CN102476490B - Method for prolonging antistatic capacity of transparent antistatic film, and transparent antistatic film - Google Patents
Method for prolonging antistatic capacity of transparent antistatic film, and transparent antistatic film Download PDFInfo
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- CN102476490B CN102476490B CN201010571394.8A CN201010571394A CN102476490B CN 102476490 B CN102476490 B CN 102476490B CN 201010571394 A CN201010571394 A CN 201010571394A CN 102476490 B CN102476490 B CN 102476490B
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Abstract
The invention relates to a method for prolonging the antistatic capacity of a transparent antistatic film. The transparent antistatic film comprises a substrate and an antistatic layer. According to the invention, a coating liquid containing an antistatic composition and a solvent is coated on the substrate; and the solvent in the coating liquid is then removed, such that the antistatic layer is formed. The antistatic composition comprises a conductive high-molecular component and a plurality of cerium oxide particles with particle sizes of 10-190nm. If a total weight of the antistatic composition is considered as 100wt%, the antistatic composition contains 1-10wt% of cerium oxide particles. The thickness of the antistatic layer is 0.18-0.5mum. The antistatic layer has surface impedance of 105-109ohm. The antistatic film has a fog level no higher than 2%. The invention also provides a transparent antistatic film produced with the method. With the transparent antistatic film, a required antistatic capacity can be maintained for a long time. Therefore, the transparent antistatic film is suitable to be used as an electronic product packaging material.
Description
Technical field
The present invention relates to a kind of method extending the antistatic effect of antistatic film, particularly relate to a kind of method and the antistatic film of utilization made by the method that are applicable to the antistatic effect of the prolongation antistatic film of electronic packaging materials.
Background technology
Being widely used in most the material forming antistatic layer is at present PEDOT:PSS solution, it is by gathering (3,4-stretches ethyl dioxy thiophene) [Poly (3,4-ethylenedioxythiophene), namely above-mentioned PEDOT] in add poly-(styrene sulfonate) [poly (styrenesulfonate), namely above-mentioned PSS] and obtain.But, when reality uses the antistatic layer obtained by PEDOT:PSS solution, but find because PEDOT is easily subject to the impact of the factors such as environment medium ultraviolet light, oxygen and heat and situation occurs to degrade, causing the antistatic usefulness of PEDOT to weaken, more allow the life cycle of antistatic layer shorten.In order to solve the problem, mainly utilize the gimmick increasing antistatic layer thickness to slow down the decline rate of antistatic usefulness at present, but the method can make cost increase, and more causes product competitiveness to decline.
US7,087,351 disclose a kind of automatically controlled display, and it comprises at least one base material, is at least onely arranged at the automatically controlled image bearing layer (electrically modulated imaging layer) on this base material, at least one conductive layer and at least one antistatic layer.This antistatic layer can use PEDOT:PSS (trade name " Baytron "), and this conductive layer can divide and takes electric layer and the second conductive layer as the leading factor, this second conductive layer contains the oxides such as tin indium oxide (indium-tin-composite oxide, ITO), zinc oxide or cerium oxide.Described conductive layer only provides the function of conduction, and there is no interactive relation between antistatic layer, also provides any contribution the service life of non-confrontational electrostatic layer.This class display is just encapsulation after producing, so antistatic layer is packaged in encapsulating shell.Under this situation, antistatic layer is completely isolated with the external world, and not by the impact of the aforesaid environmental factor, so the problem of the antistatic efficiency attenuation of unlikely generation.
US6,921,576 disclose a kind of antistatic coating constituent of antistatic film for the formation of with better hardness, abrasion resistance.This antistatic coating constituent comprises (A) multiple inorganic oxide particle with side chain; (B) antistatic additive, is selected from following formed group containing at least one: the hydrolytic condensate of the macromolecule containing quarternary ammonium salt, the silane coupling agent containing quarternary ammonium salt and silane coupling agent; And (C) has multifunctional (methyl) acrylate of at least three (methyl) acryloyl groups.This patent mainly uses the special inorganic oxide particle through upgrading to promote hardness and the abrasion resistance of antistatic film, more utilizes specific antistatic additive, the anti-static function of antistatic film just can be allowed to promote.As shown in the above, the constituent of this patent is except using certain material, also need the ancillary cost time to prepare the specific inorganic particulate through upgrading and antistatic additive, and when the follow-up constituent by this patent coats a plastic basis material, the thickness range be coated with need control
with regard to overall process and subsequent applications, step is too complicated and cannot save manufacturing cost.In addition, the technology disclosed in this patent does not address any possibility extending antistatic coating constituent and use.
From the above, the existing research and development for antistatic film, be mostly devoted to the character such as the antistatic behaviour of lifting antistatic film, hardness or abrasion resistance, and the antistatic effect not with regard to how extending antistatic film are inquired into.Particularly just for the antistatic film of electronic packaging materials, affect because electronic building brick is easily subject to electrostatic influence effective utilization or even damage, so electronic packaging materials is except need possessing transparency and good mechanical properties, more expect to maintain antistatic effect for a long time.Therefore, antistatic film how can be made to possess transparency and maintain antistatic effect for a long time, still have processing procedure yet-to-be developed can reduce simply again the method for raw materials for production cost, with the application of improving product and competitiveness.
Summary of the invention
In order to the problem that the antistatic effect solving electronic packaging materials in the past can not maintain for a long time, take into account the transparency and the manufacturing cost of packaging material simultaneously, inventor is after in many ways testing, develop a kind of effective improving countermeasure, by in the process preparing antistatic layer, the modification agent of special ratios is mixed in antistatic coating fluid in the past, just made antistatic film can be made to possess the transparency, and the surface impedance of desirable can be maintained for a long time, namely can maintain antistatic effect for a long time.
The object of the present invention is to provide a kind of thickness not needing to increase antistatic layer, only need use simple processing procedure and low cost, just effectively can extend the method for the antistatic effect of the prolongation antistatic film of the antistatic effect of antistatic film.
The present invention extends the method for the antistatic effect of antistatic film, this antistatic film comprises: a base material and an antistatic layer, the method makes this antistatic layer by being coated with the coating fluid of one deck containing an antistatic constituent and a solvent on the substrate, the solvent in this coating fluid of rear removal and being formed.This antistatic constituent comprises a conducting polymer component and multiple cerium oxide particles.In the gross weight of this antistatic constituent for 100wt%, the content range of described cerium oxide particles is
and the particle size range of described cerium oxide particles is
this antistatic layer have between
surface impedance, thickness is
and this antistatic film have not higher than 2% mist degree.
Another object of the present invention is to provide a kind of antistatic film.Antistatic film of the present invention have not higher than 2% mist degree, and one between
surface impedance, and to comprise: a base material and is arranged at the antistatic layer on this base material.The thickness of this antistatic layer is
and be made up of an antistatic constituent, this antistatic constituent comprise a conducting polymer component and multiple particle diameter between
cerium oxide particles.In the gross weight of this antistatic constituent for 100wt%, the content range of described cerium oxide particles is
Beneficial effect of the present invention is: only need be mixed into cerium oxide particles by conducting polymer coating fluid in the past, and by the consumption of controlled oxidization cerium particle and particle diameter, just by the effect of cerium oxide particles in conducting polymer coating fluid, antistatic film is made to be able to when antistatic layer thickness is lower than 1 μm and low manufacturing cost, even if allow obtained antistatic film be subject under the ambient influnence such as ultraviolet light and oxygen, still can make antistatic film under the transparency that maintenance is existing, service life is extended more than 2 times effectively.And when follow-up utilization is to electrostatic defending electronic packaging materials, because antistatic film of the present invention can provide the antistatic effect of long period, the service life of antistatic film of the present invention thus can be extended, be subject to electrostatic influence to avoid electronic building brick.
Detailed description of the invention
The method that the present invention extends the antistatic effect of antistatic film makes the antistatic layer of this antistatic film by being coated with the coating fluid of one deck containing an antistatic constituent and a solvent on the substrate, the solvent in this coating fluid of rear removal and being formed.This antistatic constituent comprises a conducting polymer component and multiple cerium oxide particles.In the gross weight of this antistatic constituent for 100wt%, the content range of described cerium oxide particles is
and the particle size range of described cerium oxide particles is
this antistatic layer have between
surface impedance, and the thickness of this antistatic layer is
this antistatic film have not higher than 2% mist degree.
Preferably, the thickness of this antistatic layer is
The content range of described cerium oxide particles is 1 ~ 10wt%, is preferably
be more preferably
when the content of described cerium oxide particles is less than 1wt%, effectively cannot extends more than antistatic effect to 60 day, so that improve limited efficiency; On the contrary, when the content of described cerium oxide particles is more than 10wt%, unnecessary manufacturing cost expenditure can be increased.
The particle size range of described cerium oxide particles is
be preferably
when the particle diameter of described cerium oxide particles is less than 10nm, easily produce agglomeration and cannot homodisperse problem; When the particle diameter of described cerium oxide particles is greater than 190nm, the transparency of antistatic film is easily made to decline.In embodiments of the invention, the particle diameter of described cerium oxide particles is 20nm.
This conducting polymer component can select the kind of applicable general conducting polymer according to the character of the antistatic layer for being formed, be not particularly limited in the present invention.Preferably, this conducting polymer component comprises polythiophene.Polythiophene is such as but not limited to poly-(3,4-stretches ethyl dioxy thiophene).Have good electric conductivity for giving antistatic layer, the number average molecular weight scope of generally comparatively suitable conducting polymer is preferably
The solvent of this coating fluid can select the solvent with cerium oxide particles and conducting polymer component compatibility, is not particularly limited in the present invention.Preferably, this solvent is selected from water, methyl alcohol, ethanol, isopropyl alcohol or these a combination.In embodiments of the invention, for mix with conducting polymer component and the solvent forming a conductive polymer solution is isopropyl alcohol, and cerium oxide particles mixes with water and forms a cerium oxide aqueous solution.
Preferably, this coating fluid also comprises a dispersant and an adhesive (binder).This dispersant is including but not limited to PSS (polystyrenesulfonate is called for short PSS).This adhesive is including but not limited to polyurethane (Polyurethane, PU) adhesive.
The preparation of coating fluid of the present invention can use general mixed method to carry out, such as: utilize solvent respectively, the conducting polymer component of antistatic constituent contained in coating fluid and cerium oxide particles are deployed into solution state, as conductive polymer solution and the cerium oxide aqueous solution, again above-mentioned two solution are mixed, just can obtain coating fluid.
In the method for the invention, the coating method of this coating fluid can select any known technology to carry out, the coating methods such as such as hand painting, roller coating, spray coating or gravure.The method removing the solvent of coating fluid also can adopt general drying or curing to carry out.
Antistatic film of the present invention have not higher than 2% mist degree, and one between
surface impedance, and comprise a base material and and be arranged at antistatic layer on this base material.This antistatic layer is made up of an antistatic constituent, and the thickness of this antistatic layer is
be preferably
In antistatic film of the present invention, aspect and the various change of this antistatic layer are described above, do not add to repeat at this.
There is no particular restriction in the present invention for this base material, any existing base material can be used, such as PET (PET), polyethylene (PE), polyvinyl chloride (PVC), polypropylene (PP), Merlon (PC), polystyrene (PS) etc.
Antistatic film of the present invention is mainly used as and follow-uply can be used for electrostatic defending electronic packaging materials.
The present invention will be described further with regard to following examples, but it is to be understood that this embodiment, only for illustrating use, and should not be interpreted as restriction of the invention process.
< embodiment 1 and 2>
prepare antistatic coating fluid
Get a conductive polymer solution (purchased from H.C.Starck, model: PVA) and a cerium oxide aqueous solution (model: BYK-3810, particle diameter 20nm).This conductive polymer solution contains the polyurethane adhesive of PEDOT:PSS, 5wt% of 0.5wt%, the isopropanol water solution of 94.5wt%.This cerium oxide aqueous solution contains the cerium oxide particles of 40wt% and the water of 60wt%.In less than 40 DEG C by above-mentioned two dissolution homogeneity mixing, to be mixed with primary antibodie electrostatic applications liquid.The component ratio of the antistatic coating fluid of embodiment 1 and 2 is specified in table one.
prepare antistatic film
By this antistatic coating solution in a PET base material, then remove the solvent (water and isopropyl alcohol) in coating fluid in the mode of heated-air drying.Bake out temperature is
between, the time is
second, to form an antistatic layer be made up of an antistatic constituent [containing PEDOT:PSS (conducting polymer component) and cerium oxide particles] on this base material, and then obtain an antistatic film respectively.Finally, respectively the thickness of the antistatic layer of embodiment 1 and 2 is measured, and the conducting polymer component contained by the antistatic constituent forming antistatic layer and the content of cerium oxide particles are calculated, and be recorded in table one.
character is tested
1. surface impedance: utilize surface impedance tester [to be sheet resistance instrument (WolfgangWarmbier; SRM-110), measuring standard method is ASTM-D257], test the antistatic layer of the antistatic film of embodiment 1 and 2, acquired results is as shown in following table one.Surface resistance value for electronic packaging materials is advised 10
5~ 10
9Ω.
2. mist degree: utilize haze meter [Hazy meter, model is NDH2000, and purchased from Japanese NIPPONDENSHOKU company, measuring standard method is ASTM-D1003], test the antistatic layer of the antistatic film of embodiment 1 and 2, acquired results is as shown in following table one.The acceptable haze value of current industry is < 5%.
3. service life: under the antistatic film of obtained embodiment 1 and 2 is placed in normal atmospheric environment, under making it be exposed to normal atmospheric environment, utilize sheet resistance instrument regularly to measure the surface impedance of antistatic layer, and the surface impedance noting down antistatic layer fails to 10
10the number of days of Ω, this number of days is the service life of this antistatic film.Acquired results is as shown in following table one.Service life number of days longer be better.
< comparative example 1 ~ 6>
The preparation process of comparative example 1 ~ 6, preparation condition and test process are identical with aforesaid embodiment 2, difference be in: in comparative example 1 ~ 3, cerium oxide particles is changed into other UV absorbers; Comparative example 1 selects zinc oxide (model: BYK-3820, particle diameter is 20nm), and comparative example 2 selects carbon black, and comparative example 3 selects organic compound (purchased from Yu Yongguang company, trade name: Eversorb80); In comparative example 4 and 5, do not use cerium oxide particles and antistatic coating fluid is made up of above-mentioned conductive polymer solution; The antistatic layer thickness of comparative example 6 is less than 0.18 μm.The composition of comparative example 1 ~ 6, thickness and test result are specified in table one.
Table one
A. content is for 100wt% calculates with the gross weight of antistatic constituent.
From the result of table one, when not adding UV absorbers, the antistatic layer thickness of comparative example 4 is 0.20 μm, then antistatic effect can only maintain 35 days.In comparative example 5, although do not adding under UV absorbers, antistatic effect can maintain more than 60 days, and coating thickness up to 0.80 μm, cost will be made significantly to increase, and mist degree also need be greater than 2%, and do not meet the demand of electronic packaging.
The organic compound that comparative example 3 adds can allow the antistatic behaviour of this conductive polymer solution decline to a great extent.The surface impedance of comparative example 1,2 is all 10
5~ 10
9within the scope of Ω and antistatic effect can maintain more than 60 days, but the transparency of made antistatic film is not good.From the result of above-mentioned comparative example 1 ~ 3, and not all UV absorbers all can allow antistatic film possess the transparency and can maintain antistatic effect for a long time.
The antistatic layer thickness of comparative example 6 is 0.16 μm, even if add the cerium oxide particles of 10wt%, service life, lower than 60 days, proves that the thickness of antistatic layer also can affect the service life of antistatic film.
The antistatic film of embodiment 1 and 2 all has between 10
5~ 10
9the surface impedance of Ω, the mist degree of 1.1%, outward appearance is transparent, and sustainable more than 60 days of service life, prove the method for the antistatic effect of prolongation antistatic film of the present invention, really can obtain and extend antistatic effect and the antistatic film having transparency concurrently.
In sum, the method for the antistatic effect of prolongation antistatic film of the present invention, by selecting cerium oxide particles and controlling its consumption
with particle diameter
and suitably control the thickness of antistatic layer
allow obtained antistatic film under the environment contacting oxygen and ultraviolet light, its surface impedance can be maintained and reach more than 60 days, therefore effectively can extend the antistatic effect of antistatic film.
Only as described above, be only preferred embodiment of the present invention, when not limiting scope of the invention process with this, as long as the simple equivalence namely done according to the present patent application the scope of the claims and invention description content changes and modifies, all still remain within the scope of the patent.
Claims (10)
1. extend a method for the antistatic effect of antistatic film, this antistatic film comprises: a base material and an antistatic layer; It is characterized in that: the method makes this antistatic layer by being coated with the coating fluid of one deck containing an antistatic constituent and a solvent on the substrate, the solvent in this coating fluid of rear removal and being formed;
This antistatic constituent comprises a conducting polymer component and multiple cerium oxide particles, and in the gross weight of this antistatic constituent for 100wt%, the content range of described cerium oxide particles is
and the particle size range of described cerium oxide particles is
This antistatic layer have between
surface impedance, and the thickness of this antistatic layer is
and
This antistatic film have not higher than 2% mist degree.
2. the method extending the antistatic effect of antistatic film as claimed in claim 1, is characterized in that: the gross weight of this antistatic constituent is in 100wt%, and the content range of described cerium oxide particles is
3. the method extending the antistatic effect of antistatic film as claimed in claim 2, is characterized in that: the gross weight of this antistatic constituent is in 100wt%, and the content range of described cerium oxide particles is
4. the method extending the antistatic effect of antistatic film as claimed in claim 1, is characterized in that: this conducting polymer component comprises polythiophene.
5. the method extending the antistatic effect of antistatic film as claimed in claim 4, is characterized in that: this polythiophene is poly-(3,4-stretch ethyl dioxy thiophene).
6. an antistatic film, is characterized in that: this antistatic film have not higher than 2% mist degree, and one between
surface impedance, comprise: a base material and is arranged at the antistatic layer on this base material; The thickness of this antistatic layer is
and be made up of an antistatic constituent, this antistatic constituent comprise a conducting polymer component and multiple particle diameter between
cerium oxide particles, in the gross weight of this antistatic constituent for 100wt%, the content range of described cerium oxide particles is
7. antistatic film as claimed in claim 6, is characterized in that: the gross weight of this antistatic constituent is in 100wt%, and the content range of described cerium oxide particles is
8. antistatic film as claimed in claim 7, is characterized in that: the gross weight of this antistatic constituent is in 100wt%, and the content range of described cerium oxide particles is
9. antistatic film as claimed in claim 6, is characterized in that: comprise polythiophene in this conducting polymer component.
10. antistatic film as claimed in claim 9, is characterized in that: this polythiophene is poly-(3,4-stretch ethyl dioxy thiophene).
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| CN102732175B (en) * | 2012-06-28 | 2014-11-26 | 昆山市诚泰电气股份有限公司 | Anti-static and anti-bubble protection film |
| CN107312189A (en) * | 2017-06-26 | 2017-11-03 | 俞秀英 | Extend the method for the antistatic effect of antistatic film |
| CN114995673A (en) | 2021-03-02 | 2022-09-02 | 群创光电股份有限公司 | Touch control electronic device |
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