CN109880509A - Aqueous allochroic paint and its painting membrane product - Google Patents
Aqueous allochroic paint and its painting membrane product Download PDFInfo
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- CN109880509A CN109880509A CN201910084448.9A CN201910084448A CN109880509A CN 109880509 A CN109880509 A CN 109880509A CN 201910084448 A CN201910084448 A CN 201910084448A CN 109880509 A CN109880509 A CN 109880509A
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Abstract
A kind of aqueous allochroic paint and its painting membrane product of technical field of aqueous paint, including matrix resin, aqueous photochromic agent, aqueous temperature induced color changing agent and reactive emulsifier；Aqueous photochromic agent and aqueous temperature induced color changing agent contain outer cladding object, and outer cladding object is polystyrene type high molecular polymer or acrylic ester high molecular type polymer, and outer cladding object and reactive emulsifier have the HLB value to match.The present invention protects oiliness colour-changing agent by using the outer claddings such as polystyrene type high molecular polymer or acrylic ester high molecular type polymer object; enable oiliness colour-changing agent is stable to be dispersed in water-based system coating; it ensure that the stability of coating color-changing ability; and at the same time realizing temperature induced color changing and photochromic, perception and the demand of other perceptional functions can satisfy.
Description
Technical field
The present invention relates to a kind of technology in water paint field, specifically a kind of aqueous allochroic paint and its film system
Product.
Background technique
Currently, allochroic paint in the market can not remain beautiful due to property of the colour-changing agent in coating is not sufficiently stable
Color change.The industries such as building decoration, table ware, manicure have more and more demands for product metachrosis, and
The stability of metachrosis and the type of color change limit the demand in market.
Furthermore all there are problems in either thermohardening type allochroic paint or UV light-cured type allochroic paint: heat cure
Type allochroic paint will increase the discharge of volatile organic matter if it is solvent type class, unfavorable in environment and Health Status For Workers Exposed,
Country is increasingly stringenter the limitation of the type coating material production condition；Thermohardening type allochroic paint is if it is aqueous, although can
Environmental pollution is reduced, but the performance of coating is slightly worse, film is not fine and close, curing time is long；UV light-cured type allochroic paint according to
Active dilution agent need to be added in solventless type, although have the characteristics that efficiently, be applicable in wide, economic, energy conservation, be environmental-friendly, it is low
The reactive diluent of degree of functionality is volatile and has certain toxicity and irritation, unfavorable in Health Status For Workers Exposed.Therefore, it opens
The allochroic paint for sending out environment-friendly type a kind of, it appears particularly important.
Summary of the invention
The present invention In view of the above shortcomings of the prior art, proposes a kind of aqueous allochroic paint and its applies membrane product.
The present invention is achieved by the following technical solutions:
The present invention relates to a kind of aqueous allochroic paints, including matrix resin, aqueous photochromic agent, aqueous temperature induced color changing agent
And reactive emulsifier, reactive emulsifier promote aqueous photochromic agent and aqueous temperature induced color changing agent and matrix resin phase
Hold；
Aqueous photochromic agent and aqueous temperature induced color changing agent contain outer cladding object, and outer cladding object is polystyrene type macromolecule
Polymer or acrylic ester high molecular type polymer, outer cladding object and reactive emulsifier have the HLB value to match, preferably
Ground, HLB value range are 2~38, are optimized for 8~20, more optimized is 12~18.
According to parts by weight, matrix resin is 30~90 parts in aqueous allochroic paint, aqueous photochromic agent and aqueous temperature
Totally 0.2~30 part of mutagens toner, reactive emulsifier is 0.5~5 part；
Aqueous allochroic paint further includes 0.05~5 part of aqueous levelling agent, 0.05~5 part of aqueous wetting dispersing agent, 1~10 part
Diluting monomer and 0.5~10 part of photoinitiator containing epoxy group.
Aqueous photochromic agent and aqueous temperature induced color changing agent are respectively powder or slurry form.
Aqueous photochromic agent includes at least one in photosensitive aqueous emulsion, photoreception microcapsule powder and sensitization discoloration PS color tablets powder
Kind；Preferably, aqueous photochromic agent parts by weight are 0.1~10 part, it is further preferred that being 1~10 part；
Preferably, the sensitization discoloration PS color tablets powder of Chemical Industry Science Co., Ltd of the same colour is ground using Dongguan City, optional color number has
701 pink, 704 daffods, 706 violets, 708 sea blue, 709 skyblues, 711 olive greens, 712 coffees ash；
Preferably, using the sensitization discoloration PS color tablets powder of Dongguan City discoloration Chemical Industry Science Co., Ltd, optional color number has 12#
Purple, 19# red, 14# skyblue, 15# blue, 22# is green, 17# is orange, 16# yellow.
Aqueous temperature induced color changing agent includes at least one of temperature-sensitive aqueous emulsion, temperature-sensitive microcapsule powder；Preferably, aqueous temperature mutagens
Toner parts by weight are 0.1~20 part, it is further preferred that being 1~10 part；
Preferably, the temperature-sensitive microcapsule powder of Chemical Industry Science Co., Ltd of the same colour is ground using Dongguan City, optional color number there are 100 ink
It is green, green, 105 sea blue, 108 bright orange, 110 bright red, 111 rose-reds in 101,114 dark brown；
Preferably, using the temperature-sensitive microcapsule powder of Dongguan City discoloration Chemical Industry Science Co., Ltd, optional color number has 186C red
Color, 807C2X rosiness, 107C yellow, 335C green, 301U blue, 497C coffee color, 2728C violet.
The heat discoloration normal temperature range of aqueous temperature induced color changing agent is -15 DEG C to 70 DEG C, becomes high temperature from low temperature is coloured
It is colourless；Preferably, heat discoloration normal temperature is 22 DEG C, 31 DEG C, 43 DEG C, and other temperature-sensitives can also be specified to become as needed certainly
Color temperature.
Reactive emulsifier includes nonyl phenolic nonionic emulsifier, nonyl phenolic anion emulsifier, phosphate type yin
At least one of ionic emulsifying agent, non-nonyl phenolic nonionic emulsifier and non-nonyl phenolic anion emulsifier；Preferably, instead
Answering type emulsifier parts by weight is 1~3 part, it is further preferred that being 1.5~2 parts.
Photoinitiator is radical photoinitiator and cationic photoinitiator；Preferably, photoinitiator parts by weight
It is 2~8 parts, it is further preferred that being 4~6 parts.
Radical photoinitiator includes at least one of cracking type initiator and hydrogen-abstraction initiator.
Cracking type initiator include 2- hydroxyl -4'- (2- hydroxy ethoxy) -2- methyl phenyl ketone, 1,1'- (methylene two -4,
1- phenylene) bis- [2- hydroxy-2-methyl-1- acetone], 2- methyl-1-(4- methyl mercapto phenyl)-2- morpholinyl-1- acetone, 2,
4,6- trimethylbenzoy-dipheny phosphine oxides, benzoin dimethylether, 2- hydroxy-2-methyl -1- phenyl -1- acetone, 1- hydroxyl
Base-at least one of cyclohexyl-phenyl ketone and benzoyl derivatives.
Hydrogen-abstraction initiator includes benzophenone, 4- benzoyl -4'- methyl-diphenyl sulfide, 2- benzoyl benzoic acid
At least one of methyl esters, isopropyl thioxanthone (2,4 isomer mixture) and 4- (N, N- dimethylamino) ethyl benzoate.
Cation light initiator is the mixing of mixing triaryl matte hexafluoro antimonic salt and propene carbonate that mass ratio is 3:2
Object, 4,4- xylyl iodine hexafluorophosphate, the 444- xylyl iodine hexafluorophosphate and 3- second that mass ratio is 3:2
The mixture of base -3- oxa- fourth ring methanol, 10- (4- xenyl) -2-isopropylthioxanthone -10- sulfonium that mass ratio is 65:35
At least one of hexafluorophosphate and gamma-butyrolacton mixture.
Matrix resin is the main component of film forming agent, is thermohardening type and/or light-cured type；Matrix resin preferably uses water
Property urethane acrylate oligomer, can be water-dispersion type, is also possible to aqueous emulsion type；Preferably, aqueous polyurethane propylene
The Solid content parts by weight of acid esters oligomer are 40~80 parts, it is further preferred that being 50~70 parts.
Aqueous levelling agent includes the polyether silicones of non-reactive, the polyethers of response type or polyester resin change properties of organic silicon, propylene
Esters of gallic acid aqueous levelling agent, fluorin modified crylic acid ester copolymer, sulfonate type fluorine aqueous levelling agent and metal carboxylate fluorocarbon surface
At least one of activating agent；Preferably, aqueous levelling agent parts by weight are 0.1~3 part, it is further preferred that being 0.2~1 part.
Aqueous wetting dispersing agent includes the alkylol amine salt of high molecular weight acidic polymer, acrylic copolymer, contains
Alkane hydroxyl amine salt, the height with acidic-group of the polynary hydroxy acid polymer of the structured copolymers of pigment affinity groups, low molecular weight
It is the polymeric alkanolamine of alkanolamine, multiple functional radical of molecule copolyesters, the polymeric alkylammonium salt of multiple functional radical, affine containing pigment
At least one of group polymer copolymerization body and the acrylic copolymer with pigment affinity groups；Preferably, aqueous wetting point
Powder parts by weight are 0.1~3 part, it is further preferred that being 0.2~1 part.
Diluting monomer containing epoxy group includes bis- ((3,4- epoxycyclohexyl) methyl) adipate esters, hexamethylene -1,2-
Dicarboxylic acids 2-glycidyl ester, 2- (3,4- 7-oxa-bicyclo[4.1.0 base) ethyl trimethoxy silane and 3- glycydoxy
At least one of triethoxysilane；Preferably, the diluting monomer parts by weight containing epoxy group are 2~8 parts, further preferably
Ground is 3~5 parts.
According to parts by weight, aqueous allochroic paint further includes 2~30 parts of fluorine compounds aqueous emulsions, so that aqueous allochroic paint
There is good anti-pollution characteristic after solidification；It preferably, is 5~20 parts, it is further preferred that being 10~15 parts.
According to parts by weight, aqueous allochroic paint further includes 0.5~5 part of mercaptan, it is preferable that and it is 1~4 part, it is further excellent
Selection of land is 2~3 parts.
According to parts by weight, aqueous allochroic paint further includes 0.1~10 part of pigment；The pigment is for aqueous pigment or with UV
Monomer is the pigment of diluent；It preferably, is 0.3~5 part, it is further preferred that being 0.5~2 part.
According to parts by weight, the aqueous allochroic paint further includes 0.1~5 part of UV absorbers and/or 0.1~5 part
Light stabilizer；
UV absorbers include at least one in oxanilide class, benzophenone, benzotriazole and phentriazine class
Kind；Preferably, UV absorbers parts by weight are 0.3~3 part, it is further preferred that being 0.5~2 part；
Light stabilizer includes hindered amine compound；Preferably, light stabilizer parts by weight are 0.3~3 part, further excellent
Selection of land is 0.5~2 part.
According to parts by weight, aqueous allochroic paint further includes 1~20 part of deionized water to adjust viscosity of the coating and solid content；
It preferably, is 3~15 parts, it is further preferred that being 5~10 parts.
The present invention relates to a kind of painting membrane products, including at least one layer of discoloration coating being arranged on ground；The discoloration applies
Layer is solidified by above-mentioned aqueous allochroic paint.
Preferably, the film products thickness is 1~20 μm；When coating layer thickness is lower than 1 μm, since oxygen prevents polymerization
It influences, the solidification of film surface layer is affected, film performance decline；At 20 μm or more, solidification is not thorough thickness, under film performance
Drop.
Technical effect
Compared with prior art, the present invention has the following technical effect that
1) by using the outer claddings object such as polystyrene type high molecular polymer or acrylic ester high molecular type polymer
Oiliness colour-changing agent is protected, enables oiliness colour-changing agent is stable to be dispersed in water-based system coating, ensure that coating color-changing
The stability of ability；And apply membrane product and can be achieved at the same time temperature induced color changing and photochromic, relative to existing photochromic product
Or temperature induced color changing product only has two kinds of colors of original state and color change state, the present invention is capable of providing at least three kinds of color instructions not
Same state has richer color change, can satisfy perception and the demand of other perceptional functions；
2) it is compounded by radical photoinitiator with cationic photoinitiator, so that solidification process is more thorough, crosslinking
Degree is closer, increases the adherence of film and ground, and enhances the curing efficiency of film, resultant performance enhancements；
3) solve the problems, such as thermohardening type allochroic paint curing rate slowly, low efficiency, and solve UV type discoloration
The problem that a large amount of solvent volatility organic emission amounts are big is used in coating；
4) without using industrial solvent in system, also without using a large amount of dilution type monomer, environmental-protecting performance is excellent, can use
In industries such as indoor and outdoor decoration, table ware, manicures, there is biggish industrialized production benefit and good application prospect.
Specific embodiment
The present invention will be described in detail With reference to embodiment.
Embodiment 1
The present embodiment is related to a kind of photosensitive heat discoloration painting membrane product, including one layer of photosensitive heat discoloration layer, photochromic layer base
Solidify in aqueous allochroic paint.
The ingredient of aqueous allochroic paint is as shown in table 1.
The aqueous allochroic paint component list of table 1
Preparation process is as follows:
By 35 parts of aqueous polyurethane acrylate oligomer UCECOAT 7200 (profound new company) and 52 parts of aqueous polyurethanes
Acrylate oligomer UCECOAT 7177 (profound new company) is added in the agitator with condenser, forms lotion after stirring
System；In the case where at the uniform velocity stirring, 1 part of reactive emulsifier ER-20 (ADEKA company), which is added in above-mentioned emulsion system, to be made
Its is evenly dispersed, mixing speed 800r/min, stirs 0.5h；
0.2 part of aqueous dispersion DISPERBYK-180 (BYK company) is added, it is made to be dispersed in above-mentioned emulsion system
In；It is gradually added into 5 parts of vermilion 186C temperature-sensitive aqueous emulsions (Dongguan City discoloration chemical industry) and 5 parts of #19 red sensitive microcapsule powders again
(Dongguan City discoloration chemical industry) improves mixing speed to 1200r/min, stirs 0.5h；Above-mentioned aqueous photochromic agent and aqueous temperature
Mutagens toner is all made of polymethyl methacrylate outer cladding, and HLB value is 8~20；
5 parts of diluting monomer EP-4231 (permanent bridge industry), 2 parts of radical photoinitiators containing epoxy group are added
IRGACURE 184 (Ciba company), 2 parts of radical photoinitiator DAROCUR TPO (Ciba company), 0.25 part of cation
Type photoinitiator Chemcure-CAT-1 (permanent bridge industry) and 2 parts of mercaptan Karen MTTMPE1 (permanent bridge industry) stablizes it and divides
It dissipates in above-mentioned emulsion system, obtains aqueous allochroic paint；
With bar spreader, which is coated on the optical grade PET film side with a thickness of 125 μm, in
80 DEG C are dried 5min in an oven, are solidified by LED light source to dry coating, and the thickness control of photochromic layer is 4~6 μ
M is made photosensitive heat discoloration and applies membrane product.
Embodiment 2
The present embodiment is related to a kind of photosensitive heat discoloration painting membrane product, including one layer of photosensitive heat discoloration layer, photochromic layer base
Solidify in aqueous allochroic paint.
The ingredient of aqueous allochroic paint is as shown in table 2.
The aqueous allochroic paint component list of table 2
Preparation process is as follows:
By 40 parts of aqueous polyurethane acrylate oligomer UCECOAT 7210 (profound new company), 45 parts of aqueous polyurethanes third
Olefin(e) acid ester oligomer UCECOAT 7689 (profound new company) and 9 parts of fluorine compounds aqueous emulsion HEXAFOR T-70 (raise pine in Guangzhou
Trade Co., Ltd), it is added in the agitator with condenser, forms emulsion system after stirring；In the case where at the uniform velocity stirring,
1.5 parts of reactive emulsifier SR-20 (ADEKA company), which is added in above-mentioned emulsion system, keeps its evenly dispersed, mixing speed
800r/min stirs 0.5h；
0.2 part of aqueous dispersion DISPERBYK-190 (BYK company) is added, it is made to be dispersed in above-mentioned emulsion system
In；It is gradually added into 5 parts of #14 blue sensitive microcapsule powders (Dongguan City discoloration chemical industry) and 5 parts of yellow 107C temperature-sensitive aqueous emulsion (east again
Guan Shi discoloration chemical industry), mixing speed is improved to 1200r/min, stirs 0.5h；Above-mentioned aqueous photochromic agent and aqueous temperature mutagens
Toner is all made of polystyrene outer cladding, and HLB value is 8~20；
6 parts of diluting monomer EP-3510 (permanent bridge industry), 2 parts of radical photoinitiators containing epoxy group are added
IRGACURE 1173 (Ciba company), 2.5 parts of radical photoinitiator IRGACURE 819 (Ciba company), 0.1 part of sun from
Subtype photoinitiator Chemcure-CAT-3 (permanent bridge industry) and 1.5 parts of mercaptan Karen MTTMPE1 (permanent bridge industry) keeps it steady
Surely it is scattered in above-mentioned emulsion system；
0.3 part of aqueous moistening flatting agent BYK-3530 (BYK company) is added in above-mentioned emulsion system, stirs evenly, obtains
To aqueous allochroic paint；
With bar spreader, the optical grade PET film side for being 125 μm by the aqueous allochroic paint coating thickness, in 80
5min to be dried DEG C in an oven, and dry coating is solidified by LED light source, the thickness control of photochromic layer is 4~6 μm,
Photosensitive heat discoloration is made and applies membrane product.
Embodiment 3
The present embodiment is related to a kind of photosensitive heat discoloration painting membrane product, including one layer of photosensitive heat discoloration layer, photochromic layer base
Solidify in aqueous allochroic paint.
The ingredient of aqueous allochroic paint is as shown in table 3.
The aqueous allochroic paint component list of table 3
Preparation process is as follows:
By 50 parts of aqueous polyurethane acrylate oligomer UCECOAT 7699 (profound new company) and 35 parts of aqueous polyurethanes
Acrylate oligomer UCECOAT 6558 (profound new company) is added in the agitator with condenser, forms lotion after stirring
System；In the case where at the uniform velocity stirring, by 0.5 part of reactive emulsifier NE-10 (ADEKA company) and 0.5 part of response type emulsification
Agent SE-10N (ADEKA company), which is added in above-mentioned emulsion system, keeps its evenly dispersed, mixing speed 800r/min, stirs 0.5h；
0.2 part of aqueous dispersion DISPERBYK-2010 (BYK company) is added, it is made to be dispersed in above-mentioned emulsion system
In；It is gradually added into 10 portions of violet 2728C temperature-sensitive microcapsule powders (Dongguan City discoloration chemical industry), 10 portions of photosensitive water and milk of #12 purple again
Liquid (Dongguan City discoloration chemical industry) and 2 parts of UV white pigment UJ-100Y (Zhejiang Na Mei new material limited liability company) improve stirring
Speed stirs 0.5h to 1200r/min；Above-mentioned aqueous photochromic agent and aqueous temperature induced color changing agent are all made of polyethyl acrylate
Outer cladding, HLB value are 8~20；
5 parts of diluting monomer CB-667 (permanent bridge industry), 1 part of radical photoinitiator containing epoxy group are added
IRGACURE 127 (Ciba company), 2 parts of radical photoinitiator IRGACURE 819 (Ciba company), 2 parts of free radical types
Photoinitiator IRGACURE 2959 (Ciba company), (Heng Qiao is produced 0.25 part of cationic photoinitiator Chemcure-CAT-5
Industry), 2 parts of mercaptan Karen MTTMPE1 (permanent bridge industry), 0.3 part of light stabilizer HALS emulsion UC-606 (ADEKA company)
With 0.3 part of light stabilizer UVA fine particles object UC-3140 (ADEKA company), it is made to be stably dispersed in above-mentioned emulsion system
In, obtain aqueous allochroic paint；
With bar spreader, which is coated on the optical grade PET film side with a thickness of 125 μm, in
80 DEG C are dried 5min in an oven, are solidified by LED light source to dry coating, and the thickness control of photochromic layer is 4~6 μ
M is made photosensitive heat discoloration and applies membrane product.
Embodiment 4
The present embodiment is related to a kind of photosensitive heat discoloration painting membrane product, including one layer of photosensitive heat discoloration layer, photochromic layer base
Solidify in aqueous allochroic paint.
The ingredient of aqueous allochroic paint is as shown in table 4.
The aqueous allochroic paint component list of table 4
Preparation process is as follows:
By 40 parts of aqueous polyurethane acrylate oligomer UCECOAT 7733 (profound new company), 45 parts of aqueous polyurethanes third
Olefin(e) acid ester oligomer UCECOAT 7571 (profound new company) and 10 parts of fluorine compounds aqueous emulsion HEXAFOR T-107 (are raised Guangzhou
Loose trade Co., Ltd), it is added in the agitator with condenser, forms emulsion system after stirring；The case where at the uniform velocity stirring
Under, 1 part of reactive emulsifier SR-20 (ADEKA company) and 1 part of reactive emulsifier PP-70 (ADEKA company) are added above-mentioned
Make its evenly dispersed in emulsion system, mixing speed 800r/min stirs 0.5h；
0.3 part of aqueous dispersion DISPERBYK-2015 (BYK company) is added, it is made to be dispersed in above-mentioned emulsion system
In；It is gradually added into 10 parts of #14 blue sensitive aqueous emulsions (Dongguan City discoloration chemical industry), 20 parts of coffee color 497C temperature-sensitive microcapsule powders again
(Dongguan City discoloration chemical industry) and 2 parts of aqueous yellow uitramarine E1300 (Zhejiang Na Mei new material limited liability company) improve stirring speed
Degree stirs 0.5h to 1200r/min；Above-mentioned aqueous photochromic agent and aqueous temperature induced color changing agent are all made of polymethylacrylic acid hydroxyl
Ethyl ester outer cladding, HLB value are 8~20；
5 parts of diluting monomer CB-660E (permanent bridge industry), 1 part of radical photoinitiator containing epoxy group are added
IRGACURE 127 (Ciba company), 2 parts of radical photoinitiator IRGACURE 184 (Ciba company), 2 parts of free radical types
Photoinitiator IRGACURE 819 (Ciba company), (Heng Qiao is produced 0.25 part of cationic photoinitiator Chemcure-CAT-6
Industry), 2 parts of mercaptan Karen MTTMPE1 (permanent bridge industry), (ADEKA is public by 0.25 part of light stabilizer HALS emulsion UC-5225
Department), 0.25 part of light stabilizer UVA fine particles object UC-3125 (ADEKA company) and 0.2 part of light stabilizer nano zine oxide
(Guangzhou Yang Song trade Co., Ltd), is stably dispersed in it in above-mentioned emulsion system, is eventually adding 0.4 part of aqueous wetting levelling
Agent BYK-3521 (BYK company) is uniformly mixing to obtain aqueous allochroic paint in system；
With bar spreader, the optical grade PET film side for being 125 μm by the aqueous allochroic paint coating thickness, in 80
5min to be dried DEG C in an oven, and dry coating is solidified by LED light source, the thickness control of photochromic layer is 4~6 μm,
Photosensitive heat discoloration is made and applies membrane product.
Comparative example 1
This comparative example prepares single photochromic coating, and the raw material being related to has:
Preparation process is as follows:
3 parts of propylene glycol monomethyl ethers, 2 parts of isopropanols, 20 parts of deionized waters are added in the agitator with condenser and are mixed, so
Afterwards in the case where at the uniform velocity stirring, it is added 50 parts of 6512 water-based polyurethane polymers of Crysol (Shi Han Chemical Co., Ltd.), 50
Part 6110 water-based polyurethane polymer of Crysol (Shi Han Chemical Co., Ltd.), makes it dissolve in above-mentioned solvent, mixing speed
600r/min stirs 0.5h, forms emulsion system；
It is gradually added into 0.2 part of aqueous wetting dispersing agent DISPERBYK-187 (BYK company), makes its evenly dispersed above-mentioned cream
In liquid system, mixing speed 2000r/min stirs 0.5h；
8 parts of #19 red sensitive aqueous emulsions (Dongguan City discoloration chemical industry), 0.3 part of 810 defoaming agent of Tego Foamex is added
(TEGO company), 0.3 part of aqueous levelling agent BYK-333 (BYK company), (real vast chemical industry has 0.5 part of Vesmody U604 thickener
Limit company) it is dissolved in above-mentioned emulsion system, mixing speed is improved to 1000r/min, stirs 1h；
6.5 parts of 161 isocyanate curing agents of Auiolin (Shi Han Chemical Co., Ltd.) are added to stir evenly, obtain aqueous
Heat cure photochromic coating.
With bar spreader, which is coated in the one side with a thickness of 125 μm of PET film, in 80 DEG C in baking oven
Middle drying 4 hours, the thickness control of photochromic coating layer are 4~6 μm, and photochromic film finished product is made.
Comparative example 2
This comparative example prepares single photochromic coating, and the raw material being related to has:
| Raw material | Model | Parts by weight |
| Aliphatic urethane acrylate | 583-1 | 30 parts |
| Aliphatic urethane acrylate | 5220 | 30 parts |
| Iso-bornyl acrylate | EM 70 | 40 parts |
| 1- hydroxy-cyclohexyl-phenyl ketone | IRGACURE 184 | 4 parts |
| 2,4,6- trimethylbenzoy-dipheny phosphine oxides | DAROCUR TPO | 1 part |
| Aqueous photochromic agent | #14 blue sensitive microcapsule powder | 5 parts |
| Aqueous wetting dispersing agent | DISPERBYK-168 | 0.3 part |
| Aqueous levelling agent | BYK-378 | 0.3 part |
Preparation process is as follows:
By 30 parts of 583-1 oligomer (Double Bond Chemical Ind.,Co.,Ltd.), (double bond chemical industry share has 30 part of 5220 oligomer
Limit company), 40 parts of 70 monomers of EM (Taiwan Changxing Chemical Co., Ltd.) are added in the agitator with condenser, it stirs evenly,
Mixing speed 1000r/min, mixing time 1h form emulsion system；
In the case where at the uniform velocity stirring, 0.3 part of aqueous wetting dispersing agent DISPERBYK-168 is added and is stirred, makes it
It is dispersed in above-mentioned emulsion system；
It is added #14 blue sensitive microcapsule powder (Dongguan City discoloration chemical industry), improves mixing speed to 2000r/min, stirring 1
Hour；
It is added 4 parts of photoinitiator IRGACURE 184 (Ciba company), (Ciba is public by 1 part of photoinitiator DAROCUR TPO
Department), it makes it dissolve in above-mentioned emulsion system；
0.3 part of aqueous levelling agent BYK-378 (BYK company) is added, stirs evenly, obtains UV type photochromic coating.
With bar spreader, which is coated on a thickness of in 125 μm of optical grade PET film one side,
Dry coating is solidified by ultraviolet light, ultraviolet irradiation light quantity is 600mj/cm2, the thickness control of dope layer
4~6 μm are made as, the photochromic film finished product of UV type is made.
Above-described embodiment and comparative example are compared:
Film finished product involved in above-mentioned comparison is using transparent hard film properties as evaluation criterion, using following equipment, method
It is tested to obtain.
1) coating layer thickness is tested: being stepped on film thickness instrument (Marl, Germany manufactures, model Millimar C1216) using foot and is surveyed
Try coating layer thickness；
2) coating storage stability: after allochroic paint obtained is placed in 25 DEG C, 60%RH atmosphere lower 6 months, observation
Whether coating is stable, no sedimentation phenomenon；
3) discoloration coating obtained the fast light xanthochromia degree measuring method of coating: is passed through into ultraviolet lighting in QUV test equipment
After penetrating 250 hours, 500 hours, 2000 hours, 2500 hours, the xanthochromia degree of film is observed；
4) coating water contact angle is tested: using optics contact angle tester after curing of coating (big Chang Hua praises business Co., Ltd)
It is tested；
5) coating adhesion: hardening film surface cross-cut tester or cutter are divided into 100 grids, and the size of each grid is
3M-600 type special test adhesive tape (Minnesota Mining and Manufacturing Company) is then adhered to the surface with the power of 2.0kg, with 180 ° by 1mm × 1mm
By 3M adhesive tape from the sur-face peeling, adhesive force is evaluated according to the hardening coat lattice number stayed on substrate film at angle, meter
For " 100/100 ".
Above-described embodiment is arranged in pairs or groups by aqueous UV resin and aqueous photochromic agent, aqueous temperature induced color changing agent, is prepared
Storage stability is long, can use the temperature-sensitive sensitization discoloration coating that LED light solidifies (UV solidification+heat cure), relative to existing light
Discoloration coating is caused there was only two kinds of colors of original state and color change state (temperature induced color changing coating there is a problem of identical), the present invention is real
It applies example and is capable of providing at least three kinds of colors, color change is more abundant, and application scenarios are more wide in range；
In aqueous UV system, Cationic curing systems are increased, further promote the curing efficiency of UV system and are consolidated
Change depth, so that the solidification of waterborne UV coating is more complete, Adhesion enhancement of the film to ground；Meanwhile having instead by introducing
The emulsifier system of answering property, so that many oil-soluble chemical substances, stable is scattered in water-based system, and response type cream
Agent itself can participate in UV curing reaction, will not be free in film in system or film coated surface, environmental-protecting performance are excellent；
In addition to this, in aqueous UV system, it joined light stabilizer, while not influencing temperature-sensitive sensitization discoloration effect,
The intensity of film tolerance ultraviolet light can be increased again.
It is emphasized that: the above is only presently preferred embodiments of the present invention, not make in any form to the present invention
Limitation, any simple modification, equivalent change and modification to the above embodiments according to the technical essence of the invention,
All of which are still within the scope of the technical scheme of the invention.
Claims (9)
1. a kind of aqueous allochroic paint, which is characterized in that including matrix resin, aqueous photochromic agent, aqueous temperature induced color changing agent
And reactive emulsifier；The aqueous photochromic agent and aqueous temperature induced color changing agent contain outer cladding object, the outer cladding object
For polystyrene type high molecular polymer or acrylic ester high molecular type polymer, the outer cladding object and reactive emulsifier have
There is the HLB value to match, it is preferable that HLB value range is 2~38.
2. aqueous allochroic paint according to claim 1, characterized in that according to parts by weight, the matrix resin be 30~
90 parts, aqueous photochromic agent and totally 0.2~30 part of aqueous temperature induced color changing agent, reactive emulsifier are 0.5~5 part；
Preferably, the aqueous allochroic paint further include 0.05~5 part of aqueous levelling agent, 0.05~5 part of aqueous wetting dispersing agent,
1~10 part of diluting monomer and 0.5~10 part of photoinitiator containing epoxy group.
3. aqueous allochroic paint according to claim 2, characterized in that the aqueous photochromic agent includes photosensitive water and milk
At least one of liquid, photoreception microcapsule powder and sensitization discoloration PS color tablets powder；Preferably, the aqueous photochromic agent parts by weight
It is 0.1~10 part；
The aqueous temperature induced color changing agent includes at least one of temperature-sensitive aqueous emulsion, temperature-sensitive microcapsule powder；Preferably, the aqueous temperature
Mutagens toner parts by weight are 0.1~20 part.
4. aqueous allochroic paint according to claim 2, characterized in that the reactive emulsifier include nonyl phenolic it is non-from
Sub- emulsifier, nonyl phenolic anion emulsifier, phosphate type anion emulsifier, non-nonyl phenolic nonionic emulsifier and non-
At least one of nonyl phenolic anion emulsifier；Preferably, the reactive emulsifier parts by weight are 1~3 part.
5. aqueous allochroic paint according to claim 2, characterized in that the photoinitiator includes radical photoinitiator
And cationic photoinitiator；Preferably, the photoinitiator parts by weight are 2~8 parts.
6. aqueous allochroic paint according to claim 2, characterized in that the matrix resin uses watersoluble polyurethane acrylic acid
Ester oligomer, the aqueous polyurethane acrylate oligomer are water-dispersion type or aqueous emulsion type；Preferably, the aqueous poly- ammonia
The Solid content parts by weight of ester acrylate oligomer are 40~80 parts.
7. aqueous allochroic paint according to claim 2, characterized in that further include that 2~30 parts of fluorinations are closed according to parts by weight
Object aqueous emulsion, 0.5~5 part of mercaptan and 0.1~10 part of pigment；The pigment is aqueous pigment or using UV monomer as the face of diluent
Material.
8. aqueous allochroic paint according to claim 2, characterized in that further include 0.1~5 part ultraviolet according to parts by weight
Light absorber and/or 0.1~5 part of light stabilizer；
The UV absorbers include at least one in oxanilide class, benzophenone, benzotriazole and phentriazine class
Kind；
The light stabilizer includes hindered amine compound.
9. a kind of painting membrane product, which is characterized in that including at least one layer of discoloration coating being arranged on ground；The discoloration coating
The aqueous allochroic paint as described in any one of claim 1~8 solidifies, and the film products thickness is 1~20 μm.
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| CN112322090A (en) * | 2020-11-15 | 2021-02-05 | 桂林理工大学 | Preparation method of ultraviolet light sensitive reversible color-changing paint for pavement marking |
| CN113150347A (en) * | 2021-04-23 | 2021-07-23 | 来奇偏光科技(中国)股份有限公司 | TAC color-changing film and preparation method thereof |
| CN113389063A (en) * | 2021-05-27 | 2021-09-14 | 合肥科天水性科技有限责任公司 | Preparation method of water-based photochromic clothing leather |
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| CN114045068A (en) * | 2021-12-10 | 2022-02-15 | 焦作卓立膜材料有限责任公司 | Multicolor hand-temperature reversible thermochromic thermal transfer ribbon and preparation method thereof |
| 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 |
| CN117247731A (en) * | 2023-09-14 | 2023-12-19 | 佛山市三水顺能化工有限公司 | Temperature-sensitive color-changing aqueous color layer coating for electrochemical aluminum and preparation method thereof |
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