CN108219174A - A kind of composite material of repeatable writing blackness handwriting and preparation method thereof - Google Patents
A kind of composite material of repeatable writing blackness handwriting and preparation method thereof Download PDFInfo
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- CN108219174A CN108219174A CN201711376161.0A CN201711376161A CN108219174A CN 108219174 A CN108219174 A CN 108219174A CN 201711376161 A CN201711376161 A CN 201711376161A CN 108219174 A CN108219174 A CN 108219174A
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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
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C09D139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C09D139/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
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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
- C09D189/00—Coating compositions based on proteins; Coating compositions based on derivatives thereof
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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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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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
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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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
- C08J2367/00—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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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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
- C08J2439/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
- C08J2439/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C08J2439/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
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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
- C08J2489/00—Characterised by the use of proteins; Derivatives thereof
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The present invention provides a kind of composite materials of repeatable writing blackness handwriting and preparation method thereof, including substrate layer and the coating layer being compounded on the substrate layer, the coating fluid includes the dyestuff of 0.01 10 parts by weight, the organic solvent of 20 200 parts by weight, the water of 5 500 parts by weight, the function additive of 0.1 30 parts by weight, the adhesive of 1 50 parts by weight.The composite material of the present invention, available for book, picture and printing.Coating layer, which meets colour developing aqua, can show black, and clear writing, contrast is high, can return to state after aqua volatilization, no background color can be kept effectively to write state and reached 20 days, reusable to reach 200 times or more.Composite material provided by the invention, coating layer color speed is fast, good film-forming property, does not stick together, is easy to preserve；Preparation process is simple, conducive to industrialized production.
Description
Technical field
The present invention relates to writing printed material technical field, more particularly to a kind of repeatable writing the compound of blackness handwriting is beaten
Print material.
Background technology
Excessive deforestation and paper consumption are energy crisis, global warming, resource and environmental degradation and malignant disease
The problems such as one of important cause.It is well known that papermaking is one of whole world energy consumption and the maximum industry of pollution, it not only to water and
Air environmental pollution is serious, and seriously destroys surface vegetation, exacerbates environmental degradation.A large amount of paper single uses cause
The serious wasting of resources and environmental pollution and the ink that inkjet printing encounters at present easily block nozzle, frequently replace print cartridge band
Carry out the problems such as consumer subsequently prints of high cost and environmental pollution.For the sustainable development of the mankind, reusable writing
Material becomes the main direction of International Technology, it is therefore necessary to which production is a kind of environmentally protective and reusable write prints
Product.
There are some reusable water writing papers currently on the market, only with water generation ink into running hand, the water writing paper drawn, using model
Enclose limitation.Meanwhile some existing products not clear enough, easy horizontal proliferation of there are water writing rear writing；After repeated writing, paper holds
It is yielding；Paper surface is coarse；Manufacturing process is complicated.The successful research and development of inkless water spray printing technique effectively overcome existing repetition
Using the disadvantage of water writing paper, it can realize single color written and the printing of multiple color.In 201610471824.6
State's patent discloses a kind of material capable of repeat printing, without ink-jet during this special file printing, sprays clear water or acid water-soluble
Liquid can show writing or pattern.Guarantor's color time is long after the file printing capable of repeat printing provided in the invention, water longtitudinal dispersion
Property is preferable, and water absorption rate is higher, and service life is long.Color during the printed material only can be presented red, yellow, blue, purple four, does not meet people
Daily be accustomed to display in black and white, therefore, the printed material it cannot still substitute office print paper completely.Application No. is
201510824186.7 Chinese patent discloses a kind of reusable water writing paper, it again may be by water and writes or spray water
Printing realizes that different colours are shown, printing liquid is less than 7 acidic aqueous solution for clear water or pH.It is well known that printer, especially
Print head has very harsh requirement to the printing liquid of loading, if printing liquid does not conform to symbol printer relevant parameter standard, inherently breaks
Bad or blocking print head, so as to increase the consumables cost of duplicate printing paper.In addition, paper capable of repeat printing is put under field conditions (factors)
Put often due to the influence of air humidity cause coating cannot complete colour killing so that water writes, contrast is low, reduce identification
Degree.Therefore, the another key technology of paper capable of repeat printing is completely restore after developing the color, i.e., complete colour killing in this way could be real
The permanently effective recycling of existing printing paper.
Invention content
The technical problems to be solved by the invention are to provide a kind of making simply, and quality is high, and high resolution can have for a long time
Effect recycling is not limited only to book, draws, while can be additionally used in the composite material of the repeatable writing blackness handwriting of printing.
Meanwhile the present invention also provides a kind of colour developing aquas that can be stored in printer for a long time.
To solve the above problems, the present invention adopts the following technical solutions：
A kind of composite material of repeatable writing blackness handwriting, including substrate layer and the coating being compounded on the substrate layer
Layer, i.e., color layer, the color layer are made by coating solution.
The composite material of above-mentioned repeatable writing blackness handwriting, the material of the substrate layer are selected from paper, polyester film, poly- third
Alkene film or polyvinyl chloride film.In the present invention, the specification of the substrate layer, thickness do not have special limitation.
The composite material of above-mentioned repeatable writing blackness handwriting, the color layer include the dyestuff of 0.01-10 parts by weight,
The organic solvent of 20-200 parts by weight, the water of 5-500 parts by weight, the function additive of 0.1-30 parts by weight, 1-50 parts by weight are glued
Mixture.
The dyestuff is selected from fluoran leuco body dyestuff, and general structure is as follows：
Heretofore described fluoran leuco body dyestuff includes 2 '-phenylamino -6 '-lignocaine -3 '-methyl fluoran
(ODB-1), 2 '-phenylamino -3 '-chloro- 6 '-lignocaine fluorane (FH-101), 2 '-phenylamino -3 '-methyl -6 '-(N- first
Base-N- n-propylamines base)-fluorane, 2 '-phenylamino -6 '-(N- cyclohexyl-N- methylaminos) -3 '-methyl fluoran, 2 '-phenylamino -
6 '-(N- ethyl-N- isobutylaminos) -3 '-methyl fluorans, 2 '-phenylamino -6 '-(N- ethyl-N- isoamylaminos) -3 ' -
Methyl fluoran, 2 '-phenylamino -6 '-[N- (3- ethoxycarbonyl propyls)-N- ethylaminos] -3 '-methyl fluoran, 2 '-phenylamino -6 ' -
(- 4 methylphenylamino of N- ethyls) -3 '-methyl fluoran, 2 '-phenylamino -6 '-(N- ethyl-N- tetrahydrofurfuryls amino) -3 ' -
Methyl fluoran,-two n-propylamine base -3 ' of 2 '-phenylamino -6 '-methyl fluoran,-two n-butyl amine base -3 ' of 2 '-phenylamino -6 '-methyl
Fluorane (ODB-2),-two pentylamine base -3 ' of 2 '-phenylamino -6 '-methyl fluoran, 2 '-phenylamino -3- methyl -6 '-tetrahydro pyrrole
It is glimmering to cough up fluorane, 2 '-phenylamino -3 '-methyl -6 '-piperidine base fluorane, 2 '-(2- chloros phenylamino) -6 '-lignocaines
Alkane, 2 '-(2- chloros phenylamino) -6 '-two n-butyl amine base fluoranes, 6 '-lignocaine -2 '-(2- chloros phenylamino) fluorane, 6 ' -
Two n-butyl amine bases -2 '-(2- fluoro phenylamino) fluorane, 6 '-lignocaine -2 '-(3- fluoroforms phenylamino) fluorane, 6 '-two
Ethylamino -2 '-(2- methoxycarbonyls phenylamino) fluorane, { 4- [6 '-(N- cyclohexyl-N-methyls amino)-the 3 '-first of 2-2- bis-
Base fluorane -2 '-amino] phenyl propane, 6 '-lignocaine -3 '-methyl -2 '-just pungent amino fluorane, 3 '-chloro- 6 '-diethylamino
It is one or more in base -2 '-(2- ethoxyethyl groups amino) fluorane.
The dyestuff that the present invention selects acts on the hydrogen ion in aqua, the lactonic ring of fluoran leuco body dyestuff is caused to be opened,
Increase double bond systems conjugation degree and aobvious black, specifically by taking ODB-2 as an example, chromogenic reaction principle is as follows：
In the present invention, the organic solvent includes alcohol compound, ester type compound, sulfone compound, amides chemical combination
It is one or more in object, silane compound, preferably ethyl alcohol, n-butanol, ethyl acetate, dimethyl sulfoxide (DMSO), N, N- diformazans
Base formamide, silane coupling agent KH560, N-Methyl pyrrolidone, tetrahydrofuran, acetone, toluene it is one or more.
In the present invention, the function additive includes surfactant, antistatic agent, ultraviolet absorber, levelling agent, moisturizing
It is one or more in agent, hardener.
The present invention does not have the type of the function additive special limitation, using phase well-known to those skilled in the art
Close auxiliary agent.In the present invention, the surfactant preferably includes perfluorooctanoic acid, to different zinc-base phenol polyoxyethylene ether
With it is one or more in diisooctyl succinate sodium sulfonate.In embodiments of the present invention, the surfactant is specially board
Number for one kind in 1283 surfactant, the surfactant that the trade mark is 1292 or surfactant that the trade mark is No. 6 or
It is a variety of；The antistatic agent preferably includes one kind in polystyrolsulfon acid, glycerine and dodecyl-dimethyl amine second lactone
It is or a variety of；The ultraviolet absorber preferably includes poplar ester phenyl ester, hydroxy-phenyl benzotriazole, 2,4 dihydroxyl benzophenone, 2- hydroxyls
Base -4- methoxy benzophenones, 2-hydroxy-4-n-octoxybenzophenone, single benzoic acid resorcinol and 2- (2 '-hydroxyl -
3 ', 5 '-two tertiary phenyl) it is one or more in -5- chlorination benzotriazole；The levelling agent preferably includes fluorine-containing levelling agent, gathers
It is one or more in ether modified organic silicon alkane, Siloxane-Oxyalkylene Copolymers copolymer and acrylic polymer.The present invention
In specific embodiment, the levelling agent be specially the trade mark be T-2 levelling agent, the trade mark be T-6 levelling agent or the trade mark be 5883
Levelling agent；The moisturizer preferably includes inorganic salts, polyvinyl alcohol, thionyl chloride, hyaluronic acid, Sodium Polyacrylate, glass urine
It is one or more in acid, urea, peptides and hydrogel.In the specific embodiment of the invention, the moisturizer is specially
It is one or more in sodium chloride, sodium nitrate and glycerine；The hardener preferably includes chrome alum, alum, s-triazine sodium salt, boron
It is one or more in acid, borax, glutaraldehyde, glyoxal and polysilicon acid.Function additive of the present invention is preferably with function additive
The form of solution prepares dispersion liquid, and there do not have in the present invention to the type of function additive, source and its dispersion preparation method to be special
Limitation, using function additive well known to those skilled in the art and technology.
In the present invention, described adhesive include gelatin, polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, cellulose and
It is one or more in starch.In embodiments of the present invention, preferably gelatin, polyvinyl alcohol, polyethylene glycol and polyvinylpyrrolidine
It is one or more in ketone.
In the present invention, the coating method includes dip-coating, slope flow coating, the coating of item seam, casting painting, scrapes rod coating, nick version
It is one or more in coating and roller coating.The present invention does not have the mode of coating special limitation, using those skilled in the art
Well known coating technique scheme.In the present invention, the mode of the coating is preferably that slope stream squeezes or scrape rod coating.
The equipment that the present invention uses coating does not have special limitation, using coating apparatus well known to those skilled in the art
.Wherein, the temperature of the coating is preferably 10-50 DEG C, and drying temperature is preferably 40-120 DEG C.
In the present invention, the preparation method of the composite material is as follows：
1) the organic solvent mixing of the dyestuff of extraction 0.01-10 parts by weight and 20-200 parts by weight is placed on 40-60 DEG C
Stirred in water bath disperses 10-60min, mixing speed 100-1000rpm, so as to which dye solution be made；
2) adhesive of extraction 1-50 parts by weight and the water of 5-500 parts by weight stir evenly；
3) function additive of extraction 0.1-30 parts by weight is added in while stirring in step 2 gained binder aqueous solution, is stirred
Speed 500-8000rpm；
4) dye solution is added in step 3 gained mixed liquor in extraction step 1, and proportioning is 0.001-0.5:1, so as to make
The coating layer coating fluid of writing composite material must be repeated；
5) it by coating requirement, is flowed and squeezed or scrape by the way of rod coating by coating solution on substrate layer using slope, adjusting
Drying temperature dries coating layer, and repeatable writing composite material is made.
The present invention is filled clear water or is soaked pen tip in water automatic colour developing aqua of inhaling and carried out using writing brush, pen or water-color paintbrush
Book, picture or with water spray printer spray colour developing aqua in above-mentioned repeatable writing composite material surface, you can display blackness handwriting or
Pattern.
In the present invention, for aqueous solution of the colour developing aqua for clear water or containing acid solution of writing brush, pen or water-color paintbrush, pH
＜ 7；Colour developing aqua for printer of spraying water is the aqueous solution containing function additive, and the surface tension of aqueous solution is 20-60mN/
M, range of viscosities 1-10mPas, pH value range 4.5-9.
The colour developing aqua includes inorganic salts, surfactant, dispersant, levelling agent and phenolic compound with function additive
In it is one or more, wherein, it is one or more in the preferred sodium chloride of inorganic salts, sodium nitrate, sodium carbonate；Surfactant is excellent
It selects one or more in the surfactant that the trade mark is 1283 and the surfactant that the trade mark is 1292；The preferably poly- second of dispersant
Glycol；The preferred trade mark of levelling agent is the levelling agent of T-2；The preferred bisphenol-A of phenolic compound, 4-HBA benzyl ester, 2- naphthalenes
Phenol, to one or more in iodophenol and paranitrobenzoic acid.
The present invention has the following advantages：
1st, the present invention prepares repeatable writing composite material, can be shown by writing brush, pen, water-color paintbrush or water spray printer
Go out the required writing or pattern of black.Treat that water volatilization or heating make water quickly volatilize under natural conditions, writing or pattern can disappear,
Writing composite material can be made to return to state, so as to fulfill the reuse of material.
2nd, in the present invention, the repeatable writing composite material is sensitive to colour developing aqua response, and colour developing has instantaneity, shows
Color speed is fast, while contrast is high before and after colour developing.
3rd, in the present invention, the coating fluid coating good film-forming property forms a film, and coating is not in stick to each other after dry
Problem is easy to preserve.
4th, in the present invention, coating fluid can be coated on by common coating method on base material, and preparation process is simple, repeated
Property it is high, be conducive to industrialized mass production.
5th, in the present invention, water spray printer is longitudinally spread and sunk in and oozed without heap pearl phenomenon with colour developing aqua printing character or image, writing
Soon, and it can be stored in printer for a long time and do not block print head.
Specific embodiment
It is right with reference to embodiments in order to which the object, technical solution and advantage in patent of the present invention are more clearly understood
The present invention is further elaborated.It should be appreciated that specific embodiment described herein is only used for explaining the skill of the present invention
Art scheme, but protection domain is not limited by this.
Embodiment 1
The composite material of the present invention is into being grouped as by following weight：6 parts of ODB-1 dyestuffs, N, N- dimethyl methyls
100 parts of amide, 20 parts of polyvinylpyrrolidone, 180 parts of deionized water, the surface that the trade mark that mass fraction is 80g/L is 1292
8 parts of activating agent, 10 parts of the organic silicon modified by polyether alkane levelling agent that the trade mark that mass fraction is 10% is T-2, the trade mark are the table of No. 6
0.5 part of face activating agent, 2 parts of sodium chloride and mass fraction are 1.8% 3 parts of boric acid solution.
The preparation method of the composite material is as follows：
1) by weight ratio, 100 parts of 6 parts of extraction ODB-1 dyestuffs, n,N-Dimethylformamide mixing are placed on 40 DEG C
Stirred in water bath disperses 30min, mixing speed 200rpm, so as to which dye solution be made；
2) by weight ratio, 180 parts of 20 parts of extraction polyvinylpyrrolidone and deionized water stir evenly, and bonding is made
Agent solution；
3) 8 parts of the surfactant that by weight ratio, the extraction trade mark is 1292, levelling agent 10 part of the trade mark for T-2, board
Number for No. 6 0.5 part of surfactant, 2 parts of sodium chloride while stirring one by one add in step 2 gained binder solution in, stirring
Speed 5000rpm；
4) gained dye solution is added in step 3 gained mixed liquor in extraction step 1, after stirring evenly, adds in quality point
Number is 1.8% 3 parts of boric acid solution, continues to stir, so as to which the coating layer coating fluid of repeatable writing composite material be made；
5) by the way of stream squeezes using slope by coating solution on the polyester film of white, drying temperature is adjusted to 50
DEG C, coating layer is dried, repeatable writing composite material is made.
Writing blackness handwriting composite material is repeated made from the present embodiment, can be dipped in writing brush with clear water text writing.It should
Composite material meets water can show black, clear writing immediately；Under natural conditions after water volatilizees or heating makes water quickly volatilize, writing
It can disappear, composite material returns to state, is reused so as to fulfill material, which can keep no background color effectively to write
State at least 10 days, Palingraphia number is up to 100 times or more.
Embodiment 2
The composite material of the present invention is into being grouped as by following weight：4 parts of ODB-2 dyestuffs, the trade mark are KH560's
140 parts of silane coupling agent, 13 parts of polyvinylpyrrolidone, 12 parts of polyethylene glycol, 300 parts of deionized water, mass fraction 80g/
The trade mark of L be 1292 5 parts of surfactant, 4 parts of the surfactant that the trade mark that mass fraction is 80g/L is 1283, quality
12 parts of the organic silicon modified by polyether alkane levelling agent that the trade mark that score is 10% is T-6,3 parts of sodium chloride and mass fraction are 1.8%
1.5 parts of boric acid solution.
The preparation method of the composite material is as follows：
1) by weight ratio, 140 parts of mixing of silane coupling agent of 4 parts of extraction ODB-2 dyestuffs, KH560 are placed on 50 DEG C
Stirred in water bath dispersion 10min, mixing speed 500rpm, so as to be made dye solution；
2) 13 parts of polyvinylpyrrolidone, the 300 parts of stirrings of 12 parts of polyethylene glycol and deionized water by weight ratio, are extracted
Uniformly, binder solution is made；
3) 5 parts of the surfactant that by weight ratio, the extraction trade mark is 1292,4 parts of 1283 surfactant, the trade mark
For 12 parts of the levelling agent of T-6,3 parts of sodium chloride is added in step 2 gained binder solution one by one while stirring, mixing speed
2000rpm；
4) gained dye solution is added in step 3 gained mixed liquor in extraction step 1, after stirring evenly, adds in quality point
Number is 1.8% 1.5 parts of boric acid solution, continues to stir, so as to which the coating layer coating of repeatable writing composite material be made
Liquid；
5) by the way of the scraper by coating solution on the polyester film of white, adjust drying temperature to 80 DEG C, dry
Repeatable writing composite material is made in dry-coated layer of cloth.
Composite material made from the present embodiment can fill clear water text writing with water-color paintbrush.The composite material meets water can be immediately
Aobvious black, text high resolution；Under natural conditions after water volatilizees or heating makes water quickly volatilize, writing can disappear, composite wood
Material returns to state, which can keep no background color effectively to write state at least 15 days, is reused so as to fulfill material,
Palingraphia number is up to 100 times or more.
Embodiment 3
The composite material of the present invention is into being grouped as by following weight：6 parts of ODB-1 dyestuffs, N, N- dimethyl methyls
150 parts of amide, 15 parts of polyvinylpyrrolidone, 10 parts of polyethylene glycol, 6 parts of polyvinyl alcohol, 400 parts of deionized water, mass fraction
6 parts of the surfactant that the trade mark for 80g/L is 1292, the trade mark are 1 part of the surfactant of No. 6, and mass fraction is 10%
The trade mark is 7 parts of the organic silicon modified by polyether alkane levelling agent of T-2, and the trade mark is 5,883 3 parts of levelling agent, and 5 parts of glycerine and polysilicon acid are molten
4 parts of liquid.
The preparation method of the composite material is as follows：
1) by weight ratio, 100 parts of 7 parts of extraction ODB-1 dyestuffs, n,N-Dimethylformamide mixing are placed on 60 DEG C
Stirred in water bath disperses 20min, mixing speed 800rpm, so as to which dye solution be made；
2) by weight ratio, extract 15 parts of polyvinylpyrrolidone, 10 parts of polyethylene glycol, 6 parts of polyvinyl alcohol and go from
Sub- 400 parts of water stirs evenly, and binder solution is made；
3) 6 parts of the surfactant that the trade mark that by weight ratio, mass fraction is 80g/L is 1292, the trade mark are No. 6
1 part of surfactant, 7 parts of the organic silicon modified by polyether alkane levelling agent that the trade mark that mass fraction is 10% is T-2, the trade mark 5883
3 parts of levelling agent, 5 parts of glycerine while stirring one by one add in step 2 gained binder solution in, mixing speed 1000rpm；
4) gained dye solution is added in step 3 gained mixed liquor in extraction step 1, after stirring evenly, adds in polysilicon acid
4 parts of solution, continues to stir, so as to which the coating layer coating fluid of repeatable writing composite material be made；
5) by the way of stream squeezes using slope by coating solution on polyvinyl chloride film, drying temperature is adjusted to 100 DEG C,
Coating layer is dried, repeatable writing composite material is made.
Composite material made from the present embodiment can use the water spray printer spray colour developing aqua repeatable book of gained in embodiment
Write composite material surface.Printing colour developing aqua includes the polyethylene glycol of 1 parts by weight, and the trade mark of 0.1 parts by weight is the levelling of T-2
The bisphenol-A of agent, the sodium chloride of 0.05 parts by weight, the deionized water of 100 parts by weight and 0.5 parts by weight, the colour developing aqua surface
Power 28mN/m, viscosity 4mPas, pH 5.64.
The composite material meets water can show black immediately, and printing obtains No. 5 clear writings, do not occur laterally spreading and sinking in and ooze；It is natural
Under the conditions of after water volatilize or heat water is made quickly to volatilize after, writing can disappear, and composite material returns to state, which can
Holding state is effectively write without background color at least 20 days, so as to fulfill material reuse, duplicate printing number up to 200 times with
On.
Embodiment 4
The composite material of the present invention is into being grouped as by following weight：0.5 part of FH-101 dyestuffs, N, N- dimethyl
20 parts of formamide, 35 parts of gelatin, 300 parts of deionized water, the surfactant 5 that the trade mark that mass fraction is 80g/L is 1292
Part, 6 parts of the organic silicon modified by polyether alkane levelling agent that the trade mark that mass fraction is 10% is T-6,1 part of sodium nitrate and s-triazine sodium salt
6 parts.
The preparation method of the composite material is as follows：
1) by weight ratio, 20 parts of 0.5 part of extraction FH-101 dyestuffs, n,N-Dimethylformamide mixing are placed on 60 DEG C
Stirred in water bath dispersion 10min, mixing speed 200rpm, so as to be made dye solution；
2) by weight ratio, 300 parts of 35 parts of extraction gelatin and deionized water adjust bath temperature to 40 DEG C, and stirring is equal
It is even, binder solution is made；
3) 5 parts of the surfactant that the trade mark that by weight ratio, mass fraction is 80g/L is 1292, mass fraction are
10% trade mark is 6 parts of the organic silicon modified by polyether alkane levelling agent of T-6, and 1 part of sodium nitrate adds in obtained by step 2 one by one while stirring
In binder solution, mixing speed 3000rpm；
4) gained dye solution is added in step 3 gained mixed liquor in extraction step 1, after stirring evenly, adds in s-triazine
6 parts of sodium salt, continues to stir, so as to which the coating layer coating fluid of repeatable writing composite material be made；
5) by the way of the scraper by coating solution on the polyester film of white, adjust drying temperature to 100 DEG C, dry
Repeatable writing composite material is made in dry-coated layer of cloth.
Composite material made from the present embodiment can be dipped in writing brush with clear water text writing.The composite material meets water can be immediately
Aobvious black, clear writing；Under natural conditions after water volatilizees or heating makes water quickly volatilize, writing can disappear, and composite material is extensive
Initial state is arrived again, is reused so as to fulfill material, which can keep no background color effectively to write state at least 3 days, repeat
Number is write up to 50 times or more.
Embodiment 5
The composite material of the present invention is into being grouped as by following weight：0.3 part of FH-101 dyestuffs, dimethyl sulfoxide (DMSO)
50 parts, 13 parts of polyvinyl alcohol, 100 parts of deionized water, 8 parts of the surfactant that the trade mark that mass fraction is 80g/L is 1292,
2 parts of the surfactant that the trade mark that mass fraction is 80g/L is 1283, the polyethers that the trade mark that mass fraction is 10% is T-2 changes
Property 10 parts of organosilan levelling agent, 5 parts of 3 parts of glycerine and polysilicon acid.
The preparation method of the composite material is as follows：
1) by weight ratio, 10 parts of 0.3 part of extraction FH-101 dyestuffs, dimethyl sulfoxide (DMSO) mixing are placed on 40 DEG C of water-bath
In be dispersed with stirring 40min, mixing speed 700rpm, so as to be made dye solution；
2) by weight ratio, 100 parts of 13 parts of extraction polyvinyl alcohol and deionized water adjust bath temperature to 45 DEG C, stir
It mixes uniformly, binder solution is made；
3) 8 parts of the surfactant that the trade mark that by weight ratio, mass fraction is 80g/L is 1292, mass fraction are
The trade mark of 80g/L is 1,283 2 parts of surfactant, the organic silicon modified by polyether alkane that the trade mark that mass fraction is 10% is T-2
10 parts of levelling agent, 3 parts of glycerine are added in step 2 gained binder solution one by one while stirring, mixing speed 2000rpm；
4) gained dye solution is added in step 3 gained mixed liquor in extraction step 1, after stirring evenly, adds in quality point
Number is 5 parts of polysilicon acid, continues to stir, so as to which the coating layer coating fluid of repeatable writing composite material be made；
5) by the way of scraper by coating solution on polypropylene film, adjust drying temperature to 60 DEG C, drying apply
Repeatable writing composite material is made in layer of cloth.
Composite material made from the present embodiment can fill the acidic aqueous solution text writing of pH ＜ 7 with pen.The composite wood
Material meets water can show black, clear writing immediately, and retention time extends；Treat that water volatilization or heating make water quickly volatilize under natural conditions
Afterwards, writing can disappear, and composite material returns to state, which can keep no background color effectively to write state at least 3 days, from
And realize that material is reused, Palingraphia number is up to 40 times or more.
Embodiment 6
The composite material of the present invention is into being grouped as by following weight：3 parts of ODB-2 dyestuffs, the trade mark are KH560's
70 parts of silane coupling agent, 35 parts of n-butanol, 110 parts of ethyl acetate, 30 parts of gelatin, 460 parts of deionized water, mass fraction 80g/
The trade mark of L is 1,283 8 parts of surfactant, and the trade mark is 2 parts of the surfactant of No. 6, and the trade mark that mass fraction is 10% is
10 parts of 8 parts of the organic silicon modified by polyether alkane levelling agent of T-2,1 part of sodium chloride and glutaraldehyde.
The preparation method of the composite material is as follows：
1) by weight ratio, 3 parts of extraction ODB-2 dyestuffs, 50 parts of the silane coupling agent that the trade mark is KH560, n-butanol 35
110 parts of part and ethyl acetate, mixing is placed on 40 DEG C of stirred in water bath dispersion 5min, mixing speed 700rpm, so as to obtained
Dye solution；
2) by weight ratio, 460 parts of 30 parts of extraction gelatin and deionized water adjust bath temperature to 40 DEG C, and stirring is equal
It is even, binder solution is made；
3) 8 parts of the surfactant that the trade mark that by weight ratio, mass fraction is 80g/L is 1283, the trade mark are No. 6
2 parts of surfactant, 8 parts of the organic silicon modified by polyether alkane levelling agent that the trade mark that mass fraction is 10% is T-2,1 part of sodium chloride
It adds in step 2 gained binder solution one by one while stirring, mixing speed 5000rpm；
4) gained dye solution is added in step 3 gained mixed liquor in extraction step 1, after stirring evenly, adds in glutaraldehyde
10 parts, continue to stir, so as to which the coating layer coating fluid of repeatable writing composite material be made；
5) by the way of stream squeezes using slope by coating solution on polyester film, drying temperature is adjusted to 120 DEG C, drying
Repeatable writing composite material is made in coating layer.
Composite material made from the present embodiment can use the water spray printer spray colour developing aqua repeatable book of gained in embodiment
Write composite material surface.Printing colour developing aqua includes the polyethylene glycol of 1 parts by weight, and the trade mark of 0.1 parts by weight is the levelling of T-2
Agent, the trades mark of 0.05 parts by weight are 1292 surfactant, the sodium nitrate sodium of 0.1 parts by weight, the deionization of 100 parts by weight
The beta naphthal of water and 0.5 parts by weight, the colour developing aqua surface tension 25mN/m, viscosity 5mPas, pH 5.76.
The composite material meets water can show black immediately, and printing obtains No. 5 clear writings, and contrast is high, transverse direction does not occur
It spreads and sinks in and oozes；Under natural conditions after water volatilizees or heating makes water quickly volatilize, writing can disappear, and composite material returns to shape
State, the coating can keep no background color effectively to write state at least 5 days, be reused so as to fulfill material, duplicate printing number can
Up to 100 times or more.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise of core technology of the present invention is not departed from, several equivalent improvements and modifications can also be made, these improvement
Protection scope of the present invention is also should be regarded as with retouching.
Claims (9)
1. a kind of composite material of repeatable writing blackness handwriting, which is characterized in that the composite material is including substrate layer and again
The coating layer on the substrate layer is closed, the coating layer is color layer, and the coating fluid includes following components：0.01-10 weights
Measure the dyestuff of part, the organic solvent of 20-200 parts by weight, the water of 5-500 parts by weight, the function additive of 0.1-30 parts by weight, 1-50
The adhesive of parts by weight.
2. the composite material of repeatable writing blackness handwriting according to claim 1, which is characterized in that the substrate layer
Material is selected from any one of paper, polyester film, polypropylene film or polyvinyl chloride film.
3. the composite material of repeatable writing blackness handwriting according to claim 1, which is characterized in that the dyestuff is glimmering
Alkane leuco dye.
4. the composite material of repeatable writing blackness handwriting according to claim 3, which is characterized in that the fluoran leuco
Body dyestuff includes 2 '-phenylamino -6 '-lignocaine -3 '-methyl fluoran (ODB-1), 2 '-phenylamino -3 '-chloro- 6 '-diethylamino
Base fluorane (FH-101), 2 '-phenylamino -3 '-methyl -6 '-(N- methyl-N- n-propylamines base)-fluorane, 2 '-phenylamino -6 '-(N-
Cyclohexyl-N- methylaminos) -3 '-methyl fluoran, 2 '-phenylamino -6 '-(N- ethyl-N- isobutylaminos) -3 '-methyl fluoran,
2 '-phenylamino -6 '-(N- ethyl-M-isoamylaminos) -3 '-methyl fluoran, 2 '-phenylamino -6 '-[N- (3- ethoxy-cs
Base)-N- ethylaminos] -3 '-methyl fluoran, 2 '-phenylamino -6 '-(- 4 methylphenylamino of N- ethyls) -3 '-methyl fluoran, 2 '-benzene
Amino -6 '-(N- ethyl-N- tetrahydrofurfuryls amino) -3 '-methyl fluoran,-two n-propylamine base -3 ' of 2 '-phenylamino -6 '-methyl
Fluorane,-two n-butyl amine base -3 ' of 2 '-phenylamino -6 '-methyl fluoran (ODB-2),-two pentylamine base -3 ' of 2 '-phenylamino -6 '-first
Base fluorane, 2 '-phenylamino -3- methyl -6 '-tetrahydropyrrole fluorane, 2 '-phenylamino -3 '-methyl -6 '-piperidine base are glimmering
Alkane, 2 '-(2- chloros phenylamino) -6 '-lignocaine fluoranes, 2 '-(2- chloros phenylamino) -6 '-two n-butyl amine base fluoranes, 6 ' -
Lignocaine -2 '-(2- chloros phenylamino) fluorane, 6 '-two n-butyl amine bases -2 '-(2- fluoro phenylamino) fluorane, 6 '-diethylamino
Base -2 '-(3- fluoroforms phenylamino) fluorane, 6 '-lignocaine -2 '-(2- methoxycarbonyls phenylamino) fluorane, 2-2- bis-
{ 4- [6 '-(N- cyclohexyl-N-methyls amino) -3 '-methyl fluoran -2 '-amino] phenyl } propane, 6 '-lignocaine -3 '-first
Base -2 '-just pungent amino fluorane or 3 '-chloro- 6 '-lignocaine -2 '-(2- ethoxyethyl groups amino) fluorane.
5. the composite material of repeatable writing blackness handwriting according to claim 1, which is characterized in that the organic solvent
It is one or more in alcohol compound, ester type compound, sulfone compound, amides compound, silane compound,
Preferably ethyl alcohol, n-butanol, ethyl acetate, dimethyl sulfoxide (DMSO), n,N-Dimethylformamide, silane coupling agent KH560, N- methyl
Pyrrolidones, tetrahydrofuran are one or more in acetone, toluene.
6. the composite material of repeatable writing blackness handwriting according to claim 1, which is characterized in that the function additive
Including one or more in surfactant, antistatic agent, ultraviolet absorber, levelling agent, moisturizer, hardener.
7. the composite material of repeatable writing blackness handwriting according to claim 1, which is characterized in that described adhesive packet
It includes one or more in gelatin, polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, cellulose and starch.Of the invention real
It applies in example, it is preferably one or more in gelatin, polyvinyl alcohol, polyethylene glycol and polyvinylpyrrolidone.
8. a kind of prepare the method for repeating writing blackness handwriting composite material such as claim 1-7 any one of them, spy
Sign is that the method carries out according to the following steps：
1) the organic solvent mixing of the dyestuff of extraction 0.01-10 parts by weight and 20-200 parts by weight is placed on 40-60 DEG C of water-bath
In be dispersed with stirring 10-60min, mixing speed 100-1000rpm, be made dye solution；
2) adhesive of extraction 1-50 parts by weight and the water of 5-500 parts by weight stir evenly；
3) function additive of extraction 0.1-30 parts by weight is added in while stirring in step 2 gained binder aqueous solution, mixing speed
500-8000rpm；
4) dye solution is added in step 3 gained mixed liquor in extraction step 1, and proportioning is 0.001-0.5:1, the painting is made
Layer of cloth coating fluid；
5) it by coating requirement, using dip-coating, slope flow coating, the coating of item seam, casting painting, scrapes in rod coating, micro- intaglio plate coating and roller coating
A kind of coating method by coating solution on substrate layer, adjust drying temperature, dry coating layer, be made the composite wood
Material.
9. a kind of claim 1-7 any one of them such as that is used for repeats the colour developing aqua of writing blackness handwriting composite material,
It is characterized in that, for aqueous solution of the colour developing aqua for clear water or containing acid solution of writing brush, pen or water-color paintbrush, pH ＜ 7；For
The colour developing aqua of printer of spraying water is the aqueous solution containing function additive, and the surface tension of aqueous solution is 20-60mN/m, viscosity model
It encloses for 1-10mPas, pH value range 4.5-9.
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| CN201711376161.0A CN108219174A (en) | 2017-12-19 | 2017-12-19 | A kind of composite material of repeatable writing blackness handwriting and preparation method thereof |
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Application publication date: 20180629 |