CN109942861A - A kind of photochromic composite membrane of flexibility and preparation method thereof - Google Patents
A kind of photochromic composite membrane of flexibility and preparation method thereof Download PDFInfo
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- CN109942861A CN109942861A CN201910184776.6A CN201910184776A CN109942861A CN 109942861 A CN109942861 A CN 109942861A CN 201910184776 A CN201910184776 A CN 201910184776A CN 109942861 A CN109942861 A CN 109942861A
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Abstract
The present invention relates to a kind of photochromic composite membranes of flexibility, which is characterized in that including polyimide-based counterdie and photochromic resin layer, the yellow colour index YI of the composite membrane is 0.1 < YI < 1.0, and total light transmittance is 90% or more.The photochromic composite membrane of flexibility of the invention is in the case where imposing the flexible display front panel materials'use of frame portion of white printing, automatic adjustment optically variable effect can be realized according to indoor and outdoor natural light intensity, any performance of display is not damaged simultaneously, the important step adjusted for the visual light of novel flexible display material, and the photochromic composite membrane of flexibility of the invention has good flexible and mechanical property, is particularly suitable for plate material before collapsible display device.
Description
Technical field
The present invention relates to polymeric material fields, and in particular to a kind of photochromic composite membrane of flexibility and preparation method thereof.
Background technique
In intelligent display field, traditional display device includes that the images such as liquid crystal display device, organic EL display device are aobvious
Showing device, they are widely used in the intelligent control panels such as television set, smart phone, smartwatch.With current Mobile phone screen
For curtain, commercial product is difficult to more than 7 inches.The too big inconvenient user of mobile phone screen carries, and too small is unable to satisfy user couple
In the bigger demand of display area.As it can be seen that portability becomes the key factor for restricting large screen cell phone.Display device court as a result,
To folding square to development.
It is foldable, rollable, display device can be stored formally become display with the commercialization of foldable flexible screen mobile phone
The new research topic in field.In order to realize that foldable flexible is shown, need to include the components such as polarizer, phase plate and front panel
Flexible nature with height, especially front panel to the transparency, it is flexible require it is higher, it is clear that traditional hardness is strong, it is upright and outspoken,
Easily rupturable glass is unsuitable to do front plate material, therefore there is good light permeability and flexible high molecular material to become
The important goal of display device front panel investigation of materials.
On the other hand, Kapton has fabulous heat resistance, dimensional stability, insulating properties, translucency, Yi Jirou
Toughness is known as gold high molecular material, is widely used in electronic product, it is considered to be before a kind of potential display device
Plate material.However, Kapton inevitable slight yellow in imidization, is being used as before display device
When plate when material, cause the white printing visuognosis of frame portion bad, white printing is sometimes band yellow by visuognosis,
The defect constrains application of the Kapton in front in plate material.For the defect, Chinese patent CN108373543 is public
A kind of Kapton has been opened, by blueing agent mixed in polyamide-acid, has realized the good visual identification of white Printing Department.
However, blue dyes can not automatically adjust in film according to the intensity of available light, Kapton is hindered aobvious
Application before showing device in plate material.
Summary of the invention
It is an object of the present invention to overcome the above deficiencies, and then to provide a kind of flexibility photochromic compound by the present invention
Film, the photochromic composite membrane of the invention are that formation is photochromic with high molecular polymer carrying on polyimide-based bottom
Photochromatic layer made of compound, the photochromic composite layer be under unactivated state it is limpid or colourless, in illumination
Presented when activation it is light blue, with as basal layer have flaxen Kapton be overlapped, be visually recognized as white；Cause
Polyimide-based bottom has good flexible and mechanical performance, thus should be by polyimide-based bottom and photochromic composite layer
The composite membrane being combined is particularly suitable for being used as plate material before folding flexible display apparatus.
According to technical solution provided by the invention, the present invention provides a kind of photochromic composite membrane of flexibility comprising polyamides
Imines basilar memebrane and photochromic resin layer.
Wherein, the yellow colour index YI of the composite membrane is 0.1 < YI < 1.0, and total light transmittance is 90% or more.
In addition, the photochromic resin layer is to carry photochromic using thermosetting property or thermoplastic polymer as carrier
Compound forms.
In addition, the photochromic compound has following general structural formula:
Wherein, R1With R2It is each independently one or more of hydrogen, alkyl, alkoxy, halogen, alkyl halide；
R3With R4It is each independently hydroxyl, arbitrarily replaces alkyl, halogen and alkoxy；
R5With R6It is each independently any substituted aryl；
R7 and R8 be each independently any substituted alkyl, alkoxy, polyaryl, in chain with ester bond or amido bond
Polyaryl.
In addition, the photochromic compound is one or more of following:
Bis- (4- the methoxyphenyl) -13- methoxyl group -13- ethyl -6- methoxyl group -7- of 3,3- (4- (4 '-(4- (trans- -4-
Pentylcyclohexyl)-[1,1 '-biphenyl] -4- carbonyloxy group) benzoyloxy)) -3,13- dihydro-indeno [2 ', 3 ': 3,4] naphtho-
[1,2-b] pyrans,
3,3- bis- (4- methoxyphenyl) -13- methoxyl group -13- ethyl -6- methoxyl group -7- ((trans-, trans-) -4 '-penta
Base-[1,1 '-bis- (hexamethylenes)] -4- carbonyloxy group) -3,13- dihydro-indeno [2 ', 3 ': 3,4] naphtho- [1,2-b] pyrans,
Bis- (4- the methoxyphenyl) -13- methoxyl group -13- ethyl -6- methoxyl group -7- (3- phenyl propyne acyloxy)-of 3,3-
3,13- dihydro-indeno [2 ', 3 ': 3,4] naphtho- [1,2-b] pyrans,
3- (4- (N- morpholinyl) phenyl) -3- phenyl -7- (4- (4 '-(trans- -4- pentylcyclohexyl)-[1,1 '-biphenyl] -
4- base formamide) phenyl) two fluoro- 13,13- dimethyl -3,13- dihydro-indeno [2 ', 3 ': 3,4] naphtho- [1,2-b] of -10,12-
Pyrans,
3- (4-N- morpholine and phenyl) -3- phenyl -6- methoxyl group -7- (4- (4 '-(trans- -4- pentylcyclohexyl)-[1,
1 '-biphenyl] -4- base formamide) phenyl) -10,12- two (trifluoromethyl) -13,13- dimethyl -3,13- dihydro-indeno [2 ',
3 ': 3,4] naphtho- [1,2-b] pyrans,
3- (4- (N- morpholine is simultaneously) phenyl) -3- phenyl -6- methoxyl group -7- (4- (4- ((trans-, trans-) -4 '-amyl-[1,
1 '-bis- (hexamethylenes)] -4- carbonyloxy group) phenyl) benzoyloxy) dimethyl -3 (the trifluoromethyl) -13,13- of -10,12- two,
13- dihydro-indeno [2 ', 3 ': 3,4] naphtho- [1,2-b] pyrans,
Bis- (4- the methoxyphenyl) -6,13- dimethoxy -7- of 3,3- (trans- -4- (4 '-(trans- -4- pentylcyclohexyl) -
[1,1 '-biphenyl] -4- Epoxide carbonyl) hexamethylene carbonyloxy group) -13- ethyl -3,13- dihydro-indeno [2 ', 3 ': 3,4] naphtho- [1,
2-b] pyrans.
In addition, the thermosetting property or thermoplastic polymer are polyacrylate, in polycarbonate, polyurethane, polyureaurethane
One or more.
In addition, the photochromic resin layer also contains one of photoinitiator, heat stabilizer, surfactant or several
Kind.
In addition, the polyimide-based carrier film thickness is 20-100 μm.
In addition, the photochromic resin layer is 10-20 μm.
The present invention also provides a kind of preparation methods of photochromic composite membrane of flexibility comprising following step:
(1) in a solvent after completely dissolution by diamine, dibasic anhydride compound is added into solvent, it is molten that polyamic acid is made
Polyimide-based counterdie is made in such a way that solution-cast, salivation or solution squeeze out in liquid；
(2) take thermosetting property or thermoplastic polymer monomer, photochromic compound, solvent, initiator, light stabilizer, heat
Stabilizer mixes 1-2h at 20-50 DEG C, obtains photochromic coating；
(3) on a face of polyimide-based counterdie, coating photochromic coating is obtained using heat cure or photocuring
To photochromic resin layer, 10-20 μm of resin layer thickness.
Beneficial effects of the present invention: pale blue is presented in actinic radiation activation in the photochromic composite membrane of flexibility of the invention
Color with as basal layer there is flaxen Kapton to be overlapped, can visually be recognized as white, impose white print
In the case where the flexible display front panel materials'use of the frame portion of brush, visibility is good, and does not influence to show screen
Visual effect, and the photochromic composite membrane of flexibility of the invention has good flexible and mechanical property, is particularly suitable for rolling over
Stacked display device.
Specific embodiment
Hereinafter, more specifically being illustrated to the present invention, but the present invention is unrestricted, in technology structure of the invention
In think of, those skilled in the art can carry out various deformation.
Polyimide-based counterdie of the invention is as obtained from diamine and the polycondensation of dibasic anhydride compound, wherein binary
Acid anhydride compound can for example enumerate aromatic tetracarboxylic dianhydride, fatty formula tetracarboxylic dianhydride, non-ring type aliphatic tetracarboxylic dianhydride, contain
The ester ring type tetracarboxylic dianhydrides of fluoro substituents, aromatic tetracarboxylic dianhydride containing fluoro substituents etc..Specifically such as: Pyromellitic Acid two
Acid anhydride, 3,3', 4,4'- bibenzene tetracarboxylic dianhydride, 3,3', 4,4'- benzophenone tetracarboxylic dianhydride (BTDA), 2,3,3', 4'- bibenzene tetracarboxylic two
Acid anhydride, 3,3', 4,4'- diphenyl sulfone tetraformic acid dianhydride, 1,4,5,8 naphthalenetetracarboxylic acid dianhydride, 2,3,6,7- naphthalenetetracarbacidic acidic dianhydride, 1,2,
5,6- naphthalenetetracarbacidic acidic dianhydride, 4,4'- oxygen bis- (phthalic anhydrides), bis- (3,4- dicarboxyphenyi) the fluorenes dianhydrides of 9,9-, 9,9'- are bis-
[4- (3,4- di carboxyl phenyloxy) phenyl] fluorenes dianhydride, 3,3', 4,4'- diphenyl ether tetracarboxylic acid dianhydride, 2,3,5,6- pyridine four
Formic acid dianhydride, 3,4,9,10- tetracarboxylic acid dianhydride, two O-phthalic acid dianhydride of 4,4'- sulphonyl, para-terpheny -3,4,3', 4'-
Tetracarboxylic acid dianhydride, meta-terphenyl -3,3', 4,4'- tetracarboxylic acid dianhydride and 3,3', 4,4'- diphenyl ether tetraformic dianhydride, (1S,
2R, 4S, 5R)-cyclohexanetetracarboxylic acid dianhydride (cis-, cis-, cis- -1,2,4,5- cyclohexanetetracarboxylic acid dianhydride), (1S, 2S,
4R, 5R)-cyclohexanetetracarboxylic acid dianhydride, (1R, 2S, 4S, 5R)-cyclohexanetetracarboxylic acid dianhydride, double spiral shells [2.2.2] octane -2,3,5,
6- tetracarboxylic acid dianhydride, double spiral shells [2.2.2] 7- octene -2,3,5,6- tetracarboxylic acid dianhydride, [5- (dioxotetrahydrofuryl) -3- first
Base -3- cyclohexene] -1,2- dicarboxylic acid anhydride, 4- (2,5- dioxotetrahydro furans -3- base) 1,2,3,4-tetralin -1,2- two
Formic anhydride, tetrahydrofuran -2,3,4,5- tetracarboxylic acid dianhydride, connection ring -3,3', 4,4'- tetracarboxylic acid dianhydride, 1,2,3,4- pentamethylene four
Formic acid dianhydride, 1,2,3,4- cyclobutanetetracarboxylic dianhydride, 1,3- dimethyl -1,2,3,4- cyclobutanetetracarboxylic dianhydride, 1,4- bis-
Methyl-1,2,3,4- cyclobutanetetracarboxylic dianhydride, the double O-phthalic acid dianhydrides of 4,4 '-(hexafluoro isopropyls), the bis- (3,4- bis- of 2,2-
Carboxyl phenyl) hexafluoropropane dianhydride etc..
As diamine, such as it can be aromatic diamine, ester ring type diamines, non-ring type aliphatic diamine, fluorine-containing substitution
The aromatic diamine of base.Specifically for example: 2,2'- bis- (trifluoromethyl) benzidine, 4,4'- diamino (N- phenyl benzoyl
Amine), p-phenylenediamine, m-phenylene diamine (MPD), 3,4'- diaminodiphenyl ether, 4,4'- diaminodiphenyl ether, 4,4' diaminodiphenyl sulfone,
9,9'- (4- aminophenyl) fluorenes, 9,9'- (4- amino -3- aminomethyl phenyl) fluorenes, 1,4'- bis- (4- amino-benzene oxygen) benzene, 2,2'-
Bis- (4- amino-benzene oxygen) biphenyl of bis- (4- aminophenoxy phenyl) propane, 4,4'-, 1,4- diaminocyclohexane, 4,4'- methylene
Base bis- (aminocyclohexanes), 3,3- diamino -4,4- dihydroxydiphenylsulisomer and bis- (the 3- amino-4-hydroxylphenyls) six of 2,2-
Fluoro-propane etc..
Organic solvent for synthesizing the polyamic acid as polyimide precursor is preferably capable of dissolving tetracid two used
The solvent of acid anhydride and diamines can more preferably dissolve the solvent of synthesized polyamic acid out.Such as it can enumerate: tetramethylurea and N,
The ureas series solvents such as N- dimethyl ethyl urea；These sulfoxide systems such as dimethyl sulfoxide, diphenyl sulphone (DPS) and sulfolane or sulfone series solvent；N,N-
Dimethyl acetamide (DMAC), N,N-dimethylformamide (DMF), N, N'- diethyl acetamide, n-methyl-2-pyrrolidone
(NMP) and the acid amides series solvents such as hexamethylphosphoramide；The ester series solvents such as gamma-butyrolacton；The halogenated alkyls such as chloroform, methylene chloride
Series solvent；The fragrance hydrocarbon system solvent such as benzene, toluene；The phenol systems solvent such as phenol, cresols；The ketone series solvents such as cyclopentanone；Tetrahydrofuran, 1,
The ether series solvents such as 3- dioxolane, 1,4- dioxane, dimethyl ether, Anaesthetie Ether, paracresol methyl ether.These
Solvent is usually single use, but optionally appropriately combined can also use two or more.
In the present invention, when preparing polyimide-based counterdie, the molar ratio of the diamine and dibasic anhydride is not particularly limited,
It is preferred that the molar ratio of diamine and dibasic anhydride is 1.1-0.9:1, it is more highly preferred to 1:1.
In addition, dibasic anhydride is slowly added in diamine when preparing polyimide-based counterdie, control solution viscosity is
10000-2000000cps(20℃)。
In the present invention, it prepares thermosetting property used in the photochromic resin layer or thermoplastic polymer is polypropylene
It is acid esters, polycarbonate, polyurethane, a kind of in polyureaurethane, as synthesis polyacrylate, polycarbonate, polyurethane, polyureas ammonia
The monomer of ester, can enumerate as methyl methacrylate monomer, ethyl methacrylate monomer, bis- (allyl carbonate) monomers,
Polyfunctional acrylate monomer, multifunctional methacrylate monomers, dimethacrylate diethylene glycol (DEG) ester monomer, diisopropenyl
Benzene monomer, glycol methacrylate monomer, urethane acrylate ester monomer, glycidyl acrylate monomer, methyl-prop
Olefin(e) acid glycidyl ester monomer etc..
Photochromic material can be " transparent first with the absorption of specific wavelength electromagnetic radiation (or " actinic radiation ")
" or " bleaching " ground state form and second " coloured " activated state form between convert.Photochromatic layer of the invention, because adding
Added with photochromic compound, in the case where the first form does not have actinic radiation, colourless, transparent state is presented, with actinic radiation, wavelength
Light near 580nm-600nm is absorbed, and the second form, which is presented, makes photochromic resin layer that " blue " be presented.
Additionally it is believed that the desired final color of photochromic resin layer and the relative intensity of color, in addition to it is photic
Except electrochromic compound type is related, there are also the content of photochromic compound is related, if the content of photochromic compound
It is too low, the visible photochromic effect of naked eye can not be generated, photochromic amount is unable to reach, if photochromic compound content
Excessively high, then overgenerous blue is presented in photochromic resin layer.It is an object of the invention to photochromic resin layers photochemical
Radiation is lower to be presented blue, to visually be superimposed with the faint yellow of polyimide-based counterdie, thus depending on thinking white.Therefore from
This respect considers, is that 5-25 weight is added in terms of 100 parts by weight by thermosetting property or thermoplastic polymer in photochromic resin layer
Measure part photochromic compound.
In addition, in the present invention, it is photochromic well in order to promote, light can also be added in photochromic resin layer
One or more of initiator, light stabilizer, heat stabilizer, as photoinitiator can enumerate as acetophenone, benzoin ether,
Benzoyl oxime, Benzophenone, thioxanthones, anthraquinone, camphorquinone etc. as heat stabilizer, such as can be enumerated such as basic nitrogen compound
Biuret, allantoin etc. can be for example enumerated as surfactant such as octyl-phenoxypolyethoxy ethanols, 2,4,7,9- tetra-
Methyl -5- decine -4,7- glycol, Octylphenoxy cetyl ethoxy benzyl ether etc..With thermosetting property or thermoplastic polymer
Total weight be 100 parts by weight meters, as additive, photoinitiator, heat stabilizer, surfactant total amount be no more than 5 weights
Measure part.
In addition, the used solvent when preparing photochromic resin layer, is selected from: or mixtures thereof organic solvent, water, tool
Solvent described in body are as follows: ethyl acetate, butyl acetate, isopropanol, n-butanol, isobutanol, dimethylbenzene, methyl ethyl ketone, cyclohexanone, second two
Alcohol monobutyl ether or it is above-mentioned be mixed with, by the total weight of thermosetting property or thermoplastic polymer be 100 parts by weight in terms of, it is described molten
The parts by weight that agent is 10~60.
In addition, photochromic coating is coated on the method on polyimide-based bottom, spin coating, spraying, curtain can choose
Painting, flow coat, dip-coating, curtain coating etc., are not particularly limited.
Embodiment 1
(1) it prepares polyimide-based counterdie: in anhydrous reactor, solvent n,N-dimethylacetamide, Xiang Qi is added
Middle that the pyromellitic acid anhydride and 4 that molar ratio is 1:1 is added, 4'- diaminodiphenyl ether reacts 12 small at normal temperatures and pressures
When, filtering obtains uniform polyamic acid solution, solid content 20%；On the glass substrate by polyamic acid solution coating, through drying
25 μm of polyimide-based counterdies of thickness are made in curing process.The technique of baking are as follows: 80 degree of 1 hours, 150 degree 20 minutes, 250 degree 20
Minute, 400 degree 10 minutes.After cooling, film is removed from substrate.
(2) it prepares photochromic coating: taking 100 parts by weight of methylmethacrylate, bis- (the 4- methoxyl groups of 10 parts by weight 3,3-
Phenyl) -13- methoxyl group -13- ethyl -6- methoxyl group -7- (4- (4 '-(4- (trans- -4- pentylcyclohexyl)-[1,1 '-biphenyl] -
4- carbonyloxy group) benzoyloxy)) -3,13- dihydro-indeno [2 ', 3 ': 3,4] naphtho- [1,2-b] pyrans, the positive fourth of 50 parts by weight
Alcohol, 1 parts by weight acetophenone, 2 parts by weight biurets, 1 parts by weight octyl-phenoxypolyethoxy ethanols, mix at 50 DEG C
1.5h obtains photochromic coating；
(3) on a face of polyimide-based counterdie, above-mentioned photochromic coating is coated with coating machine, solidification is photic
10 μm of discoloration coating thickness.
Embodiment 2
(1) it prepares polyimide-based counterdie: in anhydrous reactor, solvent n,N-dimethylacetamide, Xiang Qi is added
Middle that the pyromellitic acid anhydride and 4 that molar ratio is 1:1 is added, 4'- diaminodiphenyl ether reacts 12 small at normal temperatures and pressures
When, filtering obtains uniform polyamic acid solution, solid content 20%；On the glass substrate by polyamic acid solution coating, through drying
25 μm of polyimide-based counterdies of thickness are made in curing process.The technique of baking are as follows: 80 degree of 1 hours, 150 degree 20 minutes, 250 degree 20
Minute, 400 degree 10 minutes.After cooling, film is removed from substrate.
(2) it prepares photochromic coating: taking 100 parts by weight of methylmethacrylate, bis- (the 4- methoxyl groups of 10 parts by weight 3,3-
Phenyl) -13- methoxyl group -13- ethyl -6- methoxyl group -7- ((trans-, trans-) -4 '-amyls-[1,1 '-bis- (hexamethylenes)] -4-
Carbonyloxy group) -3,13- dihydro-indeno [2 ', 3 ': 3,4] naphtho- [1,2-b] pyrans, 50 part by weight of n-butanol, 1 parts by weight benzene second
Ketone, 2 parts by weight biurets, 1 parts by weight octyl-phenoxypolyethoxy ethanols, mix 1.5h at 50 DEG C, obtain photochromic
Coating；
(3) on a face of polyimide-based counterdie, above-mentioned photochromic coating is coated with coating machine, solidification is photic
10 μm of discoloration coating thickness.
Embodiment 3
(1) it prepares polyimide-based counterdie: in anhydrous reactor, solvent n,N-dimethylacetamide, Xiang Qi is added
Middle that the pyromellitic acid anhydride and 4 that molar ratio is 1:1 is added, 4'- diaminodiphenyl ether reacts 12 small at normal temperatures and pressures
When, filtering obtains uniform polyamic acid solution, solid content 20%；On the glass substrate by polyamic acid solution coating, through drying
25 μm of polyimide-based counterdies of thickness are made in curing process.The technique of baking are as follows: 80 degree of 1 hours, 150 degree 20 minutes, 250 degree 20
Minute, 400 degree 10 minutes.After cooling, film is removed from substrate.
(2) it prepares photochromic coating: taking 100 parts by weight of methylmethacrylate, bis- (the 4- methoxyl groups of 10 parts by weight 3,3-
Phenyl) -13- methoxyl group -13- ethyl -6- methoxyl group -7- (3- phenyl propyne acyloxy) -3,13- dihydro-indeno [2 ', 3 ': 3,
4] naphtho- [1,2-b] pyrans, 50 part by weight of n-butanol, 1 parts by weight acetophenone, 2 parts by weight biurets, 1 parts by weight octyl-benzene oxygen
Base polyethoxy ethanol mixes 1.5h at 50 DEG C, obtains photochromic coating；
(3) on a face of polyimide-based counterdie, above-mentioned photochromic coating is coated with coating machine, solidification is photic
10 μm of discoloration coating thickness.
Embodiment 4
(1) it prepares polyimide-based counterdie: in anhydrous reactor, solvent n,N-dimethylacetamide, Xiang Qi is added
Middle that the pyromellitic acid anhydride and 4 that molar ratio is 1:1 is added, 4'- diaminodiphenyl ether reacts 12 small at normal temperatures and pressures
When, filtering obtains uniform polyamic acid solution, solid content 20%；On the glass substrate by polyamic acid solution coating, through drying
25 μm of polyimide-based counterdies of thickness are made in curing process.The technique of baking are as follows: 80 degree of 1 hours, 150 degree 20 minutes, 250 degree 20
Minute, 400 degree 10 minutes.After cooling, film is removed from substrate.
(2) it prepares photochromic coating: taking 100 parts by weight of methylmethacrylate, 10 parts by weight 3- (4- (N- morpholinyl)
Phenyl) -3- phenyl -7- (4- (4 '-(trans- -4- pentylcyclohexyl)-[1,1 '-biphenyl] -4- base formamide) phenyl) -10,12-
Two fluoro- 13,13- dimethyl -3,13- dihydro-indeno [2 ', 3 ': 3,4] naphtho- [1,2-b] pyrans, 50 part by weight of n-butanol, 1 weight
Part acetophenone, 2 parts by weight biurets, 1 parts by weight octyl-phenoxypolyethoxy ethanols are measured, 1.5h is mixed at 50 DEG C, obtains
Photochromic coating；
(3) on a face of polyimide-based counterdie, above-mentioned photochromic coating is coated with coating machine, solidification is photic
10 μm of discoloration coating thickness.
Embodiment 5
(1) it prepares polyimide-based counterdie: in anhydrous reactor, solvent n,N-dimethylacetamide, Xiang Qi is added
Middle that the pyromellitic acid anhydride and 4 that molar ratio is 1:1 is added, 4'- diaminodiphenyl ether reacts 12 small at normal temperatures and pressures
When, filtering obtains uniform polyamic acid solution, solid content 20%；On the glass substrate by polyamic acid solution coating, through drying
25 μm of polyimide-based counterdies of thickness are made in curing process.The technique of baking are as follows: 80 degree of 1 hours, 150 degree 20 minutes, 250 degree 20
Minute, 400 degree 10 minutes.After cooling, film is removed from substrate.
(2) it prepares photochromic coating: taking 100 parts by weight of methylmethacrylate, 10 parts by weight 3- (4-N- morpholine acene
Base) -3- phenyl -6- methoxyl group -7- (4- (4 '-(trans- -4- pentylcyclohexyl)-[1,1 '-biphenyl] -4- base formamide) benzene
Base) -10,12- two (trifluoromethyl) -13,13- dimethyl -3,13- dihydro-indeno [2 ', 3 ': 3,4] naphtho- [1,2-b] pyrans,
50 part by weight of n-butanol, 1 parts by weight acetophenone, 2 parts by weight biurets, 1 parts by weight octyl-phenoxypolyethoxy ethanols,
1.5h is mixed at 50 DEG C, obtains photochromic coating；
(3) on a face of polyimide-based counterdie, above-mentioned photochromic coating is coated with coating machine, solidification is photic
10 μm of discoloration coating thickness.
Embodiment 6
(1) it prepares polyimide-based counterdie: in anhydrous reactor, solvent n,N-dimethylacetamide, Xiang Qi is added
Middle that the pyromellitic acid anhydride and 4 that molar ratio is 1:1 is added, 4'- diaminodiphenyl ether reacts 12 small at normal temperatures and pressures
When, filtering obtains uniform polyamic acid solution, solid content 20%；On the glass substrate by polyamic acid solution coating, through drying
25 μm of polyimide-based counterdies of thickness are made in curing process.The technique of baking are as follows: 80 degree of 1 hours, 150 degree 20 minutes, 250 degree 20
Minute, 400 degree 10 minutes.After cooling, film is removed from substrate.
(2) it prepares photochromic coating: taking 100 parts by weight of methylmethacrylate, 10 parts by weight 3- (4- (N- morpholine is simultaneously)
Phenyl) -3- phenyl -6- methoxyl group -7- (4- (4- ((trans-, trans-) -4 '-amyl-[1,1 '-bis- (hexamethylenes)] -4- carbonyl oxygen
Base) phenyl) benzoyloxy) -10,12- two (trifluoromethyl) -13,13- dimethyl -3,13- dihydro-indeno [2 ', 3 ': 3,4]
Naphtho- [1,2-b] pyrans, 50 part by weight of n-butanol, 1 parts by weight acetophenone, 2 parts by weight biurets, 1 parts by weight octyl-phenoxy group
Polyethoxy ethanol mixes 1.5h at 50 DEG C, obtains photochromic coating；
(3) on a face of polyimide-based counterdie, above-mentioned photochromic coating is coated with coating machine, solidification is photic
10 μm of discoloration coating thickness.
Embodiment 7
(1) it prepares polyimide-based counterdie: in anhydrous reactor, solvent n,N-dimethylacetamide, Xiang Qi is added
Middle that the pyromellitic acid anhydride and 4 that molar ratio is 1:1 is added, 4'- diaminodiphenyl ether reacts 12 small at normal temperatures and pressures
When, filtering obtains uniform polyamic acid solution, solid content 20%；On the glass substrate by polyamic acid solution coating, through drying
50 μm of polyimide-based counterdies of thickness are made in curing process.The technique of baking are as follows: 80 degree of 1 hours, 150 degree 20 minutes, 250 degree 20
Minute, 400 degree 10 minutes.After cooling, film is removed from substrate.
(2) it prepares photochromic coating: taking 100 parts by weight of methylmethacrylate, bis- (the 4- methoxyl groups of 15 parts by weight 3,3-
Phenyl) -6,13- dimethoxy -7- (trans- -4- (4 '-(trans- -4- pentylcyclohexyl)-[1,1 '-biphenyl] -4- Epoxide carbonyl)
Hexamethylene carbonyloxy group) -13- ethyl -3,13- dihydro-indeno [2 ', 3 ': 3,4] naphtho- [1,2-b] pyrans, the positive fourth of 50 parts by weight
Alcohol, 1 parts by weight acetophenone, 2 parts by weight biurets, 1 parts by weight octyl-phenoxypolyethoxy ethanols, mix at 50 DEG C
1.5h obtains photochromic coating；
(3) on a face of polyimide-based counterdie, above-mentioned photochromic coating is coated with coating machine, solidification is photic
10 μm of discoloration coating thickness.
Embodiment 8
(1) it prepares polyimide-based counterdie: in anhydrous reactor, solvent n,N-dimethylacetamide, Xiang Qi is added
Middle that the pyromellitic acid anhydride and 4 that molar ratio is 1:1 is added, 4'- diaminodiphenyl ether reacts 12 small at normal temperatures and pressures
When, filtering obtains uniform polyamic acid solution, solid content 20%；On the glass substrate by polyamic acid solution coating, through drying
75 μm of polyimide-based counterdies of thickness are made in curing process.The technique of baking are as follows: 80 degree of 1 hours, 150 degree 20 minutes, 250 degree 20
Minute, 400 degree 10 minutes.After cooling, film is removed from substrate.
(2) it prepares photochromic coating: taking 100 parts by weight of methylmethacrylate, bis- (the 4- methoxyl groups of 20 parts by weight 3,3-
Phenyl) -13- methoxyl group -13- ethyl -6- methoxyl group -7- (4- (4 '-(4- (trans- -4- pentylcyclohexyl)-[1,1 '-biphenyl] -
4- carbonyloxy group) benzoyloxy)) -3,13- dihydro-indeno [2 ', 3 ': 3,4] naphtho- [1,2-b] pyrans, the positive fourth of 50 parts by weight
Alcohol, 1 parts by weight acetophenone, 2 parts by weight biurets, 1 parts by weight octyl-phenoxypolyethoxy ethanols, mix at 50 DEG C
1.5h obtains photochromic coating；
(3) on a face of polyimide-based counterdie, above-mentioned photochromic coating is coated with coating machine, solidification is photic
15 μm of discoloration coating thickness.
Embodiment 9
(1) it prepares polyimide-based counterdie: in anhydrous reactor, solvent n,N-dimethylacetamide, Xiang Qi is added
Middle that the pyromellitic acid anhydride and 4 that molar ratio is 1:1 is added, 4'- diaminodiphenyl ether reacts 12 small at normal temperatures and pressures
When, filtering obtains uniform polyamic acid solution, solid content 20%；On the glass substrate by polyamic acid solution coating, through drying
100 μm of polyimide-based counterdies of thickness are made in curing process.The technique of baking are as follows: 80 degree of 1 hours, 150 degree 20 minutes, 250 degree
20 minutes, 400 degree 10 minutes.After cooling, film is removed from substrate.
(2) it prepares photochromic coating: taking 100 parts by weight of methylmethacrylate, bis- (the 4- methoxyl groups of 25 parts by weight 3,3-
Phenyl) -13- methoxyl group -13- ethyl -6- methoxyl group -7- (4- (4 '-(4- (trans- -4- pentylcyclohexyl)-[1,1 '-biphenyl] -
4- carbonyloxy group) benzoyloxy)) -3,13- dihydro-indeno [2 ', 3 ': 3,4] naphtho- [1,2-b] pyrans, the positive fourth of 50 parts by weight
Alcohol, 1 parts by weight acetophenone, 2 parts by weight biurets, 1 parts by weight octyl-phenoxypolyethoxy ethanols, mix at 50 DEG C
1.5h obtains photochromic coating；
(3) on a face of polyimide-based counterdie, above-mentioned photochromic coating is coated with coating machine, solidification is photic
10 μm of discoloration coating thickness.
Comparative example 1
(1) it prepares single layer polyimide film: in anhydrous reactor, solvent n,N-dimethylacetamide, Xiang Qi is added
Middle that the pyromellitic acid anhydride and 4 that molar ratio is 1:1 is added, 4'- diaminodiphenyl ether reacts 12 small at normal temperatures and pressures
When, filtering obtains uniform polyamic acid solution, it is added Pyromellitic Acid and 4, the 5% of the total weight of 4'- diaminodiphenyl ether
Blueing agent (refine big day (strain) system, Chromofine Blue), mixture uniformly, solid content 20%；Polyamic acid solution is applied
On the glass substrate, 25 μm of polyimide-based counterdies of thickness are made in toasted technique to cloth.The technique of baking are as follows: 80 degree of 1 hours,
150 degree 20 minutes, 250 degree 20 minutes, 400 degree 10 minutes.After cooling, film is removed from substrate.
Comparative example 2
(1) it prepares polyimide-based counterdie: in anhydrous reactor, solvent n,N-dimethylacetamide, Xiang Qi is added
Middle that the pyromellitic acid anhydride and 4 that molar ratio is 1:1 is added, 4'- diaminodiphenyl ether reacts 12 small at normal temperatures and pressures
When, filtering obtains uniform polyamic acid solution, solid content 20%；On the glass substrate by polyamic acid solution coating, through drying
25 μm of polyimide-based counterdies of thickness are made in curing process.The technique of baking are as follows: 80 degree of 1 hours, 150 degree 20 minutes, 250 degree 20
Minute, 400 degree 10 minutes.After cooling, film is removed from substrate.
(2) it prepares photochromic coating: taking 100 parts by weight of methylmethacrylate, 10 parts by weight Chromofine Blue
((strain) system of refining big day), 50 part by weight of n-butanol, 1 parts by weight acetophenone, 2 parts by weight biurets, 1 parts by weight octyl-benzene oxygen
Base polyethoxy ethanol mixes 1.5h at 50 DEG C, obtains photochromic coating；
(3) on a face of polyimide-based counterdie, above-mentioned photochromic coating is coated with coating machine, solidification is photic
10 μm of discoloration coating thickness.
Comparative example 3
(1) prepare polyimide film: in anhydrous reactor, be added solvent n,N-dimethylacetamide, thereto plus
Enter the pyromellitic acid anhydride and 4 that molar ratio is 1:1,4'- diaminodiphenyl ether reacts 12 hours, mistake at normal temperatures and pressures
Filter, obtains uniform polyamic acid solution, solid content 20%；On the glass substrate by polyamic acid solution coating, toasted work
25 μm of polyimide-based counterdies of thickness are made in skill.The technique of baking are as follows: 80 degree of 1 hours, 150 degree 20 minutes, 250 degree 20 points
Clock, 400 degree 10 minutes.After cooling, film is removed from substrate.
<measurement of yellow colour index YI value>
Utilize the yellow colour index of the UV, visible light near infrared spectrometer V-670 measurement sample of Japan's light splitting (strain) manufacture
Sample is set to specimen holder and carried out relative to 300- by (YI value) after having carried out background measurement under no sample state
The transmitance of 800nm light measures, and finds out tristimulus values (x, y, z), YI value=100 ÷ (1.2769x-1.0592z)/y
<total light transmittance>
It is measured using the full-automatic direct-reading haze computer HGM-2DP of Suga Test Instruments company manufacture
The total light transmittance of sample.
<visibility of white color phase is evaluated>
The age of 1000 people's eyesights 5.2 is young at 20-25 years old, in 1000~20001x of exposure intensity (Lux) condition
Under, the sample from the distance of 1m and 2m evaluates the white color phase of frame portion, more than 950 people will observe white edge frame
For white, the word vision identification shown on display it is good be denoted as ◎, more than 600 people white edge frame will be viewed as white
Color, the word vision identification shown on display it is bad be denoted as zero, more than 600 people white edge frame will be viewed as having occurred
Coloring, the word vision identification shown on display it is good be denoted as △, more than 600 people white edge frame will be viewed as having occurred
Coloring, the word vision identification shown on display it is bad be denoted as ×.
<folding strength>
Use the folding strength of MIT type folding strength tester assessment composite membrane.Specifically, the sample of film (1cm × 7cm) is negative
It is loaded onto folding strength tester, and is folded to the rate of 175rpm 135 ° of angle (curvature half in the left and right side of sample
Diameter is 0.8mm, load 250g), until sample is broken off.The number of cyclic bending circulation is measured as folding strength.
<thermal expansion coefficient>
Using Mei Tele company static heat mechanical tester TMA/SDTA 2+, it is 50-200 DEG C in measuring temperature range, rises
Warm speed measures under conditions of being 10 DEG C/min；
<Mechanics Performance Testing>
Composite membrane of the invention is fabricated to the membrane material that length and width dimensions are 25.4mm × 3.2mm respectively, uses universal test
Machine (being manufactured by Shimadzu scientific instrument limited liability company (SHIMADZU), the entitled AG-1S of equipment) is strong to measure the tension of membrane material
It spends (MPa).
Table 1
Seen from table 1, photochromic composite membrane of the invention has high folding strength, that is, shows composite membrane of the invention
It is flexible, it can be used as in flexible display device, also, composite membrane of the invention is not dropped because of the addition of photochromic compound
The intensity of low film itself.Composite membrane of the invention especially also has good YI value, and white color phase recognizes that performance is good, therefore especially
It is suitable for use as plate material before flexible display device.
Claims (10)
1. a kind of photochromic composite membrane of flexibility, which is characterized in that including polyimide-based counterdie and photochromic resin
Layer.
2. composite membrane according to claim 1, which is characterized in that the yellow colour index YI of the composite membrane is 0.1 < YI <
1.0, total light transmittance is 90% or more.
3. composite membrane according to claim 1, which is characterized in that the photochromic resin layer is with thermosetting property or heat
Thermoplastic polymer is carrier, carries photochromic compound and forms.
4. composite membrane according to claim 2, which is characterized in that the photochromic compound is logical with following structures
Formula:
Wherein, R1With R2It is each independently one or more of hydrogen, alkyl, alkoxy, halogen, alkyl halide；
R3With R4It is each independently hydroxyl, arbitrarily replaces alkyl, halogen and alkoxy；
R5With R6It is each independently any substituted aryl；
R7 and R8 are each independently any substituted alkyl, alkoxy, polyaryl, mostly fragrant with ester bond or amido bond in chain
Base.
5. composite membrane according to claim 4, which is characterized in that the photochromic compound be it is one of following or
It is several:
Bis- (4- the methoxyphenyl) -13- methoxyl group -13- ethyl -6- methoxyl group -7- of 3,3- (4- (4 '-(4- (trans- -4- amyls
Cyclohexyl)-[1,1 '-biphenyl] -4- carbonyloxy group) benzoyloxy)) -3,13- dihydro-indeno [2 ', 3 ': 3,4] naphtho- [1,2-
B] pyrans,
3,3- bis- (4- methoxyphenyl) -13- methoxyl group -13- ethyl -6- methoxyl group -7- ((trans-, trans-) -4 '-amyls -
[1,1 '-bis- (hexamethylenes)] -4- carbonyloxy group) -3,13- dihydro-indeno [2 ', 3 ': 3,4] naphtho- [1,2-b] pyrans,
Bis- (4- the methoxyphenyl) -13- methoxyl group -13- ethyl -6- methoxyl group -7- (3- phenyl propyne acyloxy) -3 of 3,3-,
13- dihydro-indeno [2 ', 3 ': 3,4] naphtho- [1,2-b] pyrans,
3- (4- (N- morpholinyl) phenyl) -3- phenyl -7- (4- (4 '-(trans- -4- pentylcyclohexyl)-[1,1 '-biphenyl] -4- base
Formamide) phenyl) two fluoro- 13,13- dimethyl -3,13- dihydro-indeno [2 ', 3 ': 3,4] naphtho- [1,2-b] pyrrole of -10,12-
Mutter,
3- (4-N- morpholine and phenyl) -3- phenyl -6- methoxyl group -7- (4- (4 '-(trans- -4- pentylcyclohexyl)-[1,1 '-connection
Benzene] -4- base formamide) phenyl) -10,12- two (trifluoromethyl) -13,13- dimethyl -3,13- dihydro-indeno [2 ', 3 ': 3,
4] naphtho- [1,2-b] pyrans,
3- (4- (N- morpholine is simultaneously) phenyl) -3- phenyl -6- methoxyl group -7- (4- (4- ((trans-, trans-) -4 '-amyl-[1,1 ' -
Bis- (hexamethylenes)] -4- carbonyloxy group) phenyl) benzoyloxy) -10,12- two (trifluoromethyl) -13,13- dimethyl -3,13- two
Hydrogen-indeno [2 ', 3 ': 3,4] naphtho- [1,2-b] pyrans,
Bis- (4- the methoxyphenyl) -6,13- dimethoxy -7- of 3,3- (trans- -4- (4 '-(trans- -4- pentylcyclohexyl)-[1,
1 '-biphenyl] -4- Epoxide carbonyl) hexamethylene carbonyloxy group) -13- ethyl -3,13- dihydro-indeno [2 ', 3 ': 3,4] naphtho- [1,2-
B] pyrans.
6. composite membrane according to claim 3, which is characterized in that the thermosetting property or thermoplastic polymer are polyacrylic acid
One or more of ester, polycarbonate, polyurethane, polyureaurethane.
7. composite membrane according to claim 3, which is characterized in that the photochromic resin layer also contain photoinitiator,
One or more of heat stabilizer, surfactant.
8. composite membrane according to claim 1, which is characterized in that the polyimide-based carrier film thickness is 20-100 μm.
9. composite membrane according to claim 1, which is characterized in that the photochromic resin layer is 10-20 μm.
10. a kind of preparation method of the photochromic composite membrane of flexibility as described in any one of claim 1-8, feature exist
In including the following steps:
(1) in a solvent after completely dissolution by diamine, dibasic anhydride compound is added into solvent, polyamic acid solution is made,
Polyimide-based counterdie is made in such a way that solution-cast, salivation or solution squeeze out；
(2) thermosetting property or thermoplastic polymer monomer, photochromic compound, solvent, initiator, light stabilizer, thermostabilization are taken
Agent mixes 1-2h at 20-50 DEG C, obtains photochromic coating；
(3) on a face of polyimide-based counterdie, photochromic coating is coated with using heat cure or photocuring and obtains light
Mutagens chromoresin layer, 10-20 μm of resin layer thickness.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114555676A (en) * | 2019-10-15 | 2022-05-27 | 住友化学株式会社 | Polyimide resin |
| CN115746367A (en) * | 2022-12-01 | 2023-03-07 | 北京宜刚鞋业有限公司 | Photochromic fashion rubber boots and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103328462A (en) * | 2011-08-31 | 2013-09-25 | 光学转变公司 | Indeno-fused ring compounds |
| CN103339123A (en) * | 2010-12-16 | 2013-10-02 | 光学转变公司 | Indeno- fused ring compounds having photochromic properties |
| CN103380399A (en) * | 2010-12-16 | 2013-10-30 | 光学转变公司 | Photochromic compounds, compositions and articles |
| WO2016190855A1 (en) * | 2015-05-27 | 2016-12-01 | Hewlett-Packard Development Company, L.P. | Articles having flexible substrates |
| CN106433609A (en) * | 2016-09-07 | 2017-02-22 | 温州富奇士光电材料有限公司 | Allochromatic product as well as preparation method and application thereof |
| CN107253943A (en) * | 2010-12-16 | 2017-10-17 | 光学转变公司 | Photochromic compound and composition |
| CN108373543A (en) * | 2017-02-01 | 2018-08-07 | 住友化学株式会社 | Polyimide film |
-
2019
- 2019-03-12 CN CN201910184776.6A patent/CN109942861A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103339123A (en) * | 2010-12-16 | 2013-10-02 | 光学转变公司 | Indeno- fused ring compounds having photochromic properties |
| CN103380399A (en) * | 2010-12-16 | 2013-10-30 | 光学转变公司 | Photochromic compounds, compositions and articles |
| CN107253943A (en) * | 2010-12-16 | 2017-10-17 | 光学转变公司 | Photochromic compound and composition |
| CN103328462A (en) * | 2011-08-31 | 2013-09-25 | 光学转变公司 | Indeno-fused ring compounds |
| WO2016190855A1 (en) * | 2015-05-27 | 2016-12-01 | Hewlett-Packard Development Company, L.P. | Articles having flexible substrates |
| CN106433609A (en) * | 2016-09-07 | 2017-02-22 | 温州富奇士光电材料有限公司 | Allochromatic product as well as preparation method and application thereof |
| CN108373543A (en) * | 2017-02-01 | 2018-08-07 | 住友化学株式会社 | Polyimide film |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114555676A (en) * | 2019-10-15 | 2022-05-27 | 住友化学株式会社 | Polyimide resin |
| CN115746367A (en) * | 2022-12-01 | 2023-03-07 | 北京宜刚鞋业有限公司 | Photochromic fashion rubber boots and preparation method thereof |
| CN115746367B (en) * | 2022-12-01 | 2023-09-12 | 北京宜刚鞋业有限公司 | Photochromic fashion rubber boots and preparation method thereof |
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