CN106867013A - The method of the micro- pattern of polypropylene screen surface construction - Google Patents
The method of the micro- pattern of polypropylene screen surface construction Download PDFInfo
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- CN106867013A CN106867013A CN201710156907.0A CN201710156907A CN106867013A CN 106867013 A CN106867013 A CN 106867013A CN 201710156907 A CN201710156907 A CN 201710156907A CN 106867013 A CN106867013 A CN 106867013A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
- C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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Abstract
The invention discloses a kind of method of the micro- pattern of polypropylene screen surface construction, the method using plasma-activated, UV initiated grafting polymerization and photomask technology, micro- pattern of poly- 2 hydroxyethyl methacrylate in polypropylene screen surface construction.By on the basis of plasma-activated treatment polypropylene screen, using action of ultraviolet light and it is aided with photomask, trigger 2 hydroxyethyl methacrylate monomers that graft polymerization reaction occurs on the free radical activity site on film surface, construct the pattern structure that diameter is respectively 40 μm, 20 μm, 10 μm and 5 μm, overcome the equipment investments such as photic lithographic technique, nanometer embossing it is high and operation require deficiency high.The present invention is with low cost, simple to operate, the poly- 2 hydroxyethyl methacrylate pattern structure formed on polypropylene screen surface can effectively improve the hydrophily and biocompatibility of polypropylene screen, be that polypropylene is laid a good foundation as bio-medical material and patterned surface preparation.
Description
Technical field
The invention belongs to macromolecule member material process for modifying surface field, and in particular to a kind of polypropylene membrane surface modification
Method, is more precisely polymerized, in the micro- figure of polypropylene screen surface construction by corona treatment combination UV initiated grafting
The method of case.
Background technology
Polypropylene as a kind of very important macromolecular material, with chemical stability is good, heat-resisting, acid-proof alkaline is excellent
It is the advantages of good, nontoxic, high mechanical strength, good film-forming property, and abundance, it is easy to processing and forming, cheap, in food bag
The aspects such as dress, water purification filter, medical wireway, medical blood storage bag and artificial blood vessel have extensive use.However, due to it
Surface chemistry inertia is poor compared with strong, biocompatibility and antibiotic property, so as to influence it as the performance of bio-medical material
And the life-span, and limit its application in more key areas.
Research shows that typical base material can not accurately be used for the interaction of research material and cell now, because big portion
Base material is divided all to be a flat, smooth rigid substrate, it is impossible to the characteristics of representing internal microenvironment, it is therefore desirable to artificial in material
Material surface construction pattern structure, with the interaction of research material and cell the characteristics of carry out microenvironment in analogue body.Exterior view
Case technology is a kind of by surface construction microstructure, the technology of property regulation and control being carried out to surface film micro area, have at present compared with
Many surface patterning techniques, such as photic lithographic technique, nano impression, inkjet printing technology, but all have more obvious
Deficiency, such as photic lithographic technique equipment investment it is high and operation require it is high.
The content of the invention
Present invention aim to address existing bio-medical polypropylene screen hydrophily is poor, poor biocompatibility and patterning knot
The problems such as structure is standby complicated, there is provided a kind of binding plasma activation, UV initiated grafting polymerization and photomask technology, poly- third
The method of the alkene film micro- pattern of surface construction different size.
The technical scheme that solution above-mentioned technical problem is used is made up of following step：
1st, radio frequency argon plasma activation polypropylene screen
In the airtight cavity being placed in after polypropylene screen is cleaned up between the electrode of plasma two, using vacuum pump system
Pressure in cavity is evacuated to below 2Pa, then using argon gas feed system to pressure in applying argon gas in cavity to cavity be 30~
60Pa, recycles radio frequency discharge to excite argon gas to produce plasma, and the discharge power of plasma is 10~50W, discharge process
Time is 60~300s, finally gives activation polypropylene screen.
2nd, UV graft polymerization prepares the polypropylene screen of poly- 2- hydroxyethyl methacrylates patterning
Activation polypropylene screen is taken out to be placed in air and is fixed on glass plate after 10~20min, then in activation poly- third
One layer of volume fraction of alkene film surface spreading is 10%~25% 2- hydroxyethyl methacrylate ethanol solutions, covers photomask,
The glycerol polymerization time is 1~3h under ultraviolet light, obtains the polypropylene of the poly- 2- hydroxyethyl methacrylates patterning in surface
Film.
In above-mentioned step 1, preferably by argon gas feed system to pressure in applying argon gas in cavity to cavity be 50Pa, then
Argon gas is excited to produce plasma using radio frequency discharge, the preferred 30W of discharge power of plasma, the discharge process time is preferred
240s。
In above-mentioned step 2, in the circular pattern of a diameter of 40 μm of polypropylene screen surface construction, preferably in activation poly- third
One layer of volume fraction of alkene film surface spreading is 15% 2- hydroxyethyl methacrylate ethanol solutions, and covering diameter is 40 μm of circle
The photomask of shape pattern, the glycerol polymerization 2h under ultraviolet light.
In above-mentioned step 2, in the circular pattern of a diameter of 20 μm of polypropylene screen surface construction, preferably in activation poly- third
One layer of volume fraction of alkene film surface spreading is 20% 2- hydroxyethyl methacrylate ethanol solutions, and covering diameter is 20 μm of circle
The photomask of shape pattern, the glycerol polymerization 2h under ultraviolet light.
In above-mentioned step 2, in the circular pattern of a diameter of 10 μm of polypropylene screen surface construction, preferably in activation poly- third
One layer of volume fraction of alkene film surface spreading is 20% 2- hydroxyethyl methacrylate ethanol solutions, and covering diameter is 10 μm of circle
The photomask of shape pattern, the glycerol polymerization 1.5h under ultraviolet light.
In above-mentioned step 2, in the circular pattern of a diameter of 5 μm of polypropylene screen surface construction, preferably in activation poly- third
One layer of volume fraction of alkene film surface spreading is 15% 2- hydroxyethyl methacrylate ethanol solutions, and covering diameter is 5 μm of circle
The photomask of shape pattern, the glycerol polymerization 1.5h under ultraviolet light.
The present invention is polymerized and photomask technology using plasma-activated, UV initiated grafting, in polypropylene screen surface structure
Micro- pattern of poly- 2- hydroxyethyl methacrylates is built.By on the basis of plasma-activated treatment polypropylene screen, utilizing
Action of ultraviolet light is simultaneously aided with photomask, triggers 2- hydroxyethyl methacrylates monomer to be sent out on the free radical activity site on film surface
Raw graft polymerization reaction, constructs the pattern structure that diameter is respectively 40 μm, 20 μm, 10 μm and 5 μm, overcomes photic etching
The equipment investments such as technology, nanometer embossing are high and operation requires deficiency high.The present invention is with low cost, simple to operate, poly-
Propylene film surface formed poly- 2- hydroxyethyl methacrylates pattern structure can effectively improve polypropylene screen hydrophily and
Biocompatibility, is that polypropylene is laid a good foundation as bio-medical material and patterned surface preparation.
Brief description of the drawings
Fig. 1 is 40 μm of SEM figures of the polypropylene screen of poly- 2- hydroxyethyl methacrylates patterning in embodiment 1.
Fig. 2 is 20 μm of SEM figures of the polypropylene screen of poly- 2- hydroxyethyl methacrylates patterning in embodiment 2.
Fig. 3 is 10 μm of SEM figures of the polypropylene screen of poly- 2- hydroxyethyl methacrylates patterning in embodiment 3.
Fig. 4 is 5 μm of SEM figures of the polypropylene screen of poly- 2- hydroxyethyl methacrylates patterning in embodiment 4.
Fig. 5 is the XPS full scan spectrograms of the polypropylene screen of poly- 2- hydroxyethyl methacrylates patterning in embodiment 1~4.
Fig. 6 is the water contact angle on original polypropylene screen surface.
Fig. 7 is the water contact angle of the polypropylene screen of the poly- 2- hydroxyethyl methacrylates of covalence graft in comparative example 1.
Fig. 8 is 40 μm of water contact angles of the polypropylene screen of poly- 2- hydroxyethyl methacrylates patterning in embodiment 1.
Fig. 9 is 20 μm of water contact angles of the polypropylene screen of poly- 2- hydroxyethyl methacrylates patterning in embodiment 2.
Figure 10 is 10 μm of water contact angles of the polypropylene screen of poly- 2- hydroxyethyl methacrylates patterning in embodiment 3.
Figure 11 is 5 μm of water contact angles of the polypropylene screen of poly- 2- hydroxyethyl methacrylates patterning in embodiment 4.
Figure 12 is the cell adherence situation shows fluorescent microscopy images on original polypropylene screen surface.
Figure 13 is the cell adherence feelings on the polypropylene screen surface of the poly- 2- hydroxyethyl methacrylates of covalence graft in comparative example 1
Condition shows fluorescent microscopy images.
Figure 14 is 40 μm of cell adherences on the polypropylene screen surface of poly- 2- hydroxyethyl methacrylates patterning in embodiment 1
Situation shows fluorescent microscopy images.
Figure 15 is 20 μm of cell adherences on the polypropylene screen surface of poly- 2- hydroxyethyl methacrylates patterning in embodiment 2
Situation shows fluorescent microscopy images.
Figure 16 is 10 μm of cell adherences on the polypropylene screen surface of poly- 2- hydroxyethyl methacrylates patterning in embodiment 3
Situation shows fluorescent microscopy images.
Figure 17 is that the cell on 5 μm of surfaces of the polypropylene screen of poly- 2- hydroxyethyl methacrylates patterning in embodiment 4 glues
Attached situation shows fluorescent microscopy images.
Figure 18 be in embodiment 1~4 in the polypropylene screen and comparative example 1 of poly- 2- hydroxyethyl methacrylates patterning covalently
It is grafted the proliferative conditions statistical chart of the polypropylene screen superficial cell culture 1,3,5 days of poly- 2- hydroxyethyl methacrylates.
Specific embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but the invention is not restricted to these embodiments.
Embodiment 1
1st, radio frequency argon plasma activation polypropylene screen
By size for the polypropylene screen of 1.5cm × 1.5cm is cleaned by ultrasonic three respectively with acetone, ethanol, deionized water successively
It is secondary, 10 minutes every time, then 35 DEG C of dryings 48 hours in vacuum drying chamber；Polypropylene screen after cleaning up is positioned over
In airtight cavity between the electrode of gas ions two, pressure in cavity is evacuated to below 2Pa using vacuum pump system, then using argon
Gas feed system is 50Pa to applying argon gas in cavity (gas flow rate is fixed as 100sccm) to pressure in cavity；Then set and put
Electrical power is 30W, and process time is 240s, excites argon gas to produce plasma using radio frequency discharge, with this attack polypropylene screen
The C-C on surface, c h bond, promote to form living radical on film, finally give activation polypropylene screen.
2nd, UV graft polymerization prepares the polypropylene screen of the poly- micro- pattern of 2- hydroxyethyl methacrylates
Activation polypropylene screen is taken out to be placed in air and is fixed on glass plate after 20min, 20 μ L bodies are drawn with liquid-transfering gun
Fraction is that 15% 2- hydroxyethyl methacrylate ethanol solutions spread in activation polypropylene screen surface, then in film surface cover
The photomask of a diameter of 40 μm of circular pattern, deoxygenation exhaust bubble, in then putting it to ultraviolet reactor, in ultraviolet lighting
Lower initiation grafting polymerization is penetrated, polymerization time is 2 hours, and the film after having reacted is cleaned through EtOH Sonicate, dried, that is, obtain surface and gather
The polypropylene screen of 2- hydroxyethyl methacrylates patterning.
Embodiment 2
The step of method of radio frequency argon plasma activation polypropylene screen is with embodiment 1 in the present embodiment 1 is identical.In step
In rapid 2, activation polypropylene screen is taken out to be placed in air and is fixed on glass plate after 20min, 20 μ L volumes are drawn with liquid-transfering gun
Fraction is that 20% 2- hydroxyethyl methacrylate ethanol solutions spread in activation polypropylene screen surface, then in film surface cover it is straight
Footpath is the photomask of 20 μm of circular pattern, deoxygenation exhaust bubble, in then putting it to ultraviolet reactor, in ultraviolet light
Lower initiation grafting polymerization, polymerization time is 2 hours, and the film after having reacted is cleaned through EtOH Sonicate, dried, that is, obtain the poly- 2- in surface
The polypropylene screen of hydroxyethyl methacrylate patterning.
Embodiment 3
The step of method of radio frequency argon plasma activation polypropylene screen is with embodiment 1 in the present embodiment 1 is identical.In step
In rapid 2, activation polypropylene screen is taken out to be placed in air and is fixed on glass plate after 20min, 20 μ L volumes are drawn with liquid-transfering gun
Fraction is that 20% 2- hydroxyethyl methacrylate ethanol solutions spread in activation polypropylene screen surface, then in film surface cover it is straight
Footpath is the photomask of 10 μm of circular pattern, deoxygenation exhaust bubble, in then putting it to ultraviolet reactor, in ultraviolet light
Lower initiation grafting polymerization, polymerization time is 1.5 hours, and the film after having reacted is cleaned through EtOH Sonicate, dried, that is, obtain surface and gather
The polypropylene screen of 2- hydroxyethyl methacrylates patterning.
Embodiment 4
The step of method of radio frequency argon plasma activation polypropylene screen is with embodiment 1 in the present embodiment 1 is identical.In step
In rapid 2, activation polypropylene screen is taken out to be placed in air and is fixed on glass plate after 20min, 20 μ L volumes are drawn with liquid-transfering gun
Fraction is that 15% 2- hydroxyethyl methacrylate ethanol solutions spread in activation polypropylene screen surface, then in film surface cover it is straight
Footpath is the photomask of 5 μm of circular pattern, deoxygenation exhaust bubble, in then putting it to ultraviolet reactor, in ultraviolet light
Lower initiation grafting polymerization, polymerization time is 1.5 hours, and the film after having reacted is cleaned through EtOH Sonicate, dried, that is, obtain surface and gather
The polypropylene screen of 2- hydroxyethyl methacrylates patterning.
Embodiment 5
In the radio frequency argon plasma activation polypropylene screen step 1 of the present embodiment, setting discharge power is 40W, treatment
Time is 180s, and 1 is identical the step of other steps of the step are with embodiment 1, finally gives activation polypropylene screen.The present embodiment
UV graft polymerization prepare the polypropylene screen step 2 of the poly- micro- pattern of 2- hydroxyethyl methacrylates, polymerization time is 1.5 small
When, 2 is identical the step of other steps of the step are with embodiment 1, that is, obtain the poly- 2- hydroxyethyl methacrylates patterning in surface
Polypropylene screen.
Embodiment 6
In the radio frequency argon plasma activation polypropylene screen step 1 of the present embodiment, setting discharge power is 30W, treatment
Time is 300s, and 1 is identical the step of other steps of the step are with embodiment 1, finally gives activation polypropylene screen.The present embodiment
UV graft polymerization prepare the polypropylene screen step 2 of the poly- micro- pattern of 2- hydroxyethyl methacrylates, polymerization time is 1.5 small
When, 2 is identical the step of other steps of the step are with embodiment 2, that is, obtain the poly- 2- hydroxyethyl methacrylates patterning in surface
Polypropylene screen.
Embodiment 7
In the radio frequency argon plasma activation polypropylene screen step 1 of the present embodiment, setting discharge power is 40W, treatment
Time is 240s, and 1 is identical the step of other steps of the step are with embodiment 1, finally gives activation polypropylene screen.The present embodiment
UV graft polymerization prepare the polypropylene screen step 2 of the poly- micro- pattern of 2- hydroxyethyl methacrylates, polymerization time is 2 small
When, 2 is identical the step of other steps of the step are with embodiment 3, that is, obtain the poly- 2- hydroxyethyl methacrylates patterning in surface
Polypropylene screen.
Embodiment 8
In the radio frequency argon plasma activation polypropylene screen step 1 of the present embodiment, setting discharge power is 30W, treatment
Time is 240s, and 1 is identical the step of other steps of the step are with embodiment 1, finally gives activation polypropylene screen.The present embodiment
UV graft polymerization prepare the polypropylene screen step 2 of the poly- micro- pattern of 2- hydroxyethyl methacrylates, 2- hydroxyethyl methacrylates
The fraction of ethyl ester ethanol solution body is 20%, and 2 is identical the step of other steps of the step are with embodiment 4, that is, obtain surface
The polypropylene screen of poly- 2- hydroxyethyl methacrylates patterning.
Comparative example 1
Method radio frequency argon plasma according to the step 1 of embodiment 1 activates polypropylene screen, and activation polypropylene screen is taken out
It is placed in air and is fixed on glass plate after 20min, the 2- methacrylic acids that 20 μ L volume fractions are 20% is drawn with liquid-transfering gun
Hydroxyl ethyl ester ethanol solution spreads in activation polypropylene screen surface, then the quartz plate in film surface cover, deoxygenation exhaust bubble, then by it
It is put into ultraviolet reactor, the initiation grafting polymerization under ultraviolet light, polymerization time is 1.5 hours, the film after having reacted
Through EtOH Sonicate cleaning, dry, that is, obtain the polypropylene screen of the poly- 2- hydroxyethyl methacrylates of surface covalence graft.
Inventor utilizes SEM (SEM), x-ray photoelectron power spectrum (XPS), video optics Contact-angle measurement
Instrument (CA) is characterized to the polypropylene screen that embodiment 1~4 and comparative example 1 are obtained, and as a result sees Fig. 1~11.From Fig. 1~4
, it is apparent that the inventive method can be in the regular pattern structure of polypropylene screen surface construction.By the XPS analysis of Fig. 5
Result is visible, with the reduction of 2- hydroxyethyl methacrylate patterned dimensions, the grafting density on surface (2- first i.e. in unit area
The content of base hydroxy-ethyl acrylate) increase, the peak intensity of the O1s in spectrogram increases successively.From Fig. 6~11 as can be seen that relative
It is of the invention after patterning molecular layer in polypropylene screen surface construction 2- hydroxyethyl methacrylates in original polypropylene screen,
The water contact angle on film surface is obviously reduced, and improves the hydrophily of polypropylene screen.
The polypropylene that inventor is obtained using mouse fibrocyte to original polypropylene screen and embodiment 1~4 and comparative example 1
Film has carried out superficial cell growth analysis and toxotest, as a result sees Figure 12~18.It can be seen that the adhesion life of cell
Situation long is different, and the polypropylene screen after 2- hydroxyethyl methacrylate-modifieds does not have toxicity to cell, cultivates by the 5th day,
Cell proliferative conditions are good, and the polypropylene screen of poly- 2- hydroxyethyl methacrylates patterning is substantially better than original polypropylene screen, and 5
The polypropylene screen of μm poly- 2- hydroxyethyl methacrylates patterning has the effect for remarkably promoting cell proliferation and differentiation, illustrates this hair
Bright method can effectively improve the biocompatibility of polypropylene screen.
Claims (6)
1. a kind of method of the micro- pattern of polypropylene screen surface construction, it is characterised in that it is made up of following step：
(1) radio frequency argon plasma activation polypropylene screen
In the airtight cavity being placed in after polypropylene screen is cleaned up between the electrode of plasma two, using vacuum pump system by chamber
Internal pressure is evacuated to below 2Pa, and it is 30~60Pa to pressure in applying argon gas in cavity to cavity then to utilize argon gas feed system,
Radio frequency discharge is recycled to excite argon gas to produce plasma, the discharge power of plasma is 10~50W, the discharge process time is
60~300s, finally gives activation polypropylene screen；
(2) UV graft polymerization prepares the polypropylene screen of poly- 2- hydroxyethyl methacrylates patterning
Activation polypropylene screen is taken out to be placed in air and is fixed on glass plate after 10~20min, then in activation polypropylene screen
One layer of volume fraction of surface spreading is 10%~25% 2- hydroxyethyl methacrylate ethanol solutions, photomask is covered, in purple
The glycerol polymerization time is 1~3h under outer light irradiation, obtains the polypropylene screen of the poly- 2- hydroxyethyl methacrylates patterning in surface.
2. the method for the micro- pattern of polypropylene screen surface construction according to claim 1, it is characterised in that：Described step
(1) in, using argon gas feed system to pressure in applying argon gas in cavity to cavity be 50Pa, recycle radio frequency discharge excite argon gas
Plasma is produced, the discharge power of plasma is 30W, and the discharge process time is 240s.
3. the method for the micro- pattern of polypropylene screen surface construction according to claim 1, it is characterised in that：Described step
(2) in, activation polypropylene screen is taken out to be placed in air and is fixed on glass plate after 10~20min, then in activation polypropylene
One layer of volume fraction of film surface spreading is 15% 2- hydroxyethyl methacrylate ethanol solutions, and covering diameter is 40 μm of circle
The photomask of pattern, the glycerol polymerization 2h under ultraviolet light obtains the poly- of the poly- 2- hydroxyethyl methacrylates patterning in surface
Propylene film.
4. the method for the micro- pattern of polypropylene screen surface construction according to claim 1, it is characterised in that：Described step
(2) in, activation polypropylene screen is taken out to be placed in air and is fixed on glass plate after 10~20min, then in activation polypropylene
One layer of volume fraction of film surface spreading is 20% 2- hydroxyethyl methacrylate ethanol solutions, and covering diameter is 20 μm of circle
The photomask of pattern, the glycerol polymerization 2h under ultraviolet light obtains the poly- of the poly- 2- hydroxyethyl methacrylates patterning in surface
Propylene film.
5. the method for the micro- pattern of polypropylene screen surface construction according to claim 1, it is characterised in that：Described step
(2) in, activation polypropylene screen is taken out to be placed in air and is fixed on glass plate after 10~20min, then in activation polypropylene
One layer of volume fraction of film surface spreading is 20% 2- hydroxyethyl methacrylate ethanol solutions, and covering diameter is 10 μm of circle
The photomask of pattern, the glycerol polymerization 1.5h under ultraviolet light obtains the poly- 2- hydroxyethyl methacrylates patterning in surface
Polypropylene screen.
6. the method for the micro- pattern of polypropylene screen surface construction according to claim 1, it is characterised in that：Described step
(2) in, activation polypropylene screen is taken out to be placed in air and is fixed on glass plate after 10~20min, then in activation polypropylene
One layer of volume fraction of film surface spreading is 15% 2- hydroxyethyl methacrylate ethanol solutions, and covering diameter is 5 μm of circle
The photomask of pattern, the glycerol polymerization 1.5h under ultraviolet light obtains the poly- 2- hydroxyethyl methacrylates patterning in surface
Polypropylene screen.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109206828A (en) * | 2018-08-14 | 2019-01-15 | 上海交通大学 | UV light-induced surface is from the preparation method of pleated pattern and its constructs the application of anti-counterfeiting mark |
| CN112693210A (en) * | 2020-12-29 | 2021-04-23 | 业成科技（成都）有限公司 | Method for manufacturing panel module |
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| CN102504305A (en) * | 2011-10-16 | 2012-06-20 | 天津工业大学 | Preparation method of micro-pattern organic film |
| CN105131318A (en) * | 2015-09-16 | 2015-12-09 | 中物院成都科学技术发展中心 | Method of regulating surface wettability of parylene c by virtue of surface patterning |
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| CN1171412A (en) * | 1996-06-19 | 1998-01-28 | 希尔斯股份公司 | Hydrophilic coating surfaces of polymeric substrates |
| CN101831079A (en) * | 2009-03-13 | 2010-09-15 | 中国纺织科学研究院 | Method and device for modifying surface of polymer material |
| CN102504305A (en) * | 2011-10-16 | 2012-06-20 | 天津工业大学 | Preparation method of micro-pattern organic film |
| CN105161621A (en) * | 2015-09-01 | 2015-12-16 | 华南理工大学 | Film patterning preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109206828A (en) * | 2018-08-14 | 2019-01-15 | 上海交通大学 | UV light-induced surface is from the preparation method of pleated pattern and its constructs the application of anti-counterfeiting mark |
| CN109206828B (en) * | 2018-08-14 | 2021-08-10 | 上海交通大学 | Preparation method of ultraviolet light induced surface self-wrinkling pattern and application of ultraviolet light induced surface self-wrinkling pattern in anti-counterfeiting mark construction |
| CN112693210A (en) * | 2020-12-29 | 2021-04-23 | 业成科技（成都）有限公司 | Method for manufacturing panel module |
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Application publication date: 20170620 |