CN110256724A - A kind of anti-adherency method for manufacturing thin film for the molding 3D printing of photocuring continuous surface - Google Patents
A kind of anti-adherency method for manufacturing thin film for the molding 3D printing of photocuring continuous surface Download PDFInfo
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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
- B33Y70/00—Materials specially adapted for additive manufacturing
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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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
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
- C08J7/065—Low-molecular-weight organic substances, e.g. absorption of additives in the surface of the article
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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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
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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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
- C08J9/42—Impregnation with macromolecular compounds
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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
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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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
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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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
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
-
- 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
- C08J2345/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
-
- 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
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
Abstract
A kind of anti-adherency method for manufacturing thin film for the molding 3D printing of photocuring continuous surface.The porous material for the saturating ultraviolet light that fluorination treatment is crossed is immersed in fluorination liquid or fluorine-containing nanoscale lubricating oil, through after a period of time, allowing fluorination liquid, perhaps fluorine-containing nanoscale lubricating oil sufficiently infiltrates inside porous material then using organic solvent by extra fluorination liquid or the removal of fluorine-containing nanoscale lubricating oil.Utilize the capillarity of the chemical compatibility and porous material of porous material and oleophobic phase, so that forming one layer of stable micron-sized fluid film in porous material surface, " admittedly the adhering knot " of forming part and light transmission porous film material is changed into " the solid-liquid bonding " of forming part Yu liquid oleophobic phase, forming part and porous material are separated, reduce the adhesion strength between them, print procedure is carried out continuously, the preparation method is low in cost, simple and quick.
Description
Technical field
It is the invention belongs to 3D printing technique field, in particular to a kind of for the anti-sticking of photocuring continuous surface molding 3D printing
Attached method for manufacturing thin film.
Background technique
Stereo Lithography Apparatus Rapid Prototyping technology (stereo lithography apparatus, SLA), is to develop earliest
Come, and one of increases material manufacturing technology more mature at present.By years development, traditional Introduction To Stereolithography from
The SLA molding mode transition of " point arrive line, line to face, face to body " till now direct by " face to body " DLP molding mode, still
Since the cohesive force between forming part and release film is larger, the shaping speed and precision of DLP are limited.In recent years, the U.S.
" continuous liquid interface manufacturing technology " (CLIP) of Carbon3D company exploitation, makes resin and molded part using oxygen inhibition principle
Between there are the uncured liquid resins of certain thickness, i.e., " solidification blind area ", thus reduce forming part and molding window it
Between peeling force so that shaping speed rapidly improves, speed can achieve 500mm/h.Then, Chinese Academy of Sciences's object structure institute is to this
Item technology is improved, and speed has reached 650mm/h.But since CLIP technology also deposits some limitations:
(1) the molding window of CLIP technique is needed using oxygen flow and saturating ultraviolet light thin-film material, price costly, and
And print procedure needs constantly consumption oxygen, the high requirements on the equipment；
(2) continuously shaped due to being based primarily upon the realization of " oxygen inhibition " principle, resin is needed with oxygen inhibition,
So that used material receives certain limitation；
(3) since oxygen inhibition exists, making piece surface, there are up to a hundred microns of uncured resins, to influence part
Performance and precision.
Summary of the invention
The purpose of the present invention is to provide a kind of anti-adherency film preparation sides for the molding 3D printing of photocuring continuous surface
Method, to solve the above problems.
To achieve the above object, the invention adopts the following technical scheme:
A kind of anti-adherency method for manufacturing thin film for the molding 3D printing of photocuring continuous surface, comprising the following steps:
Step 1, fluorination treatment is carried out to basis material using silicon fluoride coupling agent, basis material is immersed in liquid oleophobic
In material, under the physical field auxiliary of sonic oscillation, heating or microwave treatment, impregnate 0~2400 hour, or pass through plated film
Mode is adhered to oleophobic material on basis material；
Step 2, extra liquid oleophobic material is removed using organic solvent, obtains putting adhering film material.
Further, basis material is light transmission porous organic polymer thin-film material, low-density organic polymer thin film material
Material or the organic polymer thin film material with micro-structure.
Further, basis material is porous polyfluorinated ethylene film, polytetrafluoroethylene (PTFE) nucleopore film, the poly- second of extremely-low density
Alkene film, medium density polyethylene film, linear low-density polyethylene film, low-density polyethylene film, cyclenes hydrocarbon type copolymer
Film or PDMS film.
Further, silicon fluoride coupling agent is complete (17) fluorine ruthenium trimethoxysilane, complete (13) fluorine octyl front three
One of oxysilane, complete (17) fluorine ruthenium triethoxysilane or complete (13) fluorine ruthenium triethoxysilane are a variety of
Mix silicon fluoride coupling agent.
Further, liquid oleophobic material is the liquid material of the light transmission insoluble in photosensitive resin.
Further, liquid oleophobic material is fluorination liquid, perfluoro polyether oil or silicone oil.
Further, the method for plated film is infusion method, spin-coating method, czochralski method or spray coating method.
Compared with prior art, the present invention has following technical effect:
1) using the chemical compatibility of porous material and oleophobic phase and the capillarity of porous material so that fluorination liquid or
The fluorine-containing nanoscale lubricating oil of person can form one layer of stable micron order liquid level in porous material, so that molding window and molding
There are one layer of micron-sized fluid films between part, thus reduce forming part and form the adhesive force between window, so that
Whole printing process can be carried out continuously, and reduce the requirement of equipment；
(2) has certain chemical stability by fluorination liquid or fluorine-containing nanoscale lubricating oil, therefore will not with photosensitive resin
It mixes, therefore the anti-adhering film can be applicable to the continuous of the photo-curing material of cation or mixing photoinitiator system
In the moulding process of face；
(3) due to being participated in print procedure without oxygen, therefore there is no oxygen inhibitions to influence part
Energy and precision.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the anti-adhesion material cross section of porous membrane of the present invention
Fig. 2 is the structural schematic diagram of the anti-adhesion material cross section of microstructure film of the present invention
Fig. 3 is antiseize membrane material preparation route figure of the present invention
Fig. 4 is the light microscope photo of the anti-adhesion material cross section of the present invention
Fig. 5 is a kind of photocuring continuous surface molding 3D printing device structure signal using the anti-adherency thin-film material of the present invention
Figure
Specific embodiment
The present invention will be further described in detail With reference to embodiment.
It is a kind of for photocuring continuous surface molding 3D printing anti-adherency method for manufacturing thin film, which is characterized in that including with
Lower step:
Step 1, fluorination treatment is carried out to basis material using silicon fluoride coupling agent, basis material is immersed in liquid oleophobic
In material, under the physical field auxiliary of sonic oscillation, heating or microwave treatment, impregnate 0~2400 hour, or pass through plated film
Mode is adhered to oleophobic material on basis material；
Step 2, extra liquid oleophobic material is removed using organic solvent, obtains putting adhering film material.
Basis material is light transmission porous organic polymer thin-film material, low-density organic polymer thin film material or has micro-
The organic polymer thin film material of structure.
Basis material be porous polyfluorinated ethylene film, polytetrafluoroethylene (PTFE) nucleopore film, ultra-low density polyethylene film, in
Density polyethylene film, linear low-density polyethylene film, low-density polyethylene film, cyclenes hydrocarbon type copolymer film or PDMS
Film.
Silicon fluoride coupling agent be complete (17) fluorine ruthenium trimethoxysilane, complete (13) fluorine octyl trimethoxy silane,
One of (17) fluorine ruthenium triethoxysilane or complete (13) fluorine ruthenium triethoxysilane or a variety of mixing fluorine silicon entirely
Alkane coupling agent.
Liquid oleophobic material is the liquid material of the light transmission insoluble in photosensitive resin.
Liquid oleophobic material is fluorination liquid, perfluoro polyether oil or silicone oil.
The method of plated film is infusion method, spin-coating method, czochralski method or spray coating method.
The present invention in view of the above-mentioned problems, chemical compatibility and porous material using porous material and oleophobic phase capillary
Effect, so that one layer of stable micron-sized fluid film is formed in porous material surface, forming part is porous thin with light transmission
" admittedly adhering knot " of membrane material is changed into " solid-liquid bonding " of the forming part with liquid oleophobic phase, thus reduce forming part and thoroughly
Ground cohesive force, is carried out continuously whole printing process, uses this anti-adhering film material between light porous film material
Material can realize that continuous surface forms without oxygen inhibition principle, and preparation method is simple
Referring to Fig. 1 to Fig. 4, a kind of anti-adherency thin-film material for photocuring continuous surface molding 3D printing equipment.It is described
Adhesive is made of substrate 1 and oleophobic phase 2, and the substrate 1 is a kind of porous organic polymer film of ultraviolet light, described
Oleophobic phase 2 is a kind of fluorination liquid or fluorine-containing nano lubricating oil, and oleophobic phase 2 does not dissolve in photosensitive resin.Substrate 1 is dipped into oleophobic
In phase 2, after a period of time, making the sufficiently infiltration of oleophobic phase 2 internal into substrate 1, then use organic solvent by extra profit
Lubricating oil 2 removes.Using the capillarity of porous material, so that oleophobic phase 2 is steadily locked in substrate 1.
Since the bonding between forming part and substrate 1 is the bonding between solid and solid, bonding between the two compared with
Greatly, if be directly separated, substrate 1 and forming part can be made by certain damage.As shown in figure 4, in the present invention, substrate 1
There are the oleophobic layer of one layer of liquid between molded part, will adhere carry down become solid-liquid bonding, thus reduce substrate 1 at
Lesser separating force can be used by the direct pull-up of forming part in cohesive force between type part, so that entirely printing
Journey can be carried out continuously.Have certain chemical stability by oleophobic phase 2, therefore will not mix with photosensitive resin, therefore this is anti-sticking
Attached thin-film material can be applicable to the continuous surface moulding process of the photo-curing material of cation or mixing photoinitiator system
In.In addition, it is anti-that polymerization occurs under ultraviolet light for photosensitive resin due to during photocuring continuous surface forms 3D printing
Answer, heat can be discharged during the reaction, due among part and substrate 1 there are oleophobic phase 2, oleophobic phase 2 can play every
Heat effect prevents in print procedure, damages substrate 1 since temperature is too high.
Specific embodiments of the present invention are given below, the present invention will be described in further detail.
Embodiment 1
Using the polyfluorinated ethylene porous membrane with gum layer as substrate 1, using perfluoro polyether oil as oleophobic phase 2, point
Film surface is not cleaned with acetone and deionized water, then with being dried with nitrogen surface.Film is immersed in perfluoro polyether oil
In, stand 24 hours.Film is then taken out, is washed away extra perfluoro polyether oil with acetone, and with being dried with nitrogen film table
Face obtains anti-adherency thin-film material.As shown in figure 4, anti-adherency thin-film material is attached to 5 bottom of resin storage tank in printing, it is photosensitive
Resin 7 is cured under UV light action, and is bonded on profiled sheeting 3, due to having one layer of liquid among forming part 6 and substrate 1
State oleophobic phase 2, the adhering to carry down of forming part 6 and substrate 1 become solid-liquid bonding, reduce cohesive force, so that entirely printing
Journey can be carried out continuously.
Embodiment 2
In conjunction with Fig. 2, using the PDMS film with micro-structure as substrate 1, using perfluoro polyether oil as oleophobic phase 2, with complete
(17) fluorine ruthenium trimethoxysilane is silane coupling agent.PDMS film surface is cleaned with acetone and deionized water respectively, and
With surface is dried with nitrogen, then PDMS film is surface-treated with oxygen plasma.Then PDMS film is immersed in entirely
In (17) fluorine ruthenium trimethoxysilane, 8 hours are stood in vacuum environment, carries out fluorination treatment.Using acetone by PDMS
Extra complete (17) fluorine ruthenium trimethoxysilane removal on film, is then cleaned with deionized water, and with being dried with nitrogen.So
Afterwards by the film plating process impregnated, PDMS film is immersed in perfluoro polyether oil, it is small to be placed in standing 24 under vacuum environment
When.Film is then taken out, extra perfluoro polyether oil is washed away with acetone, is then cleaned with deionized water, and blown with nitrogen
Dry film surface obtains anti-adherency thin-film material.
The above-mentioned particular content being described with reference to the drawings is only schematical, not constitutes to the scope of the present invention
Limitation, the researcher of fields are not required to pay creation on the basis of anti-adherency method for manufacturing thin film provided by the invention
Property labour and the various modifications or changes made are still within the scope of the present invention.
Claims (7)
1. a kind of anti-adherency method for manufacturing thin film for the molding 3D printing of photocuring continuous surface, which is characterized in that including following
Step:
Step 1, fluorination treatment is carried out to basis material using silicon fluoride coupling agent, basis material is immersed in liquid oleophobic material
In, under the physical field auxiliary of sonic oscillation, heating or microwave treatment, impregnate 0~2400 hour, or pass through plated film side
Formula is adhered to oleophobic material on basis material；
Step 2, extra liquid oleophobic material is removed using organic solvent, obtains putting adhering film material.
2. a kind of anti-adherency method for manufacturing thin film for the molding 3D printing of photocuring continuous surface according to claim 1,
It is characterized in that, basis material is light transmission porous organic polymer thin-film material, low-density organic polymer thin film material or tool
There is the organic polymer thin film material of micro-structure.
3. a kind of anti-adherency method for manufacturing thin film for the molding 3D printing of photocuring continuous surface according to claim 2,
It is characterized in that, basis material is that porous polyfluorinated ethylene film, polytetrafluoroethylene (PTFE) nucleopore film, ultra-low density polyethylene are thin
Film, medium density polyethylene film, linear low-density polyethylene film, low-density polyethylene film, cyclenes hydrocarbon type copolymer film
Or PDMS film.
4. a kind of anti-adherency method for manufacturing thin film for the molding 3D printing of photocuring continuous surface according to claim 1,
It is characterized in that, silicon fluoride coupling agent is complete (17) fluorine ruthenium trimethoxysilane, complete (13) fluorine octyl trimethoxy silicon
One of alkane, complete (17) fluorine ruthenium triethoxysilane or complete (13) fluorine ruthenium triethoxysilane or a variety of mixing fluorine
Silane coupling agent.
5. a kind of anti-adherency method for manufacturing thin film for the molding 3D printing of photocuring continuous surface according to claim 1,
It is characterized in that, liquid oleophobic material is the liquid material of the light transmission insoluble in photosensitive resin.
6. a kind of anti-adherency method for manufacturing thin film for the molding 3D printing of photocuring continuous surface according to claim 4,
It is characterized in that, liquid oleophobic material is fluorination liquid, perfluoro polyether oil or silicone oil.
7. a kind of anti-adherency method for manufacturing thin film for the molding 3D printing of photocuring continuous surface according to claim 1,
It is characterized in that, the method for plated film is infusion method, spin-coating method, czochralski method or spray coating method.
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| CN112331381A (en) * | 2020-10-12 | 2021-02-05 | 青岛理工大学 | Manufacturing method of high-performance metal grid transparent electrode, transparent electrode obtained by manufacturing method and application of transparent electrode |
| CN112778447A (en) * | 2020-12-31 | 2021-05-11 | 西安交通大学 | Soluble photosensitive resin and preparation method thereof and cured lamination inhibition method |
| WO2021170105A1 (en) * | 2020-02-28 | 2021-09-02 | 先临三维科技股份有限公司 | Photocuring 3d printing material box and preparation method therefor, photocuring 3d printing device, and photocuring 3d printing method |
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| US20160288060A1 (en) * | 2015-03-31 | 2016-10-06 | Pall Corporation | Hydrophilically modified fluorinated membrane (v) |
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Cited By (3)
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| WO2021170105A1 (en) * | 2020-02-28 | 2021-09-02 | 先临三维科技股份有限公司 | Photocuring 3d printing material box and preparation method therefor, photocuring 3d printing device, and photocuring 3d printing method |
| CN112331381A (en) * | 2020-10-12 | 2021-02-05 | 青岛理工大学 | Manufacturing method of high-performance metal grid transparent electrode, transparent electrode obtained by manufacturing method and application of transparent electrode |
| CN112778447A (en) * | 2020-12-31 | 2021-05-11 | 西安交通大学 | Soluble photosensitive resin and preparation method thereof and cured lamination inhibition method |
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