JP2008196017A - Sputtering device, laminate, optical functional filter, optical display device, and optical article - Google Patents

Abstract

The present invention provides a sputtering apparatus capable of stably performing sputter deposition on a substrate and a base material at a high speed for a long time, and a laminate formed using the sputtering apparatus, and An optical functional filter and an optical display device having a laminate are provided.
A sputtering apparatus having at least one or more magnetron electrodes for forming a thin film layer on a substrate, wherein anode electrodes 5 and 6 of the magnetron electrodes are rotary electrodes. Sputtering equipment.
[Selection] Figure 1

Description

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

  Large-area sputtering film forming apparatuses include a batch type film forming apparatus for forming a film while conveying a glass substrate and a roll-to-roll type film forming apparatus for forming 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. Sputtering cathodes used for these are various, such as a single magnetron cathode and a dual magnetron cathode, and the structure of the cathode itself includes a flat plate type and a rotating type (see Patent Document 1).

  In these large area sputter deposition 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. This is a magnetron sputtering method in which a thin film layer forming material is arranged as a target on each pair of electrodes, an alternating voltage is applied between the electrodes, and each electrode alternately serves as a cathode and an anode. The dual magnetron sputtering method (hereinafter referred to as DMS method) has become the mainstream.

  In the DMS method, a voltage is alternately applied to a pair of electrodes alternately, so that bombardment to the substrate side due to high-energy particles during film formation is large, and plasma assistance is possible compared to normal DC sputtering and RF sputtering. A film having a large effect, a dense film, and a 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 vapor deposition film and the usual magnetron sputtering method. On the other hand, it becomes a thin film with strong film stress. When a laminated body is provided on the film, there is a problem that it is difficult to handle after the post-processing because the laminated film and the hard coat are easily cracked. On the other hand, when a certain level of water vapor permeability is required, the film quality is too dense, which may be problematic. Regarding the sputtering method, these solutions include setting the film formation pressure at the time of film formation in the DMS method to be high and forming a film, or forming a film with a long target-substrate distance. The former is prone to arcing and it is difficult to generate stable sputter discharge continuously for a long time, and the latter is not suitable for actual production due to problems such as extremely low deposition rate. It was. These DMS methods are bipolar methods. On the other hand, there is a method using unipolar magnetron sputtering in which the anode and the cathode are not interchanged and the sputtering target side electrode is always the cathode. It is possible to form a flexible thin film, and there is no problem in terms of film formation speed. However, when it is desired to form an insulating film, the insulating film is coated on the anode as time passes. Since charge-up occurs and arcing begins to occur, stable film formation for a long time is difficult.

In addition, the DMS method can ease the charge-up, so that high power can be input and the film formation rate is high. However, since the anode and cathode are switched every half cycle of voltage application, only one target is sputtered. Was not efficient.

In addition, it is possible to obtain a film with low film hardness and low film stress if it is a vapor deposition film rather than sputtering, but productivity such as frequent exchange of materials during production, There were various problems such as weak mechanical properties of the thin film.
JP-A-8-188873

  Therefore, an object of the present invention is to provide a sputtering apparatus capable of stably performing sputtering film formation on a substrate and a base material at a high speed for a long time, and using this, a film is formed. An object of the present invention is to provide a laminate, and an optical functional filter and an optical display device having the laminate.

  The invention of claim 1 has at least one pair of magnetron sputtering electrodes for forming a thin film layer on a substrate and a film, and the anode electrode in the electrodes is a rotary electrode. It is to provide a sputtering apparatus characterized.

  According to a second aspect of the present invention, a plurality of the magnetron sputtering electrodes according to the first aspect are arranged in a casing, and the electrodes are partitioned so that the respective vacuum degrees can be set. It is an object of the present invention to provide a sputtering apparatus characterized in that a multilayer film can be formed during substrate transportation and film transportation.

  A third aspect of the present invention is to provide a sputtering apparatus according to the first or second aspect, wherein a DC pulse power source is used as the power source.

  In the invention of claim 4, when using the DC pulse power source, after applying a negative voltage by a rectangular wave to the sputtering target, the polarity is reversed, and a negative voltage is applied to the rotary electrode by a rectangular wave to charge up. The sputtering apparatus according to claim 1, 2, or 3 is characterized by relaxation.

  The invention of claim 5 is characterized in that two or more pairs of magnetron sputtering electrodes are arranged in one film forming chamber. 4 is a sputtering apparatus.

  The invention of claim 6 is capable of high-speed film formation while performing transition region control using plasma parameters. A sputtering apparatus according to claim 5 is provided.

  The invention according to claim 7 provides a laminate characterized in that it is deposited using the sputtering apparatus according to claim 1, claim 2, claim 3, claim 4, claim 5, and claim 6. It is to be.

  The eighth, ninth, and tenth inventions provide an optical functional filter, an optical display device, and an optical article characterized by using the laminate according to the seventh aspect.

With the apparatus of the present invention, arcing is very difficult to occur over a long period of time without slowing down the film formation speed in long-time sputter film formation, and stable long-run film formation becomes possible. At the same time, it is possible to provide a laminate with stable quality.

  The optical functional filter of the present invention is a filter having a stable quality with few defects and a thin film having a lower film hardness than a thin film formed by a bipolar DMS method.

  The optical display device of the present invention is an optical display device having a stable quality with few defects and a thin film having a lower film hardness than a thin film formed by a bipolar DMS method.

  The optical article of the present invention is an optical article having a stable quality with few defects and a thin film having a lower film hardness than a thin film formed by a bipolar DMS method.

<Sputtering apparatus 1>
The concept of the magnetron sputtering apparatus of the present invention is shown in FIG.

  As an example, a roll-to-roll type winding film forming apparatus for forming a film while conveying a plastic film or the like as shown in FIG. The present invention may be a batch type film forming apparatus that forms a film on a glass substrate or a metal substrate.

  The plastic film 2 is conveyed to the film forming main roller 1. Cathodes 3 and 4 to which flat plate type sputtering targets are attached as film forming sources, and anodes 5 and 6 for the respective cathodes are installed, and these anodes 5 and 6 are rotary anodes. The size of the rotary anodes 5 and 6 is not particularly limited as long as abnormal discharge does not occur. However, when the inside is water-cooled, the flow rate is such that the water temperature does not extremely increase in the anode. Must be large enough to secure The cathodes 3 and 4 may be rotary cathodes. In the case of a rotary cathode, the use efficiency of the target is high, which is advantageous. Further, DC pulse power supplies 7 and 8 are attached between the respective anodes and cathodes. Molecules and atoms sputtered at the cathodes 3 and 4 are deposited on the film being transported in the deposition main can, but the atoms and molecules that pop out at this time are not necessarily deposited only on the film. It is knocked out in various directions. In addition, the knocked out atoms and molecules collide with various gas species in the plasma space, losing the energy that was retained when knocked out, and re-deposited in the cathode direction. There is also a case. When these protruding atoms, molecules, re-deposited atoms, and molecules are coated on the anodes 5 and 6, arcing takes place in a short time. Therefore, in order to prevent this coating as much as possible, deposition prevention plates 9 and 10 are installed. ing. There are no particular restrictions on the protective plates 9 and 10, plasma is generated between the cathodes 3 and 4 and the anodes 5 and 6 without any problem, and molecules and atoms knocked out from the cathode are not directly formed on the anode. It is. The sputter deposition chamber is partitioned by partition plates 11 and 12, and even if a cathode other than the cathodes 3 and 4 is disposed in the deposition main can, the introduced gas type and deposition pressure are set separately. Is possible.

  In the present invention, the most characteristic feature is that a rotary electrode is used for the anode. This is because, when a fixed electrode such as a flat plate or a prismatic plate is used as the anode, even if there are the deposition plates 9 and 10, atoms and molecules struck out from the target in long-run sputtering over a long period of time. Gradually coats the anode. If this coating film exceeds a certain level, it will lead to arcing due to charge-up or disappearance of the anode, and it will be difficult to continue stable discharge. The fact that stable discharge becomes difficult reduces the quality of the deposited film itself, but when arcing begins to occur, the vacuum deposition apparatus must be opened to the atmosphere to clean and replace the anode, This is very time consuming and leads to reduced productivity. On the other hand, in the present invention, by rotating the anode, it is possible to suppress the disappearance of the anode as much as possible by uniformly coating the rotating cathode with the coating that is deposited locally.

  In addition, by using DC pulse power supplies 7 and 8 as a power source, in the film formation of a plastic film, the polarity of the rotary anode is reversed to be a cathode and pre-sputtered at the timing of replacing the original film. In addition, a long run is possible for a longer time. In addition, when forming a film on a substrate such as glass, the anode is cleaned by flowing a substrate for pre-sputtering between a plurality of substrates to be continuously formed, and a long run for a long time is performed. It becomes possible.

  The frequency of the DC pulse power supply 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, by using DC pulse power supplies 7 and 8 as power sources, a negative voltage is applied to the cathodes 3 and 4 on which the targets are arranged, and then the target side is inverted to the anode, and the rotary anodes 5 and 6 are inverted as the rotary cathode. By doing so, the charge-up can be mitigated. By this reversal, since the film coated on the rotary anodes 5 and 6 is sputter-cleaned, it is possible to protect the sputter discharge from arcing and anode disappearance for a longer period of time, enabling stable long-run film formation. Become. In this case, pre-sputtering as described above is almost unnecessary, and an efficient and stable long-run film formation is possible.

  Further, one of the features of the present invention is that two cathodes 3 and 4 are arranged in one film forming chamber like a dual magnetron cathode. In this case, since the two DC pulse power supplies 7 and 8 are attached to the respective cathodes, the bipolar DMS method can be sputtered only alternately for each one of the cathodes, whereas the present invention simultaneously sputters. (Plasma flows 13, 14 are shown in FIG. 1). As a result, it is possible to achieve a film formation rate about twice that of the bipolar DMS method, and to cover the slow film formation rate of the sputtering method.

  Further, as one of the features of the present invention, two or more DC pulse power supplies may be used for a pair of cathodes / anodes. In this case, a DC pulse power supply for applying a voltage to the cathode to which the target is attached; Also, it can be used separately from a DC pulse power source that applies a negative voltage when the polarity of the rotary anode is reversed.

  In FIG. 1, although there is only one film forming main roller, it may be an apparatus equipped with two or more. Depending on the number of layers to be formed on the plastic film, the film quality, and the desired film forming speed. Therefore, a free design can be made.

<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. It is sectional drawing which shows an example of the reflection preventing laminated body of this 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 generally configured.

(Base material)
As a base material used for this invention, the organic compound molding which has transparency is mentioned. 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 a base material is suitably selected according to the target use, and is 25-300 micrometers normally. 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 may be provided between the base material and the antireflection layer. The hard coat layer is a layer that protects each layer from mechanical trauma such as scratches caused by pencils and the like, and scratches caused by steel wool. The material for forming the hard coat layer 3 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 Relate, 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 ((meta ) 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.

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

  Further, it is preferable to use a binder matrix having a high hardness so that the base material is a plastic film and mechanical strength is supplemented. 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 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, 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 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.

(Primer layer)
In the present invention. A primer layer may be provided to improve the adhesion between the hard coat layer and the antireflection layer.

  Examples of the material for the primer layer 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; oxides thereof , Fluoride, sulfide, nitride 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 primer layer may be of a thickness that does not impair the transparency of the substrate 60, and is preferably a physical film thickness of 0.1 to 10 nm.

  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.

(Antireflection layer)
The antireflection layer includes a single layer of a low refractive index transparent thin film 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. One obtained by laminating a plurality of different 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.

  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 side: high refractive index transparent thin film layer, low refractive index transparent thin film layer, high refractive index transparent thin film layer, low The thing comprised from a refractive index transparent thin film layer is mention | raise | lifted.

  The antireflection layer 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.

<Optical functional filter>
In addition to the antireflection laminate of the present invention, the optical functional filter of the present invention has a reflection-enhancing film, a semi-reflective / semi-transmissive film, a dichroic mirror, an ultraviolet cut filter, an infrared cut filter, a band pass filter, and the like. 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, a rear projection television filter, and the like. Is mentioned.

<Optical display device>
The optical display device of the present invention has an optical functional filter formed using the device of the present invention. 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.

<Optical article>
The optical article of the present invention is an optical article having an optical functional filter formed using the apparatus of the present invention, specifically, an optical lens coated with a mirror, an optical prism, a hologram, for example, an antireflection laminate, For example, a window glass on which LoY-E coating has been applied, or an optical storage medium such as a CD or a DVD.

  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)
An outline of the vacuum film forming apparatus shown in FIG. 3 will be described. First, unwinding and winding rollers 15 and 16 and film forming main rollers 17 and 18 are provided. Five film forming chambers in which different film forming pressures can be set are arranged for the film forming main rollers. Two sputtering targets are arranged side by side in one film forming chamber. Sputtering targets 19 and 20 are equipped with Si, 21 and 22 with Ti, 23 and 24 with Si, 25 and 26 with Ti, and 27 and 28 with Si, respectively.

  Each sputtering target has one anode, the sputtering targets 19 and 20 have rotary anodes 29 and 30, and the sputtering targets 21 and 22 have rotary anodes 31 and 32, and the sputtering target. 23 and 24 are equipped with rotary anodes 33 and 34, sputtering targets 25 and 26 are equipped with rotary anodes 35 and 36, and sputtering targets 27 and 28 are equipped with rotary anodes 37 and 38, respectively. For this reason, between the unwinding roller 15 and the winding roller 16, a maximum of 5 layers can be formed in one outgoing path.

  Since two sputtering targets are arranged in each film forming chamber, a high-speed switchable power supply UBS-C2 manufactured by Fraunhofer Institute Elektronenstrahl-und Plasmatechnik is installed on the sputtering cathode. In the case of using the DMS method, two DC pulse power supplies can be alternately switched at high speed, and a positive and negative DC pulse voltage can be alternately applied between two targets.

  In addition, when a unipolar magnetron sputtering method is used, a negative voltage can be simultaneously applied to two side-by-side sputtering targets, and a high deposition rate can be obtained because two targets are sputtered simultaneously. However, it is also possible to apply a negative voltage to only one target.

  Moreover, it is also possible to apply a negative voltage to each rotating anode by reversing the polarity. After the sputtering film is formed by applying a negative voltage to the sputtering target, the charge-up can be avoided by applying a negative voltage by reversing the polarity of the rotating anode with no voltage applied.

  By using the film forming apparatus, the raw material is set on the unwinding roller 15 and the film is conveyed in the direction of the winding roller 16, whereby the primer layer 62 in the antireflection laminate 59 exemplified in the present invention, the reflection It is possible to laminate all the prevention functional layers 63 by only one outward path.

<Example 1>
In the roll-to-roll vacuum film forming apparatus shown in FIG. 3, a SiO ₂ film is formed on the sputtering targets 27 and 28 while a PET film is set on the unwinding roller 15 and conveyed in the direction of the winding roller 16. The film was formed for 1000 minutes, and the film formation rate was investigated and the number of occurrences of arcing was counted. At this time, the sputtering targets 27 and 28 are subjected to unipolar sputtering using a DC pulse power source, Ar is used as the sputtering gas, O ₂ is used as the reactive gas, and the flow rates are 180 sccm and 120 sccm, respectively. The atmospheric pressure was 0.3 Pa, and the input power was 8.3 W / cm ² each. At this time, a voltage was applied to each target at a frequency of 50 kHz and a duty cycle of 80%, and high-speed film formation was performed in transition region control using plasma parameters. At that time, the rotary anode was rotated at 20 rpm.

<Example 2>
In the roll-to-roll vacuum film forming apparatus shown in FIG. 3, a SiO ₂ film is formed on the sputtering targets 27 and 28 while a PET film is set on the unwinding roller 15 and conveyed in the direction of the winding roller 16. The film was formed for 1000 minutes, and the film formation rate was investigated and the number of occurrences of arcing was counted. At this time, the sputtering targets 27 and 28 are subjected to unipolar sputtering using a DC pulse power source, Ar is used as the sputtering gas, O ₂ is used as the reactive gas, and the flow rates are 180 sccm and 120 sccm, respectively. The atmospheric pressure was 0.3 Pa, and the input power was 8.3 W / cm ² each. At this time, voltage was applied to each target at a frequency of 50 kHz and a duty cycle of 80%, 10% of 20% off time was reversed in polarity, a rotating anode was used as a cathode, and a negative voltage was applied. The charge-up was eased. The input power for this negative voltage application was 3.5 W / cm ² . At the same time, a long run was performed with high-speed film formation in transition region control using plasma parameters. At that time, the rotary anode was rotated at 20 rpm.

<Example 3>
A triacetyl cellulose 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 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. The primer layer 62 and the antireflection functional layer 63 were formed by a film forming apparatus, and the antireflection laminate 59 shown in FIG. 2 was created.

Using the film forming apparatus shown in FIG. 3, while transporting the TAC film, SiOx is deposited on the hard coat layer 61 by the bipolar DMS method using the sputtering targets 19 and 20 on which the Si target is disposed, A primer layer 62 having a thickness of 3 nm was formed. 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 . The duty cycle was 80%.

  Subsequently, an antireflection functional layer 63 composed of 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.

Using the film forming apparatus shown in FIG. 3, while transporting the TAC film, the sputtering targets 21 and 22 both use the two targets, and on the primer layer 62 by the unipolar magnetron sputtering method. A TiO ₂ thin film was deposited to form a high refractive index transparent thin film layer 64 with 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, a voltage was applied to each target at a frequency of 50 kHz and a duty cycle of 80%. At that time, the rotating anode was rotated at 20 rpm.

Next, using the film forming apparatus shown in FIG. 3, while transporting the TAC film, both of the two targets are used in the sputtering targets 23 and 24, and a high refractive index is obtained by a unipolar magnetron sputtering method. A SiO ₂ thin film was deposited on the transparent thin film layer 64 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, a voltage was applied to each target at a frequency of 50 kHz and a duty cycle of 80%. At that time, the rotating anode was rotated at 20 rpm.

Further, using the film forming apparatus shown in FIG. 3, while transporting the TAC film, both of the two targets are used in the sputtering targets 25 and 26, and the low refractive index transparent thin film is formed by the unipolar magnetron sputtering method. A TiO ₂ thin film was deposited on the layer 65 to form a high refractive index transparent thin film layer 66 having an optical film thickness of 220 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 11.2 W / cm ^2, respectively. . At this time, a voltage was applied to each target at a frequency of 50 kHz and a duty cycle of 80%. At that time, the rotating anode was rotated at 20 rpm.

Next, using the film forming apparatus shown in FIG. 3, while transporting the TAC film, the sputtering targets 27 and 28 both use the two targets, and the high refractive index transparent by the unipolar magnetron sputtering method. A SiO ₂ thin film was deposited on the thin film layer 66 to form a low refractive index transparent thin film layer 67 having an optical film thickness of 120 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 8.3 W / cm ^2, respectively. . At this time, a voltage was applied to each target at a frequency of 50 kHz and a duty cycle of 80%. At that time, the rotating anode was rotated at 20 rpm.

<Example 4>
In the same procedure as in 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, the high refractive index transparent thin film layer 66, and the low refractive index transparent thin film layer 67 are formed. Film formation was performed. However, here, when forming a film, all the cathodes were not subjected to high-speed film formation control by the plasma parameters, but were formed by sputtering in the oxide mode.

<Comparative Example 1>
In the same procedure as in Example 1, a PET film was set on the unwinding roller 15 and the SiO ₂ film was formed on the sputtering targets 27 and 28 for 1000 minutes while being conveyed in the direction of the winding roller 16. The film speed was investigated and the number of arcing occurrences was counted. However, here, the rotating anode was not rotated, and a long run was performed in a stationary state.

<Comparative example 2>
In the same procedure as in Example 2, a PET film was set on the unwinding roller 15 and the SiO ₂ film was formed on the sputtering targets 27 and 28 for 1000 minutes while being conveyed in the direction of the winding roller 16. The film speed was investigated and the number of arcing occurrences was counted. However, here, the rotating anode was not rotated, and a long run was performed in a stationary state.

<Comparative Example 3>
In the roll-to-roll vacuum film forming apparatus shown in FIG. 3, a SiO ₂ film is formed on the sputtering targets 27 and 28 while a PET film is set on the unwinding roller 15 and conveyed in the direction of the winding roller 16. The film was formed for 1000 minutes, and the film formation rate was investigated and the number of occurrences of arcing was counted. At this time, a voltage is applied to the sputtering targets 27 and 28 by applying a voltage by a bipolar DMS method, Ar is used as a sputtering gas, O ₂ is used as a reactive gas, and flow rates are 180 sccm and 120 sccm, respectively. Yes, the film formation pressure was 0.3 Pa, and the input power was 8.3 W / cm ² each. At this time, a voltage was applied to each target at a frequency of 50 kHz, and high-speed film formation was performed in transition region control using plasma parameters.

<Comparative Example 4>
In the same procedure as in 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, the high refractive index transparent thin film layer 66, and the low refractive index transparent thin film layer 67 are formed. Film formation was performed. However, in this case, the film was formed by a bipolar DMS method as a voltage application method. The frequency at this time was 50 kHz. The duty cycle was 80%.

<Comparative Example 5>
Example 1, Example 2, Example 3, Example 4, Comparative Example 1, Comparative Example 2, Comparative Example 3, and a roll-to-roll type electron beam evaporation apparatus different from FIG. 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.

<Evaluation>
The following evaluation was performed about Examples 1, 2, 3, 4 and Comparative Examples 1, 2, 3, 4, 5. The results are shown in Tables 1-6.

(1) Arc generation investigation in long run During the long run over 1000 minutes performed in Examples 1 and 2 and Comparative Examples 1, 2 and 3, discharge was performed at the sputtering cathodes of targets 44, 45, 48 and 49 equipped with Si. The emission spectrum was measured, and the stability of light emission, that is, the rapid fluctuation of light emission at the moment when the arc occurred, was observed, and the number of occurrences was investigated. This is when the emission calibration is 35% for 251.6 nm Si emission under film formation conditions, and the instantaneous emission fluctuation at the time of arc occurrence is less than 5%. In the case of 10% or more and less than 30%, the case of 30% or more and less than 40% is investigated with respect to the elapsed time. The survey results are shown in Table 1.

(2) Film formation speed investigation Table 2 shows the film formation speed in film formation according to Examples 1 and 2 and Comparative Examples 1, 2, and 3. Table 3 shows the winding speed of the film forming apparatus when forming Examples 3 and 4 and Comparative Example 4.

(3) Indentation hardness test:
The indentation hardness (GPa) with an indentation depth of 100 nm was measured for the samples formed in Examples 3 and 4 and Comparative Examples 4 and 5 using an NEC thin film evaluation apparatus MHA-400. 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 4.

(4) Steel wool scratch test:
Steel wool # 0000 was fixed to a scratch tester (TESTER SANGYO CO., Ltd., Gakushin-type friction fastness tester AB-301) for the samples formed in Examples 3 and 4 and Comparative Examples 4 and 5. A load of 2.45N and 4.90N was applied, and a 100-round reciprocal scratch test was performed on each sample, and the wear state (number of scratches) of the sample was visually observed. The results are shown in Table 5.

(5) Bending test:
The samples formed in Examples 3 and 4 and Comparative Examples 4 and 5 are wound around stainless steel rods of 6 mmφ, 8 mmφ, 10 mmφ, and 14 mmφ for half a half each. Thereafter, whether or not cracks occurred in the antireflection functional layer and the HC layer was visually observed. The results are shown in Table 6.

  In the investigation of the number of arc occurrences shown in Table 1, less than 5% of arcs were generated less than 10 times during running for 1000 minutes in both Examples 1 and 2. On the other hand, in Comparative Examples 1 and 2 in which the rotary anode was not rotated, arcs frequently occurred. In particular, it can be seen that, in Comparative Example 1, a considerable number of occurrences occur because the anode does not rotate and the bias for reducing the charge-up is not applied. Further, since Comparative Example 3 is a normal bipolar DMS method, the polarity is changed every half cycle, so that the charge-up is mitigated and the number of occurrences of arc is reduced. In Examples 1 and 2, it can be seen that the level of arc generation is better than that in Comparative Example 3, and it can be seen that the present invention is effective in reducing arc generation.

  Also, from Table 2, Examples 1 and 2 were able to achieve a film formation rate nearly double that of Comparative Example 3 in terms of film formation rate. This is because two targets are sputtered at the same time, and it can be seen that there is an advantage in film formation speed as compared with the bipolar DMS method.

  Also, at the winding speed when forming the antireflection laminate 59 in Table 3, Example 3 of the present invention is Example 4 in which film formation was performed in an oxide mode by a unipolar method, and a bipolar DMS method. Compared to Comparative Example 4, the winding speed nearly doubled was achieved, and an equivalent antireflection film was obtained. Also, in Example 4 where sputtering was performed in the oxide mode, it is possible to obtain an equivalent antireflection laminate 59 at a winding speed comparable to that of Comparative Example 4.

  Further, from Table 4, Examples 3 and 4 were able to form an antireflection laminate 59 having a lower film hardness than Comparative Example 4 and a higher film hardness than Comparative Example 5. At the same time, from Table 5, the antireflection laminate 59 of Examples 3 and 4 of the present invention is inferior in scratch resistance and the film quality is sparse compared with the bipolar DMS method of Comparative Example 4. I understand that. On the other hand, compared to the vapor deposition method of Comparative Example 5, the film is more scratchable and has no practical problem.

  Further, from Table 6, the occurrence of cracks that can be visually confirmed in the bending test is only the comparative example using the bipolar DMS method of Comparative Example 4, and the antireflection laminate 59 of the present invention is the vapor deposition of Comparative Example 5. There is no crack that can be visually confirmed in the same way as the law, and it is easy to process even during cutting.

By using the laminate manufacturing apparatus of the present invention, it is possible to suppress the occurrence of arcing in unipolar sputtering during long run, which has been difficult in the past, to a negligible level. It has become possible at a higher speed than the DMS method. In addition, it has become possible to provide a laminated body having a flexible film quality with low film hardness and film stress by the bipolar DMS method, and having better mechanical properties than the deposited film.

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

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Film forming main roller 2 Plastic film 3 Sputtering target 4 Sputtering target 5 Rotating anode 6 Rotating anode 7 DC pulse power supply 8 DC pulse power supply 9 Depositing plate 10 Depositing plate 11 Partition plate 12 Partition plate 13 Plasma flow 14 Flow of plasma 15 Unwinding roller 16 Winding roller 17 Deposition main roller 18 Deposition main roller 19 Sputtering target (Si)
20 Sputtering target (Si)
21 Sputtering target (Ti)
22 Sputtering target (Ti)
23 Sputtering target (Si)
24 Sputtering target (Si)
25 Sputtering target (Ti)
26 Sputtering target (Ti)
27 Sputtering target (Si)
28 Sputtering target (Si)
29 Rotating anode 30 Rotating anode 31 Rotating anode 32 Rotating anode 33 Rotating anode 34 Rotating anode 35 Rotating anode 36 Rotating anode 37 Rotating anode 38 Rotating anode 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 (9)

In a sputtering apparatus characterized by having at least one or more magnetron electrodes to form a thin film layer on a substrate,
The sputtering apparatus, wherein the anode electrode in the magnetron electrode is a rotary electrode.   2. The sputtering apparatus according to claim 1, wherein a plurality of the magnetron electrodes are arranged in a housing and are partitioned so that a degree of vacuum can be set respectively.   The sputtering apparatus according to claim 1, wherein two or more magnetron electrodes are arranged in one film forming chamber.   The sputtering apparatus according to claim 1, wherein a power source of the magnetron electrode is a DC pulse power source.   The sputtering apparatus according to claim 1, further comprising transition region control means using plasma parameters.   A laminate formed using the sputtering apparatus according to claim 1.   An optical functional filter using the laminate according to claim 6.   An optical display device using the laminate according to claim 6.   An optical article using the laminate according to claim 6.