CN109535952A - A kind of ability of reverse photochromism coating and preparation method thereof - Google Patents
A kind of ability of reverse photochromism coating and preparation method thereof Download PDFInfo
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- CN109535952A CN109535952A CN201811398779.1A CN201811398779A CN109535952A CN 109535952 A CN109535952 A CN 109535952A CN 201811398779 A CN201811398779 A CN 201811398779A CN 109535952 A CN109535952 A CN 109535952A
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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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
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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
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/14—Copolymers of styrene with unsaturated esters
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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
- C09D133/04—Homopolymers or copolymers of esters
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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
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/29—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for multicolour effects
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2255—Oxides; Hydroxides of metals of molybdenum
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
Abstract
The present invention provides a kind of ability of reverse photochromism coating and preparation method thereof.Coating provided by the invention includes: color-change powder 0.2%~5%, dispersing agent 1%~5%, polymer dispersion 4%~15%, balance of solvent；Wherein, dispersing agent is selected from one or more of starch, cellulose, natural plant gum, animal glue and polymer A；Polymer A includes one or more of polyacrylamide, hydrolyzed polyacrylamide, polyvinylpyrrolidone and polyvinyl alcohol；Polymer dispersion includes one or more of polyurethane, styrene-acrylic emulsion, polyacrylic acid, alkyd resin, hydroxylated cellulose, polyvinyl alcohol, polyacrylate and copolymer B；Copolymer B includes the copolymer that two or more copolymerization in polyurethane, styrene-acrylic emulsion, polyacrylic acid, alkyd resin, hydroxylated cellulose, polyvinyl alcohol and polyacrylate is formed.Coating of the invention can be obviously improved discoloration colour fading efficiency and coating performance.
Description
Technical field
The present invention relates to off-color material technical field, in particular to a kind of ability of reverse photochromism coating and preparation method thereof.
Background technique
Ability of reverse photochromism coating is the functional material with certain photo absorption property, specifically, it is swashed by light source
Color change can occur after hair, after removing light source, color is gradually recovered again.Such coating can answer extensively as functional priming paint
For visible signal, such as laser scribing, light drawing composite drawing board, without color spray and the anti-fake equal fields of being self-possessed.
Currently, common photochromic coating is mainly the suspension of photochromic powder, when use directly painting or with
Other way coating.However, the coating composition is simple, and since drying process is difficult to control, lead to color-change powder in drying process
Body is reunited, and loses the property of nano-powder, photo absorption property is caused to decline；Specifically, when occurring photochromic, most grains
Son leads to not realize discoloration due to being shielded, and keeps poor color changeable effect, low efficiency, color change slow.On the other hand, above-mentioned painting
Capillarity is unique water lock method in Material system, and powder adsorbs fixed a small amount of water through capillary action, and water lock amount is limited, makes
Coating system water content is low, and the shortage of water also leads to the colour fading efficiency reduction that changes colour.In addition, the discoloration invertibity of photochromic powder
It needs to realize by oxidisability, realizes and fade by the oxygen in air under naturally open environment, efficiency is lower, and is sealing
Under the conditions of lack oxidant, colour fading efficiency is lower.Therefore, existing photochromic coating color changeable effect is poor, low efficiency, and effect of fading
Rate is relatively low, i.e., its photo absorption property is poor, defines application and the range of photochromic coating.In addition, existing coating
Film fastness it is poor, actual paint film is that nano-powder is fixed to each other with Van der Waals force and is fixed on coating carrier, lack
Weary fastness, easy-weathering fall off or wash away removing.Therefore, discoloration colour fading efficiency, the coating performance of photochromic coating are improved
Etc. having become urgent problem to be solved.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of ability of reverse photochromism coating and preparation method thereof.The present invention
The ability of reverse photochromism coating of offer has sensitive photo absorption property, and discoloration fade rates are obviously improved, and film adheres to
Property is preferable.
The present invention provides a kind of ability of reverse photochromism coating, by quality ratio, including following components:
The dispersing agent is selected from one or more of starch, cellulose, natural plant gum, animal glue and polymer A；
The polymer A includes in polyacrylamide, hydrolyzed polyacrylamide, polyvinylpyrrolidone and polyvinyl alcohol
It is one or more of；
The polymer dispersion includes polyurethane, styrene-acrylic emulsion, polyacrylic acid, alkyd resin, hydroxylated cellulose, poly- second
One or more of enol, polyacrylate and copolymer B；
The copolymer B includes polyurethane, styrene-acrylic emulsion, polyacrylic acid, alkyd resin, hydroxylated cellulose, polyvinyl alcohol
Copolymer is formed by with two or more copolymerization in polyacrylate.
Preferably, the color-change powder is transition metal oxide.
Preferably, the color-change powder includes one or more of titanium dioxide, tungstic acid and molybdenum trioxide.
Preferably, the granularity of the color-change powder is 10nm~10 μm.
It preferably, further include catalyst；The catalyst includes in polyacrylic acid, polyvinyl acetate and polyvinyl alcohol
It is one or more of；
Mass ratio of the catalyst in the coating is 0.2%~2%.
It preferably, further include decolourant；Mass ratio of the decolourant in coating is 0.05%~1%.
Preferably, the decolourant is Photosensitive decolourant or non-photosensitivity type decolourant；
The Photosensitive decolourant includes semiconductor type metal oxide, porphyrins, Benzazole compounds, thiophene
One or more of class compound and azoles；
The non-photosensitivity type decolourant includes hydrogen peroxide, persulfate, hypochlorite, chlorite, chlorate, manganese
One or more of acid, permanganate, chromic acid and high chromic acid content salt.
The present invention also provides the coatings that ability of reverse photochromism coating described in a kind of above-mentioned technical proposal is formed.
The present invention also provides a kind of preparation method of ability of reverse photochromism coating described in above-mentioned technical proposal, features
It is, comprising the following steps:
A color-change powder suspension is mixed with dispersant solution), obtains mixed liquor a；
B the mixed liquor a is mixed with aqueous polymer dispersions), obtains ability of reverse photochromism coating.
10, preparation method according to claim 9, which is characterized in that the step B) include:
B1 the mixed liquor a is mixed with aqueous polymer dispersions), obtains mixed liquor b；
B2 the mixed liquor b is mixed with colour fading agent solution), obtains mixed liquor c；
B3 the mixed liquor c is mixed with catalyst solution), obtains ability of reverse photochromism coating；
The mass concentration of the color-change powder suspension is 20wt%~25wt%；
The mass concentration of the dispersant solution is 5wt%~10wt%；
The mass concentration of the aqueous polymer dispersions is 8wt%~20wt%；
The mass concentration of the colour fading agent solution is 0.5wt%~2wt%；
The mass concentration of the catalyst solution is 5wt%~10wt%.
The present invention provides a kind of ability of reverse photochromism coating, comprising: color-change powder 0.2%~5%, dispersing agent 1%~
5%, polymer dispersion 4%~15%, balance of solvent；The dispersing agent be selected from starch, cellulose, natural plant gum, animal glue and
One or more of polymer A；The polymer A includes polyacrylamide, hydrolyzed polyacrylamide, polyvinylpyrrolidone
One or more of with polyvinyl alcohol；The polymer dispersion includes polyurethane, styrene-acrylic emulsion, polyacrylic acid, alkyd tree
One or more of rouge, hydroxylated cellulose, polyvinyl alcohol, polyacrylate and copolymer B；The copolymer B includes poly- ammonia
Two or more copolymerization in ester, styrene-acrylic emulsion, polyacrylic acid, alkyd resin, hydroxylated cellulose, polyvinyl alcohol and polyacrylate
It is formed by copolymer.The present invention mixes color-change powder with specific dispersing agent and polymer dispersion, and in certain proportion
Collocation, dispersing agent first make the powder homogenization that changes colour, and polymer dispersion plays redispersion, make the powder nano particle quilt that changes colour
Milk-globule cladding, the two synergistic effect is conducive to be promoted the dispersion effect of discoloration powder, and passes through dispersing agent and dispersibility polymerization
Object water lock promotes content of water in system, and the discoloration colour fading efficiency of coating is obviously improved by above-mentioned many-sided effect, makes coating
With sensitive photoresponse reversible color performance；In addition, also making coating under the synergistic effect of dispersing agent and polymer dispersion
With good storage stability and coating adhesion.
The experimental results showed that the Coloring Time < 2s of coating provided by the present invention, fading time < 72h, storage stability
> 30 days, coating adhesion reached 1 grade.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the schematic diagram that pattern is projected obtained by embodiment 1；
Fig. 2 is the schematic diagram of 1 gained pierced pattern of embodiment.
Specific embodiment
The present invention provides a kind of ability of reverse photochromism coating, by quality ratio, including following components:
The dispersing agent is selected from one or more of starch, cellulose, natural plant gum, animal glue and polymer A；
The polymer A includes in polyacrylamide, hydrolyzed polyacrylamide, polyvinylpyrrolidone and polyvinyl alcohol
It is one or more of；
The polymer dispersion includes polyurethane, styrene-acrylic emulsion, polyacrylic acid, alkyd resin, hydroxylated cellulose, poly- second
One or more of enol, polyacrylate and copolymer B；
The copolymer B includes polyurethane, styrene-acrylic emulsion, polyacrylic acid, alkyd resin, hydroxylated cellulose, polyvinyl alcohol
Copolymer is formed by with two or more copolymerization in polyacrylate.
The present invention mixes color-change powder with specific dispersing agent and polymer dispersion, and arranges in pairs or groups in certain proportion, point
Powder first makes the powder homogenization that changes colour, and polymer dispersion plays redispersion, and the powder nano particle that makes to change colour is by milk-globule packet
It covers, the two synergistic effect is conducive to be promoted the dispersion effect of discoloration powder；Meanwhile water is the key that one of powder discoloration, ginseng
With metachromasia, the present invention promotes content of water in system by above-mentioned dispersing agent and polymer dispersion water lock；By above-mentioned multi-party
Face collective effect can be obviously improved the discoloration efficiency and colour fading efficiency of coating, and coating is made to have sensitive photoresponse reversible color
Performance.
Ability of reverse photochromism coating provided by the invention includes color-change powder.The color-change powder is for receiving excitation light source and making
Coating generates responsiveness discoloration.In the present invention, the color-change powder is preferably transition metal oxide；It more preferably include titanium dioxide
One or more of titanium, tungstic acid and molybdenum trioxide.The present invention is not particularly limited the source of the color-change powder, is one
As commercially available product.
In the present invention, the granularity of the color-change powder is preferably 10nm~10 μm.If granularity is excessive, white powder will lead to
Performance decline, and will lead to powder transparency variation, there is certain influence for the transparency requirement of the transparent materials substrate such as glass.
In the present invention, mass ratio of the color-change powder in coating is 0.2%~5%.
Ability of reverse photochromism coating provided by the invention includes dispersing agent.In the present invention, the dispersing agent is selected from starch, fibre
Tie up one or more of element, natural plant gum, animal glue and polymer A.Wherein, the starch preferably include hydroxymethyl starch and/
Or acetic starch.The cellulose preferably includes hydroxymethyl cellulose and/or carboxymethyl cellulose.The natural plant gum preferably includes
Guar gum and/or fenugreek gum.The animal glue preferably includes gelatin and/or agar.The polymer A include polyacrylamide,
One or more of hydrolyzed polyacrylamide, polyvinylpyrrolidone and polyvinyl alcohol.The weight average molecular weight of the polymer A
Preferably 2000~100000.The dispersing agent does not chemically react with other components in coating system of the present invention, and
It can well realize the peptizaiton to discoloration powder.The present invention is not particularly limited the source of the dispersing agent, is general
Commercially available product.In the present invention, mass ratio of the dispersing agent in coating is 1%~5%.
Ability of reverse photochromism coating provided by the invention includes polymer dispersion.The polymer dispersion includes poly- ammonia
One of ester, styrene-acrylic emulsion, polyacrylic acid, alkyd resin, hydroxylated cellulose, polyvinyl alcohol, polyacrylate and copolymer B
Or it is several；The copolymer B include polyurethane, styrene-acrylic emulsion, polyacrylic acid, alkyd resin, hydroxylated cellulose, polyvinyl alcohol and
Two or more copolymerization in polyacrylate is formed by copolymer.The polymer dispersion and the present invention apply Material
Other components in system do not chemically react, have certain oil resistivity, water resistance, resistance to acid and alkali, weatherability after film forming, no
Easy dusting, peeling.The present invention is not particularly limited the source of the polymer dispersion, is general commercially available product.This hair
In bright, mass ratio of the polymer dispersion in coating is 4%~15%.
Ability of reverse photochromism coating provided by the invention includes solvent.The present invention does not have special limit to the type of the solvent
System is photochromic coating solvent well known to those skilled in the art.The solvent preferably includes organic solvent and water
One or more of；More preferably water.The type of the organic solvent is not particularly limited, for known to those skilled in the art
Organic solvent, including but not limited to ethyl alcohol, isopropanol, ether, acetone, methanol, tetrahydrofuran, ethyl acetate and second two
One or more of diethylene glycol dimethyl ether etc..In some embodiments of the present invention, solvent is water, adopts water as solvent, and what is obtained is
Water paint can be realized coating safety and environmental protection, green non-pollution.
Compared with existing coating, coating provided by the invention is had the advantages that
1, the present invention mixes color-change powder with specific dispersing agent and polymer dispersion, in above-mentioned dispersing agent and dispersibility
Under the synergistic effect of polymer, the dispersion effect of discoloration powder can be obviously improved；Moreover, water is the key that powder discoloration
One, metachromasia is participated in, the present invention promotes content of water in system by above-mentioned dispersing agent and polymer dispersion water lock；By upper
The discoloration colour fading efficiency that many-sided collective effect can be obviously improved coating is stated, makes coating that there is sensitive photoresponse reversible color
Performance, experimental result show that its Coloring Time is < 2s, fading time < 72h.
2, the storage stability of existing coating is poor, storage very short time coating system just quickly occur sedimentation, flocculation, need through
The processing such as sufficient ultrasound can just restore；And coating of the invention, under the synergistic effect of dispersing agent and polymer dispersion, energy
It is enough obviously improved the storage stability of coating, placement 30 days or more are still fine dispersion system, and precipitating, flocculation does not occur.
3, after the coating of existing coating, material film is that nano-powder is fixed to each other with Van der Waals force and is fixed on coating carrier
On, adhesion is poor, and touching falls off or from falling out；And coating of the invention, there is good attachment effect after coating
Fruit is shown as level-one according to coating adhesion cross-hatching evaluation criteria (GB/T9286-88) test.
It is also preferable to include catalyst for ability of reverse photochromism coating provided by the invention.In the present invention, the catalyst is preferred
Including one or more of polyacrylic acid, polyvinyl acetate and polyvinyl alcohol.The present invention polymerize in dispersing agent with dispersibility
On the basis of object synergistic effect improves discoloration powder dispersity and coating system water signature, above-mentioned catalyst, Neng Goujin are introduced
One step accelerates metachromasia, promotes the discoloration rate of coating；I.e. catalyst can with above-mentioned dispersing agent and polymer dispersion into
The collaboration of one step, the common discoloration efficiency for promoting coating system.The present invention is not particularly limited the source of the catalyst, is one
As commercially available product.In the present invention, the weight average molecular weight of the catalyst is preferably 2000~10000.It is described to urge in the present invention
Mass ratio of the agent in coating is preferably 0.2%~2%.
It is also preferable to include decolourants for ability of reverse photochromism coating provided by the invention.In the present invention, the decolourant is preferred
For Photosensitive decolourant or non-photosensitivity type decolourant.Photosensitive decolourant is to realize to fade by light reaction, and non-photosensitivity type fades
Agent is to be faded in the coating by autoreactivity.
Wherein, the Photosensitive decolourant preferably includes semiconductor type metal oxide, porphyrins, indoles
Close one or more of object, thiophenes and azoles.The semiconductor type metal oxide preferably includes
Titanium oxide and/or tungsten oxide.The porphyrins preferably include ferriporphyrin, ferriporphyrin derivative, copper porphyrin, copper porphyrin and spread out
One or more of biology, magnesium porphyrin and magnesium derivatives of porphyrin.The Benzazole compounds preferably include indoline and its
One or more of derivative.The thiophenes preferably include to melt penthienate, melt penthienate derivative, melt thiophene more
Melt one or more of thiophene derivant with more.The azoles preferably include fluorine boron pyrroles, fluorine boron pyrrole derivatives
One or more of object, dithieno pyrroles and dithieno azole derivatives.
The non-photosensitivity type decolourant preferably include hydrogen peroxide, persulfate, hypochlorite, chlorite, chlorate,
One or more of mangaic acid, permanganate, chromic acid and high chromic acid content salt.Wherein, above-mentioned various hydrochlorates be preferably sodium salt, sylvite,
One or more of magnesium salts and ammonium salt.
The present invention is not particularly limited the source of the decolourant, is general commercially available product.It is described to take off in the present invention
The mass ratio that toner accounts for coating is preferably 0.05%~1%.The discoloration invertibity of existing photochromic powder is needed by oxidation
Property realize, realize colour fading by the oxygen in air under naturally open environment, efficiency is lower, and lacks oxygen under air-proof condition
Agent, colour fading efficiency are lower.Above-mentioned decolourant is added into coating system by the present invention, cooperates with work with polymeric system of the invention
With can further significantly improve fade rates, promote the reversible sensitivity of coating color-changing.
The present invention also provides a kind of coatings that ability of reverse photochromism coating is formed as described in above-mentioned technical proposal.This hair
It is bright to coating formed coating mode be not particularly limited, by it is well known to those skilled in the art prepare paint coatings in the way of
Progress is dried after coating is such as coated on substrate, can form coating.The drying is preferably dried in the shade, that is, is protected from light drying.
Coating is formed by using above-mentioned ability of reverse photochromism coating, there is sensitive photo absorption property, discoloration efficiency greatly promotes,
And coating adhesion is obviously improved.In the coating, discoloration powder content is 5wt%~50wt%, dispersant 10wt%
~50wt%, catalyst content are 0~10wt%, and colour fading agent content is 0~2wt%, and polymer dispersion content is 20wt%
~50wt%, surplus are water.
The present invention also provides a kind of preparation methods of ability of reverse photochromism coating described in above-mentioned technical proposal, including with
Lower step:
A color-change powder suspension is mixed with dispersant solution), obtains mixed liquor a；
B the mixed liquor a is mixed with aqueous polymer dispersions), obtains ability of reverse photochromism coating.
According to the present invention, color-change powder suspension is mixed with dispersant solution first, obtains mixed liquor a.
Wherein, the color-change powder suspension is that color-change powder is scattered in the suspension formed in solvent.The color-change powder and molten
Type, content and the source of agent with it is consistent described in above-mentioned technical proposal, details are not described herein.In the present invention, the discoloration
The mass concentration of powder suspension is preferably 20wt%~25wt%.
The dispersant solution is that dispersing agent is dissolved in solution formed in solvent.The type of the dispersing agent and solvent,
Content and source with it is consistent described in above-mentioned technical proposal, details are not described herein.In the present invention, the matter of the dispersant solution
Measuring concentration is preferably 5wt%~10wt%.
The mode that the color-change powder suspension is mixed with dispersant solution is not particularly limited, and can mix well the two
?.In some embodiments of the invention, the two is mixed using sonic oscillation.In preparation process of the invention, will first it become
Toner suspension is uniformly mixed with dispersant solution, carries out subsequent operation again after forming evenly dispersed mixed liquor a, can just be made most
Discoloration powder in whole coating system is uniformly dispersed, if upsetting the step or directly mixing all raw materials, can reduce powder
Dispersibility influences coating color-changing performance and storage stability and coating adhesion.
According to the present invention, after obtaining mixed liquor a, the mixed liquor a is mixed with aqueous polymer dispersions, obtaining can
Nagative photochromism coating.
Wherein, the aqueous polymer dispersions are the aqueous dispersion emulsions of polymer dispersion, are a kind of organic polymers
The lotion of object, the lotion have other in certain spreading ability and excellent water dispersible, with coating system of the present invention
Component does not chemically react, there is certain oil resistivity, water resistance, resistance to acid and alkali, weatherability after film forming, is not pulverized easily, rises
Skin.It is consistent described in the type and above-mentioned technical proposal of polymer dispersion in the aqueous polymer dispersions, i.e., it is described
Aqueous polymer dispersions include aqueous polyurethane, waterborne styrene-acrylic emulsion, aqueous polyacrylamide acid, aqueous alkide resin, aqueous hydroxyl
One or more of base cellulose, watersoluble polyvinyl alcohol, water polyacrylic acid and aqueous copolymer B；The aqueous copolymerization
Object B includes aqueous polyurethane, waterborne styrene-acrylic emulsion, aqueous polyacrylamide acid, aqueous alkide resin, water-based hydroxyl cellulose, aqueous
Two or more copolymerization in polyvinyl alcohol and water polyacrylic acid is formed by polyalcohol emulsion particle.In the present invention,
The mass concentration of the aqueous polymer dispersions is preferably 8wt%~20wt%.
The mode that the mixed liquor a is mixed with dispersant solution is not particularly limited, and can mix well the two.
In some embodiments of the invention, the two is mixed using sonic oscillation.
In the present invention, preferably, the step specifically includes:
B1 the mixed liquor a is mixed with aqueous polymer dispersions), obtains mixed liquor b；
B2 the mixed liquor b is mixed with colour fading agent solution), obtains mixed liquor c；
B3 the mixed liquor c is mixed with catalyst solution), obtains ability of reverse photochromism coating
Wherein, the colour fading agent solution is that decolourant is dissolved in solvent and is formed by solution.The kind of the decolourant and solvent
Class, content and source with it is consistent described in above-mentioned technical proposal, details are not described herein.In the present invention, the colour fading agent solution
Mass concentration be preferably 0.5wt%~2wt%.
The catalyst solution is dissolved in solvent for catalyst and is formed by solution.The type of the catalyst and solvent contains
Amount and source with it is consistent described in above-mentioned technical proposal, details are not described herein.In the present invention, the quality of the catalyst solution
Concentration is preferably 5wt%~10wt%.
In preparation process of the invention, every kind of material is introduced with dispersion liquid or solution form, and with certain concentration into
Row mixing, and according to the sequence mixing for first mixing color-change powder suspension with dispersant solution, be conducive to mix each component simultaneously
The dispersibility of promotion system.As can be seen that preparation process of the invention is simple and easy, only various materials are mixed, condition
Mildly, it carries out at room temperature, whole preparation method is simple and efficient, is easy to implement large-scale production, and gained coating is with excellent
Different photo absorption property, discoloration rate are obviously improved, and storage stability and coating adhesion are also obviously improved.
The present invention also provides a kind of methods for carrying out light drawing using above-mentioned ability of reverse photochromism coating, comprising: utilizes
The light source (such as straight line, cross hairs) of specific light transmission pattern, which is transmitted on coating, draws, and obtains having drawing for identical patterns
Product.In the preparation method, need to generally use two kinds of light and draw, with it is a kind of will not metachromasia wave band laser into
Row positioning, the laser for recycling another kind that can generate photochromic wave band are drawn.
The present invention also provides another methods for carrying out light drawing using above-mentioned ability of reverse photochromism coating, comprising: will
Light source is irradiated on coating through prefabricated hollowed-out board, obtains the drafting product with identical pierced pattern.In this method by by
Light area control is drawn, and has carried out pattern control using hollowed-out board.
In the present invention, above-mentioned light drawing after, can also to draw product surface selectively spray decolourant further plus
Fast fade rates.
In above two preparation method provided by the invention, the light source includes but is not limited to laser.The wave band of the light
Including but not limited to infrared light, visible light or ultraviolet light.The energy of the light source preferably≤2W/cm2.Above-mentioned smooth drawing practice exists
Pattern drafting is carried out on the coating formed after ability of reverse photochromism coating as described in the above technical scheme is dry, by certain kind
The light source of class, wave band and energy realizes that this method develops the color at once, greatly improves discoloration efficiency, and pattern line is clear, changes colour
Comparison is obvious, reaches preferable color changeable effect；And the reversible colour fading of the above method, coating can be made to reach flexible reversible color and taken off
Color effect realizes showing and restoring for image.
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are only further explanation the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.In following embodiment, various material solutions are taken water as a solvent.
Embodiment 1
The preparation of 1.1 samples
By 0.0318g photochromic powder suspension, (concentration 25wt%, discoloration powder are nanometer MoO3) reagent is added
In bottle, 0.7105g polyvinyl alcohol water solution is added, and (concentration 5wt%, polyvinyl alcohol weight average molecular weight are that 80000), room temperature is super
Sound oscillation 1 minute.
It is added 1.5859g aqueous alkide resin (solid content 8.5wt%, model STW-301), room temperature sonic oscillation 3
Minute.
0.0828g polyacrylic acid aqueous solution is added, and (concentration 10wt%, polyacrylic acid weight average molecular weight are 3000) ultrasound
Shaken well obtains ability of reverse photochromism coating.
After test tube aspirates homogenization repeatedly, draws appropriate coating and be coated on glass slide that (glass slide uses deionization in advance
Water is rinsed and is dried), it is protected from light and dries in the shade, form the coating of 1mm thickness, obtain ability of reverse photochromism coating smear.
The test of 1.2 samples
(1) use cross laser (light source for semiconductor laser, energy 0.2mW/cm2) irradiation smear, as a result such as Fig. 1 institute
Show, Fig. 1 is the schematic diagram that pattern is projected obtained by embodiment 1.
Using blue-ray LED, (energy is < 0.2mW/cm2) through hollowed-out board irradiation smear, as a result as shown in Fig. 2, Fig. 2 is
The schematic diagram of 1 gained pierced pattern of embodiment.
After carrying out corresponding light drawing using coating provided by the invention it can be seen from Fig. 1 and Fig. 2, smear discoloration is obvious,
Svelteness, with distinct contrast, color is soft, has preferable color changeable effect.
The discoloration rate in above-mentioned smooth drawing course is recorded, test result is referring to table 1.
(2) by above-mentioned coating (20 DEG C) stored protected from light at room temperature, the storage stability of coating is investigated, record coating can
The duration for keeping fine dispersion stability, phenomena such as precipitating, flocculation not occurring, test result is referring to table 1.
(3) according to the adhesion of coating adhesion cross-hatching evaluation criteria GB/T9286-88 testing coating, test result ginseng
It is shown in Table 1.
Embodiment 2
By 0.0294g photochromic powder suspension, (concentration 25wt%, discoloration powder are nano-TiO2) reagent is added
In bottle, 0.6588g polyvinyl alcohol water solution is added, and (concentration 5wt%, polyvinyl alcohol weight average molecular weight are that 80000), room temperature is super
Sound oscillation 1 minute.
It is added 1.4688g waterborne styrene-acrylic emulsion (solid content 15wt%, model KL-420), room temperature sonic oscillation 3 divides
Clock.
0.0770g polyacrylic acid aqueous solution is added, and (concentration 10wt%, polyacrylic acid weight average molecular weight are 3000) ultrasound
Shaken well obtains ability of reverse photochromism coating.
Above-mentioned coating is handled according to the method for embodiment 1, obtains ability of reverse photochromism coating smear.
It is tested for the property according to the sample test method of embodiment 1, test result is referring to table 1.
Embodiment 3
By 0.0293g photochromic powder suspension, (concentration 25wt%, discoloration powder are nanometer WO3) reagent bottle is added
In, it is added 0.6509g hydroxymethyl cellulose aqueous solution (concentration 5wt%), room temperature sonic oscillation 1 minute.
It is added 1.4527g aqueous polyurethane (solid content 10wt%, model PU-601), room temperature sonic oscillation 3 minutes.
0.0820g polyvinyl acetate aqueous solution of ester is added, and (concentration 10wt%, polyvinyl acetate weight average molecular weight are
17000), sonic oscillation is uniform, obtains ability of reverse photochromism coating.
Above-mentioned coating is handled according to the method for embodiment 1, obtains ability of reverse photochromism coating smear.
It is tested for the property according to the sample test method of embodiment 1, test result is referring to table 1.
Embodiment 4
By 0.0306g photochromic powder suspension, (concentration 25wt%, discoloration powder are nanometer WO3) reagent bottle is added
In, it is added 0.6767g hydroxymethyl cellulose aqueous solution (concentration 5wt%), room temperature sonic oscillation 1 minute.
It is added 1.5005g water polyacrylic acid (solid content 20wt%, model YZ-128), room temperature sonic oscillation 3
Minute.
0.0789g polyvinyl acetate aqueous solution of ester is added, and (concentration 10wt%, polyvinyl acetate weight average molecular weight are
50000), sonic oscillation is uniform, obtains ability of reverse photochromism coating.
Above-mentioned coating is handled according to the method for embodiment 1, obtains ability of reverse photochromism coating smear.
It is tested for the property according to the sample test method of embodiment 1, test result is referring to table 1.
The performance of coating obtained by 1 Examples 1 to 4 of table
By the above test result it is found that powder particle size is small in coating provided by the invention, coating color-changing effect is preferable, discoloration
Rate is fast, and colour fading efficiency improves (fade rates are usually 120h or more in the prior art), meanwhile, storage stability and painting
Layer adhesion is preferable.
Embodiment 5
It is carried out according to the preparation process of embodiment 1, unlike, it is added after aqueous alkide resin and is added polyacrylic acid
Before solution, it is also added into 0.3180g hydrogenperoxide steam generator (concentration 1wt%) and shaken well.
Embodiment 6
It is carried out according to the preparation process of embodiment 2, unlike, it is added after waterborne styrene-acrylic emulsion and is added polyacrylic acid
Before solution, it is also added into 0.7435g sodium peroxydisulfate solution (concentration 1wt%) and shaken well.
Embodiment 7
It is carried out according to the preparation process of embodiment 3, unlike, it is added after aqueous polyurethane and is added polyvinyl acetate
Before ester solution, it is also added into 0.1463g ammonium persulfate solution (concentration 1wt%) and shaken well.
Embodiment 8
It is carried out according to the preparation process of embodiment 4, unlike, it is added after water polyacrylic acid and is added poly-vinegar acid
Before ethylene ester solution, it is also added into 0.3082g and crosses mangaic acid solution (concentration 1wt%) and shaken well.
Embodiment 5~8 is tested for the property according to the sample test method of embodiment 1, and reversible take off is carried out to coating
Color test, records duration of fading after being protected from light, every test result is referring to table 2.
The performance of 2 embodiment of table, 5~8 gained coating
| Powder average grain diameter | Solid content | Discoloration rate | Fade rates | Storage stability | Adhesion | |
| Embodiment 5 | 54.5nm | 6.95wt% | < 2s | < 2h | > 30 days | 1 grade |
| Embodiment 6 | 57.3nm | 6.05wt% | < 2s | < 16h | > 30 days | 1 grade |
| Embodiment 7 | 49.8nm | 7.33wt% | < 2s | < 16h | > 30 days | 1 grade |
| Embodiment 8 | 53.9nm | 6.94wt% | < 2s | < 12h | > 30 days | 1 grade |
By the above test result it is found that powder particle size is small in coating provided by the invention, coating color-changing effect is preferable, discoloration
Rate is fast, and reversible fade rates are further promoted, and has sensitive photo absorption property；Meanwhile storage stability and coating
Adhesion is preferable.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.To these embodiments
A variety of modifications will be readily apparent to those skilled in the art, the general principles defined herein can be with
Without departing from the spirit or scope of the present invention, it realizes in other embodiments.Therefore, the present invention will not be limited
In the embodiments shown herein, and it is to fit to widest model consistent with the principles and novel features disclosed in this article
It encloses.
Claims (10)
1. a kind of ability of reverse photochromism coating, which is characterized in that by quality ratio, including following components:
The dispersing agent is selected from one or more of starch, cellulose, natural plant gum, animal glue and polymer A；
The polymer A includes one of polyacrylamide, hydrolyzed polyacrylamide, polyvinylpyrrolidone and polyvinyl alcohol
Or it is several；
The polymer dispersion includes polyurethane, styrene-acrylic emulsion, polyacrylic acid, alkyd resin, hydroxylated cellulose, polyethylene
One or more of alcohol, polyacrylate and copolymer B；
The copolymer B includes polyurethane, styrene-acrylic emulsion, polyacrylic acid, alkyd resin, hydroxylated cellulose, polyvinyl alcohol and gathers
Two or more copolymerization in acrylate is formed by copolymer.
2. coating according to claim 1, which is characterized in that the color-change powder is transition metal oxide.
3. coating according to claim 1 or 2, which is characterized in that the color-change powder include titanium dioxide, tungstic acid and
One or more of molybdenum trioxide.
4. coating according to claim 1 or 2, which is characterized in that the granularity of the color-change powder is 10nm~10 μm.
5. coating according to claim 1, which is characterized in that further include catalyst；The catalyst include polyacrylic acid,
One or more of polyvinyl acetate and polyvinyl alcohol；
Mass ratio of the catalyst in the coating is 0.2%~2%.
6. coating according to claim 1, which is characterized in that further include decolourant；Matter of the decolourant in coating
Amount is than being 0.05%~1%.
7. coating according to claim 6, which is characterized in that the decolourant is that Photosensitive decolourant or non-photosensitivity type take off
Toner；
The Photosensitive decolourant includes semiconductor type metal oxide, porphyrins, Benzazole compounds, thiophene-based
Close one or more of object and azoles；
The non-photosensitivity type decolourant includes hydrogen peroxide, persulfate, hypochlorite, chlorite, chlorate, mangaic acid, height
One or more of manganate, chromic acid and high chromic acid content salt.
8. a kind of coating that ability of reverse photochromism coating according to any one of claims 1 to 7 is formed.
9. a kind of preparation method of ability of reverse photochromism coating according to any one of claims 1 to 7, which is characterized in that packet
Include following steps:
A color-change powder suspension is mixed with dispersant solution), obtains mixed liquor a；
B the mixed liquor a is mixed with aqueous polymer dispersions), obtains ability of reverse photochromism coating.
10. preparation method according to claim 9, which is characterized in that the step B) include:
B1 the mixed liquor a is mixed with aqueous polymer dispersions), obtains mixed liquor b；
B2 the mixed liquor b is mixed with colour fading agent solution), obtains mixed liquor c；
B3 the mixed liquor c is mixed with catalyst solution), obtains ability of reverse photochromism coating；
The mass concentration of the color-change powder suspension is 20wt%~25wt%；
The mass concentration of the dispersant solution is 5wt%~10wt%；
The mass concentration of the aqueous polymer dispersions is 8wt%~20wt%；
The mass concentration of the colour fading agent solution is 0.5wt%~2wt%；
The mass concentration of the catalyst solution is 5wt%~10wt%.
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| CN110551432A (en) * | 2019-09-09 | 2019-12-10 | 天津孚信阳光科技有限公司 | Photochromic spray for fresh flowers |
| CN110747641A (en) * | 2019-11-29 | 2020-02-04 | 武汉纺织大学 | Photochromic carbon fiber based on inorganic material and preparation method thereof |
| CN112322134A (en) * | 2020-09-23 | 2021-02-05 | 中昊北方涂料工业研究设计院有限公司 | Aqueous single-color-changing irreversible temperature indicating coating |
| CN114752297A (en) * | 2022-04-19 | 2022-07-15 | 浙江大瑞漆业科技有限公司 | Special light sensitive coating and preparation method thereof |
| CN114958176A (en) * | 2022-06-23 | 2022-08-30 | 湖北大学 | Water-based photochromic composite coating material and preparation method thereof |
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| CN114958176A (en) * | 2022-06-23 | 2022-08-30 | 湖北大学 | Water-based photochromic composite coating material and preparation method thereof |
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