JP2015148007A - Apparatus and method for manufacturing functional film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an apparatus and method for manufacturing a functional film, capable of reducing a film defect caused by winding a film having an inorganic film formed as a functional layer on a base film and showing high functionality.SOLUTION: An apparatus A for manufacturing a functional film F, capable of forming and winding an inorganic film as a functional layer on a long base film 1 comprises: a first film forming part A1 for forming the inorganic film on the base film 1; and a second film forming part A2 for forming a protective layer on the inorganic film or the base film 1 so as to position the protective layer between the inorganic films faced to each other or between the inorganic film and the base film faced to each other in a roll body obtained by winding the base film 1 having the inorganic film and having 5-98% of a coverage represented by a proportion of the area of the protective layer to the total area of the inorganic film.

Description

  The present invention relates to a functional film manufacturing apparatus and a manufacturing method. More specifically, the present invention relates to an apparatus for producing a functional film that exhibits high functionality by reducing film defects caused by winding a film in which an inorganic film is formed as a functional layer on a long base film.

Conventionally, a functional film in which an inorganic film is formed as a functional layer on a base film has been widely used.
A gas barrier film used as a packaging material for foods, pharmaceuticals, electronic devices and the like is also one of functional films. In the gas barrier film, the gas barrier layer formed on the base film shields gas such as water and oxygen in the atmosphere to prevent deterioration of the contents.

When an inorganic film is continuously formed on a long base film by a roll-to-roll method, the inorganic film may come into contact with the base film during film winding, resulting in film defects. .
In order to reduce such film defects, a protective film is disposed and wound so as to cover the entire surface of the inorganic film, and contact between the inorganic film and the base film during winding is performed (for example, Patent Document 1).
Also, a protective layer that covers the entire surface of the inorganic film is formed on the inorganic film (see, for example, Patent Documents 2 and 3).

However, since the protective film is removed when the functional film is used, wasteful waste material increases.
The protective layer also needs to be removed by washing treatment when the functional film is used. However, if the protective layer is provided so as to cover the entire surface of the inorganic film, the washing load increases. If the cleaning process is performed for a long time, the portion of the inorganic film from which the protective layer has been previously removed by cleaning may be damaged.

  In addition, when forming an inorganic film under vacuum pressure, if a protective layer is formed continuously under atmospheric pressure after the inorganic film is formed, it is necessary to adjust the pressure from vacuum pressure to atmospheric pressure, which requires manufacturing costs. .

Japanese Patent Laid-Open No. 1-185836 JP 2003-231198 A JP 2011-222212 A

  The present invention has been made in view of the above problems and circumstances, and its solution is to reduce film defects caused by winding a film in which an inorganic film is formed as a functional layer on a base film, and to exhibit high functionality. It is providing the manufacturing apparatus and manufacturing method of a film.

In order to solve the above-mentioned problems, the present inventors are effective in forming a protective layer as a spacer in order to reduce unnecessary waste materials in the process of studying the cause of the above-mentioned problem, etc. When the layer was formed, it was considered that the washing load for removing the protective layer was large. As a result of intensive studies, the present inventors can sufficiently protect the inorganic film and easily remove it as long as the coverage is in the range of 5 to 98% without covering the entire surface with the inorganic film. And found the present invention.
That is, the subject concerning this invention is solved by the following means.

1. A functional film manufacturing apparatus for forming and winding an inorganic film as a functional layer on a long base film,
A first film forming unit that forms the inorganic film on the base film;
In the roll body in which the base film on which the inorganic film is formed is wound, the inorganic film is disposed such that a protective layer is located between the facing inorganic film and the inorganic film or between the facing inorganic film and the base film. The second film is formed by forming the protective layer on the film or the base film and having a coverage expressed by the ratio of the area of the protective layer to the total area of the inorganic film within a range of 5 to 98%. And
An apparatus for producing a functional film, comprising:

  2. The second film forming unit forms the protective layer on the inorganic film formed by the first film forming unit or on the surface opposite to the surface of the base film on which the inorganic film is formed. An apparatus for producing a functional film according to item 1, characterized in that:

3. The first film forming unit forms the inorganic film under a vacuum pressure,
The functionality according to claim 1 or 2, wherein the second film forming unit forms the protective layer under vacuum pressure continuously with the formation of the inorganic film by the first film forming unit. Film production equipment.

  4). The second film forming unit forms a protective layer having a pattern in which the coverage of the protective layer is in a range of 5 to 98%. The functional film manufacturing apparatus described.

  5. The total area of the protective layer formed by the second film forming unit is expressed as a ratio of the area of the protective layer remaining on the functional film developed by unwinding the roll body under atmospheric pressure. The functional film manufacturing apparatus according to any one of Items 1 to 4, wherein the remaining rate is in a range of 98 to 100%.

  6). 6. The apparatus for producing a functional film according to claim 5, further comprising a cleaning processing section that cleans the developed functional film and removes the protective layer under atmospheric pressure.

  7). The said 1st film-forming part forms the said inorganic film | membrane by an atomic layer deposition method, The manufacturing apparatus of the functional film as described in any one of Claim 1-6 characterized by the above-mentioned.

8). A method for producing a functional film that forms and winds an inorganic film on a long base film as a functional layer,
A first film forming step of forming the inorganic film on the base film;
In the roll body in which the base film on which the inorganic film is formed is wound, the inorganic film is disposed such that a protective layer is located between the facing inorganic film and the inorganic film or between the facing inorganic film and the base film. The second film is formed by forming the protective layer on the film or the base film and having a coverage expressed by the ratio of the area of the protective layer to the total area of the inorganic film within a range of 5 to 98%. Process,
A method for producing a functional film, comprising:

  9. In the second film forming step, the protective layer is formed on the inorganic film formed in the first film forming step or on the surface opposite to the surface of the base film on which the inorganic film is formed. The method for producing a functional film according to item 8, characterized in that:

10. In the first film forming step, the inorganic film is formed under a vacuum pressure,
The function according to item 8 or 9, wherein, in the second film formation step, the protective layer is formed under vacuum pressure continuously with the formation of the inorganic film in the first film formation step. For producing a conductive film.

  11. In the second film forming step, a protective layer having a pattern in which the coverage of the protective layer is within a range of 5 to 98% is formed. The manufacturing method of the functional film of description.

  12 The total area of the protective layer formed in the second film formation step is expressed as a ratio of the area of the protective layer remaining on the functional film unrolled and unrolled at atmospheric pressure. The method for producing a functional film according to any one of Items 8 to 11, wherein the remaining ratio is in a range of 98 to 100%.

  13. 13. The method for producing a functional film according to item 12, further comprising a washing step of washing the developed functional film under atmospheric pressure to remove the protective layer.

  14 14. The method for producing a functional film according to any one of items 8 to 13, wherein in the first film formation step, the inorganic film is formed by an atomic layer deposition method.

  By means of the above-mentioned means of the present invention, there are provided a functional film production apparatus and production method exhibiting high functionality by reducing film defects caused by winding a film in which an inorganic film is formed as a functional layer on a base film. be able to.

The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.
According to the above means of the present invention, the protective layer can be disposed as a spacer between the inorganic film and the inorganic film facing each other in the roll body or between the inorganic film and the base film facing each other in the roll body. Therefore, contact between the inorganic films at the time of winding or contact between the inorganic film and the base film can be prevented, and film defects caused by the contact at the time of winding the film can be reduced. Moreover, since the coverage of the protective layer is in the range of 5 to 98%, not only the inorganic film can be sufficiently protected, but also the protective layer can be easily removed. Film defects generated at the time of removal can be reduced, and a functional film having high functionality can be produced.

The front view which shows schematic structure of the 1st film-forming part with which the manufacturing apparatus of the functional film which concerns on this Embodiment is equipped, and a 2nd film-forming part. Top view showing an example of a protective layer pattern The top view which shows an example of the pattern which varied the coverage of the protective layer within the range of 5-98% The front view which shows schematic structure of the washing | cleaning process part with which the manufacturing apparatus of the functional film which concerns on this Embodiment is provided. The front view which shows schematic structure of the 1st film-forming part at the time of using a vacuum evaporation method Sectional view showing an example of functional film Top view showing the pattern of the protective layer used in the examples

  The functional film manufacturing apparatus of the present invention is a functional film manufacturing apparatus for forming and winding an inorganic film as a functional layer on a long base film, and forming the inorganic film on the base film. A protective film between a first inorganic film and a base film facing each other in a roll body around which the first film forming unit and the base film on which the inorganic film is formed are wound So that the protective layer is formed on the inorganic film or the base film, and the coverage represented by the ratio of the area of the protective layer to the total area of the inorganic film is 5 to 98%. And a second film forming unit within the range. This feature is a technical feature common to or corresponding to the inventions according to claims 1 to 14.

  As an embodiment of the present invention, from the viewpoint of manifestation of the effect of the present invention, the second film forming part is on the inorganic film formed by the first film forming part or the base film on which the inorganic film is formed. The protective layer is preferably formed on the surface opposite to the surface.

  The first film formation unit forms the inorganic film under a vacuum pressure, and the second film formation unit performs the protection under a vacuum pressure continuously with the formation of the inorganic film in the first film formation unit. It is preferable to form a layer from the viewpoint of improving productivity.

  Furthermore, it is preferable that the second film forming unit forms a protective layer having a pattern in which the coverage of the protective layer is within a range of 5 to 98%. The pattern makes it easy to adjust the coverage of the protective layer.

  As an embodiment of the present invention, the protection remaining on the functional film unrolled and unrolled under atmospheric pressure with respect to the entire area of the protective layer formed by the second film forming unit From the viewpoint of preventing damage to the inorganic film, it is preferable that the residual ratio represented by the ratio of the area of the layer is in the range of 98 to 100%.

Moreover, it is preferable to provide the washing | cleaning process part which wash | cleans the developed functional film and removes the said protective layer under atmospheric pressure.
From the viewpoint of forming a uniform inorganic film, etc., the first film forming unit preferably forms the inorganic film by an atomic layer deposition method.

The method for producing a functional film of the present invention is a method for producing a functional film that forms and winds an inorganic film as a functional layer on a long base film, and the inorganic film is formed on the base film. And a protective layer between the facing inorganic film and the inorganic film or between the facing inorganic film and the base film in the first film forming step and the roll body on which the base film on which the inorganic film is formed is wound So that the protective layer is formed on the inorganic film or the base film, and the coverage represented by the ratio of the area of the protective layer to the total area of the inorganic film is 5 to 98%. And a second film forming step within the range.
Since the preferable embodiment of the manufacturing method of the functional film of this invention is the same as the preferable embodiment of a manufacturing apparatus, description is abbreviate | omitted here.

Hereinafter, the present invention, its components, and modes for carrying out the present invention will be described in detail.
In addition, in this application, "-" is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

The functional film manufacturing apparatus and method of the present invention form an inorganic film as a functional layer on a long base film.
As a method for forming the inorganic film, various methods such as a CVD (Chemical Vapor Deposition) method, a PVD (Physical Vapor Deposition) method, and an atomic layer deposition (ALD) method can be adopted. It is preferable to form an inorganic film by the ALD method from the viewpoint of being able to form a thin film and having excellent coverage. In the ALD method, a film forming process in which two or more kinds of raw materials are alternately supplied onto a base film and each raw material is reacted is repeated for a plurality of cycles, and an atomic layer (actually, a molecular layer of a compound can be obtained for each cycle. ) Are deposited one layer at a time to form a thin film. As long as the ALD method is used, a PEALD (Plasma Enhanced ALD) method, a thermal ALD method, or the like, which is a kind of the ALD method, may be used.
Hereinafter, a manufacturing apparatus and a manufacturing method using the PEALD method will be described as a manufacturing apparatus and a manufacturing method of the present embodiment.

[Functional film production equipment]
FIG. 1 shows a schematic configuration of a functional film manufacturing apparatus A according to the present embodiment.
As shown in FIG. 1, the functional film manufacturing apparatus A has a first film forming portion A1 that forms an inorganic film as a functional layer on a long base film 1, and a protective film on the inorganic film or the base film. And a second film forming part A2 for forming a layer.

Further, the manufacturing apparatus A includes an unwinder 11, a winder 15, and a plurality of rollers 12 disposed between the unwinder 11 and the winder 15 for transporting the base film 1. The base film 1 is supplied as a roll body and set in the unwinder 11.
When the unwinder 11 unwinds the roll body, the base film 1 from which the plurality of rollers 12 are unwound is sequentially conveyed to the first film forming unit A1 and the second film forming unit A2. The winder 15 winds up the functional film F obtained by forming the functional layer and the protective layer on the base film 1 to obtain a roll body.

1st film-forming part A1 forms an inorganic film | membrane as a functional layer on the elongate base film 1 by PEALD method. The PEALD method is a kind of ALD method and is a method of modifying a raw material using plasma.
As shown in FIG. 1, the first film forming unit A1 includes two raw material supply units 21 and 22 and a modification processing unit 23. The raw material supply units 21 and 22 and the reforming processing unit 23 are adjusted to a vacuum pressure by a vacuum pump or the like.

Further, the first film forming unit A1 includes purge units 24 between the raw material supply unit 21 and the reforming processing unit 23 and between the raw material supply unit 22 and the reforming processing unit 23, respectively.
A partition plate is arranged between each of the raw material supply units 21 and 22, the reforming processing unit 23, and the two purge units 24, and each of the raw material supply units 21 and 22, the reforming processing unit 23, and two purges is arranged by the partition plate. Chambers C1 to C4 of the part 24 are formed. The partition plate is provided with an opening on the transport path of the base film 1 so that the long base film 1 can pass through the chambers C1 to C4.

The raw material supply units 21 and 22 supply the raw material of the inorganic film in the form of gas into the chambers C1 and C2. The raw material is also called a precursor.
In the chamber C1, the raw material supplied by the raw material supply unit 21 is adsorbed on the surface of the base film 1, and in the chamber C2, the raw material supplied by the raw material supply unit 22 is adsorbed on the surface of the base film 1.

  The reforming processing unit 23 supplies the raw material reforming gas supplied from the raw material supply units 21 and 22 into the chamber C3. Further, the reforming processing unit 23 applies an AC voltage to the reforming gas by supplying power to the pair of electrodes 231 arranged to face each other with the base film 1 interposed therebetween by an AC power source (not shown). Plasma P is generated. The modification processing unit 23 modifies the raw material on the base film 1 with the plasma P, and forms an atomic layer of an inorganic film. The atomic layer of the inorganic film can actually be a molecular layer of the compound.

  When the ALD method is used, the base film 1 is alternately exposed to different source gases supplied by the source supply units 21 and 22, and the source materials are chemically reacted to form an inorganic film such as a metal oxide. In contrast, in the PEALD method, after the raw material is adsorbed on the base film 1, an inorganic film such as a metal oxide is formed by reforming the raw material using a plasma such as oxygen or nitrogen. In the PEALD method, the raw material supply units 21 and 22 can supply the same raw material or different raw materials. When different raw materials are used, an inorganic film obtained by modifying the raw material supplied by the raw material supply unit 21 and an inorganic film obtained by modifying the raw material supplied by the raw material supply unit 22 They can be stacked alternately.

  As raw materials for the inorganic film, aluminum (Al), titanium (Ti), silicon (Si), zirconium (Zr), hafnium (Hf), lanthanum (La), niobium (Nb), tantalum (Ta), magnesium (Mg) ), A metal compound containing a metal element such as zinc (Zn) can be used. The inorganic film may contain a metal compound such as a metal oxide or metal nitride obtained by modifying the raw material.

  When the raw material supplied by the raw material supply units 21 and 22 is the first raw material and the reforming gas used by the reforming processing unit 23 is the second raw material, the first raw material and the second raw material are formed according to the inorganic film to be formed. Can be selected.

For example, when a metal compound such as aluminum oxide (Al ₂ O ₃ ) or aluminum nitride is obtained by the modification treatment, there is no particular limitation as long as the first raw material contains aluminum and can be vaporized. Examples of such an aluminum compound include aluminum chloride (Al ₂ Cl ₆ ), trimethylaluminum (Al (CH ₃ ) ₃ ), triethylaluminum (TEA), and trichloroaluminum.

When obtaining a metal compound such as silicon oxide (SiO ₂ ) and silicon nitride (SiN) by the modification treatment, the first raw material is trisilane (Si ₃ H ₈ ), disilane (Si ₂ H ₆ ), monosilane (SiH ₄ ). Besides, chlorosilanes such as monochlorosilane (SiH ₃ Cl), dichlorosilane (SiH ₂ Cl ₂ ), hexachlorodisilane (Si ₂ Cl ₆ ), tetrachlorosilane (SiCl ₄ ), trichlorosilane (SiHCl ₃ ), tetrakisdimethylaminosilane (Si [N (CH ₃ ) 2] ₄ ), trisdimethylaminosilane (Si [N (CH ₃ ) ₂ ] ₃ H), bisdiethylaminosilane (Si [N (C ₂ H ₅ ) ₂ ] ₂ H ₂ ), Bicester tertiary-butylamino silane _{(SiH 2 [NH (C 4} H 9)] 2) Aminoshira such _{System, Si (OC 2 H 5)} 4, SiH 2 Cl 2, Si (NO 3) 4 , and the like.

When obtaining a metal compound such as titanium oxide (TiO ₂ ), titanium nitride, and titanium carbonitride by the modification treatment, the first raw material is TiF ₄ , titanium tetrachloride (TiCl ₄ ), TiBr ₄ , TiI ₄ , tetrakisdimethylamino. Titanium ([(CH ₃ ) ₂ N] ₄ Ti), tetrakisdiethylamino titanium Ti [N (C ₂ H ₅ ) ₂ ] ₄ , Ti [N (C ₂ H ₅ CH ₃ )] ₄ , titanium (IV) isopropoxy (Ti [(OCH) (CH ₃ ) ₂ ] ₄ ).

When a metal compound such as zirconium oxide (ZrO ₂ ) is obtained by the modification treatment, the first raw materials are Zr (NO ₃ ) ₄ , ZrCl ₄ , tetrakisdimethylaminozirconium (IV) (Zr [(CH ₃ ) ₂ N]. ₄ ), tetrakis (ethylmethylamino) zirconium (IV) (Zr [N (CH ₃ ) CH ₂ CH ₃ ] ₄ ) and the like.
Also, the case of obtaining a metal compound such as zinc oxide (ZnO) by the reforming process, as the first raw material include zinc dichloride (ZnCl ₂₎ or the like.

As the second raw material, water (H ₂ O), oxygen, ozone (O ₃ ), methanol, ethanol, or the like can be used when the first raw material is oxidized. When nitriding the first raw material, nitrogen, ammonia (NH ₃ ) or the like can be used. These gases may be used in combination with hydrogen (H ₂₎ gas.

  When the functional layer is a gas barrier layer, the inorganic film contains at least one metal element of metal elements of Al, Ti, Si, Zr and Zn from the viewpoint of enhancing gas barrier properties. Preferably, the compound is formed using the first raw material. Thereby, even if the base film 1 is resin, a good quality inorganic film can be formed in a temperature range of 50 to 120 ° C.

From the same viewpoint, when the functional layer is a gas barrier layer, the inorganic film is made of aluminum oxide, titanium oxide, silicon oxide, zirconium oxide, zinc oxide, magnesium oxide (MgO), hafnium oxide (HfO ₂ ), lanthanum oxide. It is preferable to contain a metal oxide such as (La ₂ O ₃ ). Aluminum oxide and titanium oxide using trimethylaluminum, titanium tetrachloride or the like as the first raw material are particularly preferable because the molecular weight is suitable for repairing film defects and the coverage is improved.
Further, by adjusting film forming conditions such as supply time of each source gas, film forming temperature, pressure during film forming, intermediate oxides such as AlO _x , TiO _x , SiO _x , and ZrO _x , intermediate nitrides Can also be used as a material for the gas barrier layer, and may be used as necessary.

The supply time of the first raw material is preferably in the range of 0.05 to 10.00 seconds, more preferably in the range of 0.1 to 3.0 seconds, and 0.5 to 2.0. More preferably, it is in the range of seconds.
If the supply time is within the above range, the first raw material can be adsorbed to the surface of the base film 1 sufficiently and sufficiently.

The treatment time for the reforming treatment is preferably in the range of 0.05 to 10.00 seconds, more preferably in the range of 0.1 to 3.0 seconds, and 0.5 to 2.0. More preferably, it is in the range of seconds.
If the treatment time is within the above range, the second raw material can be subjected to a necessary and sufficient reforming reaction with the first raw material on the base film 1.

The temperature of the base film 1 when the inorganic film is formed by the raw material supply units 21 and 22 and the modification processing unit 23 is preferably 350 ° C. or less, more preferably 250 ° C. or less, and 150 ° C. or less. Is more preferable, and it is especially preferable that it is 120 degrees C or less.
If the temperature of the base film 1 is 350 ° C. or lower, the heat resistance required for the base film 1 may be 350 ° C. or lower, and the manufacturing cost of the base film 1 can be reduced.

The purge unit 24 supplies an inert gas into the chamber C4 and exhausts and removes the excess first raw material or second raw material on the base film 1 together with the inert gas.
The inert gas refers to a gas having low reactivity with the first raw material or the second raw material. As the inert gas that can be used, for example, a rare gas or the like can be used. If the reactivity with the first raw material or the second raw material is low, nitrogen gas or the like can also be used.

The inert gas introduction time for purging the first raw material and the second raw material is preferably in the range of 0.05 to 10.00 seconds, and in the range of 0.5 to 6.0 seconds. It is preferable that it is in the range of 1 to 4 seconds.
If the introduction time is within the above range, the excessive first raw material and second raw material can be removed sufficiently and sufficiently.

The first film forming unit A1 supplies a first raw material onto the base film 1 by the raw material supply unit 21, and then supplies a second raw material from the raw material supply unit 22 to react with the first raw material for one cycle. By carrying out, one atomic layer of an inorganic film can be formed on the base film 1.
In order to repeat the film forming process for a plurality of cycles until the target film thickness is obtained, the plurality of rollers 12 are arranged to repeatedly convey the long base film 1 to the two raw material supply units 21 and 22 alternately. ing.

  According to the configuration of the first film forming portion A1 shown in FIG. 1, the inorganic film is formed on both surfaces of the base film 1, but the inorganic film is formed only on one surface of the base film 1 by the first film forming portion A1. You may do it. For example, by transporting the base film 1 as a belt transport instead of a roller transport, by repeatedly arranging the raw material supply unit 21, the reforming processing unit 23, the raw material supply unit 22, and the reforming processing unit 23 on the transport path in this order, An inorganic film can be formed only on one side.

2nd film-forming part A2 protects between the inorganic film and the base film 1 which faced between the inorganic film and the inorganic film which face in the roll body by which the base film 1 in which the inorganic film was formed was wound up A protective layer is formed on the inorganic film or the base film 1 so that the layer is positioned, and the coverage represented by the ratio of the area of the protective layer to the total area of the inorganic film is within a range of 5 to 98%. .
By the protective layer having a coverage of 5% or more, damage to the inorganic film due to contact between the inorganic films or between the inorganic film and the base film 1 can be sufficiently prevented. On the other hand, since the coverage of the protective layer is 98% or less, it is easy to remove the protective layer by the cleaning treatment, and it is possible to reduce the film load generated during the cleaning load and the cleaning processing.

  The second film forming portion A2 can form a protective layer having a pattern in which the coverage of the protective layer is in the range of 5 to 98%. The coverage can be easily adjusted within the range of 5 to 98% by changing the pattern.

  In particular, when the coverage of the protective layer of the pattern is in the range of 30 to 80%, the contact area of the front and back when the roll body is made is reduced as compared with the case where the coverage of the protective layer is 100%. be able to. Further, even when the base film 1 is slightly deformed by the winding tension, contact between the inorganic films or contact between the inorganic film and the base film 1 can be easily avoided. Furthermore, in the cleaning process of the protective layer, the cleaning liquid, the cleaning member, and the like are likely to enter the interface between the inorganic layer and the protective layer from a region not covered with the protective layer, and the cleaning property is improved.

FIG. 2 shows patterns 101 to 105, which are examples of protective layer patterns that can be used.
As shown in FIG. 2, the pattern 101 is a stripe pattern, the pattern 102 is a lattice pattern, and the pattern 103 is a polka dot pattern. The pattern 104 is an AM (Amplitude Modulation) screen pattern, and the pattern 105 is an FM (Frequency Modulation) screen pattern. In the AM screen pattern 104, a collection of dots (dots) having the same area is periodically arranged, and in the FM screen pattern 105, dots having the same area are arranged aperiodically.

  In order to adjust the coverage of the protective layer within the range of 5 to 98%, in the case of the stripe pattern 101 and the lattice pattern 102, the line width, the line period, and the like may be adjusted. In the case of the polka dot pattern 103, the diameter or density of the polka dots may be adjusted. In the case of the AM screen pattern 104, the size of the halftone dots, the number of screen lines, etc. may be adjusted, and in the case of the FM screen pattern 105, the dot density may be adjusted.

FIG. 3 shows an AM screen pattern 104 and an FM screen pattern 105 with different coverages in the range of 5 to 98%.
In the case of patterning with dots as in the AM screen and FM screen, the cleaning property of the protective layer is improved as the diameter of the aggregate formed by adjoining the dots is smaller. In the case of an AM screen, the diameter of the aggregate can be reduced even with the same coverage by increasing the number of screen lines. In the case of an FM screen, the diameter of the aggregate can be reduced even with the same coverage by increasing the frequency of dots.

When the roll body of the functional film F obtained by the winder 15 is unrolled and expanded under the atmospheric pressure, the protective layer formed by the second film forming unit A2 is based on the total area of the formed protective layer. The residual ratio represented by the ratio of the area of the protective layer remaining on the developed functional film F is preferably in the range of 98 to 100%.
If the residual ratio is 98 to 100%, the protective layer is hardly peeled off during unwinding, and the inorganic film can be sufficiently protected.

The residual ratio of the protective layer can be within the above range by adjusting the thickness of the protective layer.
Usually, the thicker the protective layer, the easier it is to peel off. Since the ease of peeling varies depending on the adhesion between the inorganic film and the protective layer, the thickness of the protective layer may be determined when the remaining ratio of the protective layer falls within the range of 98 to 100% according to the adhesion. .

As a material for the protective layer, a carbon-containing polymer is preferable, and a curable resin is particularly preferable. The curable resin is not particularly limited, and examples thereof include an active energy ray curable resin, a thermosetting resin, and the like, but an active energy ray curable resin is preferable because it is easy to mold.
The active energy ray-curable resin refers to a resin that is cured through a crosslinking reaction or the like by irradiation with active energy rays such as ultraviolet rays and electron beams. Typical examples of the active energy ray curable resin include an ultraviolet curable resin and an electron beam curable resin, and among them, an electron beam curable resin is preferable.

  Examples of the active energy ray-curable resin that can be used include a composition containing an acrylate compound, a composition containing an acrylate compound and a mercapto compound containing a thiol group, epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, Examples include compositions containing polyfunctional acrylate monomers such as polyethylene glycol acrylate and glycerol methacrylate. Specifically, curable bifunctional acrylate NK ester A-DCP (tricyclodecane dimethanol diacrylate) from Shin-Nakamura Chemical Co., Ltd., UV curable organic / inorganic hybrid hard coat material OPSTAR (registered by JSR Corporation) Trademark) series (compounds obtained by bonding an organic compound having a polymerizable unsaturated group to silica fine particles) and the like can be used.

It is also possible to use any mixture of the above-mentioned compositions, and an active energy ray-curable material containing a reactive monomer having at least one photopolymerizable unsaturated bond in the molecule. If there is no restriction in particular.
Examples of reactive monomers having at least one photopolymerizable unsaturated bond in the molecule include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, and n-pentyl. Acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, dicyclo Pentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycy Acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, phenoxyethyl acrylate, stearyl acrylate, Ethylene glycol diacrylate, diethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexadiol diacrylate, 1,3-propanediol acrylate, 1,4-cyclohexanediol Diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate, tripropylene Glycol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, polyoxyethyltrimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethylene oxide modified pentaerythritol triacrylate, ethylene oxide modified pentaerythritol tetraacrylate, propylene Oxide modified pentaerythritol triacrylate, propylene oxide modified pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyoxypropyltrimethylolpropane triacrylate, butylene glycol diacrylate, 1,2,4-butanediol triacrylate, 2,2, 4-to Limethyl-1,3-pentadiol diacrylate, diallyl fumarate, 1,10-decanediol dimethyl acrylate, pentaerythritol hexaacrylate, and acrylate replaced with methacrylate, γ-methacryloxypropyltrimethoxysilane, Examples thereof include 1-vinyl-2-pyrrolidone and the like. Said reactive monomer can be used as a 1 type, or 2 or more types of mixture, and can also be used as a mixture with another compound.

The composition containing the active energy ray-curable resin preferably contains a photopolymerization initiator.
Examples of the photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone, α-amino acetophenone, 4,4-dichlorobenzophenone. 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert -Butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethyl ketal, benzylmethoxyethyl acetal, benzoin Tyl ether, benzoin butyl ether, anthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, 4-azidobenzylacetophenone, 2,6-bis (p-azidobenzylidene ) Cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- ( o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxime Michler's ketone, 2-methyl [4- (methylthio) phenyl] -2-monoforino-1-propane, 2-benzyl-2-dimethylamino-1- (4-monoforinophenyl) -butanone-1, naphthalenesulfonyl chloride, Quinolinesulfonyl chloride, n-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabromide, tribromophenylsulfone, benzoin peroxide, Examples include a combination of a photoreducible pigment such as eosin and methylene blue and a reducing agent such as ascorbic acid and triethanolamine. These photopolymerization initiators can be used alone or in combination of two or more.

  Specific examples of thermosetting materials include TutProm Series (Organic Polysilazane) manufactured by Clariant, SP COAT heat-resistant clear paint manufactured by Ceramic Coat, Nanohybrid Silicone manufactured by Adeka, Unicom manufactured by DIC, Inc. Dick (registered trademark) V-8000 series, EPICLON (registered trademark) EXA-4710 (ultra-high heat resistant epoxy resin), silicon resin X-12-2400 manufactured by Shin-Etsu Chemical Co., Ltd., inorganic manufactured by Nitto Boseki Co., Ltd. Organic nanocomposite material SSG coat, thermosetting urethane resin composed of acrylic polyol and isocyanate prepolymer, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicon resin, polyamidoamine-epichlorohydrin resin, etc. That.

  Solvents that can be used to dissolve or disperse the curable resin during the preparation of the curable resin coating solution include alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, and propylene glycol, α- or Terpenes such as β-terpineol, etc., ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone and 4-heptanone, and aromatic carbonization such as toluene, xylene and tetramethylbenzene Hydrogen, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropiate Glycol ethers such as lenglycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, Acetic esters such as ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-methoxyethyl acetate, cyclohexyl acetate, 2-ethoxyethyl acetate, 3-methoxybutyl acetate, diethylene glycol Dialkyl ether, dipropylene glycol Alkyl ethers, ethyl 3-ethoxypropionate, methyl benzoate, N, N- dimethylacetamide, N, may be mentioned N- dimethylformamide.

  From the viewpoint of improving the film formability and preventing the occurrence of pinholes, it is possible to use additives such as thermoplastic resins, antioxidants, ultraviolet absorbers, and plasticizers together with the curable resin in the formation of the protective layer. it can. Examples of the thermoplastic resin include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose, and methylcellulose, vinyl acetate or a copolymer thereof, vinyl chloride or a copolymer thereof, vinylidene chloride or a vinyl such as a copolymer thereof, and the like. Examples thereof include resins, acetal resins such as polyvinyl formal and polyvinyl butyral, acrylic resins or copolymers thereof, acrylic resins such as methacrylic resins or copolymers thereof, polystyrene resins, polyamide resins, linear polyester resins, and polycarbonate resins.

  The second film forming unit A2 includes a protective layer positioned between the inorganic film facing each other or the inorganic film facing the base film 1 in the roll body in which the base film 1 is wound by the winder 15. In order to form, a protective layer can be formed on the inorganic film formed by 1st film-forming part A1, or the surface on the opposite side to the surface of the base film 1 in which the said inorganic film was formed.

When forming the protective layer using the curable resin, the second film forming unit A2 can include a coating device 251 and a curing device 252 as shown in FIG.
According to 1st film-forming part A1, since an inorganic film is formed on both surfaces of the base film 1, in FIG. 1, when the base film 1 is wound up, it protects only on the inorganic film of the surface located inside. One set of coating device 251 and curing device 252 are arranged to form the layers. Not only such an arrangement example but also two sets of coating device 251 and curing device 252 face each other with the base film 1 interposed therebetween so as to form a protective layer on any of the inorganic films respectively formed on both sides. It may be arranged as follows.
Moreover, when an inorganic film is formed only on one surface of the base film 1 by the first film forming unit A1, the coating device 251 and the curing device 252 are opposite to the surface of the base film 1 on which the inorganic film is formed. It may be arranged so as to form a protective layer on the surface.

The coating device 251 forms a coating film containing a curable resin.
The formation method of the coating film containing the curable resin is not particularly limited, and the curable resin may be formed by a wet coating method such as a spin coating method, a spray method, or a blade coating method, a dry coating method such as a vapor deposition method, or a flash deposition method. The method of apply | coating the coating liquid containing this is mentioned.
From the viewpoint of improving productivity, it is possible to form a protective layer under vacuum pressure using a coating method capable of forming a film under vacuum pressure, such as a spray method, in succession to the formation of the inorganic film under vacuum pressure. preferable. Among the spray methods, an ultrasonic spray method or an electrospray method is preferable.

The ultrasonic spray method is a method in which a liquid film in an ultrasonic spray nozzle (atomizer) is vibrated by piezoceramic to form fine particles and spray them. Liquid can be formed into particles without applying pressure, and fine curable resin particles can be sprayed.
The electrospray method uses a phenomenon in which a liquid in a container is sprayed by electric field concentration by applying a high voltage to the container having a sharp tip. Also called an electrospray deposition method (ESD method), nano-sized curable resin particles can be deposited and fixed on the base film 1 using electrostatic force.
As described above, the ultrasonic spray method and the electrospray method are preferable because a solvent is not required for forming the coating film of the protective layer and a denser coating film can be formed under vacuum conditions.

Does the curing device 252 irradiate the coating film of the curable resin formed by the coating device 251 with active energy rays such as visible rays, infrared rays, ultraviolet rays, X rays, α rays, β rays, γ rays, and electron beams? The curable resin is cured by heating.
In the case of irradiating with ultraviolet rays, as the curing device 252, an ultra high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a metal halide lamp, or the like is used, preferably 100 to 400 nm, more preferably 200 to 400 nm. To do. When irradiating an electron beam, it is preferable to irradiate an electron beam having a wavelength region of 100 nm or less using a scanning or curtain type electron beam accelerator as the curing device 252. It is preferable to irradiate an electron beam as an active energy ray from the viewpoint of ease of device design and improvement of the barrier property of the film.

  When forming the protective layer of a pattern, the coating film of a protective layer can be patterned by arrange | positioning the several coating device 251 along with the direction orthogonal to the conveyance direction of the base film 1. FIG. Moreover, the coating film of a protective layer can also be patterned by arrange | positioning a mask between the coating device 251 and the base film 1. FIG.

  The functional film manufacturing apparatus A unwinds and unfolds the roll body of the functional film F obtained by the winder 15 under atmospheric pressure, cleans the unfolded functional film, A cleaning processing unit for removing the protective layer formed by the film forming unit A2 can be further provided.

Examples of the cleaning method that can be used by the cleaning processing unit include a dry cleaning method, a wet cleaning method, and a physical peeling method.
Examples of the dry cleaning method include a plasma cleaning method, an ion beam cleaning method, a UV ozone cleaning method, a UV excimer irradiation method, and a laser cleaning method.
The wet cleaning method is a method in which the functional film F is immersed in a cleaning liquid, for example, jet cleaning, bubbling cleaning, ultrasonic cleaning, or running water cleaning. As the cleaning liquid, an acidic, neutral or alkaline detergent solution or an organic solvent can be used.
The physical peeling method is a method in which a physical force is directly applied to the surface of the protective layer for cleaning, and examples thereof include scrub cleaning, shower cleaning, and ice blast cleaning. Since the physical peeling method directly acts on the surface of the protective layer, its cleaning power is extremely high and the processing time is short.

  Specific scrub cleaning methods include a scrub roller having a sponge or brush provided on the entire surface of a metal or plastic roller, and a disc-shaped scrub having a brush or sponge provided on the contact surface with the protective layer. The method of contacting a protective layer while rotating a pad etc. is mentioned. Other scrub cleaning methods include, for example, Japanese Patent No. 4554367, International Patent Publication No. 2009/031401, Japanese Patent Application Laid-Open No. 2009-117765, Japanese Patent Application Publication No. 2010-286632, Japanese Patent Application Publication No. 2011-018668, and Japanese Patent Application Publication No. 2011-040653. The method described in JP 2011-066386 A can be referred to.

Examples of shower cleaning include high-pressure spray cleaning, ultrasonic shower cleaning, and two-fluid nozzle cleaning.
High-pressure spray cleaning is a method of spraying high-pressure water, cleaning liquid, or the like in a jet state using a spray mechanism such as a nozzle.
The ultrasonic shower cleaning is a method of showering a cleaning liquid that is vibrated ultrasonically by an ultrasonic vibration element.
The two-fluid nozzle cleaning method is a method in which two kinds of fluids, for example, water and air, cleaning agent and air, and the like are caused to associate at a nozzle portion and jetted in a jet state.

Examples of ice blast cleaning include micro ice jet and dry ice scrub cleaning.
The micro ice jet method accelerates and sends out compressed air at supersonic speed, adiabatically expands during acceleration, and supplies water when the temperature drops to produce supercooled fine ice particles that contain the ice particles. This is a method of cleaning by blowing air. It is also possible to create dry ice particles instead of ice particles and to blow air containing the dry ice particles.

FIG. 4 shows a schematic configuration of a cleaning processing unit A3 included in the manufacturing apparatus A when scrub cleaning is performed.
As shown in FIG. 4, the cleaning processing unit A3 includes a first cleaning unit 261, a second cleaning unit 262, and a drying unit 263. The cleaning unit A3 is placed under atmospheric pressure.
The cleaning processing unit A3 includes an unwinder 271 and a plurality of rollers 273 for transporting the functional film F.

  At the time of the cleaning process, the roll body of the functional film F obtained by being wound by the winder 15 shown in FIG. 1 is set in the unwinder 271 shown in FIG. When the unwinder 271 unwinds the roll body, the plurality of rollers 273 sequentially convey the developed functional film F to the first cleaning unit 261, the second cleaning unit 262, and the drying unit 263. The functional film F that has passed through the drying unit 263 is preferably transported continuously in order to shift to a process (not shown) such as a sealing process for various electronic devices.

The first cleaning unit 261 includes a cleaning tank to which a cleaning liquid is supplied. The functional film F is immersed in the cleaning liquid of this cleaning tank by the roller 273. The first cleaning unit 261 causes the scrub roller 26r rotated in the rotation direction indicated by the arrow in the cleaning liquid to contact the protective layer of the functional film F, and the protective layer is caused by friction between the roller surface of the scrub roller 26r and the protective layer. Is removed from the inorganic film.
In order to prevent damage to the inorganic film during the cleaning process, it is preferable that a non-contact type roller capable of transporting the functional film F without contact with the inorganic film is disposed as the roller 273 used in the cleaning tank. Examples of the non-contact type roller include a roller provided with a step in the axial direction so that the end of the axial direction has a diameter shorter than that of the central portion.

  The second cleaning unit 262 rinses the functional film F from which the protective layer has been removed by the first cleaning unit 261 with water, and rinses the cleaning liquid adhering to the first cleaning unit 261. As shown in FIG. 4, the functional film F may be immersed in a water tank and washed, or water may be showered.

  The drying unit 263 blows air to dry the functional film F washed with water by the second cleaning unit 262.

[Manufacturing apparatus of other embodiment]
As described above, the inorganic film may be formed by a CVD method or a PVD method. The CVD method is not particularly limited, and examples thereof include a thermal CVD method, a plasma CVD method, and a photo CVD method. The PVD method is not particularly limited, and examples thereof include a vacuum deposition method, a sputtering method, and an ion plating method.

FIG. 5 shows a schematic configuration of the first film forming unit B1 when the vacuum deposition method is used.
As shown in FIG. 5, the first film forming unit B <b> 1 includes an unwinder 11, a winder 15, a plurality of rollers 12, and a film forming unit 4. In addition, the same code | symbol is attached | subjected to the same component as the manufacturing apparatus A shown in FIG.

The film forming unit 4 forms the functional layer as a thin film by a vacuum deposition method. As shown in FIG. 5, the film forming unit 4 includes a cooling roller 41, an electron gun 42, a gas supply unit 43, a plasma generator 44, and the like.
The film forming unit 4 generates argon plasma between the base film 1 and the target T conveyed by the cooling roller 41 and supplies a reforming gas from the gas supply unit 43. The film forming unit 4 irradiates the electron beam with the electron gun 42. The electron beam is guided by a magnetic field coil or the like (not shown) and is irradiated onto the target T. The target T is heated and evaporated by irradiation with the electron beam, is reformed by the plasma of the reforming gas, and is deposited on the base film 1.

[Method for producing functional film]
In the manufacturing apparatus A, the functional film F can be manufactured by a procedure including the following first film forming process and second film forming process.

[First film formation step]
In the first film forming step, an inorganic film is formed on the base film 1.
First, the roll body of the base film 1 is unwound by the unwinder 11, and the base film 1 is conveyed to the raw material supply unit 21 by each roller 12. The raw material supply unit 21 supplies the gaseous first raw material into the chamber C1. The first raw material is adsorbed on the surface of the base film 1 in the chamber C1.
Next, the base film 1 on which the first raw material is adsorbed is conveyed to the purge unit 24, and an inert gas is supplied by the purge unit 24 to remove excess first raw material from the base film 1.

After removing the first raw material, the base film 1 is conveyed to the modification processing unit 23. The reforming processing unit 23 supplies a reforming gas into the chamber C3 and applies an AC voltage to the reforming gas to generate plasma P. The first raw material adsorbed on the surface of the base film 1 is modified by the plasma P to form an inorganic film.
The base film 1 after the modification treatment is conveyed to the purge unit 24, and the purge unit 24 supplies an inert gas to remove the active gas.
When the raw materials supplied by the raw material supply units 21 and 22 are the same, the above is the procedure of the film forming process of one cycle.

  Furthermore, the base film 1 is conveyed to the raw material supply part 22, and the first raw material is supplied into the chamber C2 by the raw material supply part 22. The first raw material is adsorbed on the surface of the base film 1 in the chamber C2. Next, the base film 1 is conveyed to the purge unit 24, and an inert gas is supplied by the purge unit 24 to remove excess first raw material from the base film 1.

After removing the first raw material, the base film 1 is conveyed to the modification processing unit 23. The reforming unit 23 supplies the reforming gas into the chamber C3, and generates plasma P by applying AC voltages having different frequencies to the reforming gas. The first raw material adsorbed on the surface of the base film 1 is modified by the plasma P to form an inorganic film.
When the raw materials supplied by the raw material supply units 21 and 22 are different, the above is the procedure of the film forming process of one cycle.
Thereafter, the base film 1 is conveyed again to the raw material supply unit 21 and the above-described procedure is repeated, whereby a plurality of cycles of film formation can be repeated, and a functional film F on which an inorganic film having a target film thickness is formed. Can be manufactured.

[Second film formation step]
In the second film forming step, the second film forming unit A2 forms a protective layer on the inorganic film formed by the first film forming unit A1. The second film forming part A2 is a protective layer between the facing inorganic film and the inorganic film or between the facing inorganic film and the base film in the roll body on which the base film 1 on which the inorganic film is formed is wound. So that the protective layer is formed on the inorganic film or the base film 1 and the coverage represented by the ratio of the area of the protective layer to the total area of the inorganic film is in the range of 5 to 98%. .

Specifically, the second film forming unit A2 forms a protective layer by applying a coating solution for the protective layer on the inorganic film using the coating device 251 and curing the coating film using the curing device 252.
The functional film F on which the protective layer is formed is wound up by the winder 15 to obtain a roll body of the functional film F.

[Washing process]
Furthermore, when removing the protective layer on the functional film F, the roll body of the functional film F obtained by the winder 15 is set in the unwinder 271 of the cleaning processing unit A3.
In the cleaning process, the cleaning processing unit A3 cleans the functional film F unrolled and unfolded by the unwinder 271 and removes the protective layer from the functional film F.
Specifically, the cleaning processing unit A3 removes the protective layer by the first cleaning unit 261, then rinses the functional film F by the second cleaning unit 262, and dries it by the drying unit 263.

[Functional film]
FIG. 6 shows a cross-sectional configuration of the functional film F obtained by the manufacturing apparatus A.
In the functional film F, as shown in FIG. 6, inorganic films are formed as functional layers 2 on both surfaces of the base film 1, and a protective layer 3 is provided on each functional layer 2.

[Base film]
The base film 1 is a base material for the functional film F and has flexibility.
As the base film 1, a film-like resin, glass, metal or the like can be used. Especially, resin is preferable and it is preferable that it is resin with high transparency. When the transparency of the resin is high and the transparency of the base film 1 is high, a functional film F with high transparency can be obtained and can be preferably used for an electronic device such as an organic EL (Electroluminescence) element.

Examples of the resin that can be used as the base film 1 include methacrylate ester, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polystyrene (PS), aromatic polyamide, and polyether ether. Ketone, polysulfone, polyethersulfone, polyimide (PI), polyetherimide and the like can be mentioned. Of these, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC) and the like are preferable from the viewpoint of cost and availability.
The base film 1 may be a laminated film in which two or more of the above resins are laminated.

  The resin base film 1 can be manufactured by a conventionally known general manufacturing method. For example, an unstretched resin base material that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching. In addition, by dissolving the resin used as a material in a solvent, casting (casting) it onto an endless metal resin support, drying, and peeling, an unstretched film that is substantially amorphous and not oriented is used as a base. It can be obtained as film 1.

  The unstretched film may be stretched in the film transport (MD) direction or the width (TD) direction orthogonal to the transport direction, and the resulting stretched film may be used as the base film 1. Examples of the stretching method include known methods such as uniaxial stretching, tenter sequential biaxial stretching, tenter simultaneous biaxial stretching, and tubular simultaneous biaxial stretching. Although a draw ratio can be suitably selected according to resin used as a raw material, both the conveyance direction and the width direction are preferably in the range of 2 to 10 times.

  The base film 1 may be the above-described unstretched film or a stretched film. A stretched film is preferable from the viewpoint of strength improvement and thermal expansion suppression. Since optical functions such as retardation of the base film 1 can be adjusted by stretching, it is preferable to use a stretched film when adjustment is necessary.

In order to obtain dimensional stability, the base film 1 may be subjected to relaxation treatment, off-line heat treatment, and the like.
The relaxation treatment is preferably carried out in the tenter extending in the width direction after the heat setting in the stretching step, or in the step up to winding after exiting the tenter. The relaxation treatment is preferably performed at a treatment temperature in the range of 80 to 200 ° C, and more preferably in the range of 100 to 180 ° C.
Although it does not specifically limit as a method of off-line heat processing, For example, the method of conveying by a plurality of roller groups, the air conveyance which blows and raises heated air to a film (specifically, heating air is supplied to one side of a film side from a plurality of slits. Or a method of spraying on both surfaces), a method of using radiant heat by an infrared heater, a conveying method of hanging the film under its own weight and winding it down. Good dimensional stability can be obtained by lowering the conveyance tension of the heat treatment as much as possible to promote thermal shrinkage. As the treatment temperature, a temperature range of (Tg + 50) to (Tg + 150) ° C. is preferable. Tg here refers to the glass transition temperature of the base film 1.

  The base film 1 preferably has a thickness in the range of 10 to 250 μm, and more preferably in the range of 20 to 100 μm.

On the base film 1, an intermediate layer located between the base film 1 and the functional layer 2 in the functional film F may be formed. The intermediate layer is formed in accordance with purposes such as enhancing adhesion with the functional layer 2, enhancing the smoothness of the base film 1, and suppressing a bleed-out phenomenon in which low molecular components in the base film 1 are deposited on the surface. Can be done.
For example, in order to improve the adhesion with the functional layer 2, the intermediate layer may be formed by applying a polysiloxane coating solution on the base film 1 and then modifying it by irradiation with vacuum ultraviolet light.
The material of the intermediate layer is not limited to the polysiloxane, and curable resins such as thermosetting resins and active energy ray curable resin curable resins can be used. Of these, active energy ray-curable resins are preferred because they are easy to mold.

The thermosetting resin is not particularly limited as long as it is cured by heat treatment, and examples thereof include phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyurethane, and thermosetting polyimide. .
The photocurable resin is not particularly limited as long as it is cured by light, a resin containing an acrylate compound having a radical reactive unsaturated bond, a resin containing an acrylate compound and a mercapto compound having a thiol group, an epoxy Examples thereof include resins containing polyfunctional acrylate monomers such as acrylate, urethane acrylate, polyester acrylate, polyether acrylate, polyethylene glycol acrylate, and glycerol methacrylate, “ORMOCER” described in US Pat. No. 6,503,634, and the like. Moreover, you may use the monomer which has one or more photopolymerizable unsaturated groups in a molecule | numerator.

(Functional layer)
The functional layer 2 is an inorganic film formed on the base film 1. Examples of the functional layer 2 include a gas barrier layer, an insulating layer, and a refractive layer having a refractive index difference with respect to the substrate of the electronic device. Among them, when the gas barrier layer has many film defects, gas such as water and oxygen penetrates through the film defect, and the gas barrier performance is remarkably deteriorated. Therefore, the manufacturing apparatus A with few film defects is formed with the gas barrier layer. It is suitable for.

When the functional layer 2 is a gas barrier layer, the gas barrier layer has a water vapor transmission rate (25 ± 0.5 ° C., relative humidity 90 ± 2%) measured by a method according to JIS-K-7129-1992. It is preferable that the gas barrier property of RH) is 0.01 g / (m ² · 24 hours) or less. Moreover, the oxygen permeability measured by the method based on JIS-K-7126-1987 is 1 × 10 ⁻³ ml / (m ² · 24 hours · atm) or less, and the water vapor permeability is 1 × 10 ^−5. It is preferable that the gas barrier property is not more than g / (m ² · 24 hours). The water vapor permeability can also be measured by the MOCON method, the calcium corrosion method described in JP-A-2005-283561, and the like.

The thickness of the functional layer 2 is not particularly limited, and an arbitrary thickness can be selected. In general, the thickness of the functional layer 2 is preferably in the range of 1 to 100 nm, preferably in the range of 5 to 70 nm, and preferably in the range of 10 to 60 nm.
If the thickness of the functional layer 2 is 1 nm or more, sufficient functionality can be obtained. Moreover, if the thickness of the functional layer 2 is 100 nm or less, the functional layer 2 can be formed in a short time. Moreover, the repair effect by the film-forming process of multiple cycles can be acquired.

[Protective layer]
The protective layer 3 is provided in order to prevent the inorganic films formed on both surfaces of the base film 1 from coming into contact with each other and being damaged during winding.
As a material of the protective layer 3, a curable resin can be used as described above.

  The smoothness of the protective layer 3 is a value expressed by the surface roughness specified in JIS B 0601: 2001, and the maximum cross-sectional height Rt (p) is preferably in the range of 1 to 80 nm. If it exists in this range, winding of the functional film F will become favorable. Moreover, it can prevent that the protective layer 3 contacts and damages the surface of the base film 1, the surface of an inorganic film, etc. which face the protective layer 3 when it is set as a roll body.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless there is particular notice, it represents "mass part" or "mass%".

[Manufacturing equipment K1]
In the manufacturing apparatus A shown in FIG. 1, a coating apparatus using an acrylic flash vapor deposition method is disposed as the coating apparatus 251 of the second film forming unit A2. Furthermore, the same coating apparatus was disposed so as to be positioned on the opposite side across the base film and the coating apparatus that was already disposed, and the manufacturing apparatus K1 was obtained.

[Manufacturing equipment K2]
In the manufacturing apparatus A shown in FIG. 1, the first film forming unit A1 using the PEALD method is replaced with the first film forming unit B1 using the vacuum vapor deposition method shown in FIG. It arrange | positioned as the coating device 251 of 2nd film-forming part A2. Furthermore, the same coating apparatus was disposed so as to be positioned on the opposite side across the base film and the coating apparatus that was already disposed, and the manufacturing apparatus K2 was obtained.

[Gas barrier film 1]
A polyester film MELINEX ST504 (DuPont Teijin Films US Limited) having a thickness of 125 μm was prepared as a base film. This polyester film is degassed for 3 hours by heating to 80 ° C. under a reduced pressure of 0.01 Torr.
Next, an aluminum oxide film having a thickness of 6 nm was formed as a gas barrier layer on the base film by the manufacturing apparatus K1, and the gas barrier film 1 was obtained.

Specific conditions for forming the aluminum oxide film are as follows.
(Deposition conditions)
First raw material of aluminum oxide film: trimethylaluminum First raw material supply time: 0.1 seconds Reforming gas: water vapor Reforming treatment time: 2.0 seconds Inert gas used for purging: nitrogen gas Purge time : 2.0 seconds Deposition rate of aluminum oxide film: 0.1 nm / cycle Base film transport speed: 8 m / min Base film temperature: 75 ° C

  Following the formation of the gas barrier layer, a protective layer having a stripe pattern was formed on the gas barrier layer in the manufacturing apparatus K1. Specifically, vapor obtained by vaporizing tripropylene glycol diacrylate was introduced onto the base film, and tripropylene glycol diacrylate molecules were deposited on the gas barrier layer to form a vapor deposition film. At this time, a vapor deposition film having a stripe pattern in which the coverage expressed by the ratio of the area of the protective layer to the total area of the gas barrier layer was 50% was formed using a mask. In addition, the final protective layer thickness was set to 2 μm by adjusting the time for introducing steam. Then, the protective layer of the stripe pattern was obtained by irradiating and hardening an electron beam to a vapor deposition film.

  The coverage of the protective layer was confirmed as follows. First, the film surface on which the protective layer was formed was photographed within an area of 100 μm square by an optical microscope to obtain an image of 400 × 400 pixels. This photographing is performed ten times while changing the photographing position, and each of the obtained ten images is analyzed to determine the ratio (%) of the number of pixels in the image area of the protective layer to the total number of pixels of each image, and the average value thereof Was determined as the coverage of the protective layer.

The gas barrier film 1 obtained by forming the protective layer was wound up in the production apparatus K1 to obtain the roll body.
Next, the roll body was unwound under atmospheric pressure to develop the gas barrier film 1, and the ratio of the area of the protective layer to the total area of the gas barrier layer was determined as the coverage (%) after development. From the coverage after the development and the coverage confirmed before the development, the residual ratio (%) represented by the ratio of the area of the protective layer remaining on the gas barrier film 1 after the development is obtained by the following formula. As a result, it was 99% or more.
Residual rate (%) = (coverage before development) / (coverage after development) × 100

[Gas barrier film 2-5]
In the production of the gas barrier film 1, the mask used for forming the protective layer was changed, and the coverage and pattern of the protective layer were changed as shown in Table 1 below. Thus, gas barrier films 2 to 4 were produced.
FIG. 7 shows patterns of stripes with a coverage of 50%, polka dots, AM screens and FM screens, lattices with a coverage of 44%, and FM screens with a coverage of 5% shown in Table 1 below.
When the residual rate of the protective layer of each gas barrier film 2-4 was calculated | required, it was 99% or more similarly to the gas barrier film 1. FIG.

[Gas barrier film 6-9]
Each gas barrier film was manufactured in the same manner as the gas barrier film 5 except that in the production of the gas barrier film 5, the FM screen pattern was changed and the coverage of the protective layer was changed as shown in Table 1 below. 6-9 were produced.
When the residual ratio of the protective layer of each of the gas barrier films 6 to 9 was determined, it was 99% or more as with the gas barrier film 1.

[Gas barrier film 10]
In the production of the gas barrier film 3, the gas barrier property is the same except that the coating device using the acrylic flash vapor deposition method of the manufacturing device K 1 is replaced with the coating device using the printing method and the protective layer is formed by the printing method. In the same manner as the film 3, a gas barrier film 10 was produced.
When the residual ratio of the protective layer of the gas barrier film 10 was determined, it was 99% or more as with the gas barrier film 1.

[Gas barrier films 11 and 12]
In the production of the gas barrier film 4, the gas barrier film 11 was similarly prepared except that the vapor introduction time was adjusted to form protective layers having final film thicknesses of 2.5 μm and 5.0 μm, respectively. And 12 were created.
When the residual ratio of the protective layer of each gas barrier film 11 and 12 was determined, it was 98% and 90%, respectively.

[Gas barrier film 13]
On the same base film as the gas barrier film 1, an aluminum oxide film having a thickness of 10 nm was formed as a gas barrier layer using the manufacturing apparatus K2.
Specific conditions for forming the aluminum oxide film are as follows.
(Deposition conditions)
Target: Aluminum
Reforming gas: Oxygen gas Plasma generating gas: Argon gas Gas supply amount: Supply so that the flow volume ratio of oxygen gas and argon gas is 9: 1 Plasma output: 1500 W

Following the formation of the gas barrier layer, an FM screen pattern protective layer having a coverage of 50% was formed on the gas barrier layer in the production apparatus K2. The protective layer was formed in the same manner as the gas barrier film 5. The gas barrier film 13 obtained by forming the protective layer was wound up in the production apparatus K2 to obtain the roll body.
When the residual ratio of the protective layer of the gas barrier film 13 was determined, it was 99% or more as with the gas barrier film 1.

[Gas barrier film 31]
In the production of the gas barrier film 1, a gas barrier film 31 was produced in the same manner as the gas barrier film 1 except that no protective layer was formed.

[Gas barrier films 32 and 33]
In the production of the gas barrier film 1, a gas barrier film 32 was produced in the same manner as the gas barrier film 5 except that an FM screen protective layer having a coverage of 4% was formed.
Further, in the production of the gas barrier film 1, the gas barrier film 33 is formed in the same manner as the gas barrier film 1 except that a covering ratio is 100%, that is, a protective layer covering the entire surface of the aluminum oxide film is formed. Manufactured.
When the residual ratio of the protective layer of each gas barrier film 32 and 33 was determined, it was 99% or more as with the gas barrier film 1.

[Gas barrier film 34]
In the production of the gas barrier film 33, a protective layer having a coverage of 100% was formed only on the gas barrier layer formed on the first surface of the two gas barrier layers formed on both surfaces of the base film. Except for this, each gas barrier film 34 was produced in the same manner as the gas barrier film 33. "The 1st surface of a base film" is a surface located inside when it is set as a roll body.
When the residual ratio of the protective layer of the gas barrier film 34 was determined, it was 99% or more as with the gas barrier film 1.

[Gas barrier films 35 and 36]
In the same manner as the gas barrier film 1, gas barrier layers are formed on both surfaces of the base film, and then a protective film is disposed only on the gas barrier layer formed on the first surface of the base film and wound up. A roll body of the barrier film 35 was obtained. As a protective film, Sanitect PAC-3-30 (manufactured by Sanei Kaken Co., Ltd.), which is a polypropylene film having a thickness of 30 μm, was used.
Similarly, a protective film was disposed and wound only on the gas barrier layer formed on the second surface instead of the first surface of the base film, and a roll body of the gas barrier film 36 was obtained.
The “first surface of the base film” is a surface positioned on the inner side when the roll body is formed, and the “second surface of the base film” is a surface positioned on the outer side when the roll body is formed.

[Evaluation]
(Rewindability)
The roll body of each gas barrier film 1-13, 31-36 was unwound and observed visually, and the winding property was evaluated according to the following criteria.
5: No turbulence, no wrinkles, and good winding. 4: No creases are observed, but no more than 1 mm of turbulence is observed at both ends in the width direction of the film. 3: No creases are observed. Disturbances of about several mm were observed at both ends in the width direction of the film 2: Slight winding wrinkles and disturbances of about several mm were observed at both ends of the film in the width direction 1: Clear wrinkles and large windings Disturbance was observed

(Cleanability)
The gas barrier films 1 to 13 and 32 to 34 provided with the protective layer were subjected to a cleaning treatment for 60 seconds under the following cleaning conditions to remove the protective layer. For the cleaning treatment, a dry ice snow precision cleaning system QuickSnow QS-1001 (manufactured by Air Water) was used.
(Cleaning conditions)
Cleaning method: Dry ice scrub cleaning method Inclined surface angle of gas outlet: 25 °
Shape of gas outlet: φ1.6mm long hole structure Dry ice snow distribution pipe outer diameter: φ1.6mm
Commutating gas supply pressure: 0.45 MPaG
Liquefied carbon dioxide supply pressure: 7.0 MPaG

The degree of removal of the protective layer by washing treatment was evaluated as washing suitability according to the following criteria.
5: All protective layers were easily removed within 5 seconds 4: All protective layers were removed within 15 seconds 3: All protective layers were removed within 60 seconds 2: Before cleaning The protective layer whose ratio of the area to the total area of the protective layer is 5% or more remains 1: The protective layer whose ratio of the area to the total area of the protective layer before the cleaning treatment is 30% or more remains The remaining protective layer The area ratio was determined in the same manner as the coverage.

(Gas barrier properties)
The water vapor permeability of each of the gas barrier films 1 to 13 and 31 to 36 was measured using a water vapor transmission rate measuring device PERMATRAN-W (manufactured by MOCON). The measurement was performed in an environment of a temperature of 38 ° C. and a relative humidity of 90% RH.
Based on the measured water vapor permeability, the gas barrier properties of the gas barrier films 1 to 13 and 31 to 36 were evaluated according to the following criteria.
5: water vapor permeability is less than 0.05g ^/ m 2 · day 4: water vapor permeability, 0.05g ^/ m 2 · day or more and less than 0.10g ^/ m 2 · day 3: water vapor permeability The degree is 0.10 g / m ² · day or more and less than 1.00 g / m ² · day 2: The water vapor permeability is 1.00 g / m ² · day or more and less than 5.00 g / m ² · day 1: Water vapor permeability is 5.00 g / m ² · day or more

Table 1 below shows the evaluation results.

As shown in Table 1 above, according to the gas barrier films 1 to 13 according to the examples of the present invention, since a high gas barrier property is obtained, a protective layer with a coverage of 5% or more is formed. This indicates that the gas barrier layer was sufficiently protected. Moreover, favorable winding-up property is obtained by formation of the protective layer. If the protective layer has a coverage of 98% or less, it can be easily removed by a cleaning treatment, so that a good cleaning property is obtained.
On the other hand, according to the gas barrier films 31 to 36 according to the comparative examples, if there is no protective layer or the coverage is less than 5% even if there is a protective layer, the winding property is low and the gas barrier property is also low. . In addition, since the protective layer with a coverage of 100% is not easily removed by a cleaning process, the cleaning suitability is low.

A Manufacturing apparatus A1 First film forming unit 21, 22 Raw material supply unit 23 Modification processing unit 231 Electrode 24 Purge unit C1 to C4 Chamber A2 Second film forming unit 251 Coating device 252 Curing device A3 Cleaning processing unit 261 First cleaning unit 26r Scrub roller 262 Second cleaning unit 263 Drying unit F Functional film 1 Base film 2 Functional layer 3 Protective layer

Claims (14)

A functional film manufacturing apparatus for forming and winding an inorganic film as a functional layer on a long base film,
A first film forming unit that forms the inorganic film on the base film;
In the roll body in which the base film on which the inorganic film is formed is wound, the inorganic film is disposed such that a protective layer is located between the facing inorganic film and the inorganic film or between the facing inorganic film and the base film. The second film is formed by forming the protective layer on the film or the base film and having a coverage expressed by the ratio of the area of the protective layer to the total area of the inorganic film within a range of 5 to 98%. And
An apparatus for producing a functional film, comprising:   The second film forming unit forms the protective layer on the inorganic film formed in the first film forming unit or on the surface opposite to the surface of the base film on which the inorganic film is formed. The apparatus for producing a functional film according to claim 1. The first film forming unit forms the inorganic film under a vacuum pressure,
3. The functionality according to claim 1, wherein the second film forming unit forms the protective layer under a vacuum pressure in succession to the formation of the inorganic film by the first film forming unit. Film production equipment.   The said 2nd film-forming part forms the protective layer of the pattern in which the coverage of the said protective layer exists in the range of 5-98%, It is any one of Claim 1 to 3 characterized by the above-mentioned. The functional film manufacturing apparatus described.   The total area of the protective layer formed by the second film forming unit is expressed as a ratio of the area of the protective layer remaining on the functional film developed by unwinding the roll body under atmospheric pressure. The functional film manufacturing apparatus according to any one of claims 1 to 4, wherein the remaining rate is in a range of 98 to 100%.   The apparatus for producing a functional film according to claim 5, further comprising a cleaning processing unit that cleans the developed functional film and removes the protective layer under atmospheric pressure.   The said 1st film-forming part forms the said inorganic film by an atomic layer deposition method, The manufacturing apparatus of the functional film as described in any one of Claim 1- Claim 6 characterized by the above-mentioned. A method for producing a functional film that forms and winds an inorganic film on a long base film as a functional layer,
A first film forming step of forming the inorganic film on the base film;
In the roll body in which the base film on which the inorganic film is formed is wound, the inorganic film is disposed such that a protective layer is located between the facing inorganic film and the inorganic film or between the facing inorganic film and the base film. The second film is formed by forming the protective layer on the film or the base film and having a coverage expressed by the ratio of the area of the protective layer to the total area of the inorganic film within a range of 5 to 98%. Process,
A method for producing a functional film, comprising:   In the second film forming step, the protective layer is formed on the inorganic film formed in the first film forming step or on the surface opposite to the surface of the base film on which the inorganic film is formed. The method for producing a functional film according to claim 8. In the first film forming step, the inorganic film is formed under a vacuum pressure,
The function according to claim 8 or 9, wherein, in the second film formation step, the protective layer is formed under vacuum pressure continuously with the formation of the inorganic film in the first film formation step. For producing a conductive film.   The said 2nd film-forming process forms the protective layer of the pattern in which the coverage of the said protective layer exists in the range of 5-98%, It is any one of Claim 8-10 characterized by the above-mentioned. The manufacturing method of the functional film of description.   The total area of the protective layer formed in the second film formation step is expressed as a ratio of the area of the protective layer remaining on the functional film unrolled and unrolled at atmospheric pressure. The method for producing a functional film according to any one of claims 8 to 11, wherein the remaining ratio is in a range of 98 to 100%.   The method for producing a functional film according to claim 12, further comprising a cleaning step of cleaning the developed functional film under atmospheric pressure to remove the protective layer.   The method for producing a functional film according to claim 8, wherein in the first film formation step, the inorganic film is formed by an atomic layer deposition method.