JP2008138229A - Roll/to/roll type magnetron/sputtering system, stacked body using the same, optically functional filter, and optional display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a roll/to/roll type stacked body production device; to provide a stacked body film-deposited using the production device; to provide an optionally functional filter using the stacked body at the front face; and to provide an optical display. <P>SOLUTION: In the roll/to/roll type magnetron/sputtering system having at least one or more magnetron electrodes for forming a thin film layer on a plastic film, capable of individually setting a vacuum degree per magnetron electrode, and provided with a film deposition roller sufficiently large to the magnetron electrode(s), rollers smaller than the film deposition roller are installed directly before and directly after the film deposition roller, and film quality can be made dense by a plasma flow between a cathode and an anode generated in the magnetron electrode(s) during the transportation of the small rollers. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a roll-to-roll laminate manufacturing apparatus, a laminate formed using the manufacturing apparatus, an optical functional filter using the laminate on the front surface, and an optical display device.

  A technique for forming a laminate on a plastic substrate using a roll-to-roll type film forming apparatus has been developed. At the beginning of development and development, multilayer film formation by vapor deposition and ion plating was predominant.

  However, for those that have a high level of judgment for defects in the laminate due to film defects such as pinholes, such as antireflection laminates, the method of clearing this judgment level is from vapor deposition, ion plating to sputtering. Deposition methods are being replaced.

  In addition, when using a roll-to-roll type film forming apparatus using the sputtering method, a technique of forming a multilayer film in a single pass is used (for example, see Patent Document 1). .

  Roll-to-roll continuous film formation using such a sputtering method is a magnetron sputtering method in which a thin film layer forming material is disposed as a target on a pair of electrodes. Then, an AC voltage is applied between the electrodes, and a discharge method in which each electrode alternately functions as a cathode and an anode, commonly called a dual magnetron sputtering method (hereinafter referred to as DMS method) is becoming mainstream.

  Since the DMS method alternately applies equal voltages to a pair of electrodes, bombardment to the substrate side due to high energy particles during film formation is large, and compared with normal DC sputtering and RF sputtering, plasma A film having a large assist effect, a dense film with high film hardness and film stress is formed.

  For this reason, it is possible to form a thin film excellent in various mechanical properties such as scratch resistance as compared with a normal sputtered film, a deposited thin film, and the like. In addition, since the anode and the cathode are alternately switched, charge-up is unlikely to occur compared to normal DC and RF sputtering, and stable film formation is possible for a long time.

  However, since the film is dense, the film hardness is higher than that of the deposited film and the usual magnetron sputtering method, but the film has a strong film stress and the film warps tightly. When a laminated body is provided on a plastic film that has been subjected to a hard coat treatment, both the laminated film and the hard coat have a problem that they are difficult to handle after post-processing, such as cracking.

  On the other hand, when a certain level of water vapor permeability is required, the film quality is too dense, which may be problematic. On the other hand, in the case of the vapor deposition method, not only the determination level with respect to the bright spot but also the film hardness was too low, so that only a film having a problem in scratch resistance could be formed.

As the above-mentioned solution, there are a method of forming a film by setting the film forming pressure at the time of film formation in the DMS method to be high, and a method of forming a film by increasing the distance between the target and the substrate. The former is prone to arcing,
It is difficult to cause stable sputter discharge continuously for a long time. The latter has problems such as extremely low film formation speed, and is not suitable for actual production.

  There is also a method for improving the film quality by an ion beam processing apparatus after film formation by ordinary magnetron sputtering. However, there is a problem that an extra space has to be provided in the sputtering apparatus and is expensive in price.

Prior art documents are shown below.
JP-A-8-188873

  The present invention has been made in view of the above-described conventional problems, and the object of the present invention is that it is possible to form a film with very few film defects on a plastic film substrate, and during sputtering. Using a roll-to-roll type magnetron sputtering apparatus and its manufacturing apparatus, which can freely form a film hardness between a DMS thin film and a normal magnetron sputtering thin film by utilizing plasma collision It is an object of the present invention to provide a laminated body in which a film is formed, an optical functional filter and an optical display device using the laminated body on the front surface.

In order to solve the above problems, the invention according to claim 1 of the present invention provides:
In order to form a thin film layer on a plastic film, it has at least one magnetron electrode, and the degree of vacuum can be individually set for each magnetron electrode, and a sufficiently large film forming roller is provided for the magnetron electrode. In the roll-to-roll type magnetron sputtering equipment provided,
A small roller compared to the film forming roller is installed immediately before and immediately after the film forming roller, or during the transfer of the small roller, and the plasma flow between the cathode and the anode generated in the magnetron electrode Thus, a roll-to-roll type magnetron sputtering apparatus characterized in that the film quality can be made dense.

Next, the invention according to claim 2 of the present invention is as follows:
The roll-to-roll according to claim 1, wherein the plastic film is capable of adjusting an impact of plasma received during conveyance of the small roller by adjusting an opening degree of the deposition preventing plate. Type magnetron sputtering equipment.

Next, the invention according to claim 3 of the present invention is the roll-to-roll type sputtering apparatus according to claim 1 or 2, wherein the power source is a DC pulse power source.

Next, the invention according to claim 4 of the present invention is
The roll-to-roll type magnetron sputtering apparatus according to any one of claims 1 to 3, further comprising transition region control means using plasma parameters.

Next, the invention according to claim 5 of the present invention comprises two magnetron electrodes in one film forming chamber,
The roll-to-roll type magnetron sputtering apparatus according to any one of claims 1 to 4, wherein unipolar sputtering and bipolar dual magnetron sputtering are possible. .

Next, an invention according to claim 6 of the present invention is a laminate characterized by being formed using the roll-to-roll type magnetron sputtering apparatus according to any one of claims 1 to 5. Is the body.

Next, an invention according to claim 7 of the present invention is an optical functional filter characterized in that the laminate according to claim 6 is molded into a filter and used.

Next, an invention according to claim 8 of the present invention is an optical display device characterized in that the laminate according to claim 6 is molded into a display device member.

  The laminate formed on the plastic film by the roll-to-roll type magnetron sputtering apparatus of the present invention has a high film stress because of the low film stress and the flexible film quality equivalent to the normal magnetron sputtering method. A film having a high hardness can be freely formed without using a special processing apparatus such as ion beam processing.

  At the same time, since the sputtering method is used, the bright spot level is better than the vapor deposition method. In addition, the deposition rate is not impaired for a long time. Furthermore, film formation can be performed in a stable state with less arcing.

  In addition, the optical functional filter of the present invention is a filter having a very good defect level and having appropriate scratch properties and film stress.

  Further, the optical display device of the present invention is an optical display device having a very good defect level and having appropriate scratch properties and film stress. These optical articles are optical articles having a very good defect level and having appropriate scratch properties and film stress.

  A roll-to-roll type magnetron sputtering apparatus according to the present invention will be described below in detail according to an embodiment with reference to the drawings.

  FIG. 1 is a schematic view for explaining an outline of an embodiment of a roll-to-roll type magnetron sputtering apparatus of the present invention.

<About sputtering equipment>
As shown in FIG. 1, the roll-to-roll type magnetron sputtering apparatus of the present invention includes an unwinding roller 1, a winding roller 2, a film forming main roller 3, a film forming sub-roller 4, a film forming sub-roller 5, The film forming sub-roller 6 is used.

  Sputtering cathodes for holding sputtering targets 8 and 9, 12 and 13, and 16 and 17 are disposed on the film forming main roller 3. Moreover, there is no restriction | limiting in the number of sputtering cathodes provided with respect to the film-forming main roller 3. FIG. Then, the size of the main film forming roller 3 and the size of the sputtering / cathode may be appropriately determined.

  Further, deposition sub-rollers 4, 5, 6 are arranged between the sputtering targets 8, 9-12, 13, 12, 12, 13-16, 17 and immediately after the sputtering cathode holding the sputtering targets 16, 17, respectively. Has been.

  Further, the films formed by sputtering with the sputtering targets 8 and 9 pass through the film formation sub-roller 4 and are then formed with the sputtering targets 12 and 13. The films formed by the sputtering targets 12 and 13 pass through the film formation sub-roller 5 and are then formed by the sputtering targets 16 and 17.

  The film formed by the sputtering targets 16 and 17 passes through the film formation sub-roller 6 and is then wound around the winding roller 2. At this time, each film forming sub-roller is provided with deposition preventing plates 25, 26, 27, 28, and 29 that can adjust the opening degree toward the plasma side.

  Further, the number of film forming sub-rollers 4, 5, and 6 is not necessarily arranged immediately after all the sputtering cathodes, but at least one is required to be equipped. The film forming chambers including the sputtering targets 8 and 9, 12 and 13, 16 and 17, respectively, are spaces including the film forming sub roller 4, the film forming sub roller 5, and the film forming sub roller 6 as shown in FIG. The film formation pressure can be set separately for each. It is also possible to start the unwinding from the roller 2 and form the film in the direction of winding onto the roller 1.

  The sputtering cathodes holding the sputtering targets 8 and 9, 12 and 13, 16 and 17 are each composed of two pairs of cathodes / anodes, and a target material is placed on the cathodes.

  Further, the electrode may be either a rotary cathode type or a flat plate type, but it is shown in FIG. 1 as a flat plate type.

  In the flat plate type, two pairs of cathodes / anodes are arranged side by side in order to increase the film formation rate, but a pair of cathodes / anodes may be used depending on the required film formation rate. The advantage of arranging the two pairs of cathodes / anodes in one film forming chamber can be applied not only to the film forming speed but also to forming a film having the finest film quality and strong stress.

  This disconnects each anode from the wiring with the cathode, electrically connects the two targets, and applies an alternating voltage between the two targets.

  Alternatively, it can be used as a so-called bipolar DMS method in which voltage is alternately applied to two targets by a DC pulse power supply.

  Further, as shown in FIG. 1, anodes 7, 10, 11, 14, 15, and 18 are provided for the sputtering targets 8, 9, 12, 13, 16, and 17, respectively. In order to prevent the sputtered material from adhering to these anodes, covers 19, 20, 21, 22, 23, and 24 are attached, respectively.

  Without the cover, the anode is gradually contaminated with sputtered particles during sputtering, and arcing occurs frequently. A cover is necessary to prevent this.

  The cover only needs to be electrically floated from the anode / cathode, and the material is not particularly limited as long as it has heat resistance. The shape is not specified as long as it is a shape that can prevent contamination of the anode.

A method for applying a voltage for performing sputtering between the cathode and the anode is not particularly specified and may be either AC or DC, but is preferably a DC pulse power source. This is because, when the voltage waveform to be applied is a pulse wave, it is more effective in mitigating charge-up at the anode during the off time of voltage application, and a stable long run is possible.

  The frequency of the DC pulse power source is preferably 0.1 kHz to 500 kHz, and more preferably 1 to 100 kHz. Although it is necessary to set the duty cycle as appropriate, it is desirable to set an off time of 0.1 μsec or more in consideration of charge relaxation.

  Further, instead of the voltage off time, the voltage is inverted, and a negative voltage sufficiently smaller than the negative voltage applied to the sputtering target is applied to the electrode that was the anode. The cathode may be instantaneously converted to positively relieve charge-up.

  The greatest feature of the roll-to-roll type magnetron sputtering apparatus of the present invention is that the deposition sub-roller is transported immediately after deposition at the sputtering cathode. For example, in the case of a sputtering cathode including the sputtering targets 16 and 17 shown in FIG. 1, in order to avoid a space where the magnetic field is dense when electrons generated in the magnetron cathode go to the anode, It passes through a bridge-like route (FIG. 2).

  For this reason, a strong plasma flow is generated in a bridge shape. The plasma flow generated when the voltage is applied collides with the deposition preventing plate 28 and the deposition sub-roller 5 and also with the deposition preventing plate 29 and the deposition sub-roller 6 (FIG. 2).

  This can improve the film quality densely with respect to the thin film formed on the sputtering cathode including the sputtering targets 12 and 13, 16 and 17. This principle is basically the same as the bipolar DMS method.

  In the case of the bipolar DMS method, the anode / cathode is alternately switched between the two targets, so that the electrons generated at the cathode avoid the region where the magnetic field is dense in the process toward the anode, so that the plasma flow is always deposited. Collides with main roller 3. This promotes improvement of the film quality of the target material that is sputtered and adheres to the film.

  In FIG. 2, the openings of the deposition preventing plates 19 and 20 can be adjusted as a method of adjusting the plasma flow that collides with the film forming sub-rollers 5 and 6.

  If the width of the opening is widened, the film quality becomes denser, and if the width of the opening is narrowed, the film quality becomes rough. If a plasma bomber is not required, the film may be flowed directly to the next sputtering cathode without passing through the film formation sub-roller, or the opening degree of the deposition preventing plate may be zero.

  In addition, this makes it possible to form a film freely from a flexible film quality having a low film stress equivalent to that of a normal magnetron sputtering method to a high film quality having a high film stress. Further, since the sputtering method is used at the same time, the bright spot level is better than the vapor deposition method. In addition, it is possible to form a film in a stable state for a long time without impairing the film formation speed and with less arcing.

  Moreover, although the film forming main roller 3 is one in FIG. 1, the apparatus provided with two or more may be sufficient. Then, it is appropriately selected depending on the number of laminated bodies to be formed on the plastic film, the film quality, and the desired film formation speed.

  Next, FIG. 4 is a cross-sectional view showing a cross section of an embodiment of the laminate of the present invention.

<About the laminate>
The laminate of the present invention can be formed using the roll-to-roll type magnetron sputtering apparatus of the present invention. Examples of the laminate of the present invention include an antireflection film, an increased reflection film, a semi-reflection / semi-transmission film, a dichroic mirror, an ultraviolet cut filter, an infrared cut filter, a band pass filter, and a gas barrier film.

  FIG. 4 shows a structural cross section of an antireflection laminate, which is one of the laminates of the present invention. The antireflection laminate 59 includes a base material 60, a hard coat layer 61 provided on the base material 60, a primer layer 62 provided on the hard coat layer 61, and a reflection provided on the primer layer 62. The prevention functional layer 63 is formed.

<About the base material>
Examples of the substrate 60 used in the laminate of the present invention include a molded product of an organic compound having transparency. The transparency means a material that transmits light having a wavelength in the visible light region. And as a shape of a molded product, it is a roll shape.

  Moreover, the base material 60 may be a laminate in which a molded product of an organic compound having transparency is laminated.

  Examples of the resin of the molded product of the organic compound having transparency include, for example, polyester, polyamide, polyimide, polypropylene, polymethylpentene, polyvinyl chloride, polyvinyl acetal, polyurethane, polymethyl methacrylate, polycarbonate, polystyrene, polyethylene sulfide, poly Examples include ether sulfone, polyolefin, polyarylate, polyether ether ketone, polyethylene terephthalate, polyethylene naphthalate, and triacetyl cellulose.

  Moreover, the thickness of the base material 60 is appropriately selected according to the purpose of use or application. And a thing about 25-300 micrometers normally is used. Furthermore, the molded product of the organic compound contains known additives, for example, ultraviolet absorbers, plasticizers, lubricants, colorants, antioxidants, flame retardants, and the like as appropriate according to the intended use or application. Also good.

<About hard coat layer>
The antireflection laminate 63 that is one of the laminates of the present invention may include a hard coat layer 61 between the substrate 60 and the antireflection layer 63.

  The hard coat layer 61 is a layer for protecting each layer from mechanical injuries such as scratches caused by pencils, scratches caused by steel wool, and the like. The material for forming the hard coat layer 61 may be any material having transparency, appropriate hardness, and mechanical strength.

  The binder matrix is an inorganic or organic material obtained by hydrolyzing and dehydrating and condensing ionizing radiation curable resins such as ultraviolet curable resins and electron beam curable resins, thermosetting resins, thermoplastic resins, and metal alkoxides. An inorganic composite matrix or the like can be used.

  Further, examples of the thermosetting resin include a thermosetting urethane resin composed of an acrylic polyol and an isocyanate prepolymer, a phenol resin, a urea melamine resin, an epoxy resin, an unsaturated polyester resin, and a silicon resin.

Examples of the monomer used as the silicon resin include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrapentaethoxysilane, tetrapentaisoproxysilane, methyltrimethoxysilane, methyltriethoxysilane, and methyltripropoxy. Examples thereof include silane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, dimethylpropoxysilane, dimethylbutoxysilane, methyldimethoxysilane, methyldiethoxysilane, and hexyltrimethoxysilane.

  The ionizing radiation curable resin may be synthesized from polyfunctional acrylate resin such as polyhydric alcohol acrylic acid or methacrylic acid ester, diisocyanate, polyhydric alcohol and acrylic acid or methacrylic acid hydroxy ester, or the like. Polyfunctional urethane acrylate resin etc. are mentioned.

  In addition to the above, 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 the said 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. And the usage-amount of a photosensitizer is 0.5-20 wt% with respect to resin. Preferably it is 1-5 wt%.

  Examples of the thermoplastic resin 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. Vinyl resins, acetal resins such as polyvinyl formal and polyvinyl butyral, acrylic resins and copolymers thereof, acrylic resins such as methacrylic resins and copolymers thereof, polystyrene resins, polyamide resins, linear polyester resins, polycarbonate resins, etc. Can be used.

As monomers used as the acrylic resin, 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) acryloyloxypro Pionate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) Acrylate, tri (2-hydroxyethyl) isocyanate di (meth) acrylate, pentaerythritol tetra (meth) acrylate, 2,3-bis (meth) acryloyloxyethyloxymethyl [2.2.1] heptane, poly 1,2 -Butadiene di (meth) acrylate, 1,2-bis (meth) acryloyloxymethylhexane, nonaethylene glycol di (meth) acrylate, tetradecane ethylene glycol di (meth) acrylate, 10-decanediol (meth) acrylate, 3, 8-bis (meth) acryloyloxymethyltricyclo [5.2.10] decane, hydrogenated bisphenol A di (meth) acrylate, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 1 , 4-bis (( (Meth) acryloyloxymethyl) 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.

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

  In addition, the plastic film of the substrate 60 preferably uses a binder matrix with high hardness in order to supplement mechanical strength. 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 61 is formed by depositing these resin materials on the substrate 60 and curing them by heat curing, ultraviolet curing, or ionizing radiation curing. The thickness of the hard coat layer 61 is 0.5 μm or more, preferably 3 to 20 μm, more preferably 3 to 6 μm in terms of physical film thickness.

  Transparent hard particles having an average particle diameter of 0.01 to 3 μm may be dispersed in the hard coat layer 61, and a treatment called antiglare may be performed. Due to the fine particles in the hard coat layer 61, the surface becomes fine irregularities, the light diffusibility is improved, and the light reflection can be further reduced.

  The hard coat layer 61 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 61 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.

<About the primer layer>
The antireflection laminate 63, which is one of the laminates of the present invention, may be provided with a primer layer 62 in order to improve the adhesion between the hard coat layer and the antireflection layer.

  Examples of the material of the primer layer 62 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; Examples thereof include oxides, fluorides, sulfides, and nitrides. 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 62 should just be a grade which does not impair the transparency of the base material 60, Preferably it is 0.1-10 nm by a physical film thickness.

  The primer layer 62 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.

<About the antireflection layer>
The antireflection layer 63 is composed of a single layer of a low refractive index transparent thin film layer having a light refractive index of less than 1.6 at a wavelength of 550 nm and a light extinction coefficient of 0.5 or less at a wavelength of 550 nm. And a plurality of laminated optical thin films.

As a laminate of a plurality of optical thin films having different refractive indexes, 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, Low refractive index transparent thin film layers alternately laminated, low refractive index transparent thin film layer, high refractive index transparent thin film layer, medium refractive index transparent thin film having a light refractive index of about 1.6 to 1.9 at a wavelength of 550 nm The thing which laminated | stacked the layer is mention | raise | lifted.

  Moreover, as what laminated | stacked the high refractive index transparent thin film layer and the low refractive index transparent thin film layer alternately, in order from the base material 60 side, a high refractive index transparent thin film layer, a low refractive index transparent thin film layer, and a high refractive index transparent thin film. And a layer composed of a low refractive index transparent thin film layer.

  The antireflection layer 63 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.

  As the material of the high refractive index transparent thin film layer, indium, tin, titanium, silicon, zinc, zirconium, niobium, magnesium, bismuth, cerium, chromium, tantalum, aluminum, germanium, gallium, antimony, neodymium, lanthanum, thorium, Metals such as hafnium; oxides, fluorides, sulfides, nitrides of these metals; oxides, fluorides, sulfides, mixtures of nitrides, and the like. In addition, the chemical composition of oxide, fluoride, sulfide, and nitride may not be the same as the stoichiometric composition as long as the chemical composition maintains transparency.

  When a plurality of the high-refractive-index transparent thin film layers are laminated, the high-refractive-index transparent thin film layers do not necessarily have to be 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, and fluoride. Examples thereof include aluminum, 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 made of 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.

<About optical functional filters>
The optical functional filter of the present invention is not only an antireflection laminate which is one of the laminates of the present invention, but also an enhanced reflection film, a semi-reflective transflective film, a dichroic mirror, an ultraviolet cut filter, an infrared cut filter, a band pass filter. Etc.

  The optical functional filter of the present invention includes a CRT filter, a liquid crystal display filter, a plasma display panel filter, an electroluminescence (EL) display filter, a field emission display (FED) filter, and a rear projection television. A filter etc. are mentioned.

<Optical display device>
The optical display device of the present invention has an optical functional filter. Specifically, a laminate comprising at least one film of the present invention or the optical functional filter of the present invention is provided on the front surface or inside of an optical display device such as a CRT, liquid crystal display device, plasma display panel or the like. It is a thing.

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.

  Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited thereto.

<Regarding the roll-to-roll vacuum deposition system used for the implementation>
It implemented using the vacuum film-forming apparatus shown in FIG. As shown in FIG. 5, the vacuum film forming apparatus includes film forming main rollers 32 and 33. Five film forming chambers capable of setting different film forming pressures are arranged for the film forming main rollers 32 and 33. Two sputtering targets 40 and 41 are arranged side by side in one film forming chamber.

  The sputtering targets 40 and 41 are equipped with Si, the sputtering targets 42 and 43 with Ti, the sputtering targets 44 and 45 with Si, the sputtering targets 46 and 47 with Ti, and the sputtering targets 48 and 49 with Si, respectively. Yes.

  For this reason, between the unwinding roller 30 and the winding roller 31, a maximum of 5 layers can be formed in one outgoing path.

  Further, since two sputter targets 40, 41 and 42, 43 and 44, 45 and 46, 47 and 48, 49 are arranged, one anode is provided.

  Further, a so-called DMS method of bipolar type is possible, and a unipolar magnetron sputtering method is also possible. Since two sputtering targets 40, 41 and 42, 43 and 44, 45 and 46, 47 and 48, 49 are arranged, high-speed switching made by Fraunhofer Institute Elektronenstrahl-und Plasmatechnik is possible for each sputtering cathode. A power supply UBS-C2 is installed.

  In the case of using the DMS method, two DC pulse power supplies can be alternately switched at a high speed. It is possible to alternately apply positive and negative DC pulse voltages between the two targets.

  Further, when the unipolar magnetron sputtering method is used, it is possible to simultaneously apply a negative voltage to the two aligned sputtering targets. Since two targets are sputtered simultaneously, a high deposition rate can be obtained, but it is also possible to apply a negative voltage to only one target.

  Further, the plasma flow between the anode and the cathode generated at this time collides with the film forming sub-rollers 34, 35, 36, 37, 38, and 39. The deposition preventing plates 50, 51, 52, 53, 54, 55, 56, 57 and 58 surrounding the film forming sub-rollers 34, 35, 36, 37, 38 and 39 can be freely opened and closed. It is possible to adjust the amount of plasma flow impinging on 34, 35, 36, 37, 38, 39.

  And by using this film-forming apparatus, a TAC original fabric is set to the unwinding roller 30, and a TAC (triacetylcellulose) film is conveyed to the winding roller 31 direction, and is one of the laminated bodies of this invention. It is possible to laminate the primer layer 62 and the antireflection functional layer 63 in the antireflection laminate 59 that are all in one outward path.

<Example 1>
A triacetyl cellulose film having a thickness of 80 μm (TD80U, made by Fuji Photo Film Co., Ltd., refractive index 1.51 of light having a wavelength of 550 nm) (hereinafter referred to as a TAC film) is used as a base 60, and an ultraviolet curable resin (Japan) Synthetic chemistry UV-7605B) is formed by wet coating (microgravure method) to form a hard coat layer 61 having a physical film thickness of 5 μm, and a roll-to-roll vacuum shown in FIG. With the film forming apparatus, the primer layer 62 and the antireflection functional layer 63 were formed, and the antireflection laminate 59 shown in FIG. 4 was produced.

Further, using the roll-to-roll vacuum film forming apparatus shown in FIG. 5, while transporting the TAC film, the sputtering targets 40 and 41 on which the Si target is disposed are used to form SiO _x on the hard coat layer 61. Were deposited by the bipolar DMS method to form a primer layer 62 having a physical thickness of 3 nm.

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 0.5 W / cm 2. At that time, the openings of the deposition preventing plates 50 and 51 were the minimum opening of zero mm.

  Next, an antireflection functional layer 63 including a high refractive index transparent thin film layer 64, a low refractive index transparent thin film layer 65, a high refractive index transparent thin film layer 66, and a low refractive index transparent thin film layer 67 was formed as follows. .

In forming, using the roll-to-roll vacuum film forming apparatus shown in FIG. 5, while transporting the TAC film, both of the two targets are used in the sputtering targets 42 and 43, and the unipolar system is used. A TiO ₂ thin film was deposited on the primer layer 62 by magnetron sputtering.

And the high refractive index transparent thin film layer 64 with an optical film thickness of 30 nm 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 1.7 W / cm ^2, respectively. .

  At this time, voltage was applied to each target at a frequency of 50 kHz and a duty cycle of 80%. At that time, the opening degree of the deposition preventing plate 52 was 150 mm, which is the maximum opening degree.

  Next, using the roll-to-roll vacuum film forming apparatus shown in FIG. 5, while transporting the TAC film, both of the two targets are used in the sputtering targets 44 and 45, and the unipolar magnetron is used. -A SiO2 thin film was deposited on the high refractive index transparent thin film layer 64 by sputtering to form a low refractive index transparent thin film layer 65 having an optical film thickness of 35 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 2.4 W / cm ^2, respectively. . At this time, voltage was applied to each target at a frequency of 50 kHz and a duty cycle of 80%. At that time, the openings of the adhesion preventing plates 53 and 54 were 150 mm, which is the maximum opening.

Further, using the roll-to-roll vacuum film forming apparatus shown in FIG. 5, while transporting the TAC film, both of the two targets are used in the sputtering targets 46 and 47, and the unipolar magnetron A TiO ₂ thin film was deposited on the low refractive index transparent thin film layer 65 by sputtering. Then, a high refractive index transparent thin film layer 66 having an optical film thickness of 220 nm 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, voltage was applied to each target at a frequency of 50 kHz and a duty cycle of 80%. At that time, the openings of the adhesion preventing plates 55 and 56 were 150 mm, which is the maximum opening.

Further, using the roll-to-roll vacuum film forming apparatus shown in FIG. 5, while transporting the TAC film, the sputtering targets 48 and 49 were used to use both of the two targets, and the unipolar magnetron A SiO ₂ thin film was deposited on the high refractive index transparent thin film layer 66 by sputtering. And the low refractive index transparent thin film layer 67 with an optical film thickness of 120 nm 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 8.3 W / cm ^2, respectively. . At this time, voltage was applied to each target at a frequency of 50 kHz and a duty cycle of 80%. At that time, the opening degree of the deposition preventing plates 57 and 58 was 150 mm, which is the maximum opening degree.

<Example 2>
A hard coat layer 61, a primer layer 62, a high-refractive-index transparent thin film layer 64, in the same procedure as in Example 1, except that the openings of the adhesion preventing plates 52, 53, 54, 55, 56, 57, 58 were set to 75 mm. The low refractive index transparent thin film layer 65, the high refractive index transparent thin film layer 66, and the low refractive index transparent thin film layer 67 were formed.

<Example 3>
The hard coat layer 61, the primer layer 62, the high refractive index transparent thin film layer 64, the low refractive index transparent thin film layer 65, and the high refractive index transparent thin film layer 66 were formed in the same procedure as in Example 1. On the other hand, only the outermost low-refractive-index transparent thin-film layer 67 has an opening of the deposition prevention plate 58 of 0 mm, and using both targets, the film formation pressure is 0.3 Pa by the unipolar magnetron sputtering method. Film formation was performed at an input power of 8.3 W / cm ² . At this time, voltage was applied to each target at a frequency of 50 kHz and a duty cycle of 80%.

<Example 4>
The hard coat layer 61 and the primer were prepared in the same procedure as in Example 1 except that the openings of the adhesion preventing plates 52, 53 and 54 were 150 mm, and the openings of the adhesion preventing plates 55, 56, 57 and 58 were 0 mm. The layer 62, the high refractive index transparent thin film layer 64, the low refractive index transparent thin film layer 65, the high refractive index transparent thin film layer 66, and the low refractive index transparent thin film layer 67 were formed.

<Example 5>
The hard coat layer 61, the primer layer 62, and the high refractive index are the same as in Example 1 except that the high-speed film formation by the transition region control using the plasma parameter is not performed and the film is formed by the sputtering in the oxide mode. A transparent thin film layer 64, a low refractive index transparent thin film layer 65, a high refractive index transparent thin film layer 66, and a low refractive index transparent thin film layer 67 were formed.

<Comparative Example 1>
The hard coat layer 61, the primer layer 62, and the high refractive index are the same as those in the first embodiment except that the openings of the adhesion preventing plates 50, 51, 52, 53, 54, 55, 56, 57, and 58 are set to zero mm. The refractive index transparent thin film layer 64, the low refractive index transparent thin film layer 65, the high refractive index transparent thin film layer 66, and the low refractive index transparent thin film layer 67 were formed.

<Comparative example 2>
Sputtering was performed on all sputtering cathodes using a bipolar DMS method. In addition, high-speed film formation was performed for all the cathodes except the sputtering cathodes of the targets 40 and 41 by transition region control using plasma parameters. The hard coat layer 61 was then processed in the same manner as in Example 1 except that the openings of all the sputtering / cathode protection plates 50, 51, 52, 53, 54, 55, 56, 57, and 58 were set to zero mm. The primer layer 62, the high refractive index transparent thin film layer 64, the low refractive index transparent thin film layer 65, the high refractive index transparent thin film layer 66, and the low refractive index transparent thin film layer 67 were formed.

<Comparative Example 3>
Regarding the film formation conditions other than the film formation pressure of each sputtering cathode being 1.0 Pa, the hard coat layer 61, the primer layer 62, the high refractive index transparent thin film layer 64, the low refractive index are processed in the same procedure as in Comparative Example 2. A transparent thin film layer 65, a high refractive index transparent thin film layer 66, and a low refractive index transparent thin film layer 67 were formed.

<Comparative Example 4>
As a power source, an MF power source is used and a bipolar DMS method in which targets are sputtered alternately is used, and the openings of the deposition preventing plates 50, 51, 52, 53, 54, 55, 56, 57, and 58 are set to zero mm. The hard coat layer 61, the primer layer 62, the high refractive index transparent thin film layer 64, the low refractive index transparent thin film layer 65, the high refractive index transparent thin film layer 66, and the low refractive index transparent thin film are the same as those in Example 1. The layer 67 was formed.

<Comparative Example 5>
The openings of the protective plates 50, 51, 52, 53, 54, 55, 56, 57, 58 were set to zero mm. In addition, the hard coat layer was formed in the same procedure as in Example 1 except that high-speed film formation by transition region control using plasma parameters was not performed, and film formation was performed by sputtering in an oxide mode at each sputtering cathode. 61, a primer layer 62, a high refractive index transparent thin film layer 64, a low refractive index transparent thin film layer 65, a high refractive index transparent thin film layer 66, and a low refractive index transparent thin film layer 67 were formed.

<Comparative Example 6>
The openings of the protective plates 50, 51, 52, 53, 54, 55, 56, 57, 58 were set to zero mm. However, with respect to the high refractive index transparent thin film layer 64, the low refractive index transparent thin film layer 65, the high refractive index transparent thin film layer 66, and the low refractive index transparent thin film layer 67, the target is formed in each film forming chamber. The hard coat layer 61, the primer layer 62, the high refractive index transparent thin film layer 64, and the low refractive index transparent thin film are processed in the same manner as in Example 1 except that film formation is performed using only 42, 44, 46, and 48. The layer 65, the high refractive index transparent thin film layer 66, and the low refractive index transparent thin film layer 67 were formed.

<Comparative Example 7>
By using a roll-to-roll type electron beam vapor deposition apparatus different from FIG. 5 used in Examples 1, 2, 3, 4 and Comparative Examples 1, 2, 3, 4, 5, 6, 7, primer layer 62, high The refractive index transparent thin film layer 64, the low refractive index transparent thin film layer 65, the high refractive index transparent thin film layer 66, and the low refractive index transparent thin film layer 67 were formed.

<Evaluation>
The antireflection laminate 59 obtained in Examples 1, 2, 3, and 4 and Comparative Examples 1, 2, 3, 4, and 5 was evaluated as follows.

(1) Indentation hardness test:
An indentation hardness (GPa) with an indentation depth of 100 nm was applied to the samples formed in Examples 1, 2, 3, 4 and Comparative Examples 1, 2, 3, 4, 7 using an NEC thin film evaluation apparatus MHA-400. ) Was measured. At this time, a triangular pyramid indenter having a tip radius of curvature of 100 nm and a ridge angle of 80 ° was used as the indenter, and the indentation speed was set to 10.5 nm / s. The results are shown in Table 1.

Table 1 shows the results of indentation hardness test evaluation.

(2) Steel wool scratch test:
Steel wool # 0000 was applied to the samples formed in Examples 1, 2, 3, and 4 and Comparative Examples 1, 2, 3, 4, and 7 using a scratch tester (manufactured by TESTER SANGYO CO. Ltd. It is fixed to the testing machine AB-301), applied with a load of 2.45N and 4.9N, and 100-round reciprocal scratch test is performed on each sample, and the wear state (number of scratches) of the sample is visually checked. Observed. The results are shown in Table 2.

Table 2 shows the results of visual observation of the steel wool scratch test.

(3) Bending test:
Samples formed according to Examples 1, 2, 3, 4 and Comparative Examples 1, 2, 3, 4, 7 were wound on stainless steel rods of 6 mmφ, 8 mmφ, 10 mmφ, and 14 mmφ for half a half respectively. Then, it was visually observed whether or not cracks occurred in the antireflection functional layer and the HC layer. The results are shown in Table 3.

Table 3 shows the result of visual observation of the bending test.

(4) Defect count measurement:
Regarding the defects of 100 μm size and 50 μm size of the samples formed in Examples 1, 2, 3, 4 and Comparative Examples 1, 2, 3, 4, 7, the number of defects (pieces / m ² ) was measured with an optical microscope. Observed and measured. The measurement results are shown in Table 4.

Table 4 shows the results of observing and measuring the number of defects (pieces / m ² ) with an optical microscope.

(5) Investigation of arc occurrence in long run:
During the 1000-minute long run performed by Examples 1, 2, 3, 4 and Comparative Examples 1, 2, 3, 4, during sputtering of Si-targeted sputtering cathodes 44, 45 and 48, 49, The emission spectroscopic measurement was performed to observe the stability of light emission, that is, the sudden light emission fluctuation at the moment when the arc occurred, and the number of occurrences was investigated.

The above is about 251.6 nm Si emission under film forming 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 5.

Table 5 shows the investigation results of arc generation in long run.

(6) Film formation rate investigation In Example 1, Example 5, Comparative Example 5, and Comparative Example 6, the film formation rate during film formation was expressed as the winding speed of the apparatus shown in FIG. The results are shown in Table 6.

Table 6 shows the investigation results of the film formation rate.

<Comprehensive evaluation results>
From the measurement results in the indentation hardness test in Table 1, the antireflection laminate 59 of the present invention is compared with the DMS method using a normal MF power source (Comparative Example 4) and the DMS method using a bipolar system (Comparative Example 2). It can be seen that (Example 1, Example 2, Example 3, and Example 4) are films having low film hardness and having a film hardness higher than that of the deposited film (Comparative Example 7).

  Further, from Table 2, the antireflection laminate 59, which is one of the laminates of the present invention, has a bipolar DMS method using a pulse wave (Comparative Example 2) and a normal DMS method using a sine wave (Comparative Example). Although the scratch resistance is inferior to 4), it can be seen that the scratch resistance is superior to the vapor deposition method (Comparative Example 7).

  From the results in Table 3, the occurrence of cracks that can be visually confirmed in the bending test is only Comparative Example 2 and Comparative Example 4 using the bipolar DMS method, and is one of the laminates of the present invention. The laminated body 59 also has ease of processing like a vapor deposition film even during processing such as cutting.

  From the results shown in Table 4, it can be seen that the antireflection laminate 59 of the present invention is clearly at a good level even at the bright spot level as compared with the deposited film (Comparative Example 5).

  Further, from the results of Table 5, in the arc count, the arc count numbers of Examples 1 to 4 of the present invention are the DMS method using the normal MF power source (Comparative Example 4) and the DMS method using the bipolar system ( Even when compared with Comparative Example 2), it can be seen that there is no fading at all and high stability is maintained in the long run. On the other hand, in the film hardness, in the high pressure film formation (Comparative Example 3) of the DMS method by the bipolar method, which can form the film quality similar to the present invention, the arc frequently occurs in the long run. And it turns out that a stable long run is difficult.

  Also, from the results in Table 6, it can be seen that a double deposition rate can be obtained by performing transition region control using plasma parameters. Further, when the film is installed as a DMS cathode, if the film is formed on each target using the respective anodes, the film formation speed is doubled as compared with the case where the film is formed with one target. It turns out that it is effective.

By using the roll-to-roll type magnetron sputtering apparatus of the present invention, the film quality can be freely changed, the film forming speed can be increased, and a flexible laminate with few defects can be formed. It is manufactured with high productivity. And an optical functional filter and an optical display apparatus can be produced using the laminated body. Furthermore, it is a wonderful invention that can be used for members in a wide range of fields such as the electrical field, precision machine field, and medical field.

It is the schematic for demonstrating the outline of one Example of the roll-to-roll type magnetron sputtering device of this invention. It is the elements on larger scale of FIG. It is the other partial enlarged view of FIG. It is sectional drawing which shows the cross section of one Example of a structure of the reflection preventing lamination which is one of the laminated bodies of this invention. It is the schematic for demonstrating the outline of other one Example of the roll-to-roll type magnetron sputtering device of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Unwinding roller 2 ... Winding roller 3 ... Film-forming main roller 4 ... Film-forming sub-roller 5 ... Film-forming sub-roller 6 ... Film-forming sub-roller 7 ... Anode 8 ... Cathode 9 ... Cathode 10 ... Anode 11 ... Anode 12 ... Cathode 13 ... Cathode 14 ... Anode 15 ... Anode 16 ... Cathode 17 ... Cathode 18 ... Anode 19 ... Anode cover 20 ... Anode cover 21 ... Anode cover 22 ... Anode cover 23 ... Anode cover 24 ... Anode cover 25 ... Open / close type adhesion Plate 26. Opening and closing type deposition plate 27. Opening and closing type deposition plate 28. Opening and closing type deposition plate 29. Opening and closing type deposition plate 30 ... Unwinding and winding roller 31 ... Unwinding and winding roller 32 ... Deposition main roller 33 ... Film formation main roller 34 ... Film formation sub-roller 35 ... Film formation sub-roller -36 ... Deposition sub-roller 37 ... Deposition sub-roller 38 ... Deposition sub-roller 39 ... Deposition sub-roller 40 ... Si target 41 ... Si target 42 ... Ti target 43 ... Ti target 44 ... Si target 45 ... Si target 46 ... Ti target 47 ... Ti target 48 ... Si target 49 ... Si target 50 ... Open / close-type deposition plate 51 ... Open / close-type deposition plate 52 ... Open / close-type deposition plate 53 ... Open / close-type deposition plate 54 ... Open / close-type deposition plate 55 ... Opening / Closing Protection Plate 56 ... Opening / Closing Protection Plate 57 ... Opening / Closing Protection Plate 58 ... Opening / Closing Protection Plate 59 ... Antireflection Laminate 60 ... Base Material 61 ... Hard Coat 62 ... Primer Layer 63 ... Antireflection Layer 64 ... high refractive index transparent thin film layer 65 ... low refractive index transparent thin film layer 66 ... high refractive index transparent thin film layer 67 ... low refractive index transparent thin film layer

Claims (8)

In order to form a thin film layer on a plastic film, it has at least one magnetron electrode, and the degree of vacuum can be individually set for each magnetron electrode, and a sufficiently large film forming roller is provided for the magnetron electrode. In the roll-to-roll type magnetron sputtering equipment provided,
A small roller compared to the film forming roller is installed immediately before and immediately after the film forming roller, or during the transfer of the small roller, and the plasma flow between the cathode and the anode generated in the magnetron electrode A roll-to-roll magnetron sputtering apparatus characterized in that the film quality can be densified by the above-described method.   The roll-to-roll according to claim 1, wherein the plastic film is capable of adjusting an impact of plasma received during the conveyance of the small roller by adjusting an opening degree of the deposition preventing plate. Type magnetron sputtering equipment.   The roll-to-roll type sputtering apparatus according to claim 1 or 2, wherein the power source is a DC pulse power source.   The roll-to-roll type magnetron sputtering apparatus according to any one of claims 1 to 3, further comprising transition region control means using plasma parameters. Two magnetron electrodes are provided in one deposition chamber,
The roll-to-roll type magnetron sputtering apparatus according to any one of claims 1 to 4, wherein unipolar sputtering and bipolar dual magnetron sputtering are possible.
Patter device.   A laminate formed by using the magnetron sputtering apparatus according to claim 1.   An optical functional filter, wherein the laminate according to claim 6 is molded into a filter and used.   An optical display device comprising the laminate according to claim 6 formed on a display device member.