CN108453017A - A kind of graphical coating and preparation method thereof - Google Patents
A kind of graphical coating and preparation method thereof Download PDFInfo
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- CN108453017A CN108453017A CN201810049452.7A CN201810049452A CN108453017A CN 108453017 A CN108453017 A CN 108453017A CN 201810049452 A CN201810049452 A CN 201810049452A CN 108453017 A CN108453017 A CN 108453017A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
- B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
- B05D3/065—After-treatment
- B05D3/067—Curing or cross-linking the coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0063—Glycosaminoglycans or mucopolysaccharides, e.g. keratan sulfate; Derivatives thereof, e.g. fucoidan
- C08B37/0072—Hyaluronic acid, i.e. HA or hyaluronan; Derivatives thereof, e.g. crosslinked hyaluronic acid (hylan) or hyaluronates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0063—Glycosaminoglycans or mucopolysaccharides, e.g. keratan sulfate; Derivatives thereof, e.g. fucoidan
- C08B37/0075—Heparin; Heparan sulfate; Derivatives thereof, e.g. heparosan; Purification or extraction methods thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0084—Guluromannuronans, e.g. alginic acid, i.e. D-mannuronic acid and D-guluronic acid units linked with alternating alpha- and beta-1,4-glycosidic bonds; Derivatives thereof, e.g. alginates
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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
- C09D105/00—Coating compositions based on polysaccharides or on their derivatives, not provided for in groups C09D101/00 or C09D103/00
- C09D105/04—Alginic acid; Derivatives thereof
-
- 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
- C09D105/00—Coating compositions based on polysaccharides or on their derivatives, not provided for in groups C09D101/00 or C09D103/00
- C09D105/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- 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
- C09D105/00—Coating compositions based on polysaccharides or on their derivatives, not provided for in groups C09D101/00 or C09D103/00
- C09D105/10—Heparin; Derivatives thereof
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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
- C09D125/00—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 aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
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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
- C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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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
- C09D139/00—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
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Abstract
The invention discloses a kind of graphical coating, preparation method includes：(1) polyanion is modified with nitrine aniline；(2) substrate impregnated to 1 in polycation aqueous solution~after sixty minutes, it takes out；(3) upper step substrate is put into modified polyanion aqueous solution and is impregnated 1~60 minute, taken out, is prepared by the coating to complete a deposition cycle；(4) step (2)~(3) are repeated, the preparation of the coating of multiple deposition cycles is completed in substrate, there is the coating material of micro-structure to obtain surface；(5) patterned photomask is covered in coating material surface, irradiating ultraviolet light causes partial cross-linking reaction；(6) coating material after partial cross-linking is placed on wet environment or contacted with water to get to the graphical coating.
Description
Technical field
The present invention relates to the preparation fields of graphical coating, and in particular to a kind of Dynamic coating that can be achieved graphically to show
And preparation method thereof.
Background technology
Coating surface patterning has great significance for the development of modern science and technology.Therefore, table is patterned for a long time
The technology of preparing in face is concerned.Either chemistry, Material Field or biological field are required for through patterned surface reality
Existing multifunction.Patterned surface technology of preparing is developed so far, and can be divided mainly into etching, template duplicating, surface chemical modification three
Class method.There is the limitation of itself in these methods, such as etching method is often corroded using solvent, have larger poison
Property and operational danger；Template duplicating method is related to staying the processes such as mould, reverse mould, and operation is complex；Surface chemical modification method is real
It is harsher etc. to test condition.The prior art, far from meet patterned surface preparation the needs of.Therefore, new patterned surface
Preparation method still needs to be continuously developed.
By dynamic regulation surface topology pattern, can realize coating material that patterned surface simplicity is accurately prepared and
Technological means, although its importance is self-evident at present still without corresponding example.
Invention content
In view of the above-mentioned problems, the present invention provides a kind of graphical coatings and preparation method thereof.By in coating material
Photo-crosslinking group is introduced, and combines the dynamic characteristic of coating itself, the regulation and control of coating surface micro-structure is realized, obtains different surfaces
The coating area of pattern obtains region light scattering otherness, based on this, realizes figure showing in coating surface.
The technical solution adopted by the present invention is as follows：
A kind of preparation method of graphical coating, includes the following steps：
(1) polyanion is modified with 4- nitrine anilinechlorides, obtained modification polyanion is soluble in water, matches
At modified polyanion aqueous solution；Polycation is soluble in water, it is made into polycation aqueous solution；
(2) substrate impregnated to 1 in polycation aqueous solution~after sixty minutes, substrate is taken out；
(3) upper step substrate is put into modified polyanion aqueous solution and is impregnated 1~60 minute, substrate is taken out, to
It is prepared by the coating for completing a deposition cycle；
(4) step (2)~(3) are repeated, the preparation of the coating of multiple deposition cycles are completed in substrate, to obtain surface
Coating material with micro-structure；
(5) patterned photomask is covered in coating material surface, irradiating ultraviolet light causes partial cross-linking reaction；
(6) coating material after partial cross-linking is placed on wet environment or contacted with water to get to described graphical
Coating.
Preferably, the preparation of the modified polyanion includes：By polyanion and nitrine aniline in molar ratio 10:1~7
It is dissolved in water, is reacted 10~60 hours under the catalysis of 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides, obtain described change
Property polyanion.Gained is modified polyanion has photolytic activity after modified, can be achieved under ultraviolet lighting and polycation
Covalent cross-linking reduces molecular chain movement ability.
In the preparation of modified polyanion, a concentration of 0.1~100mg/mL of polyanion, 1- (3- dimethylaminos third
Base) -3- ethyl carbodiimides a concentration of 10~1000mg/mL, reaction temperature be 0~40 DEG C.
The polyanion is polyacrylic acid, alginic acid, hyaluronic acid, kayexalate, heparin sodium, milt DNA
At least one of with polymethylacrylic acid；Preferably, the polyanion is polyacrylic acid, the molecular of polyacrylic acid
Amount is 10,000~1000,000；Further preferably, the mole of the polyacrylic acid is 100,000~200,000.
A concentration of 0.1~100mg/mL of the modified polyanion aqueous solution, pH value are 1~7.
The polycation is polyethyleneimine, polyallylamine hydrochloride, gelatin, diallyl dimethyl amine salt acid
At least one of salt, nucleoprotamine, chitosan and polylysine.Preferably, the polycation is polyethyleneimine, gather
The mole of aziridine is 1,000~100,000, shows good chain movement ability in an assembling process；Into
One step is preferred, and the mole of the polyethyleneimine is 20,000~50,000, the poly- second within the scope of this mole
Alkene imines strand has more preferable chain movement ability and assembly behavior.
A concentration of 0.1~100mg/mL of the polycation aqueous solution, pH value are 8~11.
The substrate is at least one of silicon chip, glass, quartz, metal, calcirm-fluoride, ceramics and plastics.Preferably,
The substrate is silicon chip, can provide deeper background colour, enhances the light and shade difference between region.
Preferably, it in step (4), repeats step (2)~(3) 5~500 times, i.e., completes 5~500 depositions in substrate
The preparation of the coating in period.
Coating material of the present invention surface in preparation process spontaneously forms the principle of micro-structure：Between polyelectrolyte molecules chain
The significantly adjustment of interaction leads to the spontaneous rearrangement of self structure.
In step (5), the intensity of ultraviolet light is 1~10000 μ W/cm2, and the irradiation time of ultraviolet light is 1~10000 second.
In step (6), the relative humidity of the wet environment is 70~100%, and the processing time in wet environment is 1
~72 hours；Preferably, the relative humidity of the wet environment is 90~100%, the processing time in wet environment is
10~24 hours.
In step (6), contacted with water refer to by the coating material after partial cross-linking be immersed in pH value be 1~12 water in or
It sprays water to coating material surface, processing time is 1~72 hour.
In the present invention, the principle of coating material after the partial cross-linking graphical presentation in wet environment or after contacting with water：
Before carrying out step (6), the cross-linked areas of coating material and uncrosslinked region surface all have micro-structure, be placed on wet environment or
After being contacted with water, a large number of water molecules of coating material intake produces plastication, enables the micro-structure of uncrosslinked region surface
Enough by the spontaneous disappearance of the movement of strand, and cross-linked areas maintains the micro- knot in original surface since molecular chain movement is limited
Structure causes the difference in the difference and light scattering on uncrosslinked region and cross-linked areas surface topology pattern, to make figure can
Depending on change.
It is a further object of the present invention to provide a kind of graphical coatings being prepared by the above method.
Compared with prior art, the present invention has the following advantages and effects：
The present invention controls the surface micro-structure evolution process of coating material using the crosslinked method of selective light, to realize
Graphical identifier showing on coating, the process are simple to operate and friendly to environment, and can be used for showing various types of figures.
Description of the drawings
Fig. 1 is photo and painting of the coating material after the partial cross-linking for not carrying out saturated humidity processing in embodiment 1
The scanning electron microscope (SEM) photograph of layer surface；
Fig. 2 be shown in embodiment 1 two-dimension code pattern the acid coated photo of polyallylamine hydrochloride/seaweed and
The scanning electron microscope (SEM) photograph of the coating surface；
Fig. 3 is the photo for polyallylamine hydrochloride/polyacrylic acid coating that two-dimension code pattern is shown in embodiment 2；
Fig. 4 is the photo for polyethyleneimine/hyaluronic acid coatings that bar code figure is shown in embodiment 3；
Fig. 5 is diallyl dimethyl amine hydrochlorate/polystyrene that quadrate array figure is shown in embodiment 4
The photo of sodium sulfonate coating and the scanning electron microscope (SEM) photograph of the coating surface；
Fig. 6 is diallyl dimethyl amine hydrochlorate/heparin sodium coating that band array pattern is shown in embodiment 5
Photo and the coating surface scanning electron microscope (SEM) photograph.
Specific implementation mode
It is further illustrated the present invention below in conjunction with specific example.
Embodiment 1
(1) by alginic acid and 4- nitrine anilinechloride in molar ratio 10:1 is dissolved in water, in 1- (3- dimethylaminos third
Base) the lower reaction of -3- ethyl carbodiimides catalysis 50 hours, in system, a concentration of 2mg/mL of alginic acid, 1- (3- dimethylaminos
Propyl) -3- ethyl carbodiimides a concentration of 500mg/mL, obtain that there is photoactive modified alginic acid；
It is soluble in water that alginic acid will be modified, be made into a concentration of 5mg/mL, the modification seaweed aqueous acid that pH value is 3.0；It will
Polyallylamine hydrochloride is soluble in water, is made into a concentration of 5mg/mL, the polyallylamine hydrochloride aqueous solution that pH value is 9.0；
(2) the silicon chip substrate cleaned up is impregnated after ten minutes in polyallylamine hydrochloride aqueous solution, is taken out, then
It is put into modified seaweed aqueous acid and impregnates 10 minutes, the two steps obtain surface after repeating 50 times have the coating of micro-structure
Material；
(3) photomask for being carved with two-dimension code pattern is covered in coating material surface, be placed under 500 μ W/cm2 ultraviolet lights
Irradiation causes partial cross-linking reaction for 100 seconds；
(4) coating material after partial cross-linking is placed on 30 hours in the environment that relative humidity is 100%, realizes figure
Shape showing to get the graphical coating (polyallylamine hydrochloride/seaweed is acid coated) on coating.
Fig. 1 does not carry out the photo and coating surface of saturated humidity processing for the coating material after partial cross-linking in the present embodiment
Scanning electron microscope (SEM) photograph, Fig. 2 is the acid coated photograph of polyallylamine hydrochloride/seaweed that two-dimension code pattern is shown in the present embodiment
The scanning electron microscope (SEM) photograph of piece and the coating surface.Observation chart 1 and Fig. 2 can have found, before carrying out saturated humidity processing, cross-linked areas and
The surface topology pattern in uncrosslinked region is not significantly different, and causes figure that can not show.And showing two-dimension code pattern
On polyallylamine hydrochloride/seaweed is acid coated, surface topology pattern has significant difference between different zones；Cross-linked areas
Since the light scattering effect presentation that micro-structure is brought is opaque, and uncrosslinked region surface is smooth, and high transparency shows bottom
The black of portion's silicon chip；The difference of surface topography leads to the variation of region light and shade and graph visualization between different zones on the coating.
Embodiment 2
(1) by mole be 25000 polyacrylic acid and 4- nitrine anilinechloride in molar ratio 10:1 is dissolved in
In water, 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides catalysis under react 20 hours, in system, polyacrylic acid it is dense
Degree is 1mg/mL, 1- (3- dimethylamino-propyls) -3- ethyl carbon
A concentration of 100mg/mL of diimine obtains having photoactive modified polyacrylic acid；
Modified polyacrylic acid is soluble in water, it is made into a concentration of 1mg/mL, the modified polyacrylic acid that pH value is 2.0 is water-soluble
Liquid；Polyallylamine hydrochloride is soluble in water, it is made into a concentration of 1mg/mL, the polyallylamine hydrochloride water that pH value is 10.0
Solution；
(2) it after impregnating the silicon chip substrate cleaned up 30 minutes in polyallylamine hydrochloride aqueous solution, takes out, then
It is put into modified polypropene aqueous acid and impregnates 30 minutes, the two steps obtain surface after repeating 100 times have micro-structure
Coating material；
(3) after the photomask for being carved with two-dimension code pattern being covered in coating material surface, 500 μ W/cm2 ultraviolet lights are placed on
Lower irradiation causes partial cross-linking reaction for 10 seconds；
(4) coating material after partial cross-linking is placed in the environment that relative humidity is 90% 30 hours, realizes figure
Showing to get the graphical coating (polyallylamine hydrochloride/polyacrylic acid coating) on coating.
Fig. 3 is the photo for polyallylamine hydrochloride/polyacrylic acid coating that two-dimension code pattern is shown in the present embodiment.
Observation chart 3 can be found, on the polyallylamine hydrochloride for showing two-dimension code pattern/polyacrylic acid coating, different zones
Light transmittance is different, and cross-linked areas light transmittance is low, shows shallower color, and does not carry out photo-crosslinking region light transmittance height, silicon chip
Base color shows very well.
Embodiment 3
(1) by hyaluronic acid and 4- nitrine anilinechloride in molar ratio 10:1 is dissolved in water, in 1- (3- dimethylaminos
Propyl) the lower reaction of -3- ethyl carbodiimides catalysis 40 hours, in system, a concentration of 2mg/mL of hyaluronic acid, 1- (3- diformazans
Aminopropyl) -3- ethyl carbodiimides a concentration of 500mg/mL, obtain that there is photoactive modified hyaluronic acid；
Modified hyaluronic acid is soluble in water, it is made into a concentration of 10mg/mL, the modified hyaluronic acid that pH value is 1.0 is water-soluble
Liquid；The polyethyleneimine for being 100000 by mole is soluble in water, is made into a concentration of 10mg/mL, the poly- second that pH value is 8.0
Alkene imines aqueous solution；
(2) the silicon chip substrate cleaned up is impregnated after twenty minutes in aq. polyethyleneimine, takes out, places into and change
Property hyaluronic acid aqueous solution in impregnate 20 minutes, the two steps repeat 200 times after obtain surface have micro-structure coating material
Material；
(3) after the photomask for being carved with bar code figure being covered in coating material surface, it is ultraviolet that 1000 μ W/cm2 are placed on
It is irradiated under light and causes within 30 seconds partial cross-linking reaction；
(4) coating material after partial cross-linking is placed in water 30 hours, realize figure on coating show to get
The graphical coating (polyethyleneimine/hyaluronic acid coatings).
Fig. 4 is the photo for polyethyleneimine/hyaluronic acid coatings that bar code figure is shown in the present embodiment.Observation chart
4 can find, have on the uncrosslinked flattened region of acquired polyethyleneimine/hyaluronic acid coatings with bar code figure good
Good translucency, the region theca interna show silicon chip base color, and cross-linked areas is due to the presence of surface topology, and light dissipates
It penetrates by force, photopermeability is poor, and Film color is partially shallow.Obtain to store the item of information by the comparison of light and shade to the coating different zones
Shape code.
Embodiment 4
(1) by kayexalate and 4- nitrine anilinechloride in molar ratio 5:1 is dissolved in water, in 1- (3- bis-
Methylaminopropyl) the lower reaction of -3- ethyl carbodiimides catalysis 48 hours, in system, a concentration of 2mg/ of kayexalate
A concentration of 500mg/mL of mL, 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides, obtains having photoactive modified polyphenyl
Vinyl sulfonic acid sodium；
Modified polystyrene sulfonic acid sodium is soluble in water, it is made into a concentration of 8mg/mL, the modified polystyrene sulphur that pH is 3.0
Acid sodium aqueous solution；Diallyl dimethyl amine hydrochlorate is soluble in water, it is made into a concentration of 15mg/mL, pH is poly- the two of 9.0
Allyl dimethyl base amine hydrochlorate aqueous solution；
(2) the silicon chip substrate cleaned up is impregnated 30 minutes in diallyl dimethyl amine hydrochlorate aqueous solution
Afterwards, it takes out, places into modified polystyrene sulfonic acid sodium water solution and impregnate 30 minutes, the two steps obtain table after repeating 50 times
Face has the coating material of micro-structure；
(3) after the photomask for being carved with square dot pattern being covered in coating material surface, it is purple that 800 μ W/cm2 are placed on
It is irradiated under outer light and causes within 60 seconds partial cross-linking reaction；
(4) coating material after partial cross-linking is placed on 50h in the environment that relative humidity is 100%, realizes square
Dot pattern showing to get graphical coating (the diallyl dimethyl amine hydrochlorate/polystyrene on coating
Sodium sulfonate coating).
Fig. 5 is diallyl dimethyl amine hydrochlorate/polyphenyl second that quadrate array figure is shown in the present embodiment
The photo of alkene sodium sulfonate coating and the scanning electron microscope (SEM) photograph of the coating surface.
Embodiment 5
(1) by heparin sodium and 4- nitrine anilinechloride in molar ratio 3:1 is dissolved in water, in 1- (3- dimethylaminos third
Base) the lower reaction of -3- ethyl carbodiimides catalysis 48 hours, in system, a concentration of 5mg/mL of heparin sodium, 1- (3- dimethylaminos
Propyl) -3- ethyl carbodiimides a concentration of 200mg/mL, obtain that there is photoactive modified heparin sodium；
Modified heparin sodium is soluble in water, it is made into a concentration of 5mg/mL, the modified heparin sodium water solution that pH is 2.0；It will gather
Diallydimethyl amine hydrochlorate is soluble in water, is made into a concentration of 15mg/mL, the diallyl dimethyl amine that pH is 9.0
Hydrochloric acid saline solution；
(2) the silicon chip substrate cleaned up is impregnated 10 minutes in diallyl dimethyl amine hydrochlorate aqueous solution
Afterwards, it takes out, places into modified heparin sodium water solution and impregnate 10 minutes, the two steps obtain surface with micro- after repeating 50 times
The coating material of structure；
(3) it after the photomask for being carved with band array being covered in coating material surface, is placed under 500 μ W/cm2 ultraviolet lights
Irradiation causes partial cross-linking reaction for 10 seconds；
(4) coating material after partial cross-linking is placed in the environment that relative humidity is 100% 20 hours, realizes band
Array showing to get the graphical coating (diallyl dimethyl amine hydrochlorate/heparin sodium coating) on coating.
Fig. 6 is diallyl dimethyl amine hydrochlorate/heparin sodium painting that band array pattern is shown in the present embodiment
The photo of layer and the scanning electron microscope (SEM) photograph of the coating surface.
Embodiment 6
(1) by milt DNA and 4- nitrine anilinechloride in molar ratio 2:1 is dissolved in water, in 1- (3- dimethylaminos third
Base) the lower reaction of -3- ethyl carbodiimides catalysis 72 hours, in system, a concentration of 10mg/mL of nucleoprotamine, 1- (3- diformazan ammonia
Base propyl) -3- ethyl carbodiimides a concentration of 100mg/mL, obtain that there is photoactive modified milt DNA；
Will modified milt DNA it is soluble in water, be made into a concentration of 15mg/mL, pH is 4.0 to change milt DNA aqueous solution；By fish
Protamine is soluble in water, is made into a concentration of 5mg/mL, the nucleoprotamine aqueous solution that pH is 8.5；
(2) the silicon chip substrate cleaned up is impregnated after twenty minutes in nucleoprotamine aqueous solution, takes out, places into modification
It is impregnated 20 minutes in milt DNA aqueous solution, the two steps obtain surface after repeating 100 times have the coating material of micro-structure；
(3) after the photomask for being carved with bar code shape being covered in coating material surface, 1000 μ W/cm2 ultraviolet lights are placed on
Lower irradiation causes partial cross-linking reaction for 15 seconds；
(4) coating material after partial cross-linking is placed in water phase 72 hours, realizes bar code figure on coating
Show to get the graphical coating (milt DNA/nucleoprotamine coating).
Claims (10)
1. a kind of preparation method of graphical coating, which is characterized in that include the following steps：
(1) polyanion is modified with 4- nitrine anilinechlorides, obtained modification polyanion is soluble in water, is made into and changes
Property polyanion aqueous solution；Polycation is soluble in water, it is made into polycation aqueous solution；
(2) substrate impregnated to 1 in polycation aqueous solution~after sixty minutes, substrate is taken out；
(3) upper step substrate is put into modified polyanion aqueous solution and is impregnated 1~60 minute, substrate taken out, to complete
It is prepared by the coating of one deposition cycle；
(4) step (2)~(3) are repeated, the preparation of the coating of multiple deposition cycles is completed in substrate, is had to obtain surface
The coating material of micro-structure；
(5) patterned photomask is covered in coating material surface, irradiating ultraviolet light causes partial cross-linking reaction；
(6) coating material after partial cross-linking is placed on wet environment or contacted with water to get to the graphical coating.
2. the preparation method of graphical coating according to claim 1, which is characterized in that the system of the modified polyanion
It is standby to include：By polyanion and nitrine aniline in molar ratio 10:1~7 is dissolved in water, in 1- (3- dimethylamino-propyls) -3-
It is reacted 10~60 hours under the catalysis of ethyl carbodiimide, obtains the modified polyanion.
3. the preparation method of graphical coating according to claim 2, which is characterized in that in the preparation of modified polyanion
In, a concentration of the 10 of a concentration of 0.1~100mg/mL of polyanion, 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides
~1000mg/mL, reaction temperature are 0~40 DEG C.
4. the preparation method of graphical coating according to claim 1, which is characterized in that the polyanion is polypropylene
At least one of acid, alginic acid, hyaluronic acid, kayexalate, heparin sodium, milt DNA and polymethylacrylic acid, institute
The mole for stating polyacrylic acid is 10,000~1000,000.
5. the preparation method of graphical coating according to claim 1, which is characterized in that the modified polyanion is water-soluble
A concentration of 0.1~100mg/mL of liquid, pH value are 1~7.
6. the preparation method of graphical coating according to claim 1, which is characterized in that the polycation is polyethylene
Imines, polyallylamine hydrochloride, gelatin, diallyl dimethyl amine hydrochlorate, nucleoprotamine, chitosan and polylysine
At least one of.
7. the preparation method of graphical coating according to claim 1, which is characterized in that the polycation aqueous solution
A concentration of 0.1~100mg/mL, pH value are 8~11.
8. the preparation method of graphical coating according to claim 1, which is characterized in that in step (5), ultraviolet light it is strong
Degree is 1~10000 μ W/cm2, and the irradiation time of ultraviolet light is 1~10000 second.
9. the preparation method of graphical coating according to claim 1, which is characterized in that in step (6), the humidity ring
The relative humidity in border is 70~100%, and the processing time in wet environment is 1~72 hour.
10. a kind of graphical coating, which is characterized in that be prepared by claim 1~9 any one of them method.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112795039A (en) * | 2021-01-15 | 2021-05-14 | 浙江理工大学 | Preparation method of foaming polyelectrolyte film |
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| US20030003272A1 (en) * | 2001-06-21 | 2003-01-02 | Bruno Laguitton | Polyanion/polycation multilayer film for DNA immobilization |
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| CN102319662A (en) * | 2011-09-26 | 2012-01-18 | 吉林大学 | Method for preparing self-repairing polyelectrolyte coating based on layer-by-layer assembly technology |
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| US20030003272A1 (en) * | 2001-06-21 | 2003-01-02 | Bruno Laguitton | Polyanion/polycation multilayer film for DNA immobilization |
| CN101792564A (en) * | 2010-03-04 | 2010-08-04 | 吉林大学 | Anti-scratch coating and preparation method thereof |
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| CN112795039A (en) * | 2021-01-15 | 2021-05-14 | 浙江理工大学 | Preparation method of foaming polyelectrolyte film |
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