 8 parts by weight of bisphenol A epoxy resin being added to 3 parts by weight (1) obtains, is warming up to
It 80 DEG C, reacts under nitrogen protection, reacts 2 hours, polyurethane modified epoxy resin can be obtained.
The matting agent is silica solution, is purchased from Zhejiang Province Yuda Chemical Co., Ltd.
The crosslinking agent is melamine.
The antistatic agent is glycerin monostearate.
The backing layer the preparation method comprises the following steps:
After 10min first is mixed in deionized water and antistatic agent, polyurethane modified epoxy resin is then added, it will
Temperature is increased to 50 DEG C, stirs 30min, then adds crosslinking agent, be again stirring for 30min, be eventually adding matting agent, and back is made
Layer.
The preparation method of thermo-chromatic, at least includes the following steps:
Thermographic layer, backing layer are respectively coated by coating machine on the two sides of substrate layer；Then protective layer is coated with again
In the another side of thermographic layer, through thermal finalization, winding obtains thermo-chromatic.
The protective layer with a thickness of 0.15 μm；The thermographic layer with a thickness of 5 μm；The substrate layer with a thickness of
180μm；The backing layer with a thickness of 0.5 μm
Embodiment 4:
Embodiment 4 is with embodiment 3, the difference lies in that substrate layer is changed to polyurethane resin and superbrnaching end-hydroxy gathers
The mixing of ester, and the weight ratio between the polyurethane resin and superbrnaching end-hydroxy polyester is 5:1.
The superbrnaching end-hydroxy polyester is purchased from Wuhan hyperbranched resin Co., Ltd.
Embodiment 5:
Embodiment 5 is with embodiment 4, the difference lies in that matting agent is changed to silane coupler modified silica solution.
The silane coupler modified silica solution the preparation method comprises the following steps:
The silica solution (silica dioxide granule content is 20wt%, partial size 15nm) of 10 parts by weight is added to three-necked flask
In and be stirred；In room temperature and under continuing stirring condition, N- (2- aminoethyl) -3- aminopropyl trimethoxy of 3 parts by weight is taken
Silane is added drop-wise in silica solution, rate of addition 10ml/min；Then the pH value of glacial acetic acid regulation system is being selected to continue to 8
Stirring obtains silane coupler modified silica solution to 20h.
Embodiment 6:
Embodiment 6 is with embodiment 4, the difference lies in that it is total that matting agent is changed to dodecyl sodium sulfate, silane coupling agent
Same modified silicasol.
The dodecyl sodium sulfate, the common modified silicasol of silane coupling agent the preparation method comprises the following steps:
The silica solution (silica dioxide granule content is 20wt%, partial size 15nm) of 10 parts by weight is added to three-necked flask
In and be stirred；In room temperature and under continuing stirring condition, N- (2- aminoethyl) -3- aminopropyl trimethoxy of 2 parts by weight is taken
Silane is added drop-wise in silica solution, rate of addition 10ml/min；Then the dodecyl sodium sulfonate of 2 parts by weight is added into system again
Sodium；Then the pH value of glacial acetic acid regulation system is being selected to continue stirring to 8 to 20h, 20h is stirred at room temperature, obtains dodecane
The common modified silicasol of base sodium sulfonate, silane coupling agent.
Comparative example 1:
Comparative example 1 of the invention is with embodiment 3, the difference lies in that not including protective layer.
Comparative example 2:
Comparative example 2 of the invention is with embodiment 3, the difference lies in that not including backing layer.
Comparative example 3:
Comparative example 3 of the invention is with embodiment 4, the difference lies in that substrate layer is changed to superbrnaching end-hydroxy polyester.
Comparative example 4:
Comparative example 4 of the invention is with embodiment 4, the difference lies in that substrate layer is changed to polypropylene.
Comparative example 5:
Comparative example 5 of the invention is with embodiment 4, the difference lies in that polyurethane modified epoxy resin is changed to polyurethane
Resin.
Comparative example 6:
Comparative example 6 of the invention is with embodiment 4, the difference lies in that polyurethane modified epoxy resin is changed to bis-phenol ring
Oxygen resin.
Performance evaluation
(1) backing layer adhesive force is tested
A, after thermo-chromatic is made, after firmly rubbing, thermographic layer is not fallen off, and is then 0 without folding line, thermographic
It is then 1 that slightly falling off and having slight folding line, which occur, in layer, and thermographic layer large area occurs to fall off and a large amount of folding lines occur then being 2；
It b, is then 0 without particle obscission in film printing, having some particles to fall off then is 1.
(2) backing layer crosses machine test
In film printing, crossing machine adhesion is then zero；Adhesion is then ×.
(3) surface roughness is tested
By in embodiment and comparative example obtain product be respectively placed in 100 degrees Celsius, humidity be 100% in the environment of put
After setting 30 days, tested using TR200 surfagauge.
(4) waterproofing tests
By in embodiment and comparative example obtain product be respectively placed in 100 degrees Celsius, humidity be 100% in the environment of put
After setting 30 days, then printed, it is 0 if having no effect to colour developing quality that whether paired observation, which influences to develop the color, respectively,
There is the case where any influence colour developing, is then 1.
1 the performance test results of table
Novel thermosensitive film in the application all has preferably between protective layer, thermographic layer, substrate layer, backing layer
Cohesive force；Adhesion during film printing has good machine excessively；There is preferable smooth performance and antistatic simultaneously
Performance, waterproof performance, comprehensive performance are more excellent.
Example above-mentioned is merely illustrative, and is used to explain the present invention some features of the method.Appended right is wanted
The range as wide as possible for being intended to require to be contemplated that is sought, and embodiments as presented herein is only according to all possible implementation
The explanation of the embodiment of the combined selection of example.Therefore, the purpose of applicant is that the attached claims are not illustrated this hair
The exemplary selectional restriction of bright feature.Some numberical ranges used also include sub- model in the claims
It encloses, the variation in these ranges should also be construed to be covered by the attached claims in the conceived case.
Claims (6)
1. a kind of thermo-chromatic, which is characterized in that the thermo-chromatic successively includes protective layer, thermographic from top to bottom
Layer, substrate layer, backing layer；
The protective layer prepares raw material including at least following in parts by weight:
The thermographic layer includes at least colour developing microcapsules, dye microcapsule, colour developing auxiliary agent, adhesive；
The substrate layer is the mixing of polyurethane resin and superbrnaching end-hydroxy polyester, and polyurethane resin and superbrnaching end-hydroxy are poly-
The weight ratio of ester is 5:1；
The backing layer prepares raw material including at least following in parts by weight:
The polyurethane modified epoxy resin the preparation method is as follows:
A. in dry three-necked flask, the hydroxy-end capped hyper-branched polyester of 3 parts by weight is dissolved in 20ml acetone soln, is obtained
Hydroxy-end capped hyperbranched poly ester solution；The isoflurane chalcone diisocyanate of 10 parts by weight is dissolved in 50ml acetone soln, is obtained
Isoflurane chalcone diisocyanate solution；Under nitrogen protection, isoflurane chalcone diisocyanate solution is added dropwise to hydroxy-end capped super
In branched polyester solution, into mixed solution, the catalyst dibutyltin dilaurylate of 0.01 parts by weight is added, by reaction temperature
85 DEG C are warming up to, reaction obtained polyurethane after 2 hours；
B. in the polyurethane step a that 8 parts by weight of bisphenol A epoxy resin are added to 3 parts by weight obtained, 80 DEG C are warming up to,
It is reacted under nitrogen protection, reacts 2 hours, polyurethane modified epoxy resin can be obtained.
The matting agent is silane coupler modified silica solution.
2. thermo-chromatic as described in claim 1, which is characterized in that the crosslinking agent is melamine.
3. thermo-chromatic as described in claim 1, which is characterized in that the partial size of the colour developing microcapsules is 0.1~1 micron.
4. thermo-chromatic as described in claim 1, which is characterized in that the partial size of the dye microcapsule is 0.1~1 micron.
5. the preparation method of thermo-chromatic as described in any one of claims 1 to 4, which is characterized in that include at least following
Step:
Thermographic layer, backing layer are respectively coated by coating technique on the two sides of substrate layer；Then protective layer is coated on again
The another side of thermographic layer, obtains thermo-chromatic after drying.
6. application of the thermo-chromatic as described in any one of claims 1 to 4 in field of medical imaging.
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| CN110042696A (en) * | 2018-01-16 | 2019-07-23 | 南昌添丽特实业有限责任公司 | The long-acting color developing agent of microencapsulation temperature-sensitive, preparation method and application |
| CN109734942B (en) * | 2018-12-26 | 2021-04-27 | 重庆市中迪医疗信息科技股份有限公司 | Medical thermosensitive film and preparation method thereof |
| CN111098618A (en) * | 2020-01-16 | 2020-05-05 | 南阳柯丽尔科技有限公司 | Thermosensitive film and preparation method thereof |
| CN111730936B (en) * | 2020-07-13 | 2022-08-02 | 焦作卓立膜材料股份有限公司 | Food plastic packaging film with hot stamping identification function and preparation method thereof |
| CN112829490B (en) * | 2020-12-29 | 2023-02-17 | 乐凯医疗科技有限公司 | Environment-friendly thermosensitive recording material |
| CN113650436B (en) * | 2021-08-18 | 2022-12-02 | 杭州梅清数码科技有限公司 | High-temperature-resistant thermosensitive medical film and preparation method thereof |
| CN115230360B (en) * | 2022-07-08 | 2024-03-12 | 广东冠豪新材料研发有限公司 | Thermosensitive imaging coating liquid and application thereof in thermosensitive recording material |
| CN115595005B (en) * | 2022-10-12 | 2024-01-30 | 东北电力大学 | Low-temperature reversible thermochromic compression-resistant anticorrosive paint and preparation method and application thereof |
| CN115612396B (en) * | 2022-12-19 | 2023-03-10 | 潍坊恒彩数码影像材料有限公司 | Degradable thermosensitive film coating based on gamma-cyclodextrin modified cellulose and preparation method thereof |
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| CN1843767A (en) * | 2006-05-10 | 2006-10-11 | 中国乐凯胶片集团公司 | Heat-sensitive recording material |
| CN101247962A (en) * | 2005-08-25 | 2008-08-20 | 王子制纸株式会社 | Thermosensitive recording material and process for production thereof |
| CN105216472A (en) * | 2015-10-30 | 2016-01-06 | 合肥乐凯科技产业有限公司 | A kind of dry type medical film polyester film base |
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| CN101247962A (en) * | 2005-08-25 | 2008-08-20 | 王子制纸株式会社 | Thermosensitive recording material and process for production thereof |
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