CN108859099A - Three-Dimensional Dynamic surface and preparation method thereof based on photoresponse liquid crystal polymer material - Google Patents
Three-Dimensional Dynamic surface and preparation method thereof based on photoresponse liquid crystal polymer material Download PDFInfo
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- CN108859099A CN108859099A CN201810545893.6A CN201810545893A CN108859099A CN 108859099 A CN108859099 A CN 108859099A CN 201810545893 A CN201810545893 A CN 201810545893A CN 108859099 A CN108859099 A CN 108859099A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/112—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using individual droplets, e.g. from jetting heads
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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Abstract
The present invention discloses the Three-Dimensional Dynamic surface and preparation method thereof based on photoresponse liquid crystal polymer material, Three-Dimensional Dynamic surface based on photoresponse liquid crystal polymer material, including the droplet array or coating on a substrate and the substrate surface, the droplet array or coating are made of ink-jet printer injection photoresponse liquid crystal compound, and the photoresponse liquid crystal compound includes nematic liquid crystal, azobenzene, photoinitiator and surfactant.In the state that ultraviolet source is closed, azobenzene molecule in photoresponse liquid crystal polymer is in the form of transisomer, in the state that ultraviolet source is opened, azobenzene molecule in photoresponse liquid crystal polymer is changed into the form of cis-isomer, the process of this cis-trans-isomer transformation does not only result in the change of the structure and size geometry of azobenzene molecule, also the order parameter of liquid crystal polymer network is changed, to drive polymer network, deformation occurs together, realizes the photoresponse Three-Dimensional Dynamic surface of macroscopic view.
Description
Technical field
The present invention relates to Three-Dimensional Dynamic surface fields, applied to tactile and the optical property of man-machine interface material surface, power
Learn the modulation of property, wetability, the dynamic autoization control of the structures of lens and focal length, in microfluidic device fluid flowing and
Dynamic control conversion of reaction etc..
Background technique
The surface topography of response type is widely present and plays a significant role in the Nature, explores the mistake of the Nature in the mankind
Cheng Zhong is inspired by natural phenomena, more and more function surface structures are designed by the mankind, for example, by lotus leaf surface from
Cleaning inspires and has devised waterproof coating；It is inspired by gecko and designs climbing robot and super viscose water.But above-mentioned surface
Pattern is static state, can not be flattened when unwanted smooth, therefore be prone to wear and damage.
In recent years, have a large amount of relevant reports that dynamic response surface is prepared using new method or new material.Wherein, it uses
It is the most common method for realizing modification of surface morphology that film shrunk, which drives deformable flexible substrate to form pleated structure,.It is similar to
Such mechanism, also may be implemented the dynamic response on surface using the swelling of the hydrogel under the restrained condition, but this side
Osmotic pressure in method is difficult to accurately control, and dynamic surface is more difficult to control, while size and shape are relatively more limited.
Liquid crystal polymer network technological means can pass through the preparation of realization dynamic surface pattern.Liquid crystal polymer network is
Particular polymer based on liquid crystal material, internal liquid crystal molecule can be arranged according to certain ordering rule.Meanwhile polymeric web
Liquid crystal molecule in network has certain freedom degree, therefore the sequence of molecule can be in the external worlds such as electric field, temperature, light, chemical elements
It changes under the influence of factor, so as to cause the change of liquid crystal polymer overall permanence or pattern.Due to taking for liquid crystal molecule
To controllable precise, therefore using the pattern variation of liquid crystal polymer prepare dynamic surface, it can be achieved that surface texture accurately controls,
It is to prepare one of most effective approach of dynamic surface.
Light stimulus response is the dynamic response remotely controlled in a non-contact manner partly or wholly, has and widely answers
With being all the time the hot spot of research.The liquid crystal polymer network of photoresponse generallys use the mode of doping azobenzene molecule
It realizes.Azobenzene has good photoresponse switching behavior, and cis-trans isomerization reaction can occur under the irradiation of specific wavelength, this
A isomers also results in the change of the structure and size geometry of molecule simultaneously, relevant to response amplitude which provides one
Photoresponse mechanism.The system has been found the effective way to realize the controllable photoresponse of dynamic surface.Therefore, pass through stimuli responsive
Realize that the dynamic surface of surface texture switching will bring new application, raising efficiency, accurate control and robustness.Dynamic surface
Some modern science and technology can be made to be benefited, such as flow and mix in liquid in control micro-fluidic chip, changed by rough surface
Realize the touch feedback etc. of touch-in-put equipment.It is extremely widely applied it can be seen that dynamic surface has, its system is unfolded
The research of Preparation Method has application value very much.
Summary of the invention
The purpose of the present invention is azobenzenes in the state that ultraviolet source opens or closes, in photoresponse liquid crystal polymer
Molecular conversion is the form of cis-isomer form or transisomer, to realize the photoresponse Three-Dimensional Dynamic surface of macroscopic view.
Technical scheme is as follows：
Three-Dimensional Dynamic surface based on photoresponse liquid crystal polymer material, including the drop battle array on a substrate and the substrate surface
Column or coating, the droplet array or coating are made of ink-jet printer injection photoresponse liquid crystal compound, the photoresponse liquid
Brilliant mixture includes nematic liquid crystal, azobenzene, photoinitiator and surfactant, in the state that ultraviolet source is closed, institute
The azobenzene molecule in photoresponse liquid crystal polymer is stated in the form of transisomer, in the state that ultraviolet source is opened, institute
The azobenzene molecule in photoresponse liquid crystal polymer is stated in the form of cis-isomer.
Aforesaid substrate is the dimethyl silicone polymer of glass, different curing degrees（PDMS）, polyimides（PI）Oriented layer,
(per) fluoropolymer（AF）Coating, polypropylene（PP）Film, polyethylene terephthalate（PET）, polymethyl methacrylate
（PMMA）, polyvinyl alcohol（PVA）Or one of flexible base board.
Above-mentioned photoresponse liquid crystal compound includes the ingredient of following mass fraction：Nematic liquid crystal A is 0 ~ 40 mass fraction；
Nematic liquid crystal B is 0 ~ 50 mass fraction；Nematic liquid crystal C is 0 ~ 80 mass fraction；Azobenzene is 1 ~ 5 mass fraction；Light draws
Hair agent is 1 ~ 2 mass fraction；0.5 ~ 1 mass fraction of surfactant.
Above-mentioned photoinitiator is that phenyl is double（2,4,6- trimethylbenzoyl）Phosphine oxide, 2- hydroxyl -4 '-(2- hydroxyl ethoxy
Base) one or more of -2- methyl phenyl ketone, benzoin dimethylether or 1- hydroxycyclohexyl phenyl ketone mixture.
Above-mentioned surfactant is methacrylic acid N- ethylperfluoro perfluorooctane sulfonyl aminoethyl.
The polymerization process of above-mentioned photoresponse liquid crystal polymer is carried out in blue light region.
Based on the preparation method of photoresponse liquid crystal polymer material, steps are as follows：
S1：Photoresponse liquid crystal compound is dissolved as the pad-ink in print cartridge using tetrahydrofuran solution；
S2：Jet printing photoresponse liquid crystal droplet array or coating on the substrate with different surfaces energy；
S3：Photoresponse liquid crystal droplet array or coating are placed on blue light region to polymerize, and complete photoresponse liquid crystal on hot plate
Polymer network is sufficiently formed process；
S4：The photoresponse liquid crystal polymer material prepared in S3 step is exposed on ultra-violet (UV) band, and controls the switch shape of ultraviolet light
State, to form the Three-Dimensional Dynamic pattern of photoresponse liquid crystal polymer material.
It is 0 ~ 40 mass fraction that the mixed proportion of photoresponse liquid crystal compound, which is nematic liquid crystal A, in above-mentioned S1 step；To
Column phase liquid crystal B is 0 ~ 50 mass fraction；Nematic liquid crystal C is 0 ~ 80 mass fraction；Azobenzene is 1 ~ 5 mass fraction；It is light-initiated
Agent is 1 ~ 2 mass fraction；0.5 ~ 1 mass fraction of surfactant.
Ink jet printing process in above-mentioned S2 step refers to the functional material solution of 1pl ~ 20pl using print cartridge with per second
Hundreds of times or more frequencies are sprayed on a special substrate and are prepared into the array or coating of large area pattern.
The Three-Dimensional Dynamic pattern of photoresponse liquid crystal polymer material in above-mentioned S4 step refers to the shadow in light stimulus factor
Under sound, the sequence of the liquid crystal molecule in polymer grid will change, and thus cause liquid crystal polymer overall permanence or pattern
Change, and then can respond realize material three-dimensional surface switching.
Beneficial effects of the present invention：Azobenzene point in the state that ultraviolet source is closed, in photoresponse liquid crystal polymer
Son is in the form of transisomer, and in the state that ultraviolet source is opened, the azobenzene molecule in photoresponse liquid crystal polymer turns
Become the form of cis-isomer, the process of this cis-trans-isomer transformation does not only result in the structure and size of azobenzene molecule
The change of geometry, also changes the order parameter of liquid crystal polymer network, to drive polymer network, deformation occurs together, realizes
The photoresponse Three-Dimensional Dynamic surface of macroscopic view.
Detailed description of the invention
Fig. 1 is the conversion process schematic diagram on the Three-Dimensional Dynamic surface of photoresponse liquid crystal polymer material of the present invention；
Fig. 2 is that the sequence of liquid crystal unit when ultraviolet source of the present invention switchs changes schematic diagram；
Fig. 3 is the exemplary schematic diagram of design in inkjet printing program of the present invention.
Specific embodiment
In order to better illustrate the present invention, it is further described now in conjunction with examples and drawings.
As shown in Figure 1, the Three-Dimensional Dynamic surface based on photoresponse liquid crystal polymer material, including a substrate and the substrate
Droplet array or coating on surface, droplet array or coating are made of ink-jet printer injection photoresponse liquid crystal compound, light
Response liquid crystal mixture includes nematic liquid crystal, azobenzene, photoinitiator and surfactant, in the state that ultraviolet source is closed
Under, the azobenzene molecule in photoresponse liquid crystal polymer is in the form of transisomer, in the state that ultraviolet source is opened, light
Azobenzene molecule in response liquid crystal polymer is in the form of cis-isomer.
Further, substrate is the dimethyl silicone polymer of glass, different curing degrees（PDMS）, polyimides（PI）It takes
To layer, (per) fluoropolymer（AF）Coating, polypropylene（PP）Film, polyethylene terephthalate（PET）, polymethylacrylic acid
Methyl esters（PMMA）, polyvinyl alcohol（PVA）Or one of flexible base board；Photoresponse liquid crystal compound includes following mass fraction
Ingredient：Nematic liquid crystal A is 0 ~ 40 mass fraction；Nematic liquid crystal B is 0 ~ 50 mass fraction；Nematic liquid crystal C is 0 ~ 80 matter
Measure number；Azobenzene is 1 ~ 5 mass fraction；Photoinitiator is 1 ~ 2 mass fraction；0.5 ~ 1 mass fraction of surfactant；Light draws
Hair agent is 1 ~ 2 mass fraction；0.5 ~ 1 mass fraction of surfactant；Photoinitiator is that phenyl is double（2,4,6- trimethylbenzoyl
Base）Phosphine oxide, 2- hydroxyl -4 '-(2- hydroxy ethoxy) -2- methyl phenyl ketone, benzoin dimethylether or 1- hydroxycyclohexylphenyl
The mixture of one or more of ketone；Surfactant is methacrylic acid N- ethylperfluoro perfluorooctane sulfonyl aminoethyl.
Preferably, the polymerization process of above-mentioned photoresponse liquid crystal polymer is carried out in blue light region.
Embodiment 1
The Three-Dimensional Dynamic surface based on photoresponse liquid crystal polymer is prepared, steps are as follows：
S1：Photoresponse liquid crystal compound is prepared, is dissolved in tetrahydrofuran solution as pad-ink, and inject in print cartridge；
S2：Prepare one block of clean simple glass as printing substrate, and utilizes ink jet printing device jet printing on glass
Photoresponse liquid crystal droplet array；
S3：The glass substrate for completing the printing of photoresponse liquid crystal compound in step S2 is placed in the box full of nitrogen, is covered
After upper filter, ultraviolet source is opened, polymerize photoresponse liquid crystal compound, then takes out glass, and be placed on one section of hot plate
Time polymerize photoresponse liquid crystal compound sufficiently, to prepare photoresponse liquid crystal polymer；
S4：By the three-dimensional surface for observing and recording photoresponse liquid crystal polymer on petrographic microscope, 3D pattern instrument, SEM instrument；
S5：Ultraviolet source is opened, after being irradiated a period of time to sample, passes through petrographic microscope, 3D pattern instrument, SEM
The three-dimensional surface of photoresponse liquid crystal polymer is observed and recorded on instrument；
S6：Sample is placed on visible region or hot plate, the surface topography of photoresponse liquid crystal polymer network is observed and recorded
Dynamic- Recovery process, the print pattern example obtained by inkjet printing programming is as shown in figure 3, obtained Three-Dimensional Dynamic surface
Conversion process schematic diagram is as shown in Figure 1.
Be prepared based on photoresponse liquid crystal polymer ultraviolet source open when three-dimensional surface as Fig. 2 the right side shown in.
By observed result, it can be concluded that, there is apparent variation in droplet surface pattern, and the image under petrographic microscope becomes mould
Paste, thus infers, the molecular order in drop has occurred significantly to change, i.e. liquid crystal unit leading in azobenzene cis-trans isomerization
Under drawing, tendency is parallel to the direction arrangement of glass substrate.So the Three-Dimensional Dynamic of the invention based on photoresponse liquid crystal polymer
When ultraviolet source is closed and is opened, the surface topology of presentation is different on surface.Meanwhile base can be printed by changing
The surface of plate can change to control the sequence of liquid crystal unit in drop.
Embodiment 2
The present embodiment is substantially the same manner as Example 1, the difference is that：Printing substrate in S2 is the poly dimethyl being fully cured
Siloxanes（PDMS）Film, dimethyl silicone polymer（PDMS）Film is by dimethyl silicone polymer mass fraction and curing agent mass fraction
With 9：1 ratio mixed preparing, and solidify one hour at a temperature of 80 DEG C and be made.
Embodiment 3
The present embodiment is substantially the same manner as Example 1, the difference is that：Printing substrate in S2 is vertically oriented polyimide
（PI）Film, polyimide（PI）Film be with after 2000r/min speed spin coating polyimide solution, and it is solid at a temperature of 90 DEG C
Change 1 minute and is made.
Claims (10)
1. the Three-Dimensional Dynamic surface based on photoresponse liquid crystal polymer material, it is characterised in that：Including a substrate and the substrate
Droplet array or coating on surface, the droplet array or coating spray photoresponse liquid crystal compound system by ink-jet printer
At the photoresponse liquid crystal compound includes nematic liquid crystal, azobenzene, photoinitiator and surfactant, in ultraviolet source
In the state of closing, the azobenzene molecule in the photoresponse liquid crystal polymer is in the form of transisomer, in ultraviolet source
In the state of opening, the azobenzene molecule in the photoresponse liquid crystal polymer is in the form of cis-isomer.
2. according to claim 1 based on the Three-Dimensional Dynamic surface of photoresponse liquid crystal polymer material, it is characterised in that：It is described
Substrate is the dimethyl silicone polymer of glass, different curing degrees（PDMS）, polyimides（PI）Oriented layer, (per) fluoropolymer
（AF）Coating, polypropylene（PP）Film, polyethylene terephthalate（PET）, polymethyl methacrylate（PMMA）, poly- second
Enol（PVA）Or one of flexible base board.
3. according to claim 1 based on the Three-Dimensional Dynamic surface of photoresponse liquid crystal polymer material, it is characterised in that：It is described
Photoresponse liquid crystal compound includes the ingredient of following mass fraction：Nematic liquid crystal A is 0 ~ 40 mass fraction；Nematic liquid crystal B
For 0 ~ 50 mass fraction；Nematic liquid crystal C is 0 ~ 80 mass fraction；Azobenzene is 1 ~ 5 mass fraction；Photoinitiator is 1 ~ 2 matter
Measure number；0.5 ~ 1 mass fraction of surfactant.
4. according to claim 1 or the 3 Three-Dimensional Dynamic surfaces based on photoresponse liquid crystal polymer material, it is characterised in that：
The photoinitiator is that phenyl is double（2,4,6- trimethylbenzoyl）Phosphine oxide, 2- hydroxyl -4 '-(2- hydroxy ethoxy) -2- first
The mixture of one or more of base propiophenone, benzoin dimethylether or 1- hydroxycyclohexyl phenyl ketone.
5. according to claim 1 or the 3 Three-Dimensional Dynamic surfaces based on photoresponse liquid crystal polymer material, it is characterised in that：
The surfactant is methacrylic acid N- ethylperfluoro perfluorooctane sulfonyl aminoethyl.
6. according to claim 1 based on the Three-Dimensional Dynamic surface of photoresponse liquid crystal polymer material, it is characterised in that：It is described
The polymerization process of photoresponse liquid crystal polymer is carried out in blue light region.
7. the preparation method based on photoresponse liquid crystal polymer material, it is characterised in that：Steps are as follows：
S1：Photoresponse liquid crystal compound is dissolved as the pad-ink in print cartridge using tetrahydrofuran solution；
S2：Jet printing photoresponse liquid crystal droplet array or coating on the substrate with different surfaces energy；
S3：Photoresponse liquid crystal droplet array or coating are placed on blue light region to polymerize, and complete photoresponse liquid crystal on hot plate
Polymer network is sufficiently formed process；
S4：The photoresponse liquid crystal polymer material prepared in S3 step is exposed on ultra-violet (UV) band, and controls the switch shape of ultraviolet light
State, to form the Three-Dimensional Dynamic pattern of photoresponse liquid crystal polymer material.
8. the preparation method according to claim 7 based on photoresponse liquid crystal polymer material, it is characterised in that：The S1 step
It is 0 ~ 40 mass fraction that the mixed proportion of photoresponse liquid crystal compound, which is nematic liquid crystal A, in rapid；Nematic liquid crystal B is 0 ~ 50 matter
Measure number；Nematic liquid crystal C is 0 ~ 80 mass fraction；Azobenzene is 1 ~ 5 mass fraction；Photoinitiator is 1 ~ 2 mass fraction；Table
0.5 ~ 1 mass fraction of face activating agent.
9. the preparation method according to claim 7 based on photoresponse liquid crystal polymer material, it is characterised in that：The S2 step
Ink jet printing process in rapid refers to the functional material solution of 1pl ~ 20pl using print cartridge with frequency more than hundreds of times every second
Spray on a special substrate and be prepared into the array or coating of large area pattern.
10. the preparation method according to claim 7 based on photoresponse liquid crystal polymer material, it is characterised in that：The S4
The Three-Dimensional Dynamic pattern of photoresponse liquid crystal polymer material in step refers under the influence of light stimulus factor, polymer grid
In the sequence of liquid crystal molecule will change, thus cause the change of liquid crystal polymer overall permanence or pattern, and then can be with
The switching on material three-dimensional surface is realized in response.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112048279A (en) * | 2020-09-11 | 2020-12-08 | 为远材料科技(辽宁)有限责任公司 | Light-release adhesive, preparation method thereof and graphene transfer method |
| CN113800464A (en) * | 2021-08-11 | 2021-12-17 | 华南师范大学 | Photoresponse liquid crystal elastomer fiber array and preparation method and application thereof |
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