KR20160141212A - Producing method of gas barrier film by vacuum deposition - Google Patents

Producing method of gas barrier film by vacuum deposition Download PDF

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KR20160141212A
KR20160141212A KR1020150075857A KR20150075857A KR20160141212A KR 20160141212 A KR20160141212 A KR 20160141212A KR 1020150075857 A KR1020150075857 A KR 1020150075857A KR 20150075857 A KR20150075857 A KR 20150075857A KR 20160141212 A KR20160141212 A KR 20160141212A
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South Korea
Prior art keywords
barrier film
polymer
gas barrier
film
vacuum
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KR1020150075857A
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Korean (ko)
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KR101763177B1 (en
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한세진
김영수
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한화첨단소재 주식회사
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12Chemical modification
    • C08J7/16Chemical modification with polymerisable compounds
    • C08J7/18Chemical modification with polymerisable compounds using wave energy or particle radiation
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523Pulsed gas flow or change of composition over time
    • C23C16/45525Atomic layer deposition [ALD]
    • C23C16/45527Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
    • C23C16/45536Use of plasma, radiation or electromagnetic fields
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/14Gas barrier composition

Abstract

The present invention relates to a method for manufacturing a vacuum-deposited gas barrier film and, more specifically, to a method for manufacturing a vacuum-deposited gas barrier film, wherein, when drying coating is performed on one surface and both surfaces of a polymer substrate containing a thermoplastic transparent base resin during the vacuum, a gas barrier film with reduced contamination and damage on a fabric surface can be manufactured through a single process, and the refractive index can be freely controlled, so the gas barrier film can be used for a transparent barrier film for a display and a transparent electrode film having barrier characteristics. According to the present invention, a gas barrier film can be manufactured while the contamination and damage on the substrate surface are reduced. Especially, since the refractive index can be freely controlled, a vacuum-deposited gas barrier film can be manufactured that is suitable for a transparent barrier film for a display or a transparent electrode film having barrier characteristics.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a gas barrier film,

More particularly, the present invention relates to a method of producing a gas barrier film by vacuum evaporation, and more particularly, to a method of manufacturing a gas barrier film by vacuum coating a polymer substrate including a thermoplastic transparent base resin, And can be used for a transparent electrode film having a barrier property as well as a transparent barrier film for a display because the gas barrier film can be manufactured and the refractive index can be freely adjusted.

Flexible display is a core technology industry that can realize low power, low cost, light weight and large size, easy to carry, and information can be easily accessed anytime and anywhere, thus attracting general consumers' attention.

In addition, flexible display using polymer film as substrate can be applied to roll-to-roll production method, and it can come to be the core of display market with commercialization of mass production technology centered on small living devices such as mobile Industry.

In particular, flexible substrates have been studied as interesting topics in many companies and research institutes.

Conventional glass is good in transparency, but due to its inherent low impact resistance, it is easily damaged by impact and has a limitation in thinning. In addition, the glass has a large weight per unit volume, making it difficult to apply it as a flexible substrate.

In order to overcome this problem, it is necessary to use a polymer which is light, thin, flexible and easy to apply to a flexible substrate, for example, a polycarbonate (PC) having excellent optical properties, Polyimide (PI), polyethersulfone (PES), polyarylate (PAR), polyethylene naphthalate (PEN), polyethylene terephthalate (PET), cycloolefin A transparent film produced by using a thermoplastic polymer such as a cycloolefin copolymer, a polymer obtained by curing a curable resin such as an acrylic resin, an epoxy resin and an unsaturated polyester is used.

In order to fulfill its role as a substrate used in a flexible display product, a film made of such a polymer is required to have a function as a display such as excellent moisture barrier property and oxygen barrier property which directly affects the life of the display Excellent properties are required. However, since the polymer transparent film is inferior in moisture and oxygen barrier properties, attempts have been actively made to achieve the above properties by coating the functional coating layer in multiple layers. Basically, in order to increase the moisture and oxygen barrier properties, An inorganic-gas barrier layer and an organic-inorganic hybrid coating layer which is coated in a wet process in the air so that the barrier property can be further enhanced and an excellent surface hardness can be imparted.

A number of related technologies are disclosed, for example, in Japanese Patent Registration No. 1421973 (Apr. 14, 2014), European Patent No. EP2168644 (Nov.

Conventional gas barrier film production is carried out by dry-type wet-coating (including rear-side dry-coating) or after wet-type dry-coating (including rear-side dry-coating). For example, in the case of wet- .

That is, after the surface of the fabric (substrate) is subjected to a plasma treatment in a vacuum to increase the adhesion, a silicon oxynitride or a silicon nitride film is coated to a thickness of about ten nanometers in an oxygen and nitrogen atmosphere using a silicon target by a sputtering method, A silicon target was continuously used in an oxygen atmosphere to coat the silicon oxide film several tens of nanometers and then transferred to the atmosphere to protect the silicon oxide film. In order to overcoat the silicon oxide film, a UV or thermosetting liquid such as acrylate or urethane acrylate was wet- And a transparent inorganic layer which is attached to the back surface of the gas barrier layer in order to adhere to the device, if necessary, in a vacuum.

However, this method does not have process contamination problem due to impurity gas during vacuum deposition compared with wet post-dry coating method. However, silicon oxynitride or silicon nitride film formed by sputtering has a slow reaction rate and stoichiometry difficult to meet, There is a problem that the refractive index is changed over time and the process speed is 5 to 10 times slower than that of the wet coating, and a maximum of 5 processes are required.

On the other hand, the wet post-dry coating method has a layered structure as shown in Fig. 2, in which a UV or thermosetting liquid such as acrylate or urethane acrylate is wet-coated by wet coating in order to form a planarizing layer on a fabric (SiOC) or silicon oxide film by a plasma chemical vapor deposition (CVD) method. In the wet coating layer, there is a large amount of moisture and residual solvent in the chamber. Therefore, due to the influence of impurity gas during the vacuum vapor deposition process, It is difficult to obtain the optical characteristics of the gas barrier layer and the wet scrubber and the dry roll-to-roll process twice, which increases the process cost and increases the possibility of surface scratches and contamination.

Of course, up to three processes are needed to coat the transparent inorganic layer in vacuum to increase the adhesion to the back of the gas barrier layer for attachment to the device as needed.

DISCLOSURE Technical Problem The present invention has been made in view of the above-described problems in the prior art as described above, and it is an object of the present invention to provide a method of manufacturing a semiconductor device, The present invention provides a method for manufacturing a vacuum vapor deposited gas barrier film suitable for a transparent barrier film for displays or a transparent electrode film having a barrier property because the refractive index can be freely adjusted by changing the composition ratio.

In order to achieve the above object, the present invention provides a method for manufacturing a polymer substrate (F), comprising the steps of: polymerizing a polymer substrate (F) in one vacuum process, ≪ / RTI > And a third step of dry-depositing an inorganic barrier layer on the other side of the polymer substrate (F).

At this time, the first organic or inorganic barrier layer is also characterized in that the powder or liquid combined with the thermosetting polymer and silicon is deposited by resistance heating or by sputtering.

The second inorganic barrier layer is also deposited by plasma chemical vapor deposition (PECVD).

In addition, the first organic barrier layer is a polymer-based deposition layer, and the second and third inorganic barrier layers are ceramic layers.

According to the present invention, a gas barrier film can be produced while reducing contamination and damage on the surface of the substrate. In particular, since the refractive index can be freely controlled, a vacuum deposited gas barrier film suitable for a transparent barrier film for a display or a transparent electrode film having a barrier property can be produced.

1 and 2 are exemplary cross-sectional views showing a layered structure of a gas barrier film produced according to a conventional method.
3 is a schematic block diagram of a manufacturing apparatus for implementing a vacuum deposited gas barrier film production method according to the present invention.
4 is an enlarged view of the third inorganic layer coating apparatus of Fig.
5 is an exemplary cross-sectional view showing the layered structure of the gas barrier film produced by the manufacturing method according to the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

Before describing the present invention, the following specific structural or functional descriptions are merely illustrative for the purpose of describing an embodiment according to the concept of the present invention, and embodiments according to the concept of the present invention may be embodied in various forms, And should not be construed as limited to the embodiments described herein.

In addition, since the embodiments according to the concept of the present invention can make various changes and have various forms, specific embodiments are illustrated in the drawings and described in detail herein. However, it should be understood that the embodiments according to the concept of the present invention are not intended to limit the present invention to specific modes of operation, but include all modifications, equivalents and alternatives falling within the spirit and scope of the present invention.

Before describing the manufacturing method of the present invention in detail, the deposition system for implementing the manufacturing method according to the present invention will be described first.

The deposition system (FIG. 3) for implementing the manufacturing method according to the present invention includes a first chamber 100, a second chamber 200, and a third chamber 300.

The first, second, and third chambers 100, 200, and 300 are partially communicated with each other to enable continuous processing.

The present invention relates to a method for coating both sides of a polymer substrate (F) comprising a thermoplastic transparent base resin in one step in the case of dry coating in vacuum on one side and the other side, And the gas barrier film can be manufactured while reducing the damage.

For this purpose, the first chamber 100 is a chamber for a resistance heating deposition apparatus 140 of a powder or solution in which a thermosetting polymer and silicon are combined, and an ion assist processor 142 or a sputtering apparatus 150 for curing the same. The third chamber 300 is a space for winding the coated polymer base material F. The second chamber 200 may be a vacuum chamber for plasma chemical vapor deposition, There is no need.

In addition, the first chamber 100 is a space for forming an organic oxygen barrier on one side of the polymer substrate F, and the organic or inorganic oxygen barrier may be a melamine (C 3 H 6 N 6 ) resin, polytetrafluoroethylene (PTFE), or a resin powder or liquid phase in which melamine and silicon are mixed and heated in vacuum to form a coating on one surface of the polymer substrate (F).

A plurality of tension rolls 120 for conveying the polymer base material F in an appropriate tension and a plurality of tension rolls 120 for applying the polymer base material F to the first and second chambers 100, A deposition guide drum 130 for guiding the polymer substrate F so as to facilitate the deposition of the polymer substrate F and a polymer base material F formed on one side of the polymer base material F moving along the surface of the deposition guide drum 130 A polymer evaporator 140 for depositing a polymer is installed.

At this time, an ion assist processor 142 may be additionally provided for enhancing the adhesion of the polymer substrate F to the polymer substrate 140 and for curing the deposited polymer layer before the polymer evaporator 140. When the ion assist processor 142 processes the ion assist processor 142 An effect similar to the plasma surface modification in the related art can be obtained.

In addition, the ion assist processor 142 and the polymer evaporator 140 are configured to rotate in the film advancing direction (MD) so as to adjust the growth direction of the polymer thin film to be coated.

In addition, a sputtering unit 150 may be provided in place of the polymer evaporator 140, and a ceramic coating layer having excellent oxygen barrier properties may be formed by sputtering using a high frequency power source.

As described above, the melamine deposited on the polymer substrate F through the first chamber 100 is preferentially oriented on the surface of a large amount of the hydrogen bonding layer, and the effect of reducing the oxygen permeability by about two orders is obtained .

In addition, the temperature of the polymer evaporator 140 is 220 to 350 ° C. and 3.8 to 7.5E-5 torr. In order to adjust the refractive index of 1.4 to 1.8 (500 nm), a variety of synthetic resin powders can be prepared, The reactive gas of the high refractive index has a merit that it is easier to control the stoichiometric ratio than the case of using nitrogen only by using a mixture gas of nitrogen and hydrogen and makes the high refractive index film easier to apply to both high refractive index and low refractive index substrates.

The second chamber 200 is a space for forming an inorganic barrier on both sides of the polymer substrate F. The inorganic barrier is a kind of ceramic layer and is coated with the organic barrier by the polymer evaporator 140 Silicon oxycarbide (SiOC), silicon oxycarbonitride (SiOCN), or silicon oxide (SiO) is coated continuously by plasma chemical vapor deposition.

In this case, if necessary, the transparent inorganic material layer may be coated once more on the back surface to improve adhesion and barrier properties, and both surfaces are preferably coated in one step.

The second chamber 200 is provided with a deposition drum 210 for performing plasma chemical vapor deposition of the polymer substrate F transported from the first chamber 100 and a deposition drum 210 disposed below the deposition drum 210, A plurality of showerheads 220 arranged to be spaced apart from each other in accordance with a radius of curvature of the showerhead 210 to perform plasma chemical vapor deposition, a high frequency power source 240 for applying a high frequency to the deposition drum 210, And a plurality of permanent magnets 250 installed in the deposition drum 210 in opposition to the deposition chamber 220.

In this case, a head high-frequency power source 230 for applying a high frequency to the showerhead 220 may be further provided.

The polymeric substrate F is transferred from the deposition drum 210 to the polymeric substrate F through the showerhead 220 so that the polymeric substrate F is plasma-chemically deposited on the other surface of the polymeric substrate F, A plasma chemical vapor deposition unit 260 is further installed.

Therefore, when the polymer base material F is passed through the second chamber 200, the both surfaces of the polymer substrate F are subjected to plasma chemical vapor deposition with an inorganic barrier.

Herein, the above-mentioned organic oxygen barrier and inorganic oxygen barrier all refer to a layer.

In addition, the permanent magnet 250 accelerates the ceramic layer, which is a chemical reaction product of the precursor and the process gas supplied from the showerhead 220, onto the polymer deposition layer of the polymer substrate F to improve the adhesion and the deposition rate .

Therefore, there is no contamination of the deposition drum 210, which serves as an electrode of the plasma generation source, and power is not directly applied to the showerhead 220, so that arcing does not occur during deposition, thereby improving the deposition quality.

If necessary, a high-frequency power is applied to the showerhead 220 to form a plasma, and ions dissociated from the showerhead are focused on the polymer layer on the polymer substrate F by using a DC bias power source for the deposition drum 210 It is possible.

This plasma focusing method is also applied to the rear plasma chemical vapor deposition unit 260 to easily deposit an inorganic layer on the rear surface.

The characteristics of the plasma chemical vapor deposition method using the deposition drum 210 and the showerhead 220 and the method using the rear surface plasma chemical vapor deposition unit 260 are that the refractive index is optically good using a high frequency power source And has the advantage that the plasma electrode is not contaminated.

At this time, the reason for using the high frequency power source is to increase the ion density and to decrease the pinhole and increase the filling rate of the film.

2 through 1E-3 g / m < 2d > and an oxygen permeability of 5.0E-2 to 1E-3 cc / m2d at a total coating thickness of 1.5um or less when passing through the second chamber 200. [ It becomes possible to produce a film having barrier properties.

4, the rear surface plasma chemical vapor deposition unit 260 includes a rear permanent magnet 262 arranged on the upper surface of the polymer substrate F opposite to the deposition layer, A plasma electrode 264 to which a high frequency or a medium frequency power is applied, and a gas line 266 capable of supplying gas are arranged together.

At this time, the high frequency or medium frequency range is in the range of 30 kHz to 13.56 MHz.

In the third chamber 300, a winding roll 310 is provided, and the polymer substrate F having been deposited is wound to form a coil.

As described above, the present invention can dry the two layers continuously in vacuum on the polymer substrate (F) to produce a barrier film that minimizes contamination and damage to the surface of the polymer substrate (F), and melamine or melamine (SiOC) using a plasma chemical vapor deposition (CVD) method on the top and the other surfaces of the supercrystal layer, and then, , Silicon oxycarbonide (SiOCN), or silicon oxide (SiO) can be coated to produce a barrier film having low moisture and oxygen transmittance. Thus, both sides can be processed in one step, the refractive index can be freely controlled, Can be reduced.

When this deposition system is used for deposition, a gas barrier film having a layered structure as shown in FIG. 5 can be formed.

That is, the polymer substrate (F) can be dry-coated by a single vacuum process to deposit the inorganic or organic barrier and the inorganic barrier on one side of the polymer substrate (F), and the inorganic barrier can be deposited on the other side, (Water permeability and oxygen permeability) can be improved as well as adhesion strength and barrier properties.

100: first chamber 200: second chamber
300: Third chamber

Claims (4)

During the one-step vacuum process, the polymer substrate (F)
The inorganic barrier layer and the inorganic barrier layer are successively dry-deposited on one side of the polymer substrate (F);
Wherein the inorganic barrier layer is dry-deposited on the other side of the polymer substrate (F).
The method of claim 1,
Wherein the organic or inorganic barrier layer is deposited by resistance heating deposition or sputtering of a polymer or a polymer and a silicon bond.
The method of claim 1,
Wherein the inorganic barrier layer is deposited by a plasma chemical vapor deposition (CVD) process.
The method of claim 1,
Wherein the organic or inorganic barrier layer is a ceramic layer, wherein the organic or inorganic barrier layer is a vapor-deposited layer of a polymer or polymer and a silicon-bonded material, and the inorganic barrier layer is a ceramic layer.
KR1020150075857A 2015-05-29 2015-05-29 Producing method of gas barrier film by vacuum deposition KR101763177B1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20180089138A (en) 2017-01-31 2018-08-08 주식회사 케이씨씨 Barrier coating composition and barrier film manufactured using the same

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5542072B2 (en) * 2011-01-31 2014-07-09 富士フイルム株式会社 Gas barrier film and organic device using the same
JP2014240051A (en) 2013-06-12 2014-12-25 コニカミノルタ株式会社 Gas barrier film, manufacturing method of gas barrier film, and manufacturing apparatus of gas barrier film

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20180089138A (en) 2017-01-31 2018-08-08 주식회사 케이씨씨 Barrier coating composition and barrier film manufactured using the same

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