CN106565981B - Antistatic film and preparation method thereof - Google Patents
Antistatic film and preparation method thereof Download PDFInfo
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- CN106565981B CN106565981B CN201510654104.9A CN201510654104A CN106565981B CN 106565981 B CN106565981 B CN 106565981B CN 201510654104 A CN201510654104 A CN 201510654104A CN 106565981 B CN106565981 B CN 106565981B
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Abstract
The invention discloses a kind of antistatic films and preparation method thereof.The preparation method includes: that laminated film is obtained after dry in the resin for coating low Tg in substrate；Apply nano-carbon material in the resin layer surface of the laminated film；And the viscous state temperature of the resin layer to the resin is heated, so that part nano-carbon material at least be made to incorporate the resin layer automatically.The present invention utilizes the bigger serface characteristic of nano-carbon material, it is realized in the spontaneous involvement resin of nano-carbon material by the thermal contraction of molten resin, surface conductance characteristic is obtained, and can also remove the nano-carbon material for being not embedded into resin and the Antistatic surface that obtains stable structure.Present invention process has the characteristics that easy, adaptation is wide, it is antistatic thin large-area nano carbon can quickly to be prepared, and obtained product has the advantages such as good surface conductance stability, rub resistance, organic solvent-resistant wiping, has important commercial value in fields such as all kinds of antistatic packagings, pallets.
Description
Technical field
The present invention is more particularly directed to a kind of antistatic film and preparation method thereof based on nano-carbon material, belongs to nano material skill
Art field.
Background technique
Protective film is widely used in the protection of LCD, touch display screen at present, the processing of cross cutting in FPC manufacturing process and
The manufacturing procedure of each IT associated components.Generally there is the requirement of antistatic in the application of these electronic products, because electrostatic
It is easy absorption dust in the presence of product surface is not only, more influences the precision of touch screen, or lead to electronic product machining process
Middle route breakdown, makes product failure.Therefore, it is necessary to do electrostatic protection processing to protective film.
Currently marketed electrostatic prevention film is generally by the common small molecule antistatic agent of addition or filling carbon black system system
It is standby.Common antistatic agent prepares antistatic material to be influenced by ambient humidity, and antistatic performance is unstable, and validity period is short；Carbon black
The antistatic material of system is greatly limited their application since the product transparency that the color of its material itself makes is low.
Nano-carbon material, such as carbon nanotube have excellent electricity, mechanics, flexibility and tensile property, can be made very thin film,
Further increase its transparency by stretching appropriate, lasting antistatic may be implemented in the electric conductivity of carbon nanotube, by environment
Humidity influences small, transparency height, therefore is increasingly paid close attention to by people.
Carbon nanotube can be prepared by different complex methods with enhancing, conductive and electromagnetic shielding etc. from macromolecular sheet material
The elite clone of function, therefore carbon nanotube and high molecular composite material prospect are very tempting, but there are still many to ask at present
Topic.The technical way of preparation carbon nanotube macromolecular sheet material composite material is that reinforced phase carbon nanotube and matrix is straight now
It connects and is mixed to get composite material, such as CN 100488758C discloses a kind of preparation side of carbon nanotube/polymer composite
Method, this method is to disperse carbon nano-tube solution in the epoxy, cured to obtain composite material, this composite material
Poor processability, content of carbon nanotubes are low.In another example CN104476869A discloses a kind of preparation side of carbon nanotube electrostatic prevention film
Composite force between adhesive increase carbon nanotube and sheet material is selected from the macromolecular sheet material of adherency or coated on sheet material to method, but
This method is difficult to realize that carbon nanotube is evenly dispersed in laminated film, and it is miscellaneous to introduce the adhesive for being difficult to remove etc.
Matter.
Summary of the invention
In view of the deficiencies of the prior art, the main purpose of the present invention is to provide a kind of antistatic films and preparation method thereof.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:
A kind of preparation method of antistatic film is provided in some embodiments comprising:
In the resin for coating low Tg in substrate, laminated film is obtained after dry；
Apply nano-carbon material in the resin layer surface of the laminated film；
And the viscous state temperature of the resin layer to the resin is heated, so that part nano-carbon material at least be made to melt
Enter the resin layer.
In some more specific embodiments, the preparation method may include:
(1) laminated film is obtained after the resin of substrate surface coating low Tg, drying；
(2) by nano-sized carbon dispersion in the resin layer surface of laminated film, low-temperature bake is removed in the dispersion liquid
Solvent；
(3) it after being cooled to room temperature the laminated film handled through step (2), then is rapidly heated to the viscous state of the resin
Temperature makes at least partly nano-carbon material incorporate the resin layer automatically.
Further, the preparation method of the antistatic film may also include that removing is distributed in antistatic film surface and does not melt
Enter the nano-carbon material of resin layer.Preferably, wherein the sweep-out method used may include air-blowing or cleaning, but not limited to this.
Further, the substrate can be selected from plastic-substrates, for example, adoptable plastics include polystyrene, polysulfones, gather
Amide, polybutadiene, polytetrafluoroethylene (PTFE), polyvinyl chloride, polycarbonate, polyphenylene oxide, polymethyl methacrylate, acrylic nitrile-butadiene
In styrene, polyethylene terephthalate or polybutylene terephthalate any one or it is two or more
Combination, but not limited to this.
Further, the low Tg resin preferably is selected from the resin that glass transition temperature is lower than -20 DEG C, such as thermoplastic
Property polyurethane elastomer, ethylene-vinyl acetate copolymer, polypropylene, polyethylene, natural rubber, polyethyl acrylate, poly- first
Any one in aldehyde, polycaprolactone or two or more combinations, but not limited to this.
In some embodiments, the preparation method may include: and the resin be dissolved in organic solvent formation concentration to be
The resin solution is coated in substrate later, forms laminated film after drying by the resin solution of 0.01~30wt%.
Preferably, the organic solvent may include n,N-Dimethylformamide, n,N-dimethylacetamide, tetrahydro furan
It mutters, any one or two or more combinations in n-butanol, dimethyl sulfoxide, but not limited to this.
Preferably, wherein the coating method used include spraying, roller coating, spin coating, blade coating, in dip-coating any one or two
Kind or more combination, but not limited to this.
Preferably, the resin layer with a thickness of 500nm~50 μm.
Further, the nano-carbon material includes any one of single-walled carbon nanotube, multi-walled carbon nanotube, graphene
And two or more combination.
Preferably, wherein the caliber of carbon nanotube is 0.4~30nm, and length is 0.1~50um, purity >=95%.
Preferably, the concentration of the nano-sized carbon dispersion liquid is 0.001~10wt%.
Preferably, the solvent in the nano-sized carbon dispersion liquid includes any one of water, alcohols, ethers, lipid, alcohol ethers
Or two or more combinations, but not limited to this.
Preferably, wherein the coating method used includes spraying, roller coating, spin coating, blade coating, any one in silk-screen printing
Or two or more combinations, but not limited to this.
Preferably, the nano-sized carbon dispersion liquid in the resin layer surface coated weight be 50mg~10g/m2。
The low-temperature bake temperature used in some more preferred embodiments, in step (2) is 50~80 DEG C, when heat preservation
Between be 10min~10h.
In some more preferred embodiments, the viscous state temperature of resin described in step (3) is 80~140 DEG C,
The middle heating rate used keeps the temperature 5s~5min for 50~300 DEG C/min.
It is additionally provided in some embodiments by the antistatic film of aforementioned any method preparation.
Preferably, the light transmittance of the antistatic film is 90% or more, particularly preferably 95% or more.
Preferably, the conductivity of the antistatic film is higher than e1s/m, especially preferred above e2s/m.
Compared with prior art, antistatic film preparation method provided by the invention is by coating nano-carbon material dispersion liquid
In resin surface, using the characteristic of the big specific surface area of nano-carbon material, can method it is easy, quickly prepare large-area nano
Carbon is antistatic thin, and technique adaptation is wide, method is easy, is easy to the advantages such as large scale preparation.Postscript, preparation of the invention
The nano-carbon material that method is not embedded into resin in coating procedure can recycle after removing, environmentally protective, to guarantee
The excellent properties of antistatic film.
Detailed description of the invention
Fig. 1 is a kind of preparation technology flow chart of antistatic film among a typical embodiments of the invention.
Specific embodiment
In view of deficiency in the prior art, inventor is studied for a long period of time and is largely practiced, and is able to propose of the invention
Technical solution is received by dispersing laminated film surface layer resin surface for nano-sized carbon by the thermal contraction realization of surface layer resin
Rice carbon material, which spontaneously partially incorporates, obtains surface conductance characteristic in the resin of surface layer.
In some more specific case study on implementation, the preparation method of the carbon antistatic film can specifically include following step
It is rapid:
(1) resin B of one layer of low Tg is coated on the surface substrate plastic A, obtains laminated film after drying；
(2) by nano-sized carbon dispersion in the resin B surface of the laminated film, low-temperature bake waves dispersion liquid solvent
Hair；
(3) it after being cooled to room temperature, is further rapidly heated to the viscous state temperature range of resin B, utilizes nano-carbon material
Bigger serface characteristic realizes that nano-carbon material part incorporates resin B by the thermal contraction of resin B automatically；
(4) film can further remove the nano-carbon material for being not embedded into resin B, obtain the antistatic membrane material of stable structure
Material.
Wherein, the selection range of the substrate plastic A, low Tg resin B etc. and the process conditions of each process can
As it was noted above, details are not described herein again.
By preparation process of the invention, carbon nanomaterial effectively dividing on antistatic film surface layer can be utmostly kept
Cloth obtains good light transmittance and conductivity so as to simultaneous, and is remarkably improved water-fast, the resistance to alcohol of antistatic film, wearability etc.,
With excellent comprehensive performance, and the technique also has that adapt to that wide, method is easy, is easy to large scale preparation etc. excellent
Gesture.
Technical solution of the present invention, its implementation process and principle etc. will further be solved in conjunction with several embodiments as follows
Release explanation.
The preparation method of the antistatic film provided in the embodiment of embodiment 1 a kind of specifically includes the following steps:
(1) polyethylene that one layer of glass transition temperature is -68 DEG C is coated in polystyrene surface, polyphenyl is obtained after drying
Ethylene/polyethylene co-extruded film；
(2) by mass concentration be 10% multi-walled carbon nanotube dispersion in the polyethylene surface of the laminated film,
Coating thickness is 10 microns, toasts at 70 DEG C and the solvent of carbon nano tube dispersion liquid volatilizees, and keeps the temperature 5 hours；
(3) it after being cooled to room temperature, is further rapidly heated to 100 DEG C of viscous state temperature of polyethylene, heating rate 100
DEG C/min, keep the temperature 2 minutes.Using the bigger serface characteristic of carbon nanotube, nano carbon material is realized by the thermal contraction of polyethylene
Material part incorporates in polyvinyl resin；
(4) film can remove the carbon nano tube dispersion liquid being not embedded into polyethylene, obtain the antistatic membrane material of stable structure
Material, measurement polystyrene/polyethylene antistatic film conductivity are 2.34e2s/m, light transmittance 96%.
2 the present embodiment of embodiment is with embodiment 1 the difference lies in that the quality of carbon nano tube dispersion liquid is dense in step (2)
Degree is 0.01%, and measurement polystyrene/polyethylene antistatic film conductivity is 4.25e-3s/m, light transmittance 90%.
3 the present embodiment of embodiment is with embodiment 1 the difference lies in that the quality of carbon nano tube dispersion liquid is dense in step (2)
Degree is 30%, and measurement polystyrene/polyethylene antistatic film conductivity is 5.66e4s/m, light transmittance 95%.
4 the present embodiment of embodiment and embodiment 1 the difference lies in that in step (2) coating of carbon nano tube dispersion liquid it is thick
Degree is 500 nanometers, and measurement polystyrene/polyethylene antistatic film conductivity is 3.22e-1s/m, light transmittance 90%.
5 the present embodiment of embodiment and embodiment 1 the difference lies in that in step (2) coating of carbon nano tube dispersion liquid it is thick
Degree is 30 microns, and measurement polystyrene/polyethylene antistatic film conductivity is 4.23e3s/m, light transmittance 92%.
6 the present embodiment of embodiment is with embodiment 1 the difference lies in that using single-walled carbon nanotube point in step (2)
Dispersion liquid, measurement polystyrene/polyethylene antistatic film conductivity are 6.23e5s/m, light transmittance 98%.
7 the present embodiment of embodiment, the difference lies in that using graphene dispersing solution in step (2), is surveyed with embodiment 1
Determining polystyrene/polyethylene antistatic film conductivity is 5.47e1s/m, light transmittance 94%.
Reference examples 1: raw material used in the reference examples and its usage ratio are same as Example 1, and implementation process is such as
Under: after taking polyethylene and carbon nanotube to mix, it is coated on polystyrene film, and drying forms laminated film.
Respectively to the light transmittance of embodiment 1- embodiment 7 and the obtained product of reference examples 1, conductivity, water-fast, resistance to alcohol, wear-resisting
Property is tested, it can be found that the resistance in each region of 1 product surface of comparative example differs greatly, need higher conductivity threshold and compared with
High nano-carbon material additive amount (1wt% or more) could obtain preferable antistatic property, but light transmittance sharply declines at this time.
And embodiment 1-7 product is in the lower situation of nano-carbon material additive amount, still has a high electrical conductivity, and each region in surface
Resistance is uniform, also has higher light transmittance concurrently, therefore comprehensive performance is superior.
It should be noted that the attached drawing of the present embodiment is all made of very simplified form and uses non-accurate ratio,
It is only used for convenience, lucidly aids in illustrating the embodiment of the present invention.In addition, various products and correlation used by embodiment as above
Parameter, various reaction partners and process conditions are more typical examples, but are verified by inventor's a large number of experiments,
In the other different types of reaction partners of those listed above and other process conditions etc. be also applicable, and it is also reachable
The technical effect claimed at the present invention.
It is summarized, the present invention utilizes nano-carbon material bigger serface characteristic, realizes by the thermal contraction of molten resin
Nano-carbon material spontaneously partially incorporates in resin, obtains surface conductance characteristic, and further can also remove and be not embedded into resin
In nano-carbon material and obtain the Antistatic surface of stable structure.Present invention process has the characteristics that easy, wide, the energy of adaptation
The enough large-area nano carbon that quickly prepares is antistatic thin, and obtained product with surface conductance stability good, rub resistance, resistance to organic molten
The advantages such as agent wiping have important commercial value in fields such as all kinds of antistatic packagings, pallets.
It should be appreciated that the technical concepts and features of above-described embodiment only to illustrate the invention, its object is to allow be familiar with this
The personage of item technology cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all
Equivalent change or modification made by Spirit Essence according to the present invention, should be covered by the protection scope of the present invention.
Claims (17)
1. a kind of preparation method of antistatic film, characterized by comprising:
(1) it is lower than -20 DEG C of low Tg resin in substrate surface coating glass temperature, is obtained after drying compound
Film；
(2) by nano-sized carbon dispersion in the resin layer surface of laminated film, low-temperature bake removes molten in the dispersion liquid
Agent, wherein the low-temperature bake temperature used is 10min~10h for 50~80 DEG C, soaking time；
(3) after the laminated film handled through step (2) being cooled to room temperature, then it is fast using the heating rate of 50~300 DEG C/min
Speed is warming up to the viscous state temperature of the resin, keeps the temperature 5s~5min, at least partly nano-carbon material is made to incorporate the tree automatically
Rouge layer, the viscous state temperature of the resin are 80~140 DEG C.
2. the preparation method of antistatic film according to claim 1, it is characterised in that further include: removing is distributed in antistatic film
Surface and the nano-carbon material for not incorporating resin layer.
3. the preparation method of antistatic film according to claim 2, it is characterised in that further include: use air-blowing or cleaning method
Remove the nano-carbon material for being distributed in antistatic film surface and not incorporating resin layer.
4. the preparation method of antistatic film according to claim 1, it is characterised in that: the substrate is selected from plastic-substrates,
The plastics of middle use include polystyrene, polysulfones, polyamide, polybutadiene, polytetrafluoroethylene (PTFE), polyvinyl chloride, polycarbonate, gather
Phenylate, polymethyl methacrylate, acrylonitrile-butadiene-styrene (ABS), polyethylene terephthalate or poly terephthalic acid
Any one in fourth diester or two or more combinations.
5. the preparation method of antistatic film according to claim 1, it is characterised in that: the low Tg resin includes
Thermoplastic polyurethane elastomer, polypropylene, polyethylene, natural rubber, polyethyl acrylate, is gathered ethylene-vinyl acetate copolymer
Any one in formaldehyde, polycaprolactone or two or more combinations.
6. the preparation method of antistatic film according to claim 1, which is characterized in that step (1) includes: that the resin is molten
The resin solution that concentration is 0.01~30wt% is formed in organic solvent, the resin solution is coated in substrate later, through drying
Laminated film is formed after dry.
7. the preparation method of antistatic film according to claim 6, it is characterised in that: the organic solvent includes N, N- diformazan
Base formamide, DMAC N,N' dimethyl acetamide, tetrahydrofuran, n-butanol, in dimethyl sulfoxide any one or it is two or more
Combination.
8. the preparation method of antistatic film according to claim 6, which is characterized in that step (1) includes: using spraying, rolling
The resin solution is coated in substrate by painting, spin coating, blade coating, any one mode in dip-coating, is formed after drying compound
Film.
9. the preparation method of antistatic film according to claim 1, it is characterised in that: the resin layer with a thickness of 500nm
~50 μm.
10. the preparation method of antistatic film according to claim 1, it is characterised in that: the nano-carbon material includes single wall
Any one and two or more combinations of carbon nanotube, multi-walled carbon nanotube, graphene.
11. the preparation method of antistatic film according to claim 10, it is characterised in that: the caliber of the carbon nanotube is
0.4~30nm, length are 0.1~50um, purity >=95%.
12. the preparation method of antistatic film according to claim 1, it is characterised in that: the concentration of the nano-sized carbon dispersion liquid
For 0.001~10wt%.
13. the preparation method of antistatic film according to claim 1, it is characterised in that: molten in the nano-sized carbon dispersion liquid
Agent includes any one or two or more combinations of water, alcohols, ethers, esters, alcohol ethers.
14. the preparation method of antistatic film according to claim 1, which is characterized in that step (2) includes: using spraying, rolling
Painting, spin coating, blade coating, any one mode in silk-screen printing are by the nano-sized carbon dispersion in the resin layer of laminated film
Surface.
15. the preparation method of 4 antistatic films according to claim 1, it is characterised in that: the nano-sized carbon dispersion liquid is in described
The coated weight of resin layer surface is 50mg~10g/m2。
16. the antistatic film prepared by any one of claim 1-15 the method, the light transmittance of the antistatic film is 90%
More than, conductivity is higher than e1 S/m.
17. antistatic film as claimed in claim 16, it is characterised in that: the light transmittance of the antistatic film is 95% or more, electricity
Conductance is higher than e2 S/m.
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| CN109016579B (en) * | 2018-07-26 | 2021-05-18 | 昱天(上海)新材料有限公司 | Preparation method of three-layer structure durable and non-hydrolytic type static elimination microporous film |
| CN109721887A (en) * | 2018-12-29 | 2019-05-07 | 武汉华星光电技术有限公司 | The preparation method of high molecule nano composite material |
| CN113322744B (en) * | 2021-04-25 | 2022-08-16 | 中路交科科技股份有限公司 | Antistatic cover for road maintenance and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104449010A (en) * | 2014-12-26 | 2015-03-25 | 苏州格瑞丰纳米科技有限公司 | Polymer/graphene anti-static coating, preparation method and application thereof |
| CN105153448A (en) * | 2015-09-14 | 2015-12-16 | 苏州纳塑众福新材料有限公司 | Carbon nano tube antistatic film and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104449010A (en) * | 2014-12-26 | 2015-03-25 | 苏州格瑞丰纳米科技有限公司 | Polymer/graphene anti-static coating, preparation method and application thereof |
| CN105153448A (en) * | 2015-09-14 | 2015-12-16 | 苏州纳塑众福新材料有限公司 | Carbon nano tube antistatic film and preparation method thereof |
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