JP2007271958A - Antireflection laminate, its manufacturing method, optical functional filter and optical display system - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To form a thin film which has abrasion resistance stronger than that of an evaporation thin film, has film hardness lower than that of a DMS thin film and higher than that of the evaporation film on the other hand by a magnetron sputtering method onto a base material and to provide an antireflection laminate having very few luminescent spot, an optical functional filter having the antireflection laminate and optical display system having the optical functional filter. <P>SOLUTION: The antireflection laminate comprises an antireflection layer on the base material. Physical film thickness of the antireflection layer is ≥100 nm and indentation hardness of the antireflection laminate is ≥11 GPa and ≤15 GPa at an indentation test of 100 nm push-in depth. <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.

Japanese Patent Laid-Open No. 11-218603

  Therefore, an object of the present invention is to form a thin film on the base material by magnetron sputtering, which has a higher scratch resistance than the vapor deposited thin film, while having a film hardness lower than that of the DMS thin film and higher than that of the vapor deposited method. An object of the present invention is to provide an antireflection laminate having very few bright spots, an optical functional filter having the antireflection laminate, and an optical display device.

  The invention of claim 1 is an antireflection laminate having an antireflection layer on a substrate, the physical thickness of the antireflection layer is 100 nm or more, and the indentation hardness of the antireflection laminate is indentation. It is an antireflection laminate having a pressure of 11 GPa to 15 GPa with respect to an indentation test at a depth of 100 nm.

  The invention according to claim 2 is the antireflection laminate according to claim 1, wherein the antireflection layer is formed by laminating a plurality of optical thin film layers having different refractive indexes.

  Invention of Claim 3 is a manufacturing method of the antireflection laminated body which forms an antireflection layer on a base material using a magnetron sputtering method, Comprising: This magnetron sputtering method is 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 by a pulse packet method, and the paired electrodes alternately become a cathode and an anode, respectively, to prevent reflection It is a manufacturing method of a laminated body.

  The invention according to claim 4 has an antireflection layer formed by laminating a plurality of optical thin film layers having different refractive indexes on a substrate, and at least one optical thin film layer is formed by using a magnetron sputtering method. A method of manufacturing an antireflection laminate, wherein the magnetron sputtering method includes an optical thin film layer forming material as a sputtering target, and at least one pair of electrodes connected to a power source, and a DC pulse voltage by a pulse packet method. Is applied, and the paired electrodes alternately become a cathode and an anode, respectively.

  Invention of Claim 5 is a manufacturing method of the antireflection laminated body which forms an antireflection layer on a base material using a magnetron sputtering method, Comprising: This magnetron sputtering method is an antireflection layer forming material as a sputtering target. And a method of manufacturing an antireflection laminate, comprising: an electrode composed of two pairs of cathode electrodes and anode electrodes connected to a power source, and applying a DC pulse voltage in synchronization with the two pairs of electrodes. is there.

  The invention of claim 6 has an antireflection layer formed by laminating a plurality of optical thin film layers having different refractive indexes on a base material, and at least one optical thin film layer is formed by using a magnetron sputtering method. An antireflection laminate manufacturing method, wherein the magnetron sputtering method includes an antireflection layer forming material as a sputtering target, and an electrode composed of two pairs of cathode electrodes and anode electrodes connected to a power source, and 2 A method of manufacturing an antireflection laminate, wherein a DC pulse voltage is applied in synchronization with a pair of electrodes.

  A seventh aspect of the present invention is an optical functional filter having the antireflection laminate according to the first or second aspect.

  The invention of claim 8 is an optical display device having the optical functional filter according to claim 7 on the front surface.

The antireflective laminate of the present invention has a flexible film quality with low film stress, and at the same time uses a sputtering method. Therefore, the bright spot level is good compared to vapor deposition and the like, and the film stress is weak. It is possible to provide a 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 for a long 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.
In addition, the optical article of the present invention is an optical article 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.

(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 a substrate and curing them by heat curing, ultraviolet curing, or ionizing radiation curing. The hard coat layer has a physical thickness of 0.5 μm or more, preferably 3 to 20 μm, more preferably 3 to 6 μm.

  Transparent hard particles having an average particle 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 form fine irregularities on the surface, improving the light diffusibility and further reducing the light reflection.

  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 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. And an acid treatment method.

(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 have a thickness that does not impair the transparency of the substrate, 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, 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.

  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.

  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, the dual magnetron sputtering method, which forms a film with a voltage applied in the middle frequency range, is optimal for pursuing higher film formation speed and higher production stability such as de-arcing.
In the present invention, at least one of the optical thin film layers is formed by a 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. Features.
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 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. It is possible to obtain a flexible and high-quality film quality with a better bright spot level and less 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 uppermost layer of the antireflection layer.
When the uppermost layer is a low refractive index transparent thin film layer, specifically, the reactive functional group of the fluorine-containing silicon compound is reacted with the material of the low refractive index transparent thin film layer, and the reactive functional group of the fluorine-containing silicon compound is also reacted. A layer formed by reacting groups with each other, or a layer formed by reacting a reactive functional group of an organosilicon compound having a siloxane bond as a main chain with a material of a 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 an organic material having a fluorine-containing silicon compound and a siloxane bond as the main chain. Simultaneously reacting silicon compounds with those reactive functional groups and the material of the low-refractive-index transparent thin-film layer, and reacting functional groups of fluorine-containing silicon compounds with organic silicon having siloxane bonds as the main chain A layer formed by the reactive functional groups to each other by reaction of the reactive functional groups to each other or a fluorine-containing silicon compound and an organic silicon compound a siloxane bond as a main chain, the compound.

  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. 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 dimethyl ketoxime group, a methyl ethyl ketoxime group, a diethyl ketoxime 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 —Rf—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, R ^f 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 group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group; cyclopentyl group, cyclohexyl group Cycloalkyl groups such as phenyl groups, tolyl groups, xylyl groups and the like; aralkyl groups such as benzyl groups and phenethyl groups; vinyl groups, allyl groups,
Examples thereof include alkenyl groups such as a butenyl group, a pentenyl group, and a hexenyl group. s and t are integers, preferably 0 to 100. R7 is a monovalent hydrocarbon group having 1 to 10 carbon atoms of the same or different from each other, 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 the fluorine-containing silicon compound having one or more silicon atoms bonded to the reactive functional group include CF ₃ (CF ₂ ) _p (CH ₂ ) _q Si (OCH ₃ ) ₃ , CF ₃ (CF _{2 ) p (OC 3 F 6)} q OCF 2 CF 2 CH 2 CH 2 (OCONH) CH 2 CH 2 Si (OCH 3) 3, (CH 3 O) 3 SiCH 2 CH 2 CH 2 OCH 2 CF 2 CF 2 O (CF ₂ CF ₂ CF ₂ O) _p CF ₂ CF 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 CF ₂ O (CF ₂ CF ₂ CF ₂ O) _p CF ₂ CF ₂ CH ₂ OCH ₂ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ , (CH ₃ O) 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 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 (} CF 2 CF 2 CF 2 O) p CF 2 CF 2 CH 2 OCH 2 CH 2 CH 2 (CH 2 =) CCH 2 Si (OCH 3) _{, (CH 3 O) 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 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) rOCF 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 the organosilicon compound 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 adhesive layer include acrylic adhesives, silicon adhesives, urethane adhesives, polyvinyl butyral adhesives (PVA), ethylene-vinyl acetate adhesives (EVA), polyvinyl ethers, saturated amorphous polyesters, A melamine resin etc. are mentioned.

  In the present invention, at least one of the antireflection layers is formed by a magnetron sputtering method using a pulse packet method, or by a magnetron sputtering method in which a pulse voltage is applied synchronously using two pairs of electrodes.

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 dual magnetron sputtering method (hereinafter referred to as DMS method) is a method in which a DC pulse wave of 1 k to 300 kHz, preferably 1 k to 100 kHz, is applied alternately to positive and negative voltages to form a pair of electrodes. Is a discharge method that alternately serves 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 the paired electrodes are alternately arranged by applying a DC pulse voltage by the pulse packet method. Plays the role of cathode and anode.
The magnetron sputtering method using the pulse packet method can reduce the amount of high energy particles in the plasma diffused to the substrate side by reducing the number of voltage reversals between a pair of electrodes. This is a method capable of reducing the thermal load applied to the film 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, The pulse duty cycle is 50 to 99%, and 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.

When a normal DMS method is used, sputtering is performed while a pair of targets alternately function as an anode and a cathode. At this time, the electrons in the plasma cannot move to the anode across the vicinity of the target having a high magnetic flux density, and have a bridge-type path from the center of the target having a low magnetic flux density to the center of the other target. Form and move in the vicinity of the substrate. At this time, the cations in the plasma collide with the substrate in a form that follows the moving electrons, thereby producing an ion migration effect. On the other hand, the magnetron sputtering method in which two pairs of electrodes are used to apply a pulse voltage in synchronization is a method in which two cathode electrodes are provided with separate anode electrodes, and the two cathodes are electrically insulated from each other. By applying each independently and synchronously, DC pulse sputtering is performed simultaneously on two cathodes. In this case, the electrons flowing to the anode between the pair of targets are blocked by the magnetic field, and unlike the DMS method in which the electrons are forced to pass through the vicinity of the base material, electrons flow to the separately provided anode. The diffusion of plasma to the substrate side is almost eliminated, and it becomes possible to form a thin film having a rough film quality, a low film hardness, and a low film stress. At the same time, this technique makes it possible to obtain a high deposition rate because the two cathodes are sputtered simultaneously.
The voltage to be applied is basically a voltage that causes ion acceleration that can be sputtered, and may be appropriately applied 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.

<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 DMS method is used for the sputter cathodes 1, 2, 3, 4, 5 in this embodiment 1, the DMS cathode is arranged. Partitions are provided so that different film pressures can be set. On the sputter cathodes 2, 3, 4, and 5, a power supply UBS-C2 manufactured by Fraunhofer Institute Elektronenstrahl-und Plasmatechnik is installed. In this case, two DC pulse power sources can be alternately switched at high speed, and a positive and negative DC pulse voltage can be alternately applied between the DMS targets. Further, as shown in FIG. 2, the sputter cathodes 2, 3, 4, 5 can be replaced with MF sine wave power sources. Furthermore, only the MF sine wave power source is installed on the sputter cathode 1. 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. Basically, it is equivalent to the roll-to-roll film forming apparatus shown in FIG. 2, but the sputtering cathode 6 is equipped with an MF power source, and for the sputtering cathodes 7, 8, 9, and 10, 2, different anodes are provided for the two pairs of targets, and pulse voltages are applied independently between the anodes and the cathodes, and DC pulse sputtering is simultaneously applied to the two cathodes. It is a vacuum film-forming apparatus that can be in a state where is performed.

<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 the roll-to-roll vacuum film forming apparatus shown in FIGS.
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 formation 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.
Using the film forming apparatus shown in FIG. 2, while conveying the TAC film, by a sputtering cathode 2, on the primer layer 4, the TiO ₂ film is deposited by a DMS method, high-refractive-index transparent thin film layer having an optical thickness of 30nm 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 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%.

Next, using the film forming apparatus shown in FIG. 2, while transporting the TAC film, an 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%.

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%.

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, and the low refractive index having an optical film thickness of 120 nm is obtained. 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%.

  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 CF 2 O) 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 ) Formula ₃ (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 ) Formula ₃ (5)

_{(CH 3 O) 3 Si- (} CH 2) 2 -O- (CH 2) 2 -O- (Si (CH3) 2 O) 10 - (CH 2) 2 -O- (CH 2) 2 -Si ( OCH ₃ ) Formula ₃ (6)

_{(CH 3 O) 3 Si- (} CH 2) 2 -O- (CH 2) 2 -O- (Si (CH3) 2 O) 13 - (CH 2) 2 -O- (CH 2) 2 -Si ( OCH ₃ ) Formula ₃ (7)

_{(CH 3 O) 3 Si- (} CH 2) 2 -O- (CH 2) 2 -O- (Si (CH3) 2 O) 14 - (CH 2) 2 -O- (CH 2) 2 -Si ( OCH ₃ ) Formula ₃ (8)

<Example 2>
A hard coat layer was provided on the TAC film in the same manner as in Example 1.
Using the film forming apparatus shown in FIG. 3, while transporting the TAC film, SiO _x is deposited on the hard coat layer 3 by the DMS method on the sputter cathode 6 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 formation 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.
Using the film forming apparatus shown in FIG. 3, while conveying the TAC film, by a sputtering cathode 7, on the primer layer 4, the TiO ₂ film is deposited by a DMS method, high-refractive-index transparent thin film layer having an optical thickness of 30nm 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 DC pulse voltage having a voltage waveform shown in FIG. 4B was applied to each target. The frequency was 50 kHz and the duty cycle was 80%.

Next, using the film forming apparatus shown in FIG. 3, while transporting the TAC film, an SiO ₂ thin film was deposited on the high refractive index transparent thin film layer 11 by the DMS method at the sputter cathode 8 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 DC pulse voltage having a voltage waveform shown in FIG. 4B was applied to each target. The frequency was 50 kHz and the duty cycle was 80%.

Further, using the film forming apparatus shown in FIG. 3, while transporting the TAC film, TiO ₂ was deposited on the low refractive index transparent thin film layer 12 by the sputtering cathode 9 by the DMS method, and the optical film thickness was 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 DC pulse voltage having a voltage waveform shown in FIG. 4B was applied to each target. The frequency was 50 kHz and the duty cycle was 80%.

Next, using the apparatus shown in FIG. 3, 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 10 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 DC pulse voltage having a voltage waveform shown in FIG. 4B was applied to each target. The frequency was 50 kHz and the duty cycle was 80%.

  Further, as in Example 1, the fluorine-containing silicon compound represented by the above formulas (3), (4), and (5) and the above formulas (6), (7) are formed on the low refractive index transparent thin film layer 14. ), (8) and the organosilicon compound having a siloxane bond as the main chain, deposited by resistance heating vacuum deposition using a vacuum deposition apparatus different from the vacuum deposition apparatus shown in FIG. The antifouling layer 6 having a physical film thickness of 6 nm was formed. 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 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 voltage waveform applied to the target 1 and target 2 of each cathode at this time is shown in FIG.

<Comparative example 2>
By using a roll-to-roll type electron beam evaporation apparatus different from Example 1, Example 2, and Comparative Example 1, primer layer 4, high refractive index transparent thin film layer 11, low refractive index transparent thin film layer 12, high refractive index transparent thin film After the film formation of the layer 13 and the low-refractive-index transparent thin film layer 14, the same as in Example 1, the low-refractive-index transparent thin film layer 14 is represented by the above formulas (3), (4), and (5). The fluorine-containing silicon compound and the organosilicon compound having a siloxane bond represented by the above formulas (6), (7) and (8) as the main chain are different from the vacuum film forming apparatus shown in FIG. Using a vacuum film forming apparatus, deposition was performed by a vacuum evaporation 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.

<Evaluation>
The antireflection laminate 1 obtained in Examples 1 and 2 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 on the samples formed in Example 1, Example 2, Comparative Example 1, and Comparative Example 2 using 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 applied to the samples formed in Example 1, Example 2, Comparative Example 1, and Comparative Example 2 using a scratch tester (Scientific-type friction fastness tester AB-301 manufactured by TESTER SANGYO CO., Ltd. ), A load of 250 gf and 500 gf 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 2.

(3) Bending test:
The samples formed in Example 1, Example 2, Comparative Example 1, and Comparative Example 2 are wound on stainless steel rods of 6 mmφ, 8 mmφ, 10 mmφ, and 14 mmφ for half a half respectively. 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, Example 2, 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, Example 2, 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.

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.

It is a schematic sectional drawing which shows an example of the reflection preventing laminated body of this invention. 1 is a schematic diagram of a roll-to-roll vacuum film forming apparatus for forming an antireflection laminate of the present invention. 1 is a schematic diagram of a roll-to-roll vacuum film forming apparatus for forming an antireflection laminate of the present invention. Voltage waveform applied by the film forming apparatus used in Example 1, Example 2, and Comparative Example 1

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Antireflection laminated body 2 Base material 3 Hard coat 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 refractive index Transparent thin film layer

Claims (8)

An antireflection laminate having an antireflection layer on a substrate,
The antireflection laminate is characterized in that the physical thickness of the antireflection layer is 100 nm or more, and the indentation hardness of the antireflection laminate is 11 GPa to 15 GPa with respect to an indentation test with an indentation depth of 100 nm. .   The antireflection laminate according to claim 1, wherein the antireflection layer is formed by laminating a plurality of optical thin film layers having different refractive indexes. On the base material, a method for producing an antireflection laminate in which an antireflection layer is formed using a magnetron sputtering method,
The magnetron sputtering method has an antireflection layer forming material as a sputtering target, and at least one pair of electrodes connected to a power source,
A method for producing an antireflection laminate, wherein a DC pulse voltage is applied by a pulse packet method, and the paired electrodes alternately become a cathode and an anode, respectively. A method for producing an antireflection laminate comprising an antireflection layer comprising a plurality of optical thin film layers having different refractive indexes laminated on a base material, wherein at least one optical thin film layer is formed using a magnetron sputtering method Because
The magnetron sputtering method has an optical thin film layer forming material as a sputtering target, and at least one pair of electrodes connected to a power source,
A method for producing an antireflection laminate, wherein a DC pulse voltage is applied by a pulse packet method, and the paired electrodes alternately become a cathode and an anode, respectively. On the base material, a method for producing an antireflection laminate in which an antireflection layer is formed using a magnetron sputtering method,
The magnetron sputtering method has an electrode composed of an antireflection layer forming material as a sputtering target, and two pairs of cathode electrodes and anode electrodes connected to a power source,
A method for producing an antireflection laminate, wherein a DC pulse voltage is applied in synchronization with two pairs of electrodes. A method for producing an antireflection laminate comprising an antireflection layer comprising a plurality of optical thin film layers having different refractive indexes laminated on a base material, wherein at least one optical thin film layer is formed using a magnetron sputtering method Because
The magnetron sputtering method has an electrode composed of an antireflection layer forming material as a sputtering target, and two pairs of cathode electrodes and anode electrodes connected to a power source,
A method for producing an antireflection laminate, wherein a DC pulse voltage is applied in synchronization with two pairs of electrodes.   An optical functional filter comprising the antireflection laminate according to claim 1.   An optical display device having the optical functional filter according to claim 7 on a front surface.

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