CN102476490A - 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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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 that prolongs the antistatic effect of antistatic film, particularly relate to a kind of method and made transparent antistatic film of utilization the method for antistatic effect of the prolongation transparent antistatic film that is applicable to the electronic packaging material.
Background technology
Being widely used in most at present the material that forms antistatic layer is PEDOT:PSS solution; It is through gathering (3; 4-stretches the ethyl dioxy thiophene) [Poly (3; 4-ethylenedioxythiophene), just above-mentioned PEDOT] in add and to gather (styrene sulfonate) [poly (styrenesulfonate), just above-mentioned PSS] and make.Yet; When reality is used by the prepared antistatic layer of PEDOT:PSS solution; Find that but the situation of degrading causes the antistatic usefulness of PEDOT to weaken because PEDOT receives the influence of the factors such as environment medium ultraviolet light, oxygen and heat easily, more let the life cycle of antistatic layer shorten.In order to address the above problem, mainly be at present to utilize the gimmick that increases antistatic layer thickness to slow down the decline rate of antistatic usefulness, but the method can make cost increase, more cause product competitiveness to descend.
US 7,087, and 351 disclose a kind of automatically controlled display, and it comprises at least one base material, at least one automatically controlled image bearing layer (electrically modulated imaging layer) on this base material, at least one conductive layer and at least one antistatic layer of being arranged at.This antistatic layer can use PEDOT:PSS (trade name " Baytron "); And this conductive layer can divide and takes the electricity layer and second conductive layer as the leading factor; This second conductive layer contain tin indium oxide (indium-tin-composite oxide, ITO), oxide such as zinc oxide or cerium oxide.Said conductive layer only provides the function of conduction, and does not have interactive relation between antistatic layer, and any contribution also is provided the service life of non-confrontational electrostatic layer.Just encapsulation after this class display production is so antistatic layer is packaged in the encapsulating shell.Under this situation, antistatic layer is isolated fully with the external world, and does not receive the influence of aforementioned envirment factor, so the problem of the antistatic usefulness decay of unlikely generation.
US 6,921,576 disclose a kind of be used to form one have an antistatic film of preferable hardness, abrasion resistance antistatic coating constituent.This antistatic coating constituent comprises (A) a plurality of inorganic oxide particles with side chain; (B) antistatic additive, contain at least one following group that constitutes that is selected from: contain quarternary ammonium salt macromolecule, contain the hydrolytic condensate of the silane coupling agent and the silane coupling agent of quarternary ammonium salt; And (C) has multifunctional (methyl) acrylic acid ester of at least three (methyl) acryloyl groups.This patent mainly uses special inorganic oxide particle through upgrading to promote the hardness and the abrasion resistance of antistatic film, more utilizes specific antistatic additive, just can let the anti-static function of antistatic film promote.Can know by foregoing; The constituent of this patent uses certain material except need; Also need the ancillary cost time to prepare specific inorganic particulate and antistatic additive through upgrading, and follow-up constituent with this patent is when coating a plastic basis material, the thickness range that is coated with need be controlled at 1～50 μ m; With regard to overall process and subsequent applications, step is too complicated and can't save manufacturing cost.In addition, the disclosed technology of this patent is not addressed any possibility that antistatic coating constituent uses that prolongs.
From the above, existing research and development to antistatic film are devoted to promote the character such as antistatic behaviour, hardness or abrasion resistance of antistatic film mostly, and are not inquired into regard to the antistatic effect that how to prolong antistatic film.The antistatic film that particularly just is used for the electronic packaging material;, electronic building brick influences effective utilization because receiving electrostatic influence easily or even damage; So the electronic packaging material is except need possess transparency and good mechanical properties, more expectation can be kept antistatic effect for a long time.Therefore, how can make antistatic film possess transparency and keep antistatic effect for a long time, still remain to be researched and developed the method that processing procedure can reduce the raw materials for production cost simply again, to promote the application and the competitiveness of product.
Summary of the invention
The problem that can not keep for a long time for the antistatic effect that solves electronic packaging material in the past; Take into account the transparency and the manufacturing cost of packaging material simultaneously; This case inventor develops a kind of effective improvement scheme after testing in many ways, by in the process of preparation antistatic layer; In antistatic coating fluid in the past, sneak into the modification agent of special ratios; Just can make made antistatic film possess the transparency, and can keep the surface impedance that conforms with demand for a long time, just can keep antistatic effect for a long time.
The object of the present invention is to provide a kind of thickness that need not increase antistatic layer, only need simple processing procedure of utilization and low cost, just can effectively prolong the method for antistatic effect of prolongation transparent antistatic film of the antistatic effect of antistatic film.
The present invention prolongs the method for the antistatic effect of transparent antistatic film; This transparent antistatic film comprises: a base material and an antistatic layer; This method is to make this antistatic layer through on this base material, being coated with the coating fluid that one deck contains an antistatic constituent and a solvent, and the back is removed the solvent in this coating fluid and formed.This antistatic constituent comprises a conducting polymer component and a plurality of cerium oxide particles.Gross weight in this antistatic constituent is 100wt%, and the content range of said cerium oxide particles is 1～10wt%, and the particle size range of said cerium oxide particles is 10～190nm.This antistatic layer has between 10
5～10
9The surface impedance of Ω, thickness are 0.18～0.5 μ m, and this antistatic film has and is not higher than 2% mist degree.
Another object of the present invention is to provide a kind of transparent antistatic film.Transparent antistatic film of the present invention has and is not higher than 2% mist degree, and one between 10
5～10
9The surface impedance of Ω, and comprise: a base material and is arranged at the antistatic layer on this base material.The thickness of this antistatic layer is 0.18～0.5 μ m, and is to be made up of an antistatic constituent, and this antistatic constituent comprises a conducting polymer component and a plurality of particle diameter cerium oxide particles between 10～190nm.Gross weight in this antistatic constituent is 100wt%, and the content range of said cerium oxide particles is 1～10wt%.
Beneficial effect of the present invention is: only need by sneaking into cerium oxide particles in the conducting polymer coating fluid in the past; And by consumption and the particle diameter of controlling cerium oxide particles; Just can pass through the effect of cerium oxide particles in the conducting polymer coating fluid; Make that antistatic film is able to be lower than under the situation of 1 μ m and low manufacturing cost at antistatic layer thickness; Even if let prepared antistatic film receiving under the ambient influnences such as ultraviolet light and oxygen, antistatic film is being kept under the existing transparency, prolonged effectively more than 2 times service life.And when using,, receive electrostatic influence to avoid electronic building brick because transparent antistatic film of the present invention can provide the antistatic effect of long period, thereby can prolong the service life of transparent antistatic film of the present invention to electrostatic defending electronic packaging material when follow-up.
The specific embodiment
The method that the present invention prolongs the antistatic effect of transparent antistatic film is to make the antistatic layer of this transparent antistatic film through on this base material, being coated with the coating fluid that one deck contains an antistatic constituent and a solvent, and the back is removed the solvent in this coating fluid and formed.This antistatic constituent comprises a conducting polymer component and a plurality of cerium oxide particles.Gross weight in this antistatic constituent is 100wt%, and the content range of said cerium oxide particles is 1～10wt%, and the particle size range of said cerium oxide particles is 10～190nm.This antistatic layer has between 10
5～10
9The surface impedance of Ω, and the thickness of this antistatic layer is 0.18～0.5 μ m.This transparent antistatic film has and is not higher than 2% mist degree.
Preferably, the thickness of this antistatic layer is 0.2～0.3 μ m.
The content range of said cerium oxide particles is 1～10wt%, preferably is 3～8wt%, more preferably is 3.5～7wt%.When the content of said cerium oxide particles is less than 1wt%, can't effectively prolong more than the antistatic effect to 60 day, so that it is limited to improve effect; On the contrary, when the content of said cerium oxide particles during, can increase unnecessary manufacturing cost expenditure more than 10wt%.
The particle size range of said cerium oxide particles is 10～190nm, preferably is 20～50nm.When the particle diameter of said cerium oxide particles during, be easy to generate agglomeration and can't homodisperse problem less than 10nm; When the particle diameter of said cerium oxide particles during, be prone to make the transparency of antistatic film to descend greater than 190nm.In embodiments of the invention, the particle diameter of said cerium oxide particles is 20nm.
The character of the antistatic layer that this conducting polymer component can form according to desire is selected the kind of suitable general conducting polymer for use, in the present invention, does not have special restriction.Preferably, this conducting polymer component comprises polythiophene.Polythiophene is such as but not limited to gathering (3,4-stretches the ethyl dioxy thiophene).For giving antistatic layer good electrical conductivity is arranged, the general number average molecular weight scope of suitable conducting polymer is preferably 5,000～50,000.
The solvent of this coating fluid can be selected for use and cerium oxide particles and the compatible solvent of conducting polymer component, in the present invention, does not have special restriction.Preferably, this solvent is to be selected from water, methyl alcohol, ethanol, isopropyl alcohol or these a combination.In embodiments of the invention, be used for mixing and the solvent that forms a conductive polymer solution is an isopropyl alcohol, and cerium oxide particles is to mix with water and form a cerium oxide aqueous solution with the conducting polymer component.
Preferably, this coating fluid also comprises a dispersant and an adhesive (binder).This dispersant comprises but is not limited to polystyrolsulfon acid ester (polystyrenesulfonate is called for short PSS).This adhesive comprises but is not limited to polyurethane (Polyurethane, PU) adhesive.
The preparation of coating fluid of the present invention can use general mixed method to carry out; For example: utilize solvent respectively; The conducting polymer component and the cerium oxide particles of antistatic constituent contained in the coating fluid are deployed into solution state; Like the conductive polymer solution and the cerium oxide aqueous solution, more above-mentioned two solution are mixed, just can make coating fluid.
In the method for the invention, the coating method of this coating fluid can select for use any known technology to carry out, coating method such as for example hand is coated with, roller coating, spray coated or intaglio printing coating.The method of removing the solvent of coating fluid also can adopt general drying or curing to carry out.
Transparent antistatic film of the present invention has and is not higher than 2% mist degree, and one between 10
5～10
9The surface impedance of Ω, and comprise a base material and and be arranged at the antistatic layer on this base material.This antistatic layer is to be made up of an antistatic constituent, and the thickness of this antistatic layer is 0.18～0.5 μ m, is preferably 0.2～0.3 μ m.
In transparent antistatic film of the present invention, the aspect of this antistatic layer and various variation are as stated, do not add to give unnecessary details at this.
This base material does not have special restriction in the present invention, can use any existing base material, for example PET (PET), polyethylene (PE), polyvinyl chloride (PVC), polypropylene (PP), Merlon (PC), polystyrene (PS) etc.
Transparent antistatic film of the present invention mainly is to be used as the follow-up electrostatic defending electronic packaging material that can be used for.
The present invention will be described further with regard to following examples, but will be appreciated that, this embodiment is only for illustrating usefulness, and should not be interpreted as the restriction that the present invention implements.
< embodiment 1 and 2 >
Prepare antistatic coating fluid
Get a conductive polymer solution (available from H.C.Starck, model: PVA) with a cerium oxide aqueous solution (model: BYK-3810, particle diameter 20 μ m).This conductive polymer solution contains the PEDOT:PSS of 0.5wt%, the polyurethane adhesive of 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 below 40 ℃ above-mentioned two solution evenly being mixed, to be mixed with an antistatic coating fluid.The component ratio of embodiment 1 and 2 antistatic coating fluid is specified in table one.
The preparation antistatic film
Should coat on the PET base material by antistatic coating fluid, the mode with heated-air drying removes the solvent (water and isopropyl alcohol) in the coating fluid again.Bake out temperature is between 65～70 ℃, and the time is 15～30 seconds, on this base material, forming the antistatic layer that is made up of an antistatic constituent [containing PEDOT:PSS (conducting polymer component) and cerium oxide particles], and then makes an antistatic film respectively.At last, the thickness to the antistatic layer of embodiment 1 and 2 measures respectively, and the contained conducting polymer component of the antistatic constituent that constitutes antistatic layer and the content of cerium oxide particles are calculated, and is recorded in table one.
Property detection
1. surface impedance: utilize the surface impedance tester [to be sheet resistance appearance (Wolfgang Warmbier; SRM-110), the measurement standard method is ASTM-D257], the antistatic layer of the antistatic film of embodiment 1 and 2 is tested, the gained result is shown in following table one.The surface impedance value suggestion that is used for the electronic packaging material is 10
5～10
9Ω.
2. mist degree: utilize haze meter [Hazy meter; Model is NDH 2000, and available from Japanese NIPPONDENSHOKU company, the measurement standard method is ASTM-D1003]; Antistatic layer to the antistatic film of embodiment 1 and 2 is tested, and the gained result is shown in following table one.The acceptable haze value of industry is＜5% at present.
3. service life: the antistatic film of prepared embodiment 1 and 2 is placed under the general atmosphere environment, it is exposed under the general atmosphere environment, utilize the sheet resistance appearance regularly to measure the surface impedance of antistatic layer, and the surface impedance decline of record antistatic layer is to 10
10The fate of Ω, this fate is the service life of this antistatic film.The gained result is shown in following table one.Service life, fate was longer good for more.
< comparative example 1～6 >
Preparation process, preparation condition and the test process of comparative example 1～6 is identical with aforesaid embodiment 2, difference be in: in comparative example 1～3, change cerium oxide particles into other UV absorbers; Comparative example 1 is selected zinc oxide (model: BYK-3820, particle diameter are 20nm) for use, and comparative example 2 is selected carbon black for use, and comparative example 3 selects for use organic compound (available from Yu Yongguang company, trade name: Eversorb80); In comparative example 4 and 5, do not use cerium oxide particles and antistatic coating fluid to form by above-mentioned conductive polymer solution; The antistatic layer thickness of comparative example 6 is less than 0.18 μ m.The composition of comparative example 1～6, thickness and test result are specified in table one.
Table one
A. content is that the gross weight with antistatic constituent is that 100wt% calculates.
Result by table one can know that under the situation of not adding UV absorbers, the antistatic layer thickness of comparative example 4 is 0.20 μ m, and then antistatic effect can only be kept 35 days.In comparative example 5, though do not adding under the UV absorbers, antistatic effect can be kept more than 60 days, and coating thickness needs will to make that up to 0.80 μ m cost significantly increases, and mist degree is also greater than 2%, and did not meet the demand of electronic packaging.
The organic compound that comparative example 3 is added can let 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
9In the Ω scope and antistatic effect can keep more than 60 days, but the transparency of made antistatic film is not good.Result by above-mentioned comparative example 1～3 can know, is not that all UV absorbers all can let antistatic film possess the transparency and can keep antistatic effect for a long time.
The antistatic layer thickness of comparative example 6 is 0.16 μ m, even add the cerium oxide particles of 10wt%, is lower than 60 days service life, proves that the thickness of antistatic layer also can influence the service life of antistatic film.
Embodiment 1 and 2 antistatic film all have between 10
5～10
9The surface impedance of Ω, 1.1% mist degree, it is transparent that outward appearance is, and service life is sustainable more than 60 days, proves the method for the antistatic effect of prolongation transparent antistatic film of the present invention, can make the antistatic film that prolongs antistatic effect and have transparency concurrently really.
In sum; The method of the antistatic effect of prolongation transparent antistatic film of the present invention; By select cerium oxide particles for use and control its consumption (1～10wt%) with particle diameter (10～190nm), and suitably control the thickness (0.18～0.5 μ m) of antistatic layer, let prepared transparent antistatic film under the environment of contact oxygen and ultraviolet light; Can keep its surface impedance and reach more than 60 days, therefore can prolong the antistatic effect of antistatic film effectively.
The above person of thought; Be preferred embodiment of the present invention only; When not limiting the scope that the present invention implements,, all still belong in the scope that patent of the present invention contains just as long as the simple equivalent of doing according to claim of the present invention and invention description changes and modifies with this.
Claims (12)
1. method that prolongs the antistatic effect of transparent antistatic film, this transparent antistatic film comprises: a base material and an antistatic layer; It is characterized in that: this method is to make this antistatic layer through on this base material, being coated with the coating fluid that one deck contains an antistatic constituent and a solvent, and the back is removed the solvent in this coating fluid and formed; This antistatic constituent comprises a conducting polymer component and a plurality of cerium oxide particles; Gross weight in this antistatic constituent is 100wt%; The content range of said cerium oxide particles is 1～10wt%, and the particle size range of said cerium oxide particles is 10～190nm;
This antistatic layer has between 10
5～10
9The surface impedance of Ω, and the thickness of this antistatic layer is 0.18～0.5 μ m; And
This transparent antistatic film has and is not higher than 2% mist degree.
2. the method for the antistatic effect of prolongation transparent 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 said cerium oxide particles is 3～8wt%.
3. the method for the antistatic effect of prolongation transparent 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 said cerium oxide particles is 3.5～7wt%.
4. the method for the antistatic effect of prolongation transparent antistatic film as claimed in claim 1 is characterized in that: this conducting polymer component comprises polythiophene.
5. the method for the antistatic effect of prolongation transparent antistatic film as claimed in claim 4 is characterized in that: this polythiophene is for gathering (3,4-stretches the ethyl dioxy thiophene).
6. the method for the antistatic effect of prolongation transparent antistatic film as claimed in claim 1 is characterized in that: the thickness of this antistatic layer is 0.2～0.3 μ m.
7. transparent antistatic film is characterized in that: this transparent antistatic film has and is not higher than 2% mist degree, and one between 10
5～10
9The surface impedance of Ω comprises: a base material and is arranged at the antistatic layer on this base material; The thickness of this antistatic layer is 0.18～0.5 μ m; And be to constitute by an antistatic constituent; This antistatic constituent comprises a conducting polymer component and a plurality of particle diameter cerium oxide particles between 10～190nm; Gross weight in this antistatic constituent is 100wt%, and the content range of said cerium oxide particles is 1～10wt%.
8. transparent 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 said cerium oxide particles is 3～8wt%.
9. transparent antistatic film as claimed in claim 8 is characterized in that: the gross weight of this antistatic constituent is in 100wt%, and the content range of said cerium oxide particles is 3.5～7wt%.
10. transparent antistatic film as claimed in claim 7 is characterized in that: comprise polythiophene in this conducting polymer component.
11. transparent antistatic film as claimed in claim 10 is characterized in that: this polythiophene is for gathering (3,4-stretches the ethyl dioxy thiophene).
12. transparent antistatic film as claimed in claim 7 is characterized in that: the thickness of this antistatic layer is 0.2～0.3 μ m.
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| CN107312189A (en) * | 2017-06-26 | 2017-11-03 | 俞秀英 | Extend the method for the antistatic effect of antistatic film |
| US11579718B2 (en) | 2021-03-02 | 2023-02-14 | Innolux Corporation | Touch electronic device |
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| CN102476490B (en) | 2015-04-08 |
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