Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/11—Anti-reflection coatings
  • G02B1/113—Anti-reflection coatings using inorganic layer materials only
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/14—Protective coatings, e.g. hard coatings
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
  • G02B5/28—Interference filters

Definitions

• This disclosure relates to a method for manufacturing an optical article.
• Patent Document 1 describes an optical article in which low-refractive index layers and high-refractive index layers are alternately laminated on a plastic substrate.
• the present disclosure relates to a method for producing an optical article having a plastic substrate and a multilayer film formed by alternately laminating high and low refractive index layers on the plastic substrate, with the low refractive index layer being disposed at the position furthest from the plastic substrate, the method comprising: a step A for forming a high refractive index layer on the plastic substrate; and a step B for forming a low refractive index layer, which are repeatedly performed to form a multilayer film; and a step D for irradiating a surface of the formed low refractive index layer with an ion beam containing ions obtained by ionizing a gas containing argon gas or oxygen gas, at a current density in the range of 5 to 120 ⁇ A/cm2, after forming the low refractive index layer located at the position furthest from the plastic substrate in the multilayer film, and at least one of the steps between the step B for forming the low refractive index layer located second from the side opposite to the plastic substrate among the low ref
• FIG. 1 is a cross-sectional view of one embodiment of an optical article.
• the method for producing the optical article of the present disclosure will be described in detail below. It is desirable for the manufactured optical article to have excellent scratch resistance.
• the optical article obtained by the manufacturing method of the optical article according to the present disclosure has excellent scratch resistance.
• the word "to” is used to mean that the numerical values before and after it are included as the lower limit and upper limit.
• the refractive index is the refractive index at the e-line.
• an optical article is manufactured having a plastic substrate and a multilayer film formed by alternately laminating high refractive index layers and low refractive index layers disposed on the plastic substrate, with the low refractive index layer being disposed at a position furthest from the plastic substrate.
• FIG. 1 is a cross-sectional view of one embodiment of an optical article.
• the optical article 10 shown in FIG. 1 includes a plastic substrate 12, a primer layer 14, a hard coat layer 16, a multilayer film 18, and a water- and oil-repellent layer 20, in this order.
• the optical article 10 includes a primer layer 14, a hard coat layer 16, and a water- and oil-repellent layer 20, but the primer layer 14, the hard coat layer 16, and the water- and oil-repellent layer 20 are optional components, and it is sufficient for the optical article of the present disclosure to include at least a plastic substrate and a specified multilayer film.
• the multilayer film 18 has, in this order from the plastic substrate 12 side, a first high refractive index layer 22H, a first low refractive index layer 22L, a second high refractive index layer 24H, a second low refractive index layer 24L, a third high refractive index layer 26H, a third low refractive index layer 26L, a fourth high refractive index layer 28H, and a fourth low refractive index layer 28L. That is, in the multilayer film 18, the fourth low refractive index layer 28L is disposed at a position farthest from the plastic substrate 12. In Fig.
• the multilayer film 18 has a total of eight high and low refractive index layers, but the optical article of the present disclosure is not limited to this embodiment as long as the low refractive index layer is disposed at the position farthest from the plastic substrate in the multilayer film.
• the total number of high and low refractive index layers may be two or more, preferably four or more, more preferably six or more, and even more preferably eight or more. There is no particular upper limit on the total number of high and low refractive index layers, but from the viewpoint of productivity, it is preferably 14 or less, more preferably 12 or less.
• the high refractive index layer may be referred to as the "first high refractive index layer", the “second high refractive index layer”, etc., in order from the high refractive index layer located on the plastic substrate side.
• the low refractive index layer may be referred to as the "first low refractive index layer”, the “second low refractive index layer”, etc., in order from the low refractive index layer located on the plastic substrate side.
• each layer is disposed on only one side of the plastic substrate 12, but the primer layer 14, the hard coat layer 16, the multilayer film 18, and the water- and oil-repellent layer 20 may be disposed in this order on both sides of the plastic substrate 12.
• the optical article may have a multilayer film on both sides of the plastic substrate.
• the multilayer film is composed only of a low refractive index layer and a high refractive index layer, but in the optical article of the present disclosure, the multilayer film may include layers other than the low refractive index layer and the high refractive index layer.
• the plastic substrate is a member that supports the multilayer film.
• the type of plastic (so-called resin) contained in the plastic substrate is not particularly limited, but examples thereof include (meth)acrylic acid ester resin, thiourethane resin, allyl resin, episulfide resin, polycarbonate, urethane resin, polyester, polystyrene, polyethersulfone, poly-4-methylpentene-1, and diethylene glycol bisallyl carbonate resin (CR-39).
• thiourethane resin, episulfide resin, and diethylene glycol bisallyl carbonate resin are preferred.
• the plastic substrate is preferably a plastic eyeglass lens substrate.
• the type of plastic spectacle lens substrate is not particularly limited, but examples thereof include a form having a convex surface and a concave surface. More specifically, examples include a finished lens in which both the convex surface and the concave surface are optically finished and molded according to a desired dioptric power, a semi-finished lens in which only the convex surface is finished as an optical surface (spherical surface, rotationally symmetric aspherical surface, progressive surface, etc.), and a lens in which the concave surface of the semi-finished lens is processed and polished according to the prescription of the wearer.
• the thickness of the plastic substrate is not particularly limited, but from the viewpoint of ease of handling, it is often about 1 to 30 mm.
• the refractive index of the plastic substrate is not particularly limited, but is often 1.50 or more, preferably 1.60 to 1.80, and more preferably 1.60 to 1.74.
• the plastic substrate does not have to be colorless so long as it has light-transmitting properties, and may contain an ultraviolet absorbing agent and a dye that absorbs light in a specific wavelength range from the ultraviolet to the infrared regions.
• the plastic substrate may also contain additives such as bluing agents, light stabilizers, and antioxidants.
• the optical article may include a primer layer.
• the primer layer is preferably disposed between the plastic substrate and the hard coat layer.
• the material constituting the primer layer is not particularly limited, and known materials can be used, for example, resins are mainly used.
• the type of resin used is not particularly limited, and examples thereof include polyurethane resins, epoxy resins, phenol resins, polyimide resins, polyester resins, bismaleimide resins, and polyolefin resins, and polyurethane resins are preferred.
• the primer layer may contain components other than the above resins.
• other components include fine particles of an oxide of at least one metal selected from Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, and Ti, or fine particles of a composite oxide thereof, a hydrolyzable silicon compound and/or a hydrolyzed condensate thereof, a conductive filler, and a surfactant.
• the method for forming the primer layer is not particularly limited, and any known method can be used.
• a method can be used in which a primer layer-forming composition containing a specified resin is applied onto a plastic substrate, and a curing treatment is performed as necessary to form a primer layer.
• the method for applying the composition for forming a primer layer is not particularly limited, and examples thereof include the methods exemplified by the method for applying the composition for forming a hard coat layer onto a plastic substrate, which will be described later.
• the thickness of the primer layer is not particularly limited, but is preferably 0.3 to 2 ⁇ m.
• the optical article may include a hard coat layer.
• the hard coat layer is preferably disposed between the plastic substrate and the multilayer film, and is a layer that imparts scratch resistance to the plastic substrate.
• the hard coat layer preferably has a pencil hardness of "H" or higher according to the test method defined in the international standard ISO 15184 and the Japanese Industrial Standard JIS K5600 created based on this international standard.
• a known hard coat layer can be used as the hard coat layer, for example, an organic hard coat layer, an inorganic hard coat layer, and an organic-inorganic hybrid hard coat layer.
• an organic-inorganic hybrid hard coat layer is commonly used.
• the hard coat layer preferably contains a polymer of a polymerizable monomer (a polymer obtained by polymerizing a polymerizable monomer) and/or a condensate of a hydrolyzable organosilicon compound.
• the polymerizable monomer is not particularly limited, but examples thereof include (meth)acrylates having at least one group selected from the group consisting of phosphoric acid groups and sulfonic acid groups, silsesquioxanes having a radical polymerizable group, polyfunctional acrylates, compounds having multiple epoxy groups, and silsesquioxane compounds having an oxetanyl group.
• the (meth)acrylate means an acrylate or a methacrylate.
• the hydrolyzable organosilicon compound is not particularly limited, but examples thereof include organosilicon compounds having an epoxy group.
• the hard coat layer may also contain an inorganic component such as metal oxide fine particles.
• the type of metal oxide microparticles is not particularly limited, and includes known metal oxide microparticles.As metal oxide microparticles, for example, Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, and Ti are selected from at least one metal oxide microparticles.Among them, from the viewpoint of handling, the metal oxide microparticles are preferably Si-containing oxide microparticles (silicon oxide microparticles), Sn-containing oxide microparticles (tin oxide microparticles), Zr-containing oxide microparticles (zirconium oxide microparticles), or Ti-containing oxide microparticles (titanium oxide microparticles).
• the metal oxide fine particles may contain only one type of metal (metal atom) exemplified above, or may contain two or more types of metals (metal atoms).
• metal metal atom
• Si silicon
• Si is sometimes classified as a metalloid, in this specification, Si is included in the category of metals.
• the hard coat layer is preferably a layer formed using a composition for forming a hard coat layer that contains a polymerizable monomer.
• the composition for forming a hard coat layer may contain the above-mentioned metal oxide fine particles, other components, and a solvent in addition to the polymerizable monomer.
• other components include a radical polymerization initiator, a cationic polymerization initiator, and a curing catalyst, as well as various additives such as an ultraviolet absorber, an antiaging agent, a coating modifier, a light stabilizer, an antioxidant, a color inhibitor, a dye, a filler, and an internal mold release agent, which are added as necessary.
• the solvent may be water or an organic solvent.
• the type of the organic solvent is not particularly limited, and examples thereof include alcohol solvents, ketone solvents, ether solvents, ester solvents, hydrocarbon solvents, halogenated hydrocarbon solvents, amide solvents, sulfone solvents, and sulfoxide solvents.
• a method for forming a hard coat layer using the composition for forming a hard coat layer includes a method in which the composition for forming a hard coat layer is applied onto a plastic substrate (or onto a primer layer) to form a coating film, and then the coating film is subjected to a curing treatment such as a light irradiation treatment and a heat treatment.
• a curing treatment such as a light irradiation treatment and a heat treatment.
• the curing treatment either one of the light irradiation treatment and the heat treatment may be performed, or both may be performed. When both are performed, the light irradiation treatment and the heat treatment may be performed simultaneously, or one may be performed after the other.
• a drying treatment such as a heating treatment may be carried out, if necessary, in order to remove the solvent from the coating film.
• the method for applying the composition for forming a hard coat layer is not particularly limited, and includes known methods (for example, dipping coating, spin coating, spray coating, inkjet coating, and flow coating).
• the conditions for the light irradiation treatment are not particularly limited, and suitable conditions are selected depending on the type of polymerization initiator used.
• the type of light used for the light irradiation is not particularly limited, but examples thereof include ultraviolet light and visible light.
• Examples of the light source include a high-pressure mercury lamp.
• the integrated light quantity during light irradiation is not particularly limited, but from the viewpoints of productivity and curability of the coating film, it is preferably 100 to 3000 mJ/cm 2 , and more preferably 100 to 2000 mJ/cm 2 .
• the conditions for the heat treatment are not particularly limited, and the optimum conditions are selected depending on the type of polymerization initiator used.
• the heating temperature is preferably from 30 to 100° C., and the heating time is preferably from 5 to 360 minutes.
• the thickness of the hard coat layer is not particularly limited, but is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, and even more preferably 10 ⁇ m or more.
• the upper limit of the thickness can be, for example, 30 ⁇ m or less.
• the above film thickness is an average film thickness, and is measured by measuring the film thickness at any five points on the hard coat layer and calculating the arithmetic average thereof.
• the hard coat layer may also contain additives such as a bluing agent, a light stabilizer, and an antioxidant.
• the optical article includes a multilayer film.
• the multilayer film may function as an anti-reflection film or as an enhanced reflection film.
• the anti-reflection film is a layer having a function of preventing the reflection of incident light. Specifically, the anti-reflection film has low reflectance characteristics (broadband low reflectance characteristics) over the entire visible region of 380 to 780 nm.
• the reflection-enhancing film is a layer that has the function of reflecting a part of the incident light. Specifically, it may reflect light in a specific wavelength range, or have a reflection characteristic over the entire visible range of 380 to 780 nm.
• the specific wavelength range may be the visible light range, the infrared light range (e.g., 780 to 3000 nm), or the ultraviolet light range (e.g., 200 to 380 nm).
• the specific wavelength range may include a plurality of wavelength ranges.
• the multilayer film preferably functions as an anti-reflection film.
• the multilayer film includes alternating high and low refractive index layers, with the low refractive index layer being disposed at the position furthest from the plastic substrate.
• the predetermined high refractive index layers and the predetermined low refractive index layers may be disposed alternately. That is, a low refractive index layer is disposed between two high refractive index layers, and a high refractive index layer is disposed between two low refractive index layers.
• other layers e.g., a SnO2 layer or an ITO layer may be disposed between the high refractive index layer and the low refractive index layer.
• ITO Indium Tin Oxide
• the high refractive index layer is preferably a layer having a refractive index of 1.60 or more.
• the high refractive index layer preferably contains at least one oxide selected from the group consisting of titanium, zirconium, aluminum, niobium, tantalum, and lanthanum, and more preferably contains zirconium oxide (ZrO 2 ).
• the high refractive index layer may contain two or more materials.
• the low refractive index layer is preferably a layer having a refractive index of less than 1.60.
• the low refractive index layer preferably contains at least one selected from the group consisting of an oxide of silicon, calcium fluoride, and magnesium fluoride, and in particular, the low refractive index layer preferably contains silicon dioxide (SiO 2 ).
• the low refractive index layer may contain two or more materials.
• the total number of high refractive index layers and low refractive index layers in the multilayer film and the preferred embodiments thereof are as described above.
• the layer closest to the plastic substrate may be a low refractive index layer or a high refractive index layer.
• the thickness of each of the low refractive index layers and the high refractive index layers contained therein can be appropriately adjusted depending on the function of the multilayer film.
• the thickness of each high refractive index layer is preferably from 5 to 200 nm, more preferably from 5 to 150 nm.
• the thickness of each of the low refractive index layers is preferably from 10 to 500 nm, more preferably from 20 to 450 nm.
• the multilayer film is composed of, in order from the plastic substrate side, a first high refractive index layer, a first low refractive index layer, a second high refractive index layer, a second low refractive index layer, a third high refractive index layer, a third low refractive index layer, a fourth high refractive index layer, and a fourth low refractive index layer, and the multilayer film functions as an antireflection film, the following aspects of each layer are preferable.
• First high refractive index layer Material ZrO 2 , thickness: 5 to 10 nm First low refractive index layer Material: SiO 2 , thickness: 30 to 50 nm Second high refractive index layer Material: ZrO 2 , thickness: 10 to 20 nm Second low refractive index layer Material: SiO 2 , thickness: 80 to 450 nm Third high refractive index layer Material: ZrO 2 , thickness: 10 to 20 nm Third low refractive index layer Material: SiO 2 , thickness: 10 to 30 nm Fourth high refractive index layer Material: ZrO 2 , thickness: 80 to 120 nm Fourth low refractive index layer: Material: SiO 2 , thickness: 60 to 100 nm
• the multilayer film when the low refractive index layer arranged closest to the plastic substrate among the low refractive index layers in the multilayer film is designated as the first low refractive index layer, the low refractive index layer arranged next to the plastic substrate side after the first low refractive index layer is designated as the second low refractive index layer, and the high refractive index layer arranged closest to the plastic substrate among the high refractive index layers in the multilayer film is designated as the first high refractive index layer, it is also preferable that the multilayer film satisfies the relationships of formulas 1 to 3.
• Formula 1 L1 + L2 ⁇ 400 nm
• Formula 2 L1/H1 ⁇ 25.0
• L1 represents the physical thickness of the first low refractive index layer
• L2 represents the physical thickness of the second low refractive index layer
• H1 represents the physical thickness of the first high refractive index layer.
• Formula 1 represents the sum of the physical thickness of the first low refractive index layer and the physical thickness of the second low refractive index layer. By satisfying the relationship of Formula 1, the scratch resistance of the optical article is further improved.
• L1+L2 is preferably 450 nm or more, more preferably 480 nm or more. There is no particular upper limit to L1+L2, but from the viewpoint of productivity, it is preferably 600 nm or less, more preferably 550 nm or less.
• Equation 2 represents the ratio of the physical thickness of the first low refractive index layer to the physical thickness of the first high refractive index layer. By satisfying the relationship of Equation 2, the adhesion of the multilayer film is improved.
• L1/H1 is preferably 20.0 or less, and more preferably 8.0 or less. There is no particular lower limit to L1/H1, but it is often 3.0 or more, and more often 5.0 or more.
• Formula 3 represents the ratio of the total layer thickness of the first low refractive index layer and the second low refractive index layer to the physical thickness of the first high refractive index layer.
• (L1+L2)/H1 is preferably 46.0 or less.
• (L1+L2)/H1 it is often 25.0 or more, and more often 30.0 or more.
• the physical thickness of the first high refractive index layer is not particularly limited as long as the above relational expression is satisfied, but is preferably 5.0 to 25.0 nm, more preferably 8.0 to 20.0 nm.
• the physical thickness of the first low refractive index layer is not particularly limited as long as the above relational expression is satisfied, but is preferably 50 nm or more.
• the upper limit is not particularly limited, but is preferably 300 nm or less, and more preferably 250 nm or less.
• the physical thickness of the second low refractive index layer is not particularly limited as long as the above relational expression is satisfied, but is preferably 200 to 550 nm, more preferably 300 to 500 nm, in that the desired effect is more excellent.
• the physical thickness of the second high refractive index layer is not particularly limited, but is preferably 5.0 to 25.0 nm, and more preferably 8.0 to 20.0 nm, in terms of achieving a desired effect more excellently.
• the physical thickness of the third low refractive index layer is preferably 15 to 45 nm, and more preferably 20 to 40 nm, in terms of obtaining a superior predetermined effect.
• the physical thickness of the fourth low refractive index layer is preferably 70 to 110 nm, and more preferably 85 to 100 nm, in terms of obtaining a superior predetermined effect.
• the physical thickness of the third high refractive index layer is preferably 10 to 30 nm, and more preferably 15 to 25 nm, in terms of obtaining a superior predetermined effect.
• the physical thickness of the fourth high refractive index layer is preferably 50 to 110 nm, and more preferably 55 to 110 nm, in terms of obtaining a superior predetermined effect.
• the multilayer film may further include a SnO2 layer or an ITO layer in addition to the high refractive index layer and the low refractive index layer described above.
• the SnO2 layer and the ITO layer can function as an antistatic layer.
• the positions of the SnO 2 layer and the ITO layer in the multilayer film are not particularly limited, and may be between the high refractive index layer and the low refractive index layer.
• the SnO 2 layer or the ITO layer is disposed between the fourth high refractive index layer 28H and the fourth low refractive index layer 28L.
• the thickness of the SnO 2 layer or the ITO layer can be appropriately set, but is preferably 3 to 20 nm, and more preferably 3 to 10 nm.
• the optical article may include a water- and oil-repellent layer.
• the optical article has a water-repellent and oil-repellent layer as the outermost layer.
• the water- and oil-repellent layer reduces the surface energy of the optical article, improves the contamination prevention function of the optical article, and improves the slipperiness of the surface of the optical article, thereby improving the abrasion resistance of the optical article.
• the material constituting the water- and oil-repellent layer is not particularly limited, and examples thereof include fluorine-containing compounds (compounds containing fluorine atoms) and silicon-containing compounds (compounds containing silicon atoms).
• the water- and oil-repellent layer preferably contains a fluorine-containing compound, and more preferably contains at least one selected from the group consisting of fluorine-substituted alkyl group-containing organosilicon compounds, their hydrolysates, and their hydrolyzed condensates, in order to obtain more excellent water- and oil-repellent properties.
• the materials constituting the water- and oil-repellent layer may be used alone or in combination of two or more.
• the organosilicon compound containing a fluorine-substituted alkyl group is an organosilicon compound containing an alkyl group in which some or all of the hydrogen atoms are substituted with fluorine atoms, and has a hydrolyzable group.
• the hydrolyzable group is a group that is directly bonded to a silicon atom and can undergo hydrolysis and condensation reactions, such as an alkoxy group, a halogen atom, an acyloxy group, an alkenyloxy group, and an isocyanate group.
• the hydrolyzate of the organosilicon compound containing fluorine-substituted alkyl group refers to the compound obtained by hydrolysis of the hydrolyzable group in the organosilicon compound containing fluorine-substituted alkyl group.
• the hydrolyzate may be the one in which all the hydrolyzable groups are hydrolyzed (complete hydrolyzate), or the one in which only a part of the hydrolyzable groups are hydrolyzed (partial hydrolyzate). In other words, the hydrolyzate may be the one in which all the hydrolyzable groups are hydrolyzed, the partial hydrolyzate, or a mixture thereof.
• the hydrolysis condensate of the organosilicon compound containing fluorine-substituted alkyl group refers to the compound obtained by hydrolyzing the hydrolyzable group in the organosilicon compound containing fluorine-substituted alkyl group, and condensing the obtained hydrolyzate.
• the hydrolysis condensate may be the one in which all hydrolyzable groups are hydrolyzed and all the hydrolyzate is condensed (complete hydrolysis condensate), or the one in which some hydrolyzable groups are hydrolyzed and some of the hydrolyzate is condensed (partial hydrolysis condensate).
• the hydrolysis condensate may be the one in which all hydrolyzable groups are hydrolyzed, the one in which some hydrolyzate is condensed, or the one in which some hydrolyzable groups are hydrolyzed.
• the thickness of the water- and oil-repellent layer of the optical article there are no particular limitations on the thickness of the water- and oil-repellent layer of the optical article, but a thickness of 5 to 35 nm is preferable. If the thickness is within the above range, the optical article will have excellent water- and oil-repellent properties.
• the method for producing an optical article according to the present disclosure is a method for producing an optical article having a plastic substrate and a multilayer film formed by alternately laminating high and low refractive index layers on the plastic substrate, with the low refractive index layer being disposed at the position furthest from the plastic substrate, the method comprising: a step A for forming a high refractive index layer on the plastic substrate; and a step B for forming a low refractive index layer, which are repeatedly performed to form a multilayer film; and a step D for irradiating a surface of the formed low refractive index layer with an ion beam containing ions obtained by ionizing a gas containing argon gas or oxygen gas at a current density in the range of 5 to 120 ⁇ A/cm2 after forming the low refractive index layer located at the position furthest from the plastic substrate in the multilayer film, and at least one of
• Step C is a step including steps A and B described below, and is a step of forming a multilayer film of the optical article described above on a plastic substrate.
• Steps A and B may be alternately and repeatedly performed, and either step A or step B may be performed first.
• the multilayer film is formed so that the low refractive index layer is disposed at the position farthest from the plastic substrate.
• Step C may be performed on a plastic substrate, or on a plastic substrate having at least one of a primer layer and a hard coat layer.
• the multilayer film is formed on the surface of at least one of the primer layer and the hard coat layer, which is opposite to the plastic substrate.
• Step C is preferably performed in an environment with a pressure lower than atmospheric pressure, i.e., step C is preferably performed in a vacuum chamber. Steps A and B carried out in step C will be described below.
• a high refractive index layer is formed.
• the high refractive index layer is preferably formed by a vapor deposition method.
• the vapor deposition method include a thermal vapor deposition method, a sputtering method, and a chemical vapor deposition method, and the thermal vapor deposition method is preferred.
• the heating means in the thermal vapor deposition method include irradiation with an electron beam and resistance heating.
• the ion beam assisted method is a method in which, when performing vapor deposition, an ion beam having an energy level that does not cause sputtering of the formed film is irradiated onto the surface of the adherend on which the film is formed by vapor deposition.
• Ions used in the ion beam assisted method include known ions, such as ions obtained by ionizing argon gas, ions obtained by ionizing oxygen gas, and ions obtained by ionizing a mixed gas of argon gas and oxygen gas.
• the ion beam assisted method it is also preferable to irradiate the adherend with electrons to suppress charging of the adherend.
• the material constituting the high refractive index layer is as described above.
• the deposition raw material used for deposition may be the same material as the material forming the high refractive index layer, or may be a material containing an element contained in the material forming the high refractive index layer.
• a reactive gas oxygen gas, etc.
• ions derived from the reactive gas As a method for reacting the reactive gas or ions derived from the reactive gas with the deposition raw material, a method of supplying a reactive gas or ions derived from the reactive gas between the deposition raw material and the adherend can be mentioned.
• An example of an apparatus capable of carrying out the above-mentioned step A is a known vacuum vapor deposition apparatus. More specifically, an example of a means for carrying out step A is one that has a vapor deposition source placed in the vacuum vapor deposition apparatus, an evaporation means for evaporating the vapor deposition source, and a shutter placed between the vapor deposition source and the substrate. Any known evaporation means can be used, and examples of the evaporation means include electron beam heating, resistance heating, laser irradiation, infrared irradiation, and ion irradiation, and may be selected appropriately depending on the type of vapor deposition method to be adopted.
• step B a low refractive index layer is formed.
• the low refractive index layer is preferably formed by a vapor deposition method. Examples of the vapor deposition method and preferred embodiments thereof are the same as those in step A.
• the material constituting the low refractive index layer is as described above.
• the deposition raw material used for deposition may be the same material as the material forming the low refractive index layer, or may be a material containing an element contained in the material forming the low refractive index layer.
• a reactive gas oxygen gas, etc.
• ions derived from a reactive gas it is preferable to react it with a reactive gas (oxygen gas, etc.) or ions derived from a reactive gas.
• An example of an apparatus capable of carrying out the above-mentioned step B is a known vacuum vapor deposition apparatus.
• the means for carrying out step B may be the same as the means for carrying out step A.
• step D an ion beam containing ions obtained by ionizing argon gas or oxygen gas is irradiated at a current density in the range of 5 to 120 ⁇ A/cm 2.
• step D is performed on the surface of the formed low refractive index layer. For example, in the manufacture of the optical article 10 shown in FIG.
• step D is performed on the surface of the formed low refractive index layer. It is believed that by carrying out the above-mentioned step D, impurities adsorbed on the surface of the formed low refractive index layer are removed, resulting in the production of an optical article having excellent adhesion to the layer formed thereon and, as a result, excellent scratch resistance.
• the phrase "between step B and step A carried out thereafter" refers to a period during which neither the low refractive index layer nor the high refractive index layer is formed.
• a gas containing argon gas or oxygen gas is ionized and ions are irradiated as an ion beam.
• the gas containing argon gas or oxygen gas may be only argon gas, only oxygen gas, or a mixed gas of argon gas and oxygen gas. Therefore, the ions to be irradiated may be only argon ions, only oxygen ions ( O2 + and/or O + ), or may contain both argon ions and oxygen ions.
• the current density refers to a current flowing through the workpiece due to irradiation with an ion beam.
• a method for measuring the current density in step D includes a method of placing a conductor having a known area near the workpiece and monitoring the current flowing when the conductor is grounded.
• an Ion Current Monitor manufactured by TELEMARK can be used to measure the current density in step D.
• the current density is preferably from 10 to 100 ⁇ A/cm 2 , and more preferably from 25 to 80 ⁇ A/cm 2 .
• step D when the current density of the ion beam irradiated to the object varies with time, for example, when the ion beam is irradiated while being scanned, or when the object is moved by rotating or the like, the above current density is the average value during the time when step D is performed.
• the current density may be measured at equally spaced measurement points as the workpiece passes by as it rotates, and the average of these may be used as the above current density.
• the irradiation time of the ion beam is preferably from 5 to 600 seconds, and more preferably from 15 to 120 seconds.
• step D it is preferable to select an ion acceleration voltage that is low enough not to sputter a layer (e.g., a low refractive index layer) formed on the workpiece.
• the ion acceleration voltage is preferably 30 to 200 V, and more preferably 60 to 100 V.
• the product of the current density ( ⁇ A/cm 2 ), the ion acceleration voltage (V), and the ion beam irradiation time (seconds) is preferably 0.01 to 10 W ⁇ s/cm 2 , and more preferably 0.02 to 1 W ⁇ s/cm 2 .
• step D in addition to irradiating the ion beam, the object may be irradiated with electrons separately from the ion beam. By irradiating the object with electrons, charging of the object can be suppressed.
• step D is performed on the surface of the formed low refractive index layer.
• Step D may be performed at other times as long as it is performed at the above-mentioned timing.
• step D may be carried out between step B for forming a low refractive index layer that is the third low refractive index layer from the side opposite to the plastic substrate in the multilayer film and step A carried out thereafter. That is, in the production of the optical article 10 shown in FIG. 1, step D may be carried out between step B of forming the second low refractive index layer 24L and step A of forming the fourth high refractive index layer 28H. In addition, step D may be performed between all steps B and A.
• step D may be performed between step A and the subsequent step B. That is, step D may be performed in a state in which a high refractive index layer is formed, and before a low refractive index layer is formed on the high refractive index layer.
• step D may be performed between some of steps A and B, or step D may be performed between all of steps A and B.
• the means for carrying out step D is not particularly limited as long as it can generate and irradiate an ion beam, and a known ion source can be used.
• the ion source usually has a gas supply unit that supplies a gas, an ion generation unit that is connected to the gas supply unit and generates ions of the supplied gas by the action of discharge or the like with respect to the supplied gas, and an ion acceleration unit that is installed between the ion generation unit and the object to be treated and accelerates the ions to a predetermined energy by an electric field.
• the apparatus may have a different configuration.
• the means for carrying out the step D may be the same as the ion source used in the ion beam assisted method.
• the steps A, B, and D are performed in a vacuum chamber, it is preferable to provide in the vacuum chamber a holding mechanism for holding the plastic substrate, a vapor deposition source and a vapor deposition mechanism for forming a high refractive index layer, a vapor deposition source and a vapor deposition mechanism for forming a low refractive index layer, and an ion source for irradiating an ion beam.
• the holding mechanism may be provided with a rotation mechanism to make the film thickness of the high refractive index layer and the low refractive index layer uniform.
• the vacuum chamber preferably has a thickness meter for monitoring the thicknesses of the high refractive index layer and the low refractive index layer formed in steps A and B.
• the manufacturing method of the present disclosure may further include a step E of forming a water- and oil-repellent layer on the formed multilayer film.
• the method for forming the water- and oil-repellent layer is not particularly limited and can be arbitrarily selected depending on the material used, the desired performance or thickness, etc. Examples include a method in which a water- and oil-repellent layer-forming composition containing a fluorine-substituted alkyl group-containing organosilicon compound is applied onto a lens substrate, and a curing treatment is carried out as necessary, and a vacuum deposition method.
• Examples of the coating method include a dip coating method, a roll coating method, a bar coating method, a spin coating method, a spray coating method, a die coating method, and a gravure coating method.
• Examples of the curing treatment include light irradiation treatment, heat treatment, and water vapor contact treatment.
• Examples of the water vapor contact treatment include a treatment in which the film is brought into contact with air whose humidity is controlled to 50 to 90% RH.
• the above curing treatments may be carried out in combination.
• the vacuum deposition method can be carried out, for example, in the same manner as in the above-mentioned step A. Examples of materials constituting the water- and oil-repellent layer are as described above.
• the manufacturing method of the present disclosure may include other steps in addition to the above steps A, B, C, D, and E.
• Other steps include a step of forming a primer layer, a step of forming a hard coat layer, and a step of forming a SnO2 layer or an ITO layer.
• the method of the step of forming a primer layer and the method of the step of forming a hard coat layer are as described above.
• the step of forming a SnO2 layer or an ITO layer may be performed, for example, in step C, between step A and the step B performed thereafter, or between step B and the step A performed thereafter, or may be performed after step C.
• the formation of the SnO2 layer or the ITO layer can be performed in the same manner as step A.
• a step of cleaning the surface of the plastic substrate (when at least one of the primer layer and the hard coat layer is formed, the surface of the primer layer and the hard coat layer) may be included.
• the cleaning step may be a method of irradiating with an ion beam.
• a preferred embodiment of the ion beam irradiation is the same as that of the step D.
• the optical article obtained by the manufacturing method of the present disclosure can be used for various purposes.
• the optical article can be used as an eyeglass lens.
• Example 1 As the plastic substrate, a thiourethane-based synthetic resin substrate having a refractive index of 1.60 was prepared. Next, a polyurethane primer layer (thickness 1 ⁇ m) with a refractive index of 1.67 and a silicone-based hard coat layer (thickness: 3 ⁇ m) with a refractive index of 1.67 were formed on the surface of the plastic substrate in this order. The primer layer and the hard coat layer were formed on both sides of the plastic substrate.
• the hard coat layer was formed by thermally curing a hard coat forming composition containing an organosilicon compound having an epoxy group (including its hydrolyzate and its hydrolyzed condensate) and TiO2 -based composite oxide fine particles.
• the plastic substrate on which the primer layer and hard coat layer were formed was placed on a rotating dome in a vacuum chamber of a vacuum deposition apparatus ("MC-1200DLX2" manufactured by Satislaw Co., Ltd.)
• the vacuum deposition apparatus was equipped with an ion source (Mark II+ manufactured by Veeco), and the ion source was equipped with a neutralizer capable of irradiating electrons in the same direction as the irradiation direction of the ion beam.
• the plastic substrate After placing the plastic substrate, evacuation was performed until the degree of vacuum reached 3.5 ⁇ 10 ⁇ 3 Pa. After evacuation, the plastic substrate was irradiated with an argon ion beam from an ion source to clean the surface of the plastic substrate. The cleaning conditions were adjusted so that the acceleration voltage was 90 V and the current density of the ion beam was 40 ⁇ A/cm 2. Cleaning was performed for 60 seconds.
• high and low refractive index layers were formed as layers 1 to 6 of "Film Structure 1" shown in the table below, so as to have the layer thicknesses shown in the table below.
• zirconium oxide (ZrO 2 ) was used to form the high refractive index layer
• silicon oxide (SiO 2 ) was used to form the low refractive index layer
• the high and low refractive index layers were formed by a heating deposition method using electron beam heating.
• the sixth layer (low refractive index layer) was formed, the low refractive index layer was irradiated with an argon ion beam from an ion source at a current density of 40 ⁇ A/cm 2.
• the acceleration voltage of the ion source was 72 V, and the ion beam irradiation time was 75 seconds.
• the high refractive index layer and the low refractive index layer (the seventh layer and the eighth layer) of "film structure 1" were formed to have the layer thicknesses shown in the table below.
• the formation method was the same as for the first to sixth layers.
• a multilayer film was formed on one side of the plastic substrate by the above procedure. After the multilayer film was formed on one side of the plastic substrate, the plastic substrate was turned over and placed in a vacuum deposition apparatus, and a multilayer film was formed on the other side of the plastic substrate by the same procedure.
• the plastic substrate After forming the multilayer film on both sides of the plastic substrate, the plastic substrate is taken out of the vacuum deposition device, and a water-repellent and oil-repellent layer is formed by dipping coating.
• the composition used for the water-repellent and oil-repellent layer is a mixture of OPTOOL (registered trademark) AES4E (fluorine-substituted alkyl group-containing organosilicon compound solution, manufactured by Daikin Industries) and KY164 (manufactured by Shin-Etsu Chemical).
• OPTOOL registered trademark
• AES4E fluorine-substituted alkyl group-containing organosilicon compound solution, manufactured by Daikin Industries
• KY164 manufactured by Shin-Etsu Chemical
• Example 2 In the same manner as in Example 1, a primer layer and a hard coat layer were formed on a plastic substrate, the surface of the plastic substrate was cleaned, and then the first to sixth layers of "film structure 1" shown in the table below were formed. Next, the seventh and eighth layers of "film structure 1" were formed in the same manner as in Example 1, without irradiating with an argon ion beam. After forming the eighth layer (low refractive index layer), the low refractive index layer was irradiated with an argon ion beam from an ion source at a current density of 40 ⁇ A/ cm2 .
• the accelerating voltage of the ion source was 72 V
• the irradiation time of the ion beam was 75 seconds
• the neutralizer current was 0.35 A.
• a multilayer film was formed on one side of the plastic substrate by the above procedure. After the multilayer film was formed on one side of the plastic substrate, the plastic substrate was turned over and placed in a vacuum deposition apparatus, and a multilayer film was formed on the other side of the plastic substrate by the same procedure.
• the plastic substrate was removed from the vacuum deposition apparatus, and a water- and oil-repellent layer was formed by a dipping coating method.
• the method for forming the water- and oil-repellent layer was the same as in Example 1.
• Examples 3 to 11 and Comparative Examples 1 to 5 Except for carrying out the ion beam irradiation at the timings shown in the table below and changing the gas species, irradiation time, and current density, optical articles were obtained in the same manner as in Example 1. However, in Comparative Example 1, ion beam irradiation was not carried out after the formation of any of the layers. In the latter table, for example, notation such as "L2, L3" in Example 3 indicates that ion beam irradiation was performed after L2 (fourth layer) and L3 (sixth layer) were formed. In the latter table, the "Gas type" column indicates the gas type supplied to the ion source, and indicates that an ion beam was irradiated according to the supplied gas type.
• Example 12 In the same manner as in Example 1, a primer layer and a hard coat layer were formed on a plastic substrate, and the surface of the plastic substrate was cleaned. After cleaning, the first layer (low refractive index layer) of "film structure 2" shown in the table below was formed. After the first layer was formed, the low refractive index layer was irradiated with an argon ion beam under the same conditions as in Example 1. After the argon ion beam was irradiated, the second layer (high refractive index layer) and the third layer (low refractive index layer) were formed. After the third layer was formed, the low refractive index layer was irradiated with an argon ion beam under the same conditions as in Example 1.
• the fourth layer and the fifth layer were formed.
• a multilayer film was formed on one side of the plastic substrate by the above procedure. After the multilayer film was formed on one side of the plastic substrate, the plastic substrate was turned over and placed in a vacuum deposition apparatus, and a multilayer film was formed on the other side of the plastic substrate by the same procedure.
• the plastic substrate was removed from the vacuum deposition apparatus, and a water- and oil-repellent layer was formed by a dipping coating method.
• the method for forming the water- and oil-repellent layer was the same as in Example 1.
• Example 13 An optical article was obtained in the same manner as in Example 12, except that the argon ion beam irradiation was also performed after the formation of the second layer and the fourth layer (both high refractive index layers) in Example 12. The argon ion beam irradiation performed after the formation of the second layer and the fourth layer was performed under the same conditions as in Example 12.
• Example 14 In the same manner as in Example 1, a primer layer and a hard coat layer were formed on a plastic substrate, and the surface of the plastic substrate was cleaned. After cleaning, the first layer (high refractive index layer) and the second layer (low refractive index layer) of "film structure 3" shown in the table below were formed. After the second layer was formed, the low refractive index layer was irradiated with an argon ion beam under the same conditions as in Example 1. After the argon ion beam was irradiated, the third layer (high refractive index layer) and the fourth layer (low refractive index layer) were formed.
• the low refractive index layer was irradiated with an argon ion beam under the same conditions as in Example 1.
• the fifth layer high refractive index layer
• the sixth layer low refractive index layer
• the low refractive index layer was irradiated with an argon ion beam under the same conditions as in Example 1.
• the seventh layer high refractive index layer
• the eighth layer SnO2 layer
• the ninth layer low refractive index layer
• a multilayer film was formed on one side of the plastic substrate by the above procedure. After the multilayer film was formed on one side of the plastic substrate, the plastic substrate was turned over and placed in a vacuum deposition apparatus, and a multilayer film was formed on the other side of the plastic substrate by the same procedure.
• the plastic substrate was removed from the vacuum deposition apparatus, and a water- and oil-repellent layer was formed by dipping coating.
• the water- and oil-repellent layer was formed using the following composition F3 containing Optool (registered trademark) UF503 and FAS13E.
• Composition F3 was obtained by preparing a solution by mixing OPTOOL (registered trademark) UF503 manufactured by Daikin Industries, Ltd., FAS13E (C 6 F 13 -C 2 H 4 -Si(OC 2 H 5 ) 3 , manufactured by Tokyo Chemical Industry Co., Ltd.), and FC-3283 (C 9 F 21 N, Fluorinert, manufactured by 3M Co.) as a solvent, and stirring the solution at room temperature for a predetermined time.
• the ratio of the solid content of OPTOOL (registered trademark) UF503 was 0.425 mass% and the ratio of the solid content of FAS13E was 0.05 mass% when the total mass of composition F3 was 100 mass%.
• Composition F3 was applied onto the multilayer film formed by the above process using a dip coater under the conditions of a liquid immersion time of 10 seconds and a lifting speed of 3.5 mm/second. Then, the composition was subjected to wet heat curing at 50° C. and 80% RH for 30 minutes to form a water- and oil-repellent layer.
• an optical article having a primer layer, a hard coat layer, a multilayer film, and a water- and oil-repellent layer in this order on both sides of a plastic substrate was obtained.
• Examples 15 to 21 and Comparative Example 8 Except for carrying out the ion beam irradiation at the timings shown in the table below and changing the gas type, irradiation time, and current density, an optical article was obtained in the same manner as in Example 14. However, in Comparative Example 8, no ion beam irradiation was performed after the formation of any of the layers.
• the scratch resistance of the obtained optical articles of each of the Examples and Comparative Examples was evaluated. Specifically, the scratch resistance was evaluated by a Bayer test. More specifically, the scratch resistance was evaluated by the following procedure. First, the optical article of the Example or Comparative Example and a reference optical article (a non-coated lens made by Chemiglass, material: CR39) were set on a tray. After the optical articles were set, 500 g of corundum (product name: Alundum) was placed on the tray, and the tray was reciprocated with an amplitude of 4 inches. The tray was reciprocated 150 times per minute, and the tray was reciprocated for 4 minutes.
• the optical articles were removed from the tray, and the haze value of each optical article was measured and compared.
• the haze value was measured using Hazeguard Plus manufactured by BYK.
• the haze value of the optical article of the Example or Comparative Example was taken as Hs
• the haze value of the reference optical article was taken as Hcr
• the ratio of Hcr to Hs (Hcr/Hs) was calculated as R.
• the value of the ratio R (R) of the optical article of the example or comparative example and the value of the ratio R (R0) of the optical article that was not irradiated with an ion beam were used to calculate the R-ratio represented by the following formula, and the scratch resistance was compared.
• R-ratio [%] 100 ⁇ (R-R0) / R0
• the R-ratio was calculated between optical articles having the same film structure.
• the same film structure means, for example, a combination of the optical article of Example 1 and the optical article of Comparative Example 1 (film structure 1), a combination of the optical article of Example 12 and the optical article of Comparative Example 6 (film structure 2), and a combination of the optical article of Example 14 and the optical article of Comparative Example 8 (film structure 3).
• the value of R0 is the value of Comparative Example 1 for film structure 1, the value of Comparative Example 6 for film structure 2, and the value of Comparative Example 8 for film structure 3.
• Table 1 shows the film configuration of the optical articles of each of the Examples and Comparative Examples
• Table 2 shows the manufacturing procedures and evaluation results of the optical articles of each of the Examples and Comparative Examples.
• the notations such as "L1" and “H1” in Table 2 correspond to the notations in each film configuration in Table 1, respectively.
• the "current density” column indicates the value measured by the method described above.

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