JP2008001929A - Method for producing antireflection stacked body, optically functional filter, and optical display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an antireflection stacked body having high abrasion properties, film hardness lower than that of a DMS thin film and higher than that by a vapor deposition process, and reduced luminescent points, to provide an optically functional filter, and to provide an optical display. <P>SOLUTION: In the method for producing the antireflection stacked body where an antireflection layer having a physical film thickness of ≥100 nm is deposited on a base material, or, an antireflection layer composed of a plurality of layers of optical thin film layers with different refractive indexes and having a physical film thickness of ≥100 nm is deposited on a base material, the antireflection layer is deposited by a magnetron sputtering process using a rotary target, and also, the magnetron sputtering process using the rotary target includes: having an antireflection layer forming material as a sputtering target and at least a pair of electrodes connected to a power source; and applying DC pulse voltage to the electrodes by a pulse packet system; and inverting polarities of the respective electrodes being a pair, after the application of DC pulse voltage for a plurality of times. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an antireflection laminate and a method for producing the same. The present invention also relates to an optical functional filter and an optical display device using the antireflection laminate on the front surface.

  In an optical display device such as a CRT, a liquid crystal display device, or a plasma display panel (PDP), there is a problem that it becomes difficult to recognize an image due to reflection of external light on a display screen. In recent years, optical display devices have been increasingly taken not only indoors but also outdoors, and the reflection of external light on the display screen has become a more serious problem.

  In order to reduce reflection of external light, an antireflection laminate having a low reflectance over a wide range of wavelengths in the visible light region is provided on the front surface of the optical display device. At the beginning of the development of a technique for forming an antireflection laminate on a substrate, multilayer film formation by vapor deposition or ion plating was predominant. However, in recent years, the judgment level for the bright spot of the antireflection laminate due to film defects such as pinholes has risen, and as a method for clearing this judgment level, film formation is performed from vapor deposition and ion plating to sputtering. The method is being replaced. Particularly, the film formation of the antireflection laminate on the plastic substrate is mainly performed by roll-to-roll continuous film formation, and a technique of forming a multilayer film in a single pass is used. It has become. This is a magnetron sputtering method in which thin film layer forming materials are arranged as targets in two pairs of cathodes in roll-to-roll continuous film formation using such a sputtering method, and sine waves are applied to the two pairs of cathodes. A discharge method in which voltages are alternately applied in positive and negative directions and two pairs of cathodes alternately serve as anodes, commonly called a dual magnetron sputtering method, is becoming mainstream (see Patent Document 1).

  In the dual magnetron sputtering method, positive and negative voltages are alternately applied to the two cathodes, so bombardment to the substrate side due to high energy particles during film formation is large, compared with normal DC sputtering and RF sputtering, A film having a large ion 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 film has a strong film stress. The film warps, and the anti-reflection film and hard coat are prone to cracking during cutting. There was a problem that it was difficult to handle later. 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. These solutions include setting the film formation pressure at the time of dual magnetron sputtering film formation to be high, and forming the film with a long target-substrate distance. The arc is likely to be generated, and it is difficult to generate a 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.

  When the dual magnetron sputtering method is used, this problem can be solved by using a pulse packet method. However, both of these methods have a problem that the duty cycle must be set low in order to suppress the occurrence of arcing, and there is a problem that a drop in the film forming rate occurs. Further, unless the number of pulse packets to be applied before the polarity reversal of the applied voltage is suppressed to a low level, there is a problem that arcing is similarly facilitated.

Patent literature is described below.
Japanese Patent Laid-Open No. 11-218603

  Therefore, the object of the present invention has been made in consideration of the above-mentioned technical background, and has a higher scratch resistance than a vapor-deposited thin film on the substrate, while the film hardness is higher than the film hardness of the vapor-deposited thin film. An antireflection laminate that has a film thickness less than that of a DMS thin film of the type by magnetron sputtering and can be stably formed over a long period of time and has very few bright spots, and the antireflection laminate It is an object to provide an optical functional filter and an optical display device.

As a solution to achieve the above objective,
The invention of claim 1
In the method for producing an antireflection laminate, in which an antireflection layer having a physical film thickness of 100 nm or more is formed on a substrate,
The antireflection layer is formed by a magnetron sputtering method using a rotary target,
The magnetron sputtering method using the rotary target has an antireflection layer forming material as a sputtering target and at least one pair of electrodes connected to a power source, and a DC pulse voltage is applied to the pair of electrodes by a bipolar method. It is a manufacturing method of the antireflection laminated body characterized by repeating applying one by one alternately.

The invention of claim 2
In the method for producing an antireflection laminate, in which an antireflection layer having a physical film thickness of 100 nm or more is formed on a substrate,
The antireflection layer is formed by a magnetron sputtering method using a rotary target,
In addition, the magnetron sputtering method using the rotary target has at least one pair of electrodes connected to an antireflection layer forming material as a sputtering target and a power source, and a DC pulse voltage is applied to the electrodes by a pulse packet method. Then, after applying the DC pulse voltage a plurality of times, the polarity of each pair of electrodes is reversed, and the method for producing an antireflection laminate is characterized.

The invention of claim 3
In the method for producing an antireflection laminate, which comprises an antireflection layer comprising a plurality of optical thin film layers having different refractive indexes and a physical film thickness of 100 nm or more on a substrate.
The antireflection layer is formed by a magnetron sputtering method using a rotary target,
In addition, the magnetron sputtering method using the rotary target has at least one pair of electrodes connected to an antireflection layer forming material as a sputtering target and a power source, and a DC pulse voltage is applied to the electrodes by a pulse packet method. Then, after applying the DC pulse voltage a plurality of times, the polarity of each pair of electrodes is reversed, and the method for producing an antireflection laminate is characterized.

The invention of claim 4
It is an optical functional filter which has the reflection preventing laminated body manufactured by the manufacturing method of any one of Claims 1-3.

The invention of claim 5
An optical display device having the optical functional filter according to claim 4 on a front surface.

  The antireflection laminate manufacturing method of the present invention has a flexible film quality with low film stress, and at the same time uses a sputtering method. It is possible to provide a weak and flexible film quality. In addition, it is possible to form a film in a stable state with little arcing without losing the film formation speed with a high duty cycle and a high number of packets over a long period of time. 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.

<Antireflection laminate>
FIG. 1 is a cross-sectional view showing an example of the antireflection laminate of the present invention. The antireflection laminate 1 includes a base material 2, a hard coat layer 3 provided on the base material 2, a primer layer 4 provided on the hard coat layer 3, and a reflection provided on the primer layer 4. The anti-staining layer 5, the anti-smudge layer 6 provided on the anti-reflection function layer 5, and the adhesive layer 7 provided on the other surface of the substrate 2 are roughly configured. In addition to the hard coat layer and antifouling layer, the antireflection laminate of the present invention may be provided with other layers such as an antistatic layer. Examples of the antistatic layer include a layer containing a binder matrix containing a hydrolyzate of silicon alkoxide and antimony pentoxide fine particles having a particle diameter of 1 to 100 nm.

(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 not particularly limited as long as the surface is smooth, and examples thereof include a plate shape and a roll shape. Further, the base material may be a laminate of an organic compound molded product having transparency. The base material may be glass. Glass or plastic glasses may be used as the base material.

  An example of the organic compound molding having transparency is plastic. Examples of the plastic include polyester, polyamide, polyimide, polypropylene, polyethylpentene, polyvinyl chloride, polyvinyl acetal, polyurethane, polyethyl 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 examples thereof include resin materials such as acrylic resins, organic silicon resins, and polysiloxanes.

  Acrylic resins include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol (meth) acrylate, ethylene glycol di (meth) acrylate, and 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) acryloyloxypropionate, trimethylol Ethanetri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (2-h Roxyethyl) 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) acryloyl Oxymethyltricyclo [5.2.10] decane, hydrogenated bisphenol A di (meth) acrylate, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 1,4-bis ((meta ) Acryloyloxymethyl E) 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.

  Examples of the organic silicon resin include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrapentaethoxysilane, tetrapentaisoproxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, Examples include butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, dimethylpropoxysilane, dimethylbutoxysilane, methyldimethoxysilane, methyldiethoxysilane, and hexyltrimethoxysilane.

  The hard coat layer is formed by depositing these resin materials on the substrate 2 and curing them by heat curing, ultraviolet curing, or ionizing radiation curing. The thickness of the hard coat layer 3 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. The fine particles in the hard coat layer 3 have fine irregularities on the surface, improving the light diffusibility and further reducing the reflection of light.

  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 3 include corona treatment, vapor deposition, electron beam treatment, high frequency discharge plasma treatment, sputtering treatment, ion beam treatment, atmospheric pressure glow discharge plasma treatment, and 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 2 and is preferably a physical film thickness of 0.1 to 10 nm. The primer layer 4 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. Lead fluoride, strontium fluoride, ytterbium fluoride and the like. Moreover, an alumina containing silicon oxide etc. are mentioned.

  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.

These optical thin film layers such as a low refractive index transparent thin film layer, a high refractive index transparent thin film layer, and a medium refractive index transparent thin film layer maintain a certain hardness in a single layer or a laminated layer. Good characteristics are obtained in the scratch resistance. Therefore, in order to obtain a certain level of scratch resistance, a film hardness of a certain hardness or more is required. On the other hand, a film having a high hardness has a dense film quality and becomes a film having a strong stress. Therefore, a film quality not less than the film hardness of the deposited film and not more than the film hardness of the DMS film is required.

  An example of a method for measuring the film hardness is an indentation hardness test. In the indentation hardness test, the indentation depth is an important parameter. Basically, in order to obtain the indentation depth with good reproducibility, the indentation depth of about 100 nm is good. Further, from the viewpoint of evaluating the scratch resistance, it can be said that not only the hardness of the outermost surface but also the result of the indentation hardness with respect to the indentation depth of about 100 nm is suitable. From the viewpoint of an antireflection film, in order to exhibit antireflection performance, a physical film thickness of 100 nm or more is basically required. Accordingly, an indentation depth of 100 nm is appropriate for an antireflection film having a physical film thickness of 100 nm or more.

  These optical thin film layers such as a low refractive index transparent thin film layer, a high refractive index transparent thin film layer, and a medium refractive index transparent thin film layer are formed by sputtering, vapor deposition, chemical vapor deposition (CVD), reactive sputtering, etc. it can. In particular, in order to pursue higher production stability such as higher deposition rate and de-arcing, the dual magnetron sputtering method that performs deposition with voltage application in the medium frequency region is optimal. At least one of the thin film layers is formed by a dual magnetron sputtering method using a pulse packet method. By doing so, it is possible to obtain a flexible film quality with a good bright spot level and a low film stress. When there are a plurality of antireflection layers, the other layers are preferably formed by magnetron sputtering. Further, the other layers are preferably formed by a dual magnetron sputtering method using a pulse packet method, or a magnetron sputtering method in which a pulse voltage is applied synchronously using two pairs of electrodes. As a result, it is possible to obtain a flexible and high-quality film quality with a better bright spot level and a low film stress.

(Anti-fouling layer)
In the present invention, an antifouling layer may be provided on the outermost surface of the antireflection laminate. The antifouling layer is a layer obtained from a fluorine-containing silicon compound having one or more silicon atoms bonded to a reactive functional group, a layer obtained from an organosilicon compound having a siloxane bond as the main chain, or It is a layer obtained from both. The reactive functional group in the present invention means a group capable of reacting with and bonding to the material of the low refractive index transparent thin film layer. Therefore, the antifouling layer 6 specifically reacts the reactive functional group of the fluorine-containing silicon compound with the material of the low-refractive-index transparent thin film layer 14, and combines the reactive functional groups of the fluorine-containing silicon compound with each other. When it is a layer formed by reacting, or when it is a layer formed by reacting a reactive functional group of an organosilicon compound having a siloxane bond as the main chain with the material of the low refractive index transparent thin film layer Or a layer formed by reacting reactive functional groups of an organosilicon compound having a siloxane bond as the main chain, or a fluorine-containing silicon compound and an organosilicon compound having a siloxane bond as the main chain Are simultaneously reacted with those reactive functional groups and the material of the low-refractive-index transparent thin film layer 14, and the reactive functional groups of the fluorine-containing silicon compound and an organosilicon compound having a siloxane bond as the main chain Reactive functional groups to each other, or a layer formed by reacting the reactive functional groups to each other of the fluorine-containing silicon compound and an organic silicon compound a siloxane bond as a main chain.

  The molecules forming these antifouling layers are required to have a certain molecular weight. This is because, when a coarser film thin film obtained by the DMS method is formed, the antifouling layer constituting molecules may penetrate into the antireflection functional layer after forming the antifouling layer. For this reason, antifouling molecules are required to have a certain molecular weight.

Examples of the reactive functional group include a hydrolyzable group and a halogen atom. Examples of hydrolyzable groups include alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy groups; alkoxyalkoxy groups such as methoxymethoxy, methoxyethoxy, and ethoxyethoxy groups; alkenyloxy groups such as allyloxy and isopropenoxy groups An acyloxy group such as an acetoxy group, a propionyloxy group, a butylcarbonyloxy group or a benzoyloxy group; a ketoxime group such as a dimethylketoxime group, a methylethylketoxime group, a diethylketoxime group, a cyclopentanoxime group or a cyclohexanoxime group; Amino groups such as N-methylamino group, N-ethylamino group, N-propylamino group, N-butylamino group, N, N-dimethylamino group, N, N-diethylamino group, N-cyclohexylamino group; N -Methylacetamide , N- ethyl acetamide group, an amido group such as N- methylbenzamide group; N, N- dimethylamino group, N, an amino group, such as N- diethylamino group and the like. Examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom. Of these, a methoxy group, an ethoxy group, and an isopropenoxy group are preferable.

  As a fluorine-containing silicon compound which has one or more silicon atoms couple | bonded with the reactive functional group, the compound represented by following formula (1) is mentioned, for example. Moreover, as an organosilicon compound which has a siloxane bond in a principal chain, the compound represented by following formula (2) is mentioned, for example.

(R ¹ ) _3-m (X ¹ ) _m Si—R ³ —O—R ⁵ —R ^f —R ⁶ —O—R ⁴ —Si (R ² ) _3-n (X ² ) _n. Formula (1)

_{^{(R 1) 3-m (}} X 1) m Si-R 3 - (OSi (R 7) 2) s - (OSi (R 7) (R 8)) t -R 9 ···· formula (2)

In formulas (1) and (2), R ¹ and R ² represent a monovalent hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 3 carbon atoms, and X ¹ and X ² represent a reactive functional group. , R ³ and R ⁴ represent an alkylene group, R ⁵ and R ⁶ represent an alkylene group or an oxyalkylene group, Rf represents a perfluoroalkylene group or a perfluoro (poly) oxyalkylene group, m, n represents an integer of 1 to 3. Examples of the monovalent hydrocarbon group for R ¹ and R ² include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl; cyclopentyl and cyclohexyl Cycloalkyl groups such as phenyl groups, aryl groups such as tolyl groups and xylyl groups; aralkyl groups such as benzyl groups and phenethyl groups; alkenyl groups such as vinyl groups, allyl groups, butenyl groups, pentenyl groups and hexenyl groups. It is done. s and t are integers, preferably 0 to 100. R ⁷ is the same or different monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ⁸ is a monovalent hydrocarbon group having 1 to 10 carbon atoms which may contain a fluorine atom. R ⁹ is CH ₃ , CF ₃ or the like.

Specific examples of fluorine-containing silicon compounds having at least one silicon atom bonded to a reactive functional group include CF ₃ (CF ₂ ) _p (CH ₂ ) _q Si (OCH ₃ ) ₃ , CF ₃ (CF _{2 ) p (OC3F 6) q OCF} 2 CF 2 CH 2 CH 2 (OCONH) CH 2 CH 2 Si (OCH 3) 3, (CH3O) 3 SiCH 2 CH 2 CH 2 OCH 2 CF 2 CF 2 O (CF 2 CF _{2 CF 2 O) p CF 2} CF2CH 2 OCH 2 CH 2 CH 2 Si (OCH 3) 3, (CH 3 O) 2 CH 3 SiCH 2 CH 2 CH2OCH 2 CF 2 CF 2 O (CF 2 CF 2 CF 2 O _{) p CF 2 CF 2 CH 2} OCH 2 CH 2 CH2SiCH 3 (OCH 3) 2, (CH 3 O) 3 SiCH 2 CH 2 CH 2 OCH 2 CF 2 (OC 2 F4) q (OCF 2) r OCF 2 CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , (CH ₃ O) ₂ CH ₃ SiCH ₂ CH ₂ CH ₂ OCH ₂ CF ₂ (OC ₂ F ₄ ) _q (OCF ₂ ) _r OCF ₂ CH ₂ OCH ₂ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ , _{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 OCH 2 CF 2 (OC 2 F 4) 2 (OCF 2) r OCF 2 CH 2 OCH 2 CH 2 CH 2 Si (OC 2 H 5) 3, ( _{CH 3 O) 3 SiCH 2 C} (= CH 2) CH 2 CH 2 CH 2 OCH 2 CF 2 CF 2 O (CF2CF 2 CF 2 O) p CF 2 CF 2 CH 2 OCH 2 CH 2 CH 2 (CH 2 = ) CCH ₂ Si (OCH ₃ ) ₃ , (CH ₃ O) ₃ SiCH ₂ C (═CH _{2
) CH 2 CH 2 CH 2 OCH} 2 CF 2 (OC2F 4) q (OCF 2) r OCF 2 CH 2 OCH 2 CH 2 CH 2 (CH 2 =) CCH 2 Si (OCH 3) 3, (CH 3 O) _{2 CH 3 SiCH 2 C (=} CH 2) CH 2 CH 2 CH 2 OCH 2 CF 2 (OC 2 F 4) q (OCF 2) r OCF 2 CH 2 OCH 2 CH 2 CH 2 (CH 2 =) CCH 2 SiCH ₃ (OCH _{3) 2} and the like. However, it is an integer of p = 1-50, q = 1-50, r = 1-50, q + r = 10-100, and the repeating unit in a formula is random.

Specific examples of organosilicon compounds having a siloxane bond as the main chain include (CH ₃ O) ₃ Si— (CH ₂ ) ₂ —O— (Si (CH ₃ ) ₂ O) ₁₄ — (CH ₂ ) ₂ —Si _{(OCH 3) 3, (CH} 3 O) 3 Si- (CH 2) 2 -O- (Si (C 2 H 4 F 3) 2 O) 14 - (CH 2) 2 -Si (OCH 3) 3, _{(CH 3 O) 3 Si- (} CH 2) 2 - (OSi (CH 2) 2) 13 - (OSi (C 2 H 4 F 3) 2) , etc. ₁₃ -CH ₃ and the like.

  The antifouling layer can be formed by a wet process such as a microgravure method, a screen coating method, or a dip coating method in addition to a vacuum dry process such as an evaporation method, a sputtering method, a CVD method, or a plasma polymerization method. The physical film thickness of the antifouling layer is about 1 to 30 nm, preferably about 3 to 15 nm. The contact angle of pure water on the surface of the antifouling layer is preferably 90 ° or more from the viewpoint of waterproofing and antifouling properties in view of the antifouling performance of the antireflection film.

(Adhesive layer)
In the present invention, the antireflection laminate can be bonded to other members such as a functional member, an optical display device, and a window material using an adhesive layer. The adhesive layer may be any layer that transmits light having a wavelength in the visible light region and has adhesiveness. From the viewpoint of optical performance, the adhesive layer preferably has a refractive index of light having a wavelength of 500 to 600 nm of 1.45 to 1.7 and an extinction coefficient of approximately 0. Examples of the material for the pressure-sensitive adhesive layer include acrylic adhesives, silicon adhesives, urethane adhesives, polyvinyl butyral adhesives (PVA), ethylene-vinyl acetate adhesives (EVA), polyvinyl ether, and saturated amorphous polyesters. And melamine resin.

  In the present invention, a rotary target is used, and at least one of the antireflection layers is formed by a magnetron sputtering method using a pulse packet method.

  The sputtering method includes a material for forming an antireflection layer and an electrode, and a voltage is applied to the electrode. Among them, a method called a dual magnetron sputtering method (hereinafter referred to as DMS method) applies a sine wave or a DC pulse wave of 1 k to 300 kHz, preferably 1 k to 100 kHz, alternately applying positive and negative voltages to the paired electrodes. In this discharge method, the pair of electrodes alternately serve as a cathode and an anode. Since the voltage is applied alternately between positive and negative by the two electrodes, bombardment to the substrate side due to high energy particles during film formation is large, and the ion assist effect is large compared to vapor deposition, normal DC sputtering, and RF sputtering. A dense film having high film hardness and high film stress is formed. In the present invention, a film having a high film hardness and a high film stress peculiar to the DMS method can be freely formed from a film having a low film hardness and a low film stress with a rough film quality of DC sputtering and RF sputtering levels. There is to do.

The magnetron sputtering method using the pulse packet method has at least one pair of electrodes connected to a normal power source, and after applying a DC pulse voltage multiple times by the pulse packet method, the polarity of the paired electrodes is changed. Invert. As a result, the amount of high energy particles in the plasma diffused toward the substrate can be reduced by reducing the number of voltage reversals per unit time between a pair of electrodes, and the heat load received by the substrate can be reduced. This is a method capable of reducing and forming a flexible thin film. In this pulse packet system, after applying a DC pulse voltage at a frequency of about 1 to 300 kHz with one target as an anode and the other target as a cathode, the applied voltage between the targets is reversed, This means that the applied voltage is inverted at intervals of about 0.1 kHz to 100 kHz. The voltage to be applied is basically a voltage that causes ion acceleration that can be sputtered, and the voltage may be appropriately increased in order to obtain a desired film formation rate. However, it is necessary to set appropriately considering the generation of micro arcs, the thermal load on the substrate to be used, the generation of cracks in the target, and the like. Further, it is preferable to form the film under a pressure of about 0.1 to 10 Pa, preferably about 0.1 to 1 Pa.

  In addition, depending on the film forming material, a combination with precise process control technology based on plasma parameter monitoring, such as plasma emission during sputtering, that is, sputtering within the transition region of the sputtering hysteresis, High-speed film formation with excellent film thickness uniformity over the area is possible.

  The DMS method can prevent arcing by removing the charge-up of the insulating product formed in the erosion part of the target and its periphery during sputtering or reactive sputtering. High power input is possible. Therefore, since there is almost no arcing for a long time and film formation at high speed is possible, it is most suitable for roll-up roll film formation. In this case, depending on the film deposition material, it can be combined with precise process control technology based on plasma parameter monitoring, such as plasma emission during sputtering, and it has excellent film thickness uniformity over a large area. Film formation is possible.

  The problem here is the setting of the duty cycle. A plurality of DC pulse voltages are applied between the electrodes until the polarity of the pair of electrodes is reversed. When the voltage OFF time between the applied pulses and the applied pulse is short and the voltage ON time is long, that is, the duty cycle If it is high, arcing is likely to occur. In particular, the greater the number of DC pulse voltages that are applied before reversing the polarity between the electrodes, the higher the frequency of arcing. For this reason, in order to perform stable long-time film formation, it is necessary to set the duty cycle low, reduce the number of applied pulses until the polarity of the electrode is reversed, or both. For this reason, when the voltage ON time per unit time is reduced, the film forming speed is lowered, and when the number of applied pulses until the polarity is reversed is small, the film quality is close to that of the normal DMS method and the stress is strong. It becomes a film with high film hardness.

At present, the DMS method generally uses a planar target, and in the case of the DMS method using a planar target, the center of the target remains without being dug, but simultaneously sputtered particles are deposited in this portion. To do. In the case of forming an antireflection film, an insulating film is almost always used. During DMS sputtering, electrons try to flow into the anode, but electrons tend to flow into the insulating film deposition portion at the center of the target because they pass through a place where the magnetic flux density is low. Here, charge-up occurs in the insulating film, causing arcing. In particular, when the target usage time becomes longer, this tendency appears remarkably. In the pulse packet system, charge-up is particularly likely to occur because the number of electrode polarity inversions per unit time is small. This is the problem that the aforementioned duty cycle must be lowered. The present invention proposes and claims a manufacturing method using a rotary target as a solution. In recent years, the development of a rotary target has been developed to a practical level, and the dual magnetron sputtering cathode used for coating glass or the like is being replaced with a rotary target. In dual magnetron sputtering using a rotating target, the cylindrical target is always rotating during sputtering, so not only the erosion part is dug like the planar type, but the target is dug evenly. There is an advantage of high efficiency. Further, since it can be cut evenly, an insulating film is not deposited at the center of the target as in the planar type, so that charge-up is unlikely to occur, and arcing does not occur even with the Pulpacket DMS method. Further, the rotation speed of the rotary target is preferably within 40 rpm, and more preferably 10 rpm to 30 rpm.

<Optical functional filter>
The optical functional filter of the present invention has the antireflection laminate of the present invention. 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. In the plasma display panel filter, in addition to the antireflection layer of the present invention, as other layers, an antiglare layer that ensures antiglare properties, an antinewton ring layer that suppresses the generation of Newton rings, a color correction layer, and an infrared cut layer In addition, an ultraviolet cut layer, a gas barrier layer, an antistatic layer, an electromagnetic wave shielding layer, or the like may be provided.

<Optical display device>
The optical display device of the present invention has an optical functional filter on the front surface. Specifically, the antireflection laminate of the present invention or the optical functional filter of the present invention is provided on the front surface of an optical display device such as a CRT, liquid crystal display device or plasma display panel.

  The antireflection laminate of the present invention can also be applied to light source reflectors and window materials used in liquid crystal display devices.

  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. 2 will be described. An outline of the vacuum film forming apparatus shown in FIG. 2 will be described. First, since the sputtering cathodes 1, 2, 3, 4, and 5 use a DMS method using a rotating cathode in the first embodiment, a DMS cathode is disposed. Nos. 4 and 5 are provided with partitions so that different film forming pressures can be set as high-speed switchers for applying DC voltage. On the sputter cathodes 2, 3, 4, and 5, a power supply UBS-C2 manufactured by Fraunhofer Institute Elektronenstrahl-und Plasmatechnik and two DC power supplies for applying voltage to the cathode are installed in the UBS-C2. Thus, two DC pulse power supplies can be alternately switched on / off at high speed with respect to a pair of electrodes, and a DC pulse voltage can be alternately applied between DMS targets. Further, as shown in FIG. 2, the sputter cathodes 2, 3, 4, 5 can be replaced with MF sine wave power sources. Further, the sputter cathode 1 is provided with an MF sine wave power source TIG 100 manufactured by Hutinga. By using this film forming apparatus, the TAC raw fabric is set on the unwinding roller a, and the TAC film is conveyed in the direction of the winding roller b, whereby the primer layer 4 in the antireflection laminate 1 exemplified in the present invention. It is possible to laminate all the antireflection functional layers 5 in only one outward path.

An outline of the vacuum film forming apparatus shown in FIG. 3 will be described. First, since the sputtering cathodes 5, 6, 7, 8, and 9 use the DMS method using a planar cathode in the first embodiment, the DMS cathodes are arranged, and the sputtering cathodes 5, 6, 7 are used. , 8 and 9 are provided with partitions so that different film formation pressures can be set. For the sputter cathodes 6, 7, 8, and 9, UBS-C2 manufactured by Fraunhofer Institute Elektronenstrahl-und Plasmatechnik as a high-speed switcher for applying DC voltage, and two DC power supplies UBS-C2 for applying voltage to the cathode are used. It is installed in. As a result, two DC pulse power sources can be alternately switched ON / OFF at high speed with respect to a pair of electrodes, and a DC pulse voltage can be alternately applied between DMS targets. Further, the sputter cathode 5 is provided with an MF sine wave power source TIG 100 manufactured by Hutinga. By using this film forming apparatus, the TAC raw fabric is set on the unwinding roller a, and the TAC film is conveyed in the direction of the winding roller b, whereby the primer layer 4 in the antireflection laminate 1 exemplified in the present invention. It is possible to laminate all the antireflection functional layers 5 in only one outward path.

<Example 1>
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 material 2, and an ultraviolet curable resin (Japan) Synthetic chemistry UV-7605B) was formed by wet coating (microgravure method) to form a hard coat layer 3 having a physical thickness of 5 μm, and the antireflection laminate shown in FIG. 1 was formed. On the hard coat layer, the primer layer 4 and the antireflection functional layer 5 were formed using a roll-to-roll vacuum film forming apparatus shown in FIG. Using the film forming apparatus shown in FIG. 2, while transporting the TAC film, SiO _x is deposited on the hard coat layer 3 by the DMS method on the sputter cathode 1 on which the Si target is arranged, and the physical film thickness is 3 nm. Primer layer 4 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 0.9 W / cm ² .

Subsequently, the antireflection functional layer 5 including the high refractive index transparent thin film layer 11, the low refractive index transparent thin film layer 12, the high refractive index transparent thin film layer 13, and the low refractive index transparent thin film layer 14 was formed as follows. A TiO ₂ thin film is deposited on the primer layer 4 by the sputtering cathode 2 by the DMS method while transporting the TAC film using the film forming apparatus shown in FIG. 11 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 120 sccm, respectively, the film forming pressure was 0.3 Pa, and the input power was 1.7 W / cm ² . At this time, a voltage was applied to a pair of DMS rotary targets (target A and target B) using a pulse packet method. The packet length (pulses) at this time was set to 3 pulses as shown in FIG. The frequency was 50 kHz and the duty cycle was 80%. The rotational speed of the rotary target was 15 rpm.

Next, using the film forming apparatus shown in FIG. 2, while transporting the TAC film, a SiO ₂ thin film is deposited on the high refractive index transparent thin film layer 11 by the DMS method at the sputter cathode 3 to obtain an optical film thickness of 35 nm. The low refractive index transparent thin film layer 12 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 120 sccm, respectively, the film forming pressure was 0.3 Pa, and the input power was 2.4 W / cm ² . At this time, a voltage was applied to the DMS cathode using a pulse packet system. The packet length (pulses) at this time was set to 3 pulses as shown in FIG. The frequency was 50 kHz and the duty cycle was 80%. The rotational speed of the rotary target was 15 rpm.

Further, using the film forming apparatus shown in FIG. 2, while transporting the TAC film, TiO ₂ was deposited on the low refractive index transparent thin film layer 12 by the DMS method at the sputter cathode 4 to obtain a high optical film thickness of 220 nm. A refractive index transparent thin film layer 13 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 120 sccm, the film forming pressure was 0.3 Pa, and the input power was 12.0 W / cm ² , respectively. At this time, a voltage was applied to the DMS cathode using a pulse packet system. The packet length (pulses) at this time was set to 3 pulses as shown in FIG. The frequency was 50 kHz and the duty cycle was 80%. The rotational speed of the rotary target was 15 rpm.

Next, using the apparatus shown in FIG. 2, while transporting the TAC film, SiO ₂ is deposited on the high refractive index transparent thin film layer 13 by the DMS method at the sputter cathode 5 to obtain a low refractive index with an optical film thickness of 120 nm. A transparent thin film layer 14 was formed. At this time, the sputtering gas is Ar, the reactive gas is O ₂ , the flow rates are 200 sccm for Ar and 120 sccm for O ₂ , the deposition pressure is 0.3 Pa, and the input power is 8.3 W / cm ^2. Was done. At this time, a voltage was applied to the DMS cathode using a pulse packet system. The packet length (pulses) at this time was set to 3 pulses as shown in FIG. The frequency was 50 kHz and the duty cycle was 80%. The rotational speed of the rotary target was 15 rpm.

  Furthermore, the fluorine-containing silicon compound represented by the following formulas (3), (4), and (5) and the following formulas (6), (7), and (8) are formed on the low refractive index transparent thin film layer 14. The organic silicon compound having a siloxane bond as the main chain is deposited by a vacuum evaporation method using resistance heating using a vacuum film forming apparatus different from the vacuum film forming apparatus shown in FIG. An antifouling layer 6 was formed. As a method and conditions for resistance heating at this time, a molybdenum boat is used as a boat for resistance heating by adding an antifouling agent, and each antifouling agent is filled and a voltage is applied so as to be 35 to 50A. Film formation was performed so that the film formation rate was 5 Å / sec. The film formation rate was measured with a crystal resonator (INFICON XTC / 2). Furthermore, the adhesive layer 7 is formed on the surface of the TAC film opposite to the surface provided with the antireflection layer by applying an acrylic adhesive (Nippon Synthetic Chemical Coponil N-2233) by the microgravure method. The prevention laminated body 1 was obtained.

_{(CH 3 O) 3 Si- (} CH 2) 2 -O- (CH 2) 2 -O- (CF 2 CF 2 CO) 5 - (CH 2) 2 -O- (CH 2) 2 -Si (OCH ₃ ) ₃ ... Formula (3)

_{(CH 3 O) 3 Si- (} CH 2) 2 -O- (CH 2) 2 -O- (CF 2 CF 2 CF 2 O) 6 - (CH 2) 2 -O- (CH 2) 2 -Si (OCH ₃ ) ₃ Formula (4)

_{(CH 3 O) 3 Si- (} CH 2) 2 -O- (CH 2) 2 -O- (CF 2 CF 2 CF 2 O) 8 - (CH 2) 2 -O- (CH 2) 2 -Si (OCH ₃ ) ₃ Formula (5)

_{(CH 3 O) 3 Si- (} CH 2) 2 -O- (CH 2) 2 -O- (Si (CH 3) 2 O) 10 - (CH 2) 2 -O- (CH 2) 2 -Si (OCH ₃ ) ₃ Formula (6)

_{(CH 3 O) 3 Si- (} CH 2) 2 -O- (CH 2) 2 -O- (Si (CH 3) 2 O) 13 - (CH 2) 2 -O- (CH 2) 2 -Si (OCH ₃ ) ₃ Formula (7)

_{(CH 3 O) 3 Si- (} CH 2) 2 -O- (CH 2) 2 -O- (Si (CH 3) 2 O) 14 - (CH 2) 2 -O- (CH 2) 2 -Si (OCH ₃ ) 3 Formula (8)

<Example 2>
In the same procedure as in Example 1, the hard coat layer 3, the primer layer 4, the high refractive index transparent thin film layer 11, the low refractive index transparent thin film layer 12, the high refractive index transparent thin film layer 13, and the low refractive index transparent thin film layer 14 Film formation was performed in a long run over 1000 minutes. Here, the power length of the sputtering cathodes 2, 3, 4, and 5 is set to 3 pulses. The frequency was 50 kHz and the duty cycle was 80%. The rotational speed of the rotary target was 15 rpm.

<Example 3>
In the same procedure as in Example 1, hard coat layer 3, primer layer 4, high refractive index transparent thin film layer 1
1. The low refractive index transparent thin film layer 12, the high refractive index transparent thin film layer 13, and the low refractive index transparent thin film layer 14 were formed in a long run over 1000 minutes. Here, the packet length (pulses) of the power source for the sputtering cathodes 2, 3, 4, and 5 was set to 50 pulses. The frequency was 50 kHz and the duty cycle was 90%. The rotational speed of the rotary target was 15 rpm.

<Example 4>
In the same procedure as in Example 1, the hard coat layer 3, the primer layer 4, the high refractive index transparent thin film layer 11, the low refractive index transparent thin film layer 12, the high refractive index transparent thin film layer 13, and the low refractive index transparent thin film layer 14 Film formation was performed in a long run over 1000 minutes. Here, the packet length (pulses) of the power source of the sputtering cathodes 2, 3, 4, and 5 is set to 1 pulses, that is, a bipolar system. The frequency was 50 kHz and the duty cycle was 90%. The rotational speed of the rotary target was 15 rpm.

<Comparative Example 1>
In the same procedure as in Example 1, the hard coat layer 3, the primer layer 4, the high refractive index transparent thin film layer 11, the low refractive index transparent thin film layer 12, the high refractive index transparent thin film layer 13, the low refractive index transparent thin film layer 14 and The antifouling layer 6 and the adhesive layer 7 were formed. However, here, the power source of the sputtering cathodes 2, 3, 4, and 5 was an MF sine wave power source. The MF sine wave used 50 kHz. The voltage waveforms applied to the target 1 and target 2 of each cathode at this time are shown in FIG.

<Comparative example 2>
A roll-to-roll type electron beam evaporation apparatus different from the sputter-coated roll coater shown in FIGS. 2 and 3 is used to form a primer layer 4, a high refractive index transparent thin film layer 11, a low refractive index transparent thin film layer 12, and a high refractive index. After the transparent thin film layer 13 and the low refractive index transparent thin film layer 14 are formed, the above formulas (3), (4), and (5) are formed on the low refractive index transparent thin film layer 14 as in Example 1. 2 and the organic silicon compound having a siloxane bond as a main chain represented by the above formulas (6), (7), and (8), respectively, as shown in FIG. Using another vacuum film forming apparatus, deposition was performed by a vacuum vapor deposition method using resistance heating to form an antifouling layer 6 having a physical film thickness of 6 nm. Furthermore, the adhesive layer 7 was formed on the surface of the TAC film opposite to the surface provided with the antireflection layer by applying an acrylic adhesive in the same manner as in Example 1 to obtain the antireflection laminate 1.

<Comparative Example 3>
In the planar type sputtering cathode shown in FIG. 3, the hard coat layer 3, the primer layer 4, the high refractive index transparent thin film layer 11, the low refractive index transparent thin film layer 12, the high refractive index transparent thin film layer 13, and the low refractive index transparent thin film. Layer 14 was performed in a long run over 1000 minutes. However, the packet length (pulses) of the power source of the sputter cathodes 6, 7, 8, and 9 was set to 3 pulses. The frequency was 50 kHz and the duty cycle was 85%.

<Comparative Example 4>
In the planar type sputtering cathode shown in FIG. 3, the hard coat layer 3, the primer layer 4, the high refractive index transparent thin film layer 11, the low refractive index transparent thin film layer 12, the high refractive index transparent thin film layer 13, and the low refractive index transparent thin film. Layer 14 was performed in a long run over 1000 minutes. However, the packet length (pulses) of the power source for the sputter cathodes 6, 7, 8, and 9 was set to 15 pulses. The frequency was 50 kHz and the duty cycle was 85%.

<Evaluation>
The antireflection laminate 1 obtained in Example 1 and Comparative Examples 1 and 2 was evaluated as follows. The results are shown in Tables 1-4.
(1) Indentation hardness test:
The indentation hardness (GPa) with an indentation depth of 100 nm was measured for the samples formed in Example 1, Comparative Example 1, and Comparative Example 2 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 1.

(2) 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 Example 1, Comparative Example 1, and Comparative Example 2. Each sample was subjected to 100 reciprocal scratch tests under a load of 250 gf and 500 gf, and the wear state (number of scratches) of the sample was visually observed. The results are shown in Table 2.

(3) Bending test:
Samples deposited in Example 1, Comparative Example 1, and Comparative Example 2 are each wound around a stainless steel rod of 6 mmφ, 8 mmφ, 10 mmφ, and 14 mmφ for a half circumference. Thereafter, whether or not cracks occurred in the antireflection functional layer and the HC layer was visually observed. The results are shown in Table 3.

(4) Contact angle measurement test:
The pure water contact angle (°) of the samples formed in Example 1, Comparative Example 1 and Comparative Example 2 was measured using a contact angle meter CA-X manufactured by Kyowa Interface Chemical Co., Ltd. Table 4 shows the measurement results. At this time, the chemical formula No. The number in parenthesis just below is the molecular weight of each antifouling agent.

(5) Defect count measurement:
The number of defects (pieces / m ² ) of the samples formed in Example 1, Comparative Example 1, and Comparative Example 2 having a size of 100 μm and 50 μm was observed and measured with an optical microscope. The measurement results are shown in Table 5.

(6) Investigation of arc generation in long run Emission spectroscopic measurement in discharge of sputtered cathode loaded with Si during 1000 minutes long run performed in Example 2, Example 3, Example 4, Example 5, and Comparative Example 3 We observed the stability of light emission, that is, the sudden fluctuation of light emission at the moment when the arc occurred, and investigated the number of occurrences. For 251.6 nm Si emission under film formation conditions, the emission calibration is 35%, the instantaneous emission fluctuation at the time of arc generation is 5% or more, 10% or more, 20% or more In the case of 40% or more, the time elapsed is investigated. The results of this investigation are shown in Table 6.

  From the measurement results in the indentation hardness test shown in Table 1, the antireflection laminate 1 of the present invention is a film having a low film hardness compared to a normal DMS method using a sine wave, and a film compared to a deposited film. It turns out that it is a film | membrane with high hardness.

  Also, from Table 2, the antireflection laminate 1 of the present invention is inferior in scratch resistance as compared with a normal DMS method using a sine wave, but is superior in scratch resistance as compared with a vapor deposition method. I understand.

  Moreover, from the results of Table 3, the occurrence of cracks that can be visually confirmed in the bending test is only the ordinary DMS method using a sine wave, and the antireflection laminate 1 of the present invention is deposited even during processing such as cutting. It has the ease of processing like a film.

  Further, from the results shown in Table 4, when both the fluorine-containing silicon compound and the organosilicon compound having a siloxane bond as the main chain have a molecular weight of 1400 or more, no antifouling agent permeates into the antireflection functional layer 5. .

  Further, even at the bright spot level, the antireflection laminate 1 of the present invention is clearly at a better level than the vapor deposition film, and is at the bright spot level equivalent to the normal DMS method using a sine wave. I understood.

  Further, from the results of Table 6, the DMS method using the rotary target has higher stability in the long run than the planar type DMS method even if the pulse packet method is used for the voltage application method. I understand. It has been found that even when the number of packets is increased or the duty cycle is increased, the film can be formed without degrading the quality of the antireflection laminate when the rotary target is used.

It is a schematic sectional drawing which shows an example of the reflection preventing laminated body of this invention. It is a schematic diagram which shows an example of the roll-to-roll type vacuum film-forming apparatus which forms into a film the reflection preventing laminated body of this invention. It is a schematic diagram which shows an example of the roll-to-roll type vacuum film-forming apparatus which forms into a film the reflection preventing laminated body of this invention. It is a figure which shows the voltage waveform which the film-forming apparatus used in Example 1 and Comparative Example 1 applied.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Antireflection laminated body 2 Base material 3 Hard coat layer 4 Primer layer 5 Antireflection layer 6 Antifouling layer 7 Adhesion layer 11 High refractive index transparent thin film layer 12 Low refractive index transparent thin film layer 13 High refractive index transparent thin film layer 14 Low refraction Transparent thin film layer

Claims (5)

In the method for producing an antireflection laminate, in which an antireflection layer having a physical film thickness of 100 nm or more is formed on a substrate,
The antireflection layer is formed by a magnetron sputtering method using a rotary target,
The magnetron sputtering method using the rotary target has an antireflection layer forming material as a sputtering target and at least one pair of electrodes connected to a power source, and a DC pulse voltage is applied to the pair of electrodes by a bipolar method. The method for producing an antireflection laminate is characterized by repeating the application of each once alternately. In the method for producing an antireflection laminate, in which an antireflection layer having a physical film thickness of 100 nm or more is formed on a substrate,
The antireflection layer is formed by a magnetron sputtering method using a rotary target,
In addition, the magnetron sputtering method using the rotary target has at least one pair of electrodes connected to an antireflection layer forming material as a sputtering target and a power source, and a DC pulse voltage is applied to the electrodes by a pulse packet method. Then, after applying a DC pulse voltage a plurality of times, the polarity of each pair of electrodes is reversed, and the method for manufacturing an antireflection laminate is characterized in that In the production method of an antireflection laminate, which comprises an antireflection layer comprising a plurality of laminated optical thin film layers having different refractive indexes and a physical film thickness of 100 nm or more on a substrate.
The antireflection layer is formed by a magnetron sputtering method using a rotary target,
In addition, the magnetron sputtering method using the rotary target has an antireflection layer forming material as a sputtering target and at least one pair of electrodes connected to a power source, and a DC pulse voltage is applied to the electrodes by a pulse packet method. Then, after applying a DC pulse voltage a plurality of times, the polarity of each pair of electrodes is reversed, and the method for manufacturing an antireflection laminate is characterized in that   The optical functional filter which has an antireflection laminated body manufactured by the manufacturing method of any one of Claims 1-3.   An optical display device having the optical functional filter according to claim 4 on a front surface.

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