JP2008280569A - Vacuum film deposition system, and stacked body film-deposited using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a roll to roll type system capable of performing stable vacuum film deposition for a long time and at high speed to a substrate or a base material. <P>SOLUTION: During film deposition in the main chamber 11, a first roller unit 1402 elevates, and a state where a web 23 is stored in a first sub chamber 10 in a first film length regulation mechanism 14 is made. At the same time when it reaches the end of a material set in a delivery roller 1, a first load lock roller 2 is closed, and the web 23 is made into a stationary state between the delivery roller 1 and the first load lock roller 2, and the state of zero speed is made. Simultaneously with this, a dancer roller head 28 lowers to the lower part of the first sub chamber 10 in accordance with the carrying rate of the web 23, and the web 23 stored in the first sub chamber 10 is carried to the main chamber 11, and a state where film deposition is continued is made. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a vacuum film forming apparatus and a laminate formed using the vacuum film forming apparatus.

A large area vacuum film forming apparatus has a wide variety of film forming means such as sputtering, CVD, plasma CVD, electron beam evaporation, ion plating, cluster ion beam, and evaporation. 2. Description of the Related Art Generally, large-area vacuum film forming apparatuses include a batch type film forming apparatus that forms a film while conveying a glass substrate and a roll-to-roll type film forming apparatus that forms a film on a plastic film. In addition, there is a film forming apparatus in which a plastic film, a glass substrate, a plastic plate, a metal plate, or the like is set on a rotating body, and after sputtering in a metal mode, oxidation or nitridation is performed in a radical bath.
In these large area vacuum film forming apparatuses, a long run that is stable for a long time is required. This is because the object of film formation is building glass or plastic film, and it is important how fast and how stable the film can be formed without stopping the machine.

In the case of a roll-to-roll type vacuum film formation apparatus, after film formation is completed on one original fabric, the entire film formation apparatus is opened to the atmosphere and the original fabric is reset, or the unwinding original fabric The chamber in which the take-up web is installed and the film formation chamber are separated by a load lock, and after the film formation of one film is completed, the film formation chamber is kept in a vacuum by the load lock. This is one of the methods of reopening only the chamber that has been set to the atmosphere and resetting the original fabric. In the former method, the film formation chamber becomes the atmosphere every time film formation of one original fabric is completed. In this case, there is a problem that the film attached to the wall surface and the deposition prevention plate is peeled off and the deposition chamber is contaminated, and it is complicated because a simple cleaning of the interior of the chamber is required such as replacement of the deposition protection plate after release to the atmosphere. Further, even when a load lock is used, the atmosphere must be released and evacuated in order to remove the original fabric, resulting in time loss. In addition, even when the film formation chamber is not opened to the atmosphere, in the case of vacuum film formation using plasma such as sputtering, the temperature of the wall surface and the deposition plate is significantly lower than during film formation, and the attached film peels off. If it falls and adheres to the sputter / cathode or the like, it may cause arcing in subsequent film formation, or the film formation chamber may be contaminated with particles, leading to a decrease in quality (see Patent Document 1).
JP 2002-38265 A

  Therefore, an object of the present invention is to provide a roll-to-roll type apparatus capable of stably performing vacuum film formation at a high speed for a long time on a substrate and a base material. It is in providing the laminated body formed into a film using it.

The invention of claim 1 is a roll-to-roll type vacuum film forming apparatus, in which a film unwinding raw material film on which a film is wound is set, and a film unwinding material film is unwound from the unwinding original material. A film forming chamber for forming a film on the film, a first load lock roller provided at a communication portion between the film feeding chamber and the film forming chamber, a film forming position in the film forming chamber, and the first load. The length of the film extending to the location is adjusted by the relative movement of the first and second roller units, which are provided at a location between the lock roller and are composed of a plurality of rollers on which the film is stretched. And a first film length adjusting mechanism.
According to a second aspect of the present invention, there is provided a film take-up chamber for taking up the film formed, and a second load lock roller is provided at a communication portion between the film formation chamber and the film take-up chamber, and the film formation The third and fourth roller units, which are composed of a plurality of rollers over which the film is stretched, are extended to the place between the film forming place of the chamber and the second load lock roller. The roll-to-roll type vacuum film forming apparatus according to claim 1, further comprising a second film length adjusting mechanism for adjusting a length of the film to be adjusted.
According to a third aspect of the present invention, the film forming chamber includes a first sub chamber and a main chamber, and the first load lock roller is provided at a communication portion between the film feeding chamber and the first sub chamber. The first film extension length adjusting mechanism is provided in the first sub chamber, and a conductance roller or a load lock roller is provided in a communication portion between the first sub chamber and the main chamber. 3. The vacuum film forming apparatus according to claim 1, wherein the vacuum film forming apparatus is a vacuum film forming apparatus.

According to a fourth aspect of the present invention, the film formation chamber includes a main chamber and a second sub chamber, and the second load lock roller is provided at a communication portion between the second sub chamber and the film take-up chamber. The second film extension length adjusting mechanism is provided in the second sub chamber, and a conductance roller or a load lock roller is provided in a communication portion between the second sub chamber and the main chamber. The vacuum film-forming apparatus according to claim 2.
A fifth aspect of the present invention is a laminate formed by using the vacuum film forming apparatus according to any one of the first to fourth aspects.

With the apparatus of the present invention, there is no time loss during the desorption of the raw material and the raw material in the long-time sputter film formation on the film, and arcing is generated for a long time without reducing the film formation speed. It is possible to form a long-run film that is difficult and stable. At the same time, it is possible to provide a laminate with stable quality.
Moreover, the laminated body of this invention is the stable quality with few defects over a long length.

<Vacuum deposition apparatus 1>
The concept of the vacuum film forming apparatus of the present invention is shown in FIG.
As shown in FIG. 1, an example of a roll-to-roll type winding film forming apparatus for forming a film while conveying a plastic film or the like using a dual magnetron sputtering method (hereinafter referred to as DMS method) as a film forming source. As
The vacuum film forming apparatus 100 includes a film feeding chamber 9 in which an unwinding original film on which a film (web 23) is wound is set, and a film forming chamber for forming a film on the film unwound from the unwinding original film 102 and a film take-up chamber 13 for taking up the formed film.
The film forming chamber 102 includes a first sub chamber 10, a main chamber 11, and a second sub chamber 12.
The film feed chamber 9, the first sub chamber 10, the main chamber 11, the second sub chamber 12, and the film take-up chamber 13 are arranged in that order.

A first load lock roller 2 is provided at a communication portion between the film feeding chamber 9 and the film forming chamber 102.
In addition, the first and second roller units 1402 and 1404 composed of a plurality of rollers over which the film is stretched are moved relative to a position between the film forming position of the film forming chamber 102 and the first load lock roller 2. The 1st film length adjustment mechanism 14 in which the length of the film extended to the said location is adjusted by this is provided.
More specifically, the first load lock roller 2 is provided at a communication portion between the film feeding chamber 9 and the first sub chamber 10.
The first film extension length adjusting mechanism 14 is provided in the first sub-chamber 10.
A conductance roller 3 or a load lock roller is provided at a communication portion between the first sub chamber 10 and the main chamber 11.

Further, a second load lock roller 7 is provided at a communication portion between the film forming chamber 102 and the film take-up chamber 13.
In addition, the third and fourth roller units 1502 and 1504 made up of a plurality of rollers over which the film is stretched are moved relative to a position between the film forming position of the film forming chamber 102 and the second load lock roller 7. The 2nd film length adjustment mechanism 15 in which the length of the film extended to the said location is adjusted by this is provided.
More specifically, the second load lock roller 7 is provided at a communication portion between the second sub chamber 12 and the film take-up chamber 13.
The second film length adjusting mechanism 15 is provided in the second subchamber 12.
In addition, a conductance roller 6 or a load lock roller is provided at a communication portion between the second sub chamber 12 and the main chamber 11.

  In the film feeding chamber 9, the original film is set on the feeding roller 1, and after the web 23 passes through the first load lock roller 2 between the film feeding chamber 9 and the first sub-chamber 10, the first film length adjusting mechanism 14 is passed. After the web 23 passes through the conductance roller 3 between the first sub-chamber 10 and the film forming chamber 11, the sputter film is formed by the DMS cathodes 16, 17, and 18 in the main can 4, and the DMS is similarly formed in the main can 5. Sputter deposition is performed by the cathodes 19, 20, and 21. After the film formation is completed, the web 23 passes through the conductance roller 6 between the film formation chamber 11 and the second subchamber 12, then passes through the second film length adjusting mechanism 15, and is further wound around the second subchamber 12. After passing through the second load lock roller 7 between the take-up chambers 13, it is taken up by the take-up roller 8. However, the passing direction of the web 23 can be bidirectional, and there is no particular problem even if the film is formed from either direction. Although FIG. 1 shows a flat plate type DMS cathode, a rotating cathode type may be used.

  The DMS cathodes 16, 17, 18, 19, 20, 21, and 22 are each provided with a partition so that the film formation vacuum can be individually set. Further, the film feeding chamber 9, the first sub chamber 10, the film forming chamber 11, the second sub chamber 12, and the take-up chamber 13 are partitioned by the load lock roller 2 or the conductance roller 3, and are individually evacuated. It is possible to have a separate degree of vacuum.

The concept of the first film length adjusting mechanism 14 is shown in FIG.
In FIG. 2, the original fabric is set on the feeding roller 1, and the web 23 enters the first film length adjusting mechanism 14 after passing through the first load lock roller 2 between the film feeding chamber 9 and the first sub-chamber 10. The web 23 exits the first film length adjusting mechanism 14 and then passes through the conductance roller 3 and passes through the main chamber 11.
During film formation in the main chamber 11, the dancer roller head 28 in the first film length adjusting mechanism 14 rises to the top of the chamber, and the first roller unit 1402 attached to the dancer roller head 28 rises. As a result, the first and second roller units 1402 and 1404 are relatively separated from each other. Thereby, the sheet passing distance of the web 23 in the first film length adjusting mechanism 14 is increased, and the web 23 is stored in the first sub chamber 10. At this time, the web 23 always flows into the main chamber 11.
Next, the first load lock roller 2 is closed at the same time when the end of the original fabric set on the feed roller 1 is reached, and the web 23 becomes stationary between the feed roller 1 and the first load lock roller 2 and is in a zero speed state. It becomes.
At the same time, the dancer roller head 28 descends to the lower part of the first sub-chamber 10 in accordance with the conveyance speed of the web 23, and the relative distance between the first roller unit 1402 and the second roller unit 1404 becomes small. Thereby, the sheet passing distance of the web 23 in the first film length adjusting mechanism 14 is shortened, and the web 23 stored in the first sub-chamber 10 is conveyed to the main chamber 11.
As a result, there is no web feed from the feed roller 1, but the film formation can be continued.
At the same time, the film feeding chamber 9 is opened to the atmosphere, a new original fabric 31 is set on the feeding roller 1, and the end portion of the previous original fabric is connected.
After the setting of the new raw fabric 31 is completed, the film delivery chamber 9 is evacuated immediately. The first load lock roller 2 is opened after the film delivery chamber 9 has been evacuated. Thereby, the time loss accompanying attachment of a new original fabric does not generate | occur | produce.
The storage and discharge of the web 23 by the first film length adjusting mechanism 14 in the first sub-chamber 10 is similarly performed in the second sub-chamber 12 by the second film length adjusting mechanism 15 and the feeding is performed. Film formation is continued in a state where there is no web feed from the roller 1 so that a time loss associated with the installation of a new raw material does not occur.

<Laminated body>
The laminate of the present invention can be formed using the apparatus of the present invention. The laminate of the present invention includes, for example, an antireflection film, an enhanced reflection film, a color reflection film, and a semi-reflection / semi-transmissive film. , Dichroic mirror, ultraviolet cut filter, infrared cut filter, band pass filter, gas barrier film and the like.
As an example showing the embodiment of the present invention, an antireflection laminate is given and shown in FIG. FIG. 3 is a cross-sectional view showing an example of the antireflection laminate of the present invention.
The antireflection laminate 32 includes a base material 33, a hard coat layer 34 provided on the base material 33, a primer layer 35 provided on the hard coat layer 34, and a reflection provided on the primer layer 35. The prevention functional layer 36 is generally configured.

(Base material)
Examples of the substrate 33 used in the present invention include organic compound molded products having transparency. Transparency in the present invention means that light having a wavelength in the visible light region may be transmitted. The shape of the molded product is a roll. Further, the base material may be a laminate of an organic compound molded product having transparency.

  An example of the organic compound molding having transparency is plastic. Examples of the plastic include polyester, polyamide, polyimide, polypropylene, polymethylpentene, polyvinyl chloride, polyvinyl acetal, polyurethane, polymethyl methacrylate, polycarbonate, polystyrene, polyethylene sulfide, polyether sulfone, polyolefin, polyarylate, polyether ether. Examples thereof include ketones, polyethylene terephthalate, polyethylene naphthalate, and triacetyl cellulose.

  The thickness of the base material 33 is appropriately selected according to the intended use, and is usually from 24 to 290 μm. The organic compound molded product may contain known additives such as ultraviolet absorbers, plasticizers, lubricants, colorants, antioxidants, flame retardants and the like.

(Hard coat layer)
In the antireflection laminate of the present invention, a hard coat layer 34 may be provided between the base material 33 and the antireflection layer 36. The hard coat layer 34 is a layer that protects each layer from mechanical trauma such as scratches caused by a pencil or the like and scratches caused by steel wool. The material for forming the hard coat layer 34 may be any material having transparency, appropriate hardness and mechanical strength, and the binder matrix is an ionizing radiation curable resin such as an ultraviolet curable resin or an electron beam curable resin. Alternatively, an inorganic or organic-inorganic composite matrix obtained by hydrolysis, dehydration condensation of a metal alkoxide, a thermosetting resin, a thermoplastic resin, or the like can be used.

  Examples of the thermosetting resin include thermosetting urethane resin composed of acrylic polyol and isocyanate prepolymer, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicone resin, and the like.

  Monomers used as silicone resins include, for example, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrapentaethoxysilane, tetrapentaisoproxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane , Methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, dimethylpropoxysilane, dimethylbutoxysilane, methyldimethoxysilane, methyldiethoxysilane, hexyltrimethoxysilane, and the like.

  Examples of the ionizing radiation curable resin include polyfunctional acrylate resins such as polyhydric alcohol acrylic acid or methacrylic ester, diisocyanate, polyhydric alcohol and acrylic acid or methacrylic hydroxy ester. Examples include functional urethane acrylate resins. Besides these, polyether resins having an acrylate functional group, polyester resins, epoxy resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, and the like can also be used.

Among ionizing radiations, when using ultraviolet rays, a photopolymerization initiator is added. Although what kind of thing may be used for a photoinitiator, it is preferable to use what was suitable for resin to be used.
As the photopolymerization initiator (radical polymerization initiator), benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl methyl ketal, and alkyl ethers thereof are used. The usage-amount of a photosensitizer is 0.5-20 wt% with respect to resin. Preferably it is 1-5 wt%.

  Thermoplastic resins include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose, and methylcellulose, vinyl acetate and copolymers thereof, vinyl chloride and copolymers thereof, vinylidene chloride and copolymers thereof, and the like. Acetal resin such as acryl resin, polyvinyl formal, polyvinyl butyral, acrylic resin and its copolymer, acrylic resin such as methacryl resin and its copolymer, polystyrene resin, polyamide resin, linear polyester resin, polycarbonate resin, etc. are used it can.

  As monomers used as acrylic resins, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol (meth) acrylate, ethylene glycol di (meth) acrylate, Triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, 3-methylpentanediol di (meth) acrylate, diethylene glycol bis β- (meth) acryloyloxypropio Nate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) a Lilate, tri (2-hydroxyethyl) isocyanate di (meth) acrylate, pentaerythritol tetra (meth) acrylate, 22-bis (meth) acryloyloxyethyloxymethyl [2.2.1] heptane, poly 1,2-butadiene Di (meth) acrylate, 1,2-bis (meth) acryloyloxymethylhexane, nonaethylene glycol di (meth) acrylate, tetradecaneethylene glycol di (meth) acrylate, 10-decanediol (meth) acrylate, 37-bis ( (Meth) acryloyloxymethyltricyclo [5.2.10] decane, hydrogenated bisphenol A di (meth) acrylate, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 1,4-bis ((Meta) a (Chloroyloxymethyl) cyclohexane, hydroxypivalate ester neopentyl glycol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, epoxy-modified bisphenol A di (meth) acrylate and the like.

  As the inorganic or organic-inorganic composite matrix, a material using a silicon oxide matrix made of a silicon alkoxide material can be used.

  Moreover, in order for the base material 33 to supplement a plastic film and mechanical strength, it is preferable to use a binder matrix with high hardness. Specifically, an inorganic or organic-inorganic composite matrix obtained by hydrolysis and dehydration condensation of a curable resin or metal alkoxide can be used. In particular, when a plastic film having a film thickness of 100 μm or less is used, it is preferable to use a binder matrix having a high hardness.

  The hard coat layer 34 is formed by depositing these resin materials on the substrate 33 and curing them by heat curing, ultraviolet curing, or ionizing radiation curing. The hard coat layer 34 has a physical film thickness of 0.5 μm or more, preferably 3 to 20 μm, more preferably 3 to 6 μm.

  Transparent hard particles having an average particle size of 0.01 to 3 μm may be dispersed in the hard coat layer 34, and a treatment called antiglare may be performed. Due to the fine particles in the hard coat layer 34, the surface becomes fine irregularities, the light diffusibility is improved, and the light reflection can be further reduced.

  The hard coat layer 34 is preferably subjected to a surface treatment. By performing the surface treatment, the adhesion with an adjacent layer can be improved. Examples of the surface treatment of the hard coat layer 34 include a corona treatment method, a vapor deposition treatment method, an electron beam treatment method, a high frequency discharge plasma treatment method, a sputtering treatment method, an ion beam treatment method, an atmospheric pressure glow discharge plasma treatment method, and an alkali treatment. Method, acid treatment method and the like.

(Primer layer)
In the present invention. A primer layer 35 may be provided to improve the adhesion between the hard coat layer 34 and the antireflection layer 36.
Examples of the material of the primer layer 35 include metals such as silicon, nickel, chromium, tin, gold, silver, platinum, zinc, titanium, tungsten, zirconium, and palladium; alloys composed of two or more of these metals; Products, fluorides, sulfides, nitrides and the like. The chemical composition of oxides, fluorides, sulfides, and nitrides may not match the stoichiometric composition as long as adhesion is improved.

The thickness of the primer layer 35 should just be a grade which does not impair the transparency of the base material 33, Preferably it is 0.1-10 nm by a physical film thickness.
The primer layer 35 can be formed by a conventionally known method such as a vapor deposition method, a sputtering method, an ion plating method, an ion beam assist method, a chemical vapor deposition (CVD) method, or a wet coating method.

(Antireflection layer)
The antireflection layer 36 is composed of a single layer of a low refractive index transparent thin film layer having a refractive index of light at a wavelength of 550 nm of less than 1.6 and an extinction coefficient of light at a wavelength of 550 nm of 0.5 or less. And a plurality of laminated optical thin films.
A plurality of optical thin films having different refractive indexes are laminated, such as a high refractive index transparent thin film layer having a light refractive index of 1.9 or more at a wavelength of 550 nm and a light extinction coefficient of 0.5 or less at a wavelength of 550 nm, One having alternately laminated refractive index transparent thin film layers, a low refractive index transparent thin film layer, a high refractive index transparent thin film layer, a medium refractive index transparent thin film layer having a light refractive index of about 1.6 to 1.9 at a wavelength of 550 nm Can be mentioned.

  As the one in which the high refractive index transparent thin film layer and the low refractive index transparent thin film layer are alternately laminated, in order from the substrate 33 side, the high refractive index transparent thin film layer, the low refractive index transparent thin film layer, the high refractive index transparent thin film layer, The thing comprised from a low-refractive-index transparent thin film layer is mention | raise | lifted.

  The antireflection layer 36 is not limited as long as it basically imparts antireflection characteristics, and may be further provided with functions such as conductivity and heat ray cutting.

  Materials for the high refractive index transparent thin film layer include indium, tin, titanium, silicon, zinc, zirconium, niobium, magnesium, bismuth, cerium, chromium, tantalum, aluminum, germanium, gallium, antimony, neodymium, lanthanum, thorium, and hafnium. Metals such as oxides, fluorides, sulfides and nitrides of these metals; and mixtures of oxides, fluorides, sulfides and nitrides. The chemical composition of oxides, fluorides, sulfides, and nitrides may not match the stoichiometric composition as long as the chemical composition maintains transparency.

  When a plurality of high-refractive-index transparent thin film layers are laminated, the high-refractive-index transparent thin film layers are not necessarily made of the same material, and are appropriately selected according to the purpose.

  Examples of the material for the low refractive index transparent thin film layer include silicon oxide, titanium nitride, magnesium fluoride, barium fluoride, calcium fluoride, cerium fluoride, hafnium fluoride, lanthanum fluoride, sodium fluoride, aluminum fluoride, Examples thereof include lead fluoride, strontium fluoride, ytterbium fluoride and the like.

  When a plurality of low-refractive-index transparent thin film layers are laminated, the low-refractive-index transparent thin film layers are not necessarily the same material, and are appropriately selected according to the purpose.

  Examples of the material for the medium refractive index layer include aluminum oxide and cerium fluoride.

  The laminate of the present invention can be applied not only to the front surface of an optical display device as an optical functional filter but also to a reflector of a light source, a window material, etc. used for a liquid crystal display device.

  Examples of the present invention will be specifically described below.

(Explanation of equipment used)
The vacuum film forming apparatus shown in FIG. 1 was used.
By using this film forming apparatus, the primer layer 35 in the antireflection laminate 32 exemplified in the present invention, antireflection is set by setting the raw material on the feeding roller 1 and transporting the film in the direction of the take-up roller 8. It is possible to laminate all the functional layers 36 by only one outward path. At this time, metal targets of Si, Ti, Si, Ti, Si, and Si are mounted on the DMS cathodes 16, 17, 18, 19, 20, and 21, respectively, and the respective oxide films are formed by the DMS method. Is possible.

<Example 1>
A triacetylcellulose film having a thickness of 80 μm (TD80U manufactured by Fuji Photo Film Co., Ltd., refractive index 1.51 of light having a wavelength of 550 nm) (hereinafter referred to as TAC film) is used as a base material 33, and an ultraviolet curable resin (Japan) Synthetic Chemistry UV-7605B) is formed by wet coating (microgravure method) to form a hard coat layer 34 having a physical thickness of 5 μm, and a roll-to-roll vacuum shown in FIG. The primer layer 35 and the antireflection functional layer 36 were formed by a film forming apparatus, and the antireflection laminate 32 shown in FIG. 3 was produced.
Using the film forming apparatus shown in FIG. 1, while transporting the TAC film in the direction from the feed roller 1 to the take-up roller 8, SiO _x is formed on the hard coat layer with the sputtering target 16 on which the Si target is arranged. A primer layer 35 having a physical thickness of 3 nm was formed by deposition by a bipolar DMS method. At this time, Ar was used as the sputtering gas, O ₂ was used as the reactive gas, the flow rates were 200 sccm and 30 sccm, respectively, the film forming pressure was 0.3 Pa, and the input power was 0.3 W / cm 2.

Next, an antireflection functional layer 36 comprising a high refractive index transparent thin film layer 37, a low refractive index transparent thin film layer 38, a high refractive index transparent thin film layer 39, and a low refractive index transparent thin film layer 40 was formed as follows.
Using the film forming apparatus shown in FIG. 1, a TiO ₂ thin film was deposited on the primer layer 35 by the bipolar DMS method while transporting the TAC film to form a high refractive index transparent thin film layer 37 having an optical film thickness of 30 nm. . In addition, high-speed film formation was performed by transition region control using plasma parameters. At this time, Ar was used as the sputtering gas, O ₂ was used as the reactive gas, the flow rates were 180 sccm and 120 sccm, the film forming pressure was 0.3 Pa, and the input power was 1.7 W / cm 2, respectively. At this time, the frequency of the voltage applied to each target was performed in the MF region of 40 to 60 kHz.

Next, using the film forming apparatus shown in FIG. 1, a SiO ₂ thin film is deposited on the high refractive index transparent thin film layer 37 by the bipolar DMS method while transporting the TAC film, and a low refractive index with an optical film thickness of 35 nm is obtained. A transparent thin film layer 38 was formed. In addition, high-speed film formation was performed by transition region control using plasma parameters. At this time, Ar was used as the sputtering gas, O ₂ was used as the reactive gas, the flow rates were 180 sccm and 120 sccm, the film forming pressure was 0.3 Pa, and the input power was 2.4 W / cm 2, respectively. At this time, the frequency of the voltage applied to each target was performed in the MF region of 40 to 60 kHz.

Further, using the film forming apparatus shown in FIG. 1, a TiO ₂ thin film is deposited on the low refractive index transparent thin film layer 38 by the bipolar DMS method while transporting the TAC film, and a high refractive index transparent thin film having an optical film thickness of 220 nm. Layer 39 was formed. In addition, high-speed film formation was performed by transition region control using plasma parameters. At this time, Ar was used as the sputtering gas, O ₂ was used as the reactive gas, the flow rates were 180 sccm and 120 sccm, the film forming pressure was 0.3 Pa, and the input power was 11.2 W / cm 2, respectively. At this time, the frequency of the voltage applied to each target was performed in the MF region of 40 to 60 kHz.

Next, a SiO ₂ thin film is deposited on the high refractive index transparent thin film layer 39 by the bipolar DMS method while transporting the TAC film using the film forming apparatus shown in FIG. A thin film layer 40 was formed. In addition, high-speed film formation was performed by transition region control using plasma parameters. At this time, Ar was used as the sputtering gas, O ₂ was used as the reactive gas, the flow rates were 180 sccm and 120 sccm, the film forming pressure was 0.3 Pa, and the input power was 16 W / cm 2, respectively. At this time, the frequency of the voltage applied to each target was performed in the MF region of 40 to 60 kHz.

By the above procedure, the antireflection laminate 32 is formed at a winding speed of 1 m / min. When the end portion of the film appears on the feeding roller 1, the first and second load lock rollers 2 and 7 are closed, and the rotation of the feeding roller 1 is stopped. Next, the film feed chamber 9 and the film take-up chamber 13 are opened to the atmosphere, a new original fabric is reset, and the film-formed original fabric is taken out, and then the film feed chamber 9 and the film take-up chamber 13 are taken out. Was evacuated. Since it takes 90 minutes to complete these series of operations, the film is stored in advance in the first sub-chamber 10 for 90 m or more and the film in the reel stand is poured while the original fabric is being reset. During the exchange time, the film forming apparatus was not stopped. In addition, in the second sub-chamber 12, only the lowest pass line is set in advance so that a film having a film thickness of 90 m or more can be stored during the series of raw material replacement operations. The original fabrics to be set were all 1000 m, and 10 films were continuously formed.
<Comparative Example 1>

In the same manner as in Example 1, the film formation apparatus shown in FIG. 1 was used to form the antireflection laminate 32 in the same procedure. At this time, the end of the film appears on the feeding roller 1 and at the same time the discharge of each cathode is stopped, the conveyance of the film is stopped, the first and second load lock rollers 2 and 7 are closed, the film feeding chamber 9 and the film The winding chamber 13 was opened to the atmosphere, a new original fabric was reset, and the film-formed original fabric was taken out, and then the film feeding chamber 9 and the film winding chamber 13 were evacuated. Since these series of operations require 90 minutes, the vacuum film formation is stopped during this time.
<Comparative example 2>

In the same manner as in Example 1, the film formation apparatus shown in FIG. 1 was used to form the antireflection laminate 32 in the same procedure. At this time, the end of the film appears on the feeding roller 1 and at the same time, the discharge of each cathode is stopped, the conveyance of the film is stopped, the film feeding chamber 9, the film winding chamber 13, the first and second subchambers 10, 12. The main chamber 11 is opened to the atmosphere, and a new original fabric is set again. The film-formed original fabric that has been wound up is taken out, and the protection plate of each cathode is replaced. Evacuation was performed. Since these series of operations require 360 minutes, the vacuum film formation is stopped during this time.
<Evaluation>

  The following evaluation was performed on Example 1 and Comparative Examples 1 and 2. The results are shown in Tables 1-2.

(1) Arc generation investigation in long run During long run over 10,000 minutes performed in Example 1 and Comparative Examples 1 and 2, emission spectroscopic measurement during discharge was performed in DMS cathodes 20 and 21 equipped with Si to stabilize light emission. The number of occurrences was investigated by observing the characteristics, that is, the fluctuation of light emission at the moment when the arc occurred. For 251.6 nm Si emission under film formation conditions, the emission calibration is 35%, the instantaneous emission fluctuation at the time of arc generation is 5% or more, 10% or more, 20% or more In the case of 40% or more, the time elapsed is investigated. The survey results are shown in Table 1.

(2) Investigation of film formation amount in time Table 2 shows how much film could be formed in continuous 10,000 minutes when the antireflection laminate 32 was formed in Example 1 and Comparative Examples 1 and 2. Shown in

(3) Defect occurrence frequency investigation In the long run over 10000 minutes performed by Example 1 and Comparative Examples 1 and 2, the occurrence frequency of defects in each film forming raw material is investigated. The defect size was compared between two sizes of 50 μm or more and less than 100 μm and 100 μm or more. The results are shown in Table 3.

  By using the vacuum film-forming apparatus of the present invention, it was possible to eliminate the time loss at the time of replacing the original fabric, which was difficult in the past, and to increase the production amount per unit time. In addition, it has become possible to significantly reduce arcing caused by film peeling caused by a change in the temperature in the film forming chamber due to the stop of discharge and film defects of the laminate caused by the cause. As a result, it has become possible to provide more laminates with fewer film defects per unit time.

1 is a schematic diagram of a roll-to-roll vacuum film forming apparatus of the present invention. It is a schematic diagram of the 1st film length adjustment mechanism in the roll-to-roll type vacuum film-forming apparatus of this invention. It is a schematic sectional drawing which shows an example of the reflection preventing laminated body of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Unwinding roller 2 1st load lock roller 3 Conductance roller 4 Main can 5 Main can 6 Conductance roller 7 2nd load lock roller 8 Winding roller 9 Film delivery chamber 10 1st subchamber 11 Main chamber 12 2nd sub Chamber 13 Film winding chamber 14 First film length adjusting mechanism 15 Second film length adjusting mechanism 16 DMS cathode 17 DMS cathode 18 DMS cathode 19 DMS cathode 20 DMS cathode 21 DMS cathode 22 Unwinding roller 23 Web 28 Dancer roller head 31 New raw fabric 32 Antireflection laminate 33 Base material 34 Hard coat 35 Primer layer 36 Antireflection functional layer 37 High refractive index transparent thin film layer 38 Low refractive index transparent thin film layer 9 high-refractive-index transparent thin film layer 40 low-refractive-index transparent film layers

Claims (5)

It is a roll-to-roll type vacuum film forming apparatus,
A film unwinding chamber in which the unwinding raw material on which the film is wound is set;
A film forming chamber for forming a film on the film unwound from the unwinding raw fabric;
A first load lock roller provided at a communication portion between the film feeding chamber and the film forming chamber;
The first and second roller units, which are provided at a position between the film forming position of the film forming chamber and the first load lock roller and are composed of a plurality of rollers on which the film is stretched, move relatively. A first film length adjustment mechanism in which the length of the film extending to the part is adjusted;
A roll-to-roll type vacuum film-forming apparatus characterized by comprising: A film take-up chamber for taking up the film formed is provided,
A second load lock roller is provided at a communication portion between the film forming chamber and the film take-up chamber;
The third and fourth roller units composed of a plurality of rollers over which the film is stretched are moved relative to a position between the film formation position of the film formation chamber and the second load lock roller, thereby the position. A second film length adjustment mechanism for adjusting the length of the film extending to
The roll-to-roll type vacuum film-forming apparatus according to claim 1. The film formation chamber has a first sub-chamber and a main chamber,
The first load lock roller is provided in a communication portion between the film feeding chamber and the first sub chamber,
The first film extension length adjusting mechanism is provided in the first sub-chamber,
A conductance roller or a load lock roller is provided at a communication portion between the first sub chamber and the main chamber.
The vacuum film-forming apparatus according to claim 1 or 2. The film forming chamber has a main chamber and a second sub chamber,
The second load lock roller is provided in a communication portion between the second sub chamber and the film take-up chamber,
The second film extension length adjusting mechanism is provided in the second sub-chamber,
A conductance roller or a load lock roller is provided at a communication portion between the second sub chamber and the main chamber.
The vacuum film-forming apparatus according to claim 2.   A laminate formed by using the vacuum film forming apparatus according to any one of claims 1 to 4.

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