TW200423111A - The method to produce photo data medium - Google Patents

Abstract

There is provided a cheap method to produce a photo data medium with surface with excellent properties of anti-scraping, anit-abrasion, anti-contaminating and lubricity. The method to produce photo data medium is the method to photo data medium 1 which at least contains recording layer 7, photo transparent layer 8, hard coat layer 9, and surface layer 10 sequentially on the holder 2. The method includes that hard coat agent composition containing active energy ray hardening components is coated on to form not-cured hard coat layer on the photo transparent layer 8, make the material used for surface layer containing active energy ray hardening components with properties of lubricity and/or anti-contaminating to be film on the not-cured coat layer and to from not-cured surface layer, and the not-cured hard coat layer and not-cured surface layer formed above are exposed to electric ray, and then the both layers above are exposed to UV to cure them to form cured hard coat layer 9 and cured surface layer 10.

Description

200423111 (1) Description of the invention: (1) The technical field to which the invention belongs The present invention relates to a method for manufacturing an optical information medium. More specifically, it relates to a composite hard coating layer, abrasion resistance, abrasion resistance, and stain resistance. · Manufacturing method of optical information media with excellent lubricity. In the present invention, the so-called composite hard coating layer includes a hard coating layer provided on the surface of the optical information medium, which is responsible for abrasion resistance and abrasion resistance, and a surface provided on the surface of the hard coating layer, which is responsible for antifouling and lubricity. Floor. The optical information media includes various read-only discs, optical recording discs, and magneto-optical recording discs. (2) Prior art In recent years, for optical discs, higher recording density has been required for expanded information processing such as animation information. With the higher recording density of optical discs, the recording / reading system is extremely susceptible to scratches on the surface of the light transmitting layer as the recording / reading laser light incident side of the optical disc. Therefore, it is necessary to increase the hardness of the surface of the optical transmission layer of the optical disc. In addition, on the optical disc, due to the use of the user, there are many cases where contaminants such as fingerprints, sebum, sweat, and cosmetics are attached to the surface. Once the pollutant is attached, it is not easy to remove, and it causes significant obstacles to the recording and reading of information signals caused by the attached pollutant. For these reasons, the surface of the light transmitting layer of the recording / reading laser light incident side of the optical disc requires excellent scratch resistance, abrasion resistance, stain resistance, and lubricity. At present, in terms of optical materials such as light transmission layers of optical information media, polycarbonate, or methyl methacrylate-based resin materials are mostly used from the viewpoints of moldability, transparency, and price. However, these materials have the so-called inadequate anti-scratch resistance, abrasion resistance, or anti-fouling properties of organic pollutants. 6-200423111, and there are also so-called easy-to-charge in order to show high insulation, and the media A large amount of dust adhered to the surface during storage or use, which caused errors in the recording and reading of optical information. In order to improve the scratch resistance of the surface of the media, it is generally performed on the surface of the light transmitting layer of the media to form a transparent and scratch-resistant hard coating layer. The hard coating layer is formed by polymerizing a hardening compound by coating an active energy beam with two or more (meth) acrylfluorenyl polymerizable functional groups in the molecule on the surface of the light transmitting layer, and irradiating the active energy beam with ultraviolet rays or the like. It is hardened to proceed. However, compared with the surface of resin films such as polycarbonate or methyl methacrylate, the hard coating layer obtained is excellent in abrasion resistance, and has a limit on the level of abrasion resistance achieved, and may not necessarily be used in media. Sufficient scratch resistance. If the resin is made harder for scratch resistance, the shrinkage during hardening becomes larger, and the warpage of the obtained media-based optical disc surface becomes larger. In addition, since these hard coatings are only for the purpose of improving the scratch resistance, they cannot be expected to have antifouling effects on pollutants such as dust, atmospheric oil and gas, or fingerprint pollution. As for the hard coating layer having antifouling properties against organic pollutants, for example, in Japanese Patent Application Laid-Open No. 1 0-1 1 0 1 1 8, it is proposed to incorporate a non-crosslinking fluorine-based surfactant into the hard coating agent. . However, when a non-crosslinked fluorine-based surfactant is added to the hard coating agent, there is a problem that the so-called surfactant gradually disappears when the medium is used, for example, when wiping is performed. In Japanese Patent Application Laid-Open No. 1 1-2 1 3444, it is disclosed that a fluorine-based polymer is coated on the surface of a conventional optical disc substrate such as polycarbonate. However, the fluoropolymer is only adsorbed on the substrate surface by van der Waals force -7-200423111, and the fluoropolymer has extremely poor adhesion to the substrate surface. Therefore, there is a significant problem in durability of the surface treatment by coating with a fluoropolymer. Japanese Patent Application Laid-Open No. 2002- 1 90 1 3 6 discloses that metal chalcogenide particles containing silicon oxide particles and the like are contained in the hard coating layer to improve the abrasion resistance of the hard coating layer and further on the hard coating layer A film containing a water- or oil-repellent silane coupling agent is provided to improve the antifouling property of the surface. However, by reducing the coefficient of friction on the surface of the medium, it is possible to prevent the impact when it comes into contact with hard protrusions by sliding it over, and to prevent the occurrence of scratches. Therefore, it is desirable to reduce the coefficient of friction on the surface of the hard coating layer to further improve the scratch resistance. In particular, in recent years, the number of openings (NA) of an objective lens for focusing recording / reading laser light is 0.7 or more, for example, it has increased to about 0.85, and at the same time, the wavelength λ of the recording / reading laser light has been shortened to 400 nm. The diameter of the focal point of the laser light becomes smaller, so try to record digital information with larger capacity. In order to achieve such a high NA, the working distance between the contact lens and the surface of the optical information medium becomes smaller (for example, when the setting is about NA = 0 · 8 5 and the operating distance is about 1 〇〇 # m, it is compared In the past, it was significantly narrower). In the rotation of the optical information medium, the possibility of causing the surface of the optical information medium to contact the object lens or the support supporting the lens has become very high. Therefore, while improving the abrasion resistance of the surface of the hard coating layer, it is sought to reduce the coefficient of friction. (3) Summary of the Invention Among them, the purpose of the present invention is to solve the problems of the above-mentioned conventional technology, and provide a surface with excellent abrasion resistance, abrasion resistance, stain resistance and lubricity. 8-200423111 Inexpensive manufacturing method. As a result of intensive research, the present inventors and others have provided a surface of a light transmitting layer that is the incident side of recording / reading laser light by providing a hard coating layer that bears abrasion resistance and abrasion resistance and assuming the aforementioned hard coating. The composite hard coating layer of the antifouling and lubricating surface layer on the surface of the layer has been found to obtain an optical information medium with a surface that has abrasion resistance, abrasion resistance, and excellent antifouling and lubricity properties. Furthermore, the present inventors have studied the manufacturing method of the optical information medium to achieve the invention. It is attached to the support

The present invention includes the following inventions. (1) A method for manufacturing an optical information medium. A method for manufacturing an optical information medium having at least a recording layer, a light transmitting layer, a hard coating layer, and a surface layer. Hard coating composition to form an unhardened hard coating,

On the unhardened hard coating layer, a surface layer material containing an active energy beam hardening component having a lubricating and / or antifouling function is formed into a film to form an unhardened surface layer, and the electron beam is irradiated onto the formed unhardened The hard coating layer and the unhardened surface layer are then irradiated with ultraviolet rays to harden the aforementioned two layers to form a hardened hard coating layer and a hardened surface layer. This information medium is used for incident laser light for recording or reading through a surface layer, a hard coating layer, and a light transmitting layer. (2) The manufacturing method of the optical information medium as described in (1), wherein the active energy beam hardening component contained in the hard coating composition is ultraviolet-ray-curing component. (3) The method for manufacturing an optical information medium as described in (1) or (2), wherein the active energy beam-hardening component contained in the surface layer material is an electron beam-hardening component. (4) The method for manufacturing an optical information medium as described in (1) or (2), wherein the active energy beam hardening component contained in the surface layer material is electron beam hardening, and has a polysiloxane-based substituent and / Or a fluorine-based substituent. (5) The method for manufacturing an optical information medium as described in any one of (1) to (4), after forming an unhardened hard coating layer, drying as necessary, and irradiating ultraviolet rays to form a hardened hardened state The coating layer is then formed on the semi-hardened hard coating layer to form a film for the surface layer material to form an unhardened surface layer. In the case where the surface layer is formed by coating the material for the surface layer, the material for the surface layer is applied and then dried. (6) The method for manufacturing an optical information medium as described in (5), wherein the uncured hard coating layer is irradiated with ultraviolet rays and then subjected to an annealing treatment (heat relaxation treatment). (7) The method for producing an optical information medium as described in any one of (1) to (6), wherein the method is performed by coating the surface layer material with a film, and after the surface layer material is applied, heat treatment is performed. . (8) The method for producing an optical information medium as described in any one of (1) to (7), wherein the recording layer is coated with an active energy beam hardening material and is irradiated with ultraviolet rays to form a semi-hardened or hardened state. The light transmitting layer is then coated with a hard coating agent composition on the light transmitting layer in a semi-hardened or hardened state to form an unhardened hard coating layer. -1 0-200423111 (9) The manufacturing method described in (8), wherein the light-transmitting layer is irradiated with ultraviolet rays and then annealed (heat relaxation treatment). (1 0) The method for manufacturing an optical information medium as described in any one of (1) to (7), wherein a resin sheet is used to form a light transmitting layer on the recording layer, and then the light transmitting layer is formed on the recording layer. The hard coating composition is applied to form an unhardened hard coating layer. (1 1) The method of dressing an optical information medium as described in any one of (1) to (10), wherein the surface layer has a thickness of 1 nm to 100 nm. (1 2) The method for manufacturing an optical information medium as described in any one of (1) to (11), wherein the light transmitting layer has a thickness of 10emdOO / zm. (1 3) The method for manufacturing an optical information medium as described in any one of (1) to (1 2), wherein the acceleration voltage of the electron beam during the irradiation of the electron beam is 20 to 100 kV. The invention also includes the following inventions. (1 4) A method for manufacturing an optical information medium, which has at least a recording layer on one side of a light-transmitting support, and sequentially has a light of a hard coating layer and a surface layer on the other side of the light-transmitting support. A method for manufacturing an information medium, which comprises coating a hard coating agent composition containing an active energy beam hardening component on the other surface of a light-transmitting support to form an unhardened hard coating layer on the unhardened hard coating layer , Forming an unhardened surface layer by forming a surface layer material containing an active energy beam hardening component having a lubricating and / or antifouling function, -11- 200423111 irradiates an electron beam to the formed unhardened hard coating layer and The unhardened surface layer is then irradiated with ultraviolet rays to harden the two layers to form a hardened hard coating layer and a hardened surface layer. This optical information medium is used by, for example, incident laser light for recording or reading through a surface layer, a hard coating layer, and a light-transmitting support. (1 5) The method for manufacturing an optical information medium as described in (1 4), wherein the active energy beam-curable component contained in the hard coating composition is an ultraviolet-curable component. (16) The method for manufacturing an optical information medium as described in (14) or (15), wherein the active energy beam hardenable component contained in the material for the surface layer is divided into an electron beam hardenable component. (1 7) The method for manufacturing an optical information medium as described in (1 4) or (1 5), wherein the active energy beam hardening component contained in the surface layer material is an electron beam hardening component and has a silane-based substituent And / or a fluorine-based substituent. (1 8) The manufacturing method of the optical information medium as described in any one of (1 4) to (1 7), wherein after forming an unhardened hard coating layer, if necessary, dry and irradiate ultraviolet rays A hard coating layer in a semi-hardened state is formed, and then a material for the surface layer is formed on the semi-hardened hard coating layer to form an unhardened surface layer. (19) The manufacturing method of the optical information medium as described in (18), wherein the uncured hard coating layer is irradiated with ultraviolet rays, and then annealed (thermal relaxation treatment). (2 0) The manufacturing method of the optical information medium-1 2-200423111 as described in any one of (1 4) to (1 9), wherein the coating is performed by coating a film of a material for a surface layer, and coating After the material for the surface layer, a heat treatment is performed. (2 1) The method for producing an optical information medium as described in any one of (1 4) to (2 0), wherein the surface layer has a thickness of 1 nm to 100 nm. (22) The method for manufacturing an optical information medium as set forth in any one of (14) to (2 1), wherein the acceleration voltage of the electron beam during the irradiation of the electron beam is 20 to 100 kV. In the present invention, the optical information medium includes various media such as a read-only optical disc, an optical recording disc, and a magneto-optical recording disc. According to the present invention, there is provided an inexpensive manufacturing method of an optical information medium having a composite hard coating layer, excellent scratch resistance, abrasion resistance, and stain resistance and lubricity. Example for implementing the invention 丨 With reference to FIG. 1, the manufacturing method of the optical information medium (hereinafter, simply referred to as an optical disc) of the present invention will be described. In the following, although a phase-change type optical disc is described in an example, the present invention is not limited to this. It can be widely used for reading a dedicated disc, a disc that can be recorded only once, and the like, and does not vary depending on the type of the recording layer. Fig. 1 is a schematic sectional view of an example of an optical disc manufactured in the present invention. In the first figure, the optical disc (1) is formed on the side with fine irregularities such as information recesses or pre-grooves supporting the substrate (2), and has a reflective layer (3) and a second dielectric layer (4) in this order. ), A phase change recording material layer (5) and a first dielectric layer (6), a light transmitting layer (8) is provided on the first dielectric layer (6), and a hard coating layer is provided on the light transmitting layer (8) (9) and surface layer (10). In this example, the reflective layer (3), the second dielectric layer (4), the phase change-1 3-200423111 chemical recording material layer (5) and the first dielectric layer (6) constitute the recording layer (7) . The two layers of the hard coating layer (9) and the surface layer (10) are conveniently referred to as a composite hard coating layer. The optical disc (1) is used by passing a laser light for recording or reading through a surface layer (10), a hard coating layer (9), and a light transmitting layer (8). Although not illustrated in the drawings, a recording layer is further provided on the recording layer (7) via a spacer layer, and an optical disc having two or more recording layers is also included in the present invention. In this case, the optical disc is on the recording layer furthest from the supporting substrate (2), and has a light transmitting layer (8), a hard coating layer (9), and a surface layer (1 0). The support substrate (2) is 0.3 to 1.6 mm thick, and preferably 0.5 to 1.3 mm thick. On the side where the recording layer (7) is formed, fine irregularities such as information pits or pre-grooves are formed. In terms of supporting the substrate (2), since the optical disc (1) is used by incident laser light from the light transmitting layer (8) side as described above, although it does not necessarily need to be optically transparent, polycarbonate can be used for transparent materials. Resins, acrylic resins such as polymethyl methacrylate (PMM A), and various plastic materials such as polyolefin resins. In the case of using such a material that is easily bent, it is particularly effective because it can suppress the occurrence of warping of the optical disc. However, glass, ceramics, metal, etc. can also be used. The concave-convex pattern is mostly made by injection molding when a plastic material is used. In the case other than a plastic material, it is formed by a photopolymer method (2P method). A reflective layer (3) is usually formed on the support substrate (2) by sputtering. As for the material of the reflective layer, a metal element, a semi-metal element, a semiconductor element, or a compound thereof may be used alone or in combination. Specifically, it may be selected from, for example, 200423111

Known materials for the reaction layer such as Au, Ag, Cu, A1, and Pd. The reflective layer is preferably formed as a thin film having a thickness of 20 to 200 nm. On the reflective layer (3) or directly on the support substrate (2) without a reflective layer, a second dielectric layer (4) and a phase change recording material layer (5) are sequentially formed by a sputtering method. And a first dielectric layer (6). The phase-change recording material layer (5) is formed by a material that is reversibly changed into a crystalline state and an amorphous state by laser light irradiation, and the optical characteristics are different between the two states. Examples include Ge-Sb-Te, In-Sb-Te, Sn-Se-Te, Ge-Te-Sn, In-Se-Tl, In-Sb-Te, and the like. Furthermore, at least one metal selected from the group consisting of Co, Pt, Pd, Au, Ag, Ir, Nb, Ta, V, W, Ti, Cr, Zr, Bi, and In may be added to these materials in a trace amount. A reducing gas such as nitrogen may be added in a small amount. The thickness of the recording material layer (5) is not particularly limited, and is, for example, about 3 to 50 nm. The second dielectric layer (4) and the first dielectric layer (6) are formed by sandwiching the upper and lower sides of the recording material layer (5). The second dielectric layer (4) and the first dielectric layer (6) have a function as an interference layer that adjusts the mechanical, chemical protection, and optical characteristics of the recording material layer (5). The second dielectric layer body (4) and the first dielectric layer body (6) may be each composed of a single layer or a plurality of layers. The second dielectric layer body (4) and the first dielectric layer (6) are each composed of at least one selected from the group consisting of Si, Zn, Al, Ta, Ti, Co, Zr, Pb, Ag, Zn, Sn, It is preferable to form oxides, nitrides, sulfides, fluorides, or a combination thereof among metals of Ca, Ce, V, Cu, Fe, and Mg. The second dielectric layer body (4) and the first dielectric layer body (6) have individual decay coefficients k-1 5- 200423111 of preferably 0.1 or less. The thickness of the second dielectric layer body (4) is not particularly limited, but is preferably about 20 to 150 nm. The thickness of the first dielectric layer (6) is not particularly limited, but is preferably about 20 to 20 nm, for example. The reflection can be adjusted by choosing the thickness of the two dielectric layers (4) (6) due to these ranges. On the first dielectric layer (6), a light-transmitting layer (8) is formed using an active energy beam-hardening material or a light-transmitting sheet such as polycarbonate. In the present invention, the term "active energy beam" refers to an electron beam or ultraviolet rays. The active energy beam-hardening material used for the light-transmitting layer (8) is selected from ultraviolet-curing materials and optically transparent, less optical absorption or reflection in the wavelength range of laser light used, and low birefringence. Electron beam hardening material. Specifically, it is preferable that the active energy beam curable material is composed of an ultraviolet (electron beam) curable compound or the polymerizable composition. In these respects, examples include acrylic double chains containing or introduced by an ester compound such as acrylic acid or methacrylic acid, epoxy acrylate, acrylic urethane, such as diallyl phthalate. The functionalities that are crosslinked or polymerized by ultraviolet irradiation of allylic double bonds, unsaturated double bonds such as maleic acid derivatives, etc. are based on monomers, oligomers and polymers in the molecule. These systems are preferably multifunctional, especially trifunctional or more, and only one type or two or more types may be used. Moreover, you may use a monofunctional one as needed. The ultraviolet curable monomer is preferably a compound having a molecular weight of less than 2000, and the oligomer is preferably 2000 to 10,000. These also include styrene, ethyl acrylate, ethylene glycol diacrylate, ethylene glycol di-16-200423111 alcohol ester, diethylene glycol diacrylate, diethylene glycol methacrylate, 1,6-hexanediol diacrylate and dimethacrylic acid; [, 6-hexanediol ester, etc.] Among the particularly preferable ones, there are isopentaerythritol tetra (meth) acrylate, tris ( Isopentaerythryl methacrylate, diisopentaerythritol hexa (meth) acrylate, tris (meth) propionate, tris (meth) acrylate, tris (meth) acryl Acrylate, (meth) acrylate of phenol-based ethylene oxide adduct, etc. Other examples of the ultraviolet curable oligomer include an acrylic modified body of an ether acrylate oligomer or a urethane elastomer. The active energy beam hardening material may also contain a recognized photopolymerization initiator. 1 ° The photopolymerization initiator is not particularly necessary when an electron beam is used as the active energy beam, but it is necessary when an ultraviolet ray is used. . The photopolymerization initiator may be selected from ordinary ones such as acetophenone-based, benzoin-based, diphenylketone-based, and thioxanthone-based. Among the photopolymerization initiators, examples of the photo-radical initiator include Grand Rochuja 1 1 7 3, Iljachuya 6 5 1, Iljachuya 184, Iljachuya 907 (all (Made by Cibate Chemicals). The content of the photopolymerization initiator is, for example, about 0.5 to 5% by weight based on the active energy beam-hardening component. In terms of the ultraviolet curable material, a composition containing an epoxy resin and a photoradical polymerization catalyst is also suitably used. In terms of epoxy resins, aliphatic cyclic epoxy resins are preferred, and those having two or more epoxy groups in the molecule are particularly preferred. For aliphatic cyclic epoxy resins, one or more types of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanoate and bis (3,4-epoxycyclohexylmethyl) are used. Adipate, bis (3,4-epoxycyclohexyl) adipate, 2- (3,4-epoxycyclohexyl-5,5-spiral-3,4-epoxy) cyclohexane -M-dioxane, bis-17-200423111 (2,3-epoxycyclopentyl) ether, vinyl cyclohexene dioxide and the like are preferred. The epoxy equivalent of the aliphatic cyclic epoxy resin is not particularly limited, but from the viewpoint of obtaining good hardenability, it is preferably 60 to 300, and particularly preferably 100 to 200. The photocationic polymerization catalyst system can also use any of the recognized ones, and there is no particular limitation. For example, more than one metal fluoroborate and boron trifluoride complex, bis (perfluoroalkylsulfo) methane metal salt, aryldiazonium compound, and aromatic key of Group 6 A element can be used Salt, aromatic key salt of group 5 a element, dicarboxyl chelate of group 3 A to 5 A element, thiopyranonium salt, 6A with MF6 anion (however, M is P, As or Sb) Group element, triarylsulfonium complex salt, aromatic dihydrogen complex salt, aromatic sulfonium complex salt, etc., in particular, more than one kind of polyarylfluorene complex salt, halogen-containing halogen compound Aromatic phosphonium salts or dihydrophosphonium salts of ions, aromatic key salts of Group 3A elements, Group 5A elements, and Group 6A elements are preferred. The content of the photocationic polymerization catalyst is, for example, about 0.5 to 5% by weight of the active energy beam-curable component. As for the active energy beam hardening material used for the light transmitting layer, it is preferable to have a viscosity (25 ° C) of 1,000 to 10,000 cp. In the formation of the light transmitting layer (8), the application of the active energy beam hardening material on the first dielectric layer (6) can be performed by a spin coating method. The thickness of the light transmitting layer (8) is, for example, about 10 to 3 0 0 / zm after hardening, preferably 20 to 200 // m, particularly preferably 70 to 150 // m, and 75 to 150 # m is better. In the present invention, after the active energy beam hardening material is coated on the first dielectric layer (6), the hardening material layer is irradiated with ultraviolet rays to form -18-200423111 in a semi-hardened or hardened state. A light-transmitting layer is preferred. Then, in the next step, a hard coating composition is coated on the light-transmitting layer in a semi-hardened or hardened state to form an unhardened hard coating layer. Although the amount of ultraviolet radiation at this time depends on the thickness of the light transmitting layer (8) or the type of the active energy beam hardening material, it can be, for example, 10 to 1 when a light transmitting layer in a semi-hardened state is obtained. 5 00mJ / cm2, preferably 50 ~ 1000mJ / cm2. With this amount of ultraviolet irradiation, a light-transmitting layer in a semi-hardened state can be easily obtained. The term "semi-hardened" means that a part of the applied hardening material is not reacted. Therefore, regardless of the degree of physical hardening of the light-transmitting layer, even if the surface tackiness (adhesiveness) disappears, it does not matter. When a light-transmitting layer in a hardened state is obtained, it may be, for example, 1 00 to 5 0 0 mJ / cm2 and W 2 0 0 to 4 0 0 Om J / cm2. With the ultraviolet irradiation amount in this range, a light-transmitting layer in a cured state was obtained. In particular, since the light-transmitting layer has become a semi-hardened state, there is no fluidity, and the application of the hard coating composition in the next step will not disturb the interface, and the adhesion with the light-transmitting layer is very high. Excellent hard coating. The ultraviolet irradiation at this time may be divided into a plurality of times, and in this case, the cumulative irradiation amount of ultraviolet rays may be in the above-mentioned range. In addition, the coating operation of the active energy beam curable material may be performed in a plurality of times, or the ultraviolet operation may be performed after each coating operation. Since the resin is hardened in stages, it is divided into a plurality of resins that are irradiated with ultraviolet rays, which can reduce the stress that accumulates due to the hardening shrinkage of the optical disc, so that the stress that eventually accumulates on the optical disc is reduced. This result is preferable because the optical transmission layer (8) has a thickness as described above, because it can be made into an optical disc having excellent mechanical characteristics. -19- 200423111 After irradiating ultraviolet rays to the light transmitting layer, it is also preferable to perform annealing treatment and treatment). The stress caused by the hardening shrinkage is extremely large at the moment of hardening, and is relieved with the passage of time. Therefore, by using the principle of 'immediately releasing the stress due to hardening and shrinkage accumulated on the disc', in the case of multiple ultraviolet irradiations, it is better to perform an annealing treatment between ultraviolet irradiations under ultraviolet irradiation. result. Among them, the annealing temperature is preferably 60 ° C or more, and more preferably. Since the annealing temperature is above 80 ° C, the stress can be released more fully. Although the upper limit of the annealing temperature depends on the material of the substrate to be supported, it is generally better to perform at a temperature lower than the glass degree Tg of the material used by at least 10 ° C. The annealing treatment depends on the annealing treatment temperature. From the viewpoint of production efficiency, it is 1 to 5 minutes. Alternatively, in the present invention, a light-transmitting resin sheet may be used as the light-transmitting layer. In this case, on the first dielectric layer (6), the light-transmitting layer is made of the same active energy beam-hardening material and an uncured resin material layer. On the unhardened resin material layer, a light-transmitting sheet of a light-transmitting layer (8), and then hardening the resin material layer by irradiating an active energy beam, and then transmitting the light to form a light-transmitting layer (8) . As for the active energy curable material used for the resin material layer, the resin material layer can be applied by a spin coating method with a viscosity of 3 to 5000 cp (25 ° C). The thickness of the tree layer is, for example, about 1 to 50 // m after hardening, preferably // hi. (The thermal annealing material is better for hard annealing. It is better to spray this step and ^ 80 ° C. The branch transfer temperature time for early completion is better. It is better to form a coating and to form a wire harness that is placed as an ultraviolet sheet. For the fat material 1 0 to 4 20-20 200423111, for the light-transmitting sheet, a polycarbonate sheet having a desired thickness selected from, for example, 50 to 3 0 0 // m and preferably 50 to 150 / zm is used. The formation of the light-transmitting layer (8), more specifically, is in a vacuum (less than 0.1 atmosphere), and a polycarbonate sheet of a desired thickness is placed on the unhardened resin material layer. Next, return to A resin material layer is hardened by irradiating ultraviolet rays in an atmospheric pressure atmosphere. A composite hard coating layer composed of a hard coating layer (9) and a surface layer (10) is formed on the light transmitting layer (8). First, the description includes The hard coating layer composition of the active energy beam hardening component of the hard coating layer (9), and the surface layer containing the active energy beam hardening component having a lubricating and / or antifouling function for the surface layer (10), Material. Contained in hard coating composition The active energy beam hardening component is selected from ultraviolet hardening materials and electron beam hardening materials on the condition that it is optically transparent, has low optical absorption or reflection in the wavelength range of the laser light used, and has a small refractive index. It is preferably selected from ultraviolet curable materials. The ultraviolet curable materials included in the hard coating composition are selected from the same as the ultraviolet curable materials used for the light transmitting layer (8) described above. That is, the composition of the hard coating agent In terms of properties, acrylic resins containing or introducing an acrylic double bond such as an acrylic or methacrylic ester compound, an epoxy acrylate, or an acrylic urethane, such as diallyl phthalate, can be used. The double bonds, unsaturated double bonds, etc. of unsaturated double bonds, etc. are functionalized to be crosslinked or polymerized by ultraviolet irradiation. They are based on monomers, oligomers, and polymers in the molecule, and include photopolymerization initiators. It is also a free radical polymerizable composition. It is also suitable to use a cationic-2 containing a epoxy resin and a photocationic polymerization catalyst as a hard coat. The active energy beam hardening compound contained in the hard coating composition may be used singly or in combination of two or more. The hard coating composition may have a higher abrasion resistance when necessary. Inorganic fillers can be included. Examples of inorganic fillers include silica, alumina, oxide pins, titanium oxide, etc. The average particle size of inorganic fillers is 100 nm or less, especially if transparency is necessary. It is preferable that the thickness be 50 nm or less. In addition, in order to improve the strength or abrasion resistance of the hardened coating film, it is better to modify the surface of the inorganic filler with a compound having an active energy beam polymerizable group. The inorganic fillers having an average particle diameter of 50 nm or less and surface modification with a compound having an active energy beam polymerizable group are described in, for example, Japanese Unexamined Patent Publication No. 1 1402 35 and Japanese Unexamined Patent Publication No. 9- The reactive silica particles of Japanese Patent Publication No. 1001 1 and Japanese Patent Application Laid-Open No. 200 1-1 87 8 1 2 are preferred because they can be used in the present invention. In addition, the silica particles described in Japanese Patent Application Laid-Open No. 1 1-6023 5 contain cationically reactive oxetanyl groups as reactive groups; the oxides described in Japanese Patent Application Laid-Open No. 9-100111 The silicon particle system contains a radically reactive (meth) acrylfluorenyl group as a reactive group. The silicon oxide particles described in Japanese Patent Laid-Open No. 2000-1 878 1 2 are also free radical reactive unsaturated double bonds containing (meth) acrylfluorenyl groups, etc., and react with cations such as epoxy groups. Sex-based. By adding these inorganic fillers to the hard coating agent composition, the wear resistance of the hard coating layer can be relatively improved. The content of the inorganic filler is, for example, 5 to 80% by weight in the hard coating composition (as a solid content). / 〇-22- 200423111. Containing more than 80% by weight of inorganic filler, it is easy to weaken the film strength of the hard coating layer. In addition, the hard coating agent composition further contains a non-polymerizable diluent, an organic filler, a polymerization inhibitor, an antioxidant, an ultraviolet absorber, a light stabilizer, an antifoaming agent, a leveling agent, a pigment, and the like, as necessary. Sand compounds and the like are also fine. The surface layer (10) is made of materials that are optically transparent, have low optical absorption or reflection in the wavelength range of the laser light used, and have a small refractive index. If they have antifouling properties (water repellency and // Or oil repellent) and /%

There is no particular limitation on the compounds having a lubricating substituent or a reactive group having a reactive energy beam polymerizable group. For example, a polysiloxane-based substituent or a fluorine-based substituent is mentioned as a substituent for imparting antifouling properties and / or lubricity. In addition, the reactive energy polymerizable reactive groups include (meth) acryl fluorenyl, vinyl, and hydrogen sulfide groups such as active energy beam radical polymerizable reactive groups, or cyclic ether groups and ethyl acetate. Cationic polymerizable reactive group such as an active energy beam group such as an ether group. These radically polymerizable reactive groups or cationically polymerizable reactive groups may be used as polysiloxanes or fluorine-based compounds. In the case of polysiloxanes, a site having a polysiloxane substituent and at least one selected from (meth) acrylfluorenyl, vinyl, hydrogenthio, cyclic ether, and vinyl ether are listed. Although the compound of a reactive group is illustrated in more detail by the compound of the following general formula (1)-(3), it is not necessarily limited to these. R- [Si (CH3) 20] nR (1)-23- 200423111 R- [Si (CH3) 20] n-Si (CH3) 3 (2) (CH3) 3Si0- [Si (CH3) 20] n- [Si (CH3) (R) 0] m-Si (CH3) 3 (3) wherein R contains a (meth) acrylfluorenyl group, a vinyl group, a hydrogen thio group, a cyclic ether group, and a vinyl ether group Among them, at least one kind of substituent of a reactive group is selected, n and m are degree of polymerization, η is 5 to 1000, and m is 2 to 100. Examples of the fluorine-based compound include a fluorine-containing (meth) acrylate compound. Specific examples thereof include (meth) acrylic acid-2, 2, 3, 3, 3-pentafluoropropyl ester, and (methyl) ) Acrylic acid-2,2,3,3-tetrafluoropropyl ester, (meth) acrylic acid-2,2,2-trifluoroethyl ester, (meth) acrylic acid-1H, 1H, 5H-octafluoropentyl ester, 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl (meth) acrylate, ethyl 2- (perfluorooctyl) acrylate, 3-perfluorooctyl (meth) acrylate 2-Hydroxypropyl ester, 2- (perfluorodecyl) ethyl (meth) acrylate, 2- (perfluoro-9-methyloctyl) ethyl (meth) acrylate, (methyl) 3- (perfluoro-7-methyloctyl) ethyl acrylate, 2- (perfluoro-9-methyldecyl) ethyl (meth) acrylate, -1H, 1H (meth) acrylic acid, 9H-hexafluorononyl ester and other fluorinated acrylates, but not necessarily limited to these. For example, a polymer compound such as a perfluoropolyether into which a (meth) acrylate group is introduced, or a fluorine-based compound having a vinyl group or a hydrogen thio group having a substituted (meth) acrylate group is also preferable. As specific examples, diacrylates of Fombrin Z DOL (alcohol perfluoropolyether (manufactured by Aodimont)); fluoride ART 3, fluoride ART 4 (Kyoeisha Chemical Co., Ltd.) are given. In addition, examples of the fluorine-based compound include a compound having a fluorine-containing substituent and a reactive group selected from at least one of a cyclic ether group and a vinyl ether group. Specifically, although 3- (1Η, 1Η-perfluorooctyloxy)-24-200423111 1,2-epoxypropane, 3- (111,111-perfluorononoxy) -1 are listed, 2-epoxypropane, 3- (1H, 1H-perfluorodecyloxy) · 1,2-epoxypropane, 3 · (1H, 1H-perfluoroundecyloxy) -1,2-epoxy Propane, 3- (1H, 1H-perfluorotetradecanyloxy) -1,2-epoxypropane, 3- (1H, 1H-perfluorohexadecyloxy) -1,2-epoxypropane, 111,111,611,611-perfluoro-1,6-hexanediol diglycidyl ether, 111,111,811,811-perfluoro-1,8-octanediol diglycidyl ether, 111,111,1011,1011-Perfluoro-1,10-decanediol diglycidyl ether, 111,111,1211,1211-Perfluoro-1,12-dodecyl glycol diglycidyl oxide Ether, Fombrin Z DOL (alcohol-modified perfluoropolyether) (diepoxy ether produced by Aodimont), but it is not necessarily limited to these. For example, a compound which can use an aliphatic cyclic epoxy group such as 3,4-epoxycyclohexyl group or a vinyl ether group as a reactive group is also preferred. As for the active energy beam hardening compound contained in the material for the surface layer, only one kind may be used, or two or more kinds may be used alone. The active energy beam hardenable component contained in the surface layer material is considered to be an electron beam hardenable component. In the surface layer material, as in the case of the hard coating composition, a non-polymerizable diluent, an organic filler, an inorganic filler, a polymerization inhibitor, an antioxidant, Ultraviolet absorbers, light stabilizers, defoamers, leveling agents, pigments, silicon compounds, etc. are also fine. Next, the formation of a composite hard coating layer including a hard coating layer (9) and a surface layer (10) on the light transmitting layer (8) will be described. In the present invention, the aforementioned hard coating is applied on the surface of the light-transmitting layer (8) in a semi-hardened or hardened state using a hardening material, or on the surface of the light-transmitting layer (8) composed of a light-transmitting sheet. Agent composition to form an unhardened-25- 200423111 hardened coating. The coating method of the hard coating agent is not limited, and various coating methods such as a spin coating method, a dip coating method, and a gravure printing method can be used. The thickness of the hard coating layer after hardening can be formed from 1 // m to 10 / zm, and preferably from 1 // m to 5 // m. Below 1 // m cannot give the disc a sufficient surface hardness, while the super pan 10 // m has cracks on the one hand, and the tendency of the disc to become warped on the other hand. After the surface of the light-transmitting layer (8) is coated with the hard coating agent composition, the fluidity of the hard coating layer without hardening is preferably before the film for the surface layer is formed. Since there is no fluidity of the unhardened hard coating layer, when the surface layer material is formed thereon, it is possible to prevent the film thickness change of the hard coating layer or the deterioration of the surface property, and it is easy to uniformly form the surface material film. In order to make the non-hardened coating layer non-flowable, for example, the coating may be heated after coating, and the solvent contained in the hard coating composition may be removed from the hard coating layer. In addition, it is preferable to perform annealing treatment (heat relaxation treatment) by the heating and immediately release the stress caused by the hardening shrinkage accumulated in the optical disc. Among them, the annealing temperature is preferably 60 ° C, and more preferably 80 ° C or more. The annealing temperature is above 80 ° C, and the stress can be released completely early. Although the upper limit of the annealing temperature depends on the supporting substrate used, it is generally preferred to perform it at a temperature that is at least 10 ° C lower than the glass transition temperature Tg of the material used. In addition, although the annealing treatment time depends on the annealing treatment temperature, it is preferably 1 to 5 minutes from the viewpoint of production efficiency. Even in the case of not performing the aforementioned annealing treatment after irradiating ultraviolet rays on the light transmitting layer (that is, before forming the hard coating layer), by performing the annealing treatment after coating the hard coating layer, the stress relief effect accumulated in the optical disc is obtained. In the case of -26- 200423111, the annealing treatment time is preferably about 1 to 5 minutes. In addition, since the unhardened hard coating layer has no fluidity, the hard coating layer can be made into a semi-hardened state by heating as necessary after application and irradiating ultraviolet rays. At this time, pay attention that the hard coating layer is not completely hardened by the irradiation of ultraviolet rays. The term "semi-hardened" means that a part of the applied hard coating composition is not reacted. Therefore, in particular, regardless of the degree of physical hardening of the hard coating layer, the surface adhesiveness (adhesion) may disappear. Although the amount of ultraviolet irradiation at this time depends on the thickness of the hard coating layer, it may be, for example, 1 to 500 mJ7cm2, and preferably 1 to 200 mJ / cm2. With this amount of ultraviolet irradiation, a hard coating in a semi-hardened state is easily obtained. After the hard coating layer is irradiated with ultraviolet rays, it is preferable to perform the same annealing treatment as described above. Next, on the surface of the hard coating layer in an unhardened or semi-hardened (partly hardened) state, a film of the aforementioned surface layer material is formed to form an unhardened surface layer. The surface layer system may be formed so that the thickness obtained after hardening is 1 nm to 100 nm, and preferably 5 nm to 50 nm. Below 1 nm, antifouling properties and lubricity can hardly be obtained. Above 1000 nm, it can hardly reflect the hardness of the lower hard coating layer, reducing the effects of scratch resistance and abrasion resistance. The film formation can be performed by coating the aforementioned surface layer material, or by vapor deposition. When coating, the material for the surface layer is diluted with an appropriate solvent. The coating liquid is not limited and can be applied by various coating methods such as a spin coating method, a dip coating method, a gravure printing method, and a spray coating method. After the material for the surface layer is applied, it is preferably heat-treated. The solvent is evaporated by heat treatment, and at the same time, the surface layer material is made uniform by heat, and a smooth surface is easily obtained. At this time, the heat treatment temperature is preferably 6 ° C or higher, and more preferably 80 ° C or higher is -27-200423111. The heat treatment time is preferably about 1 to 5 minutes. For the solvent at this time, choose to use A solvent that does not substantially dissolve the active energy beam-hardening compound in the hard coating layer in an unhardened or semi-hardened (partially hardened) state is preferred. It does not only depend on the type of solvent whether the hard coating composition is substantially dissolved or not. , Also depends on the coating method. For example, when the spin coating method is used as the coating method for the surface layer material, in many cases, since the diluting solvent contained in the coating solution is mostly volatile during spin coating, even if it is dissolved to some extent The solvent of the hard coating agent composition is not practically problematic. In addition, for example, when a dip coating method is used as a coating method for a surface layer material, the surface of the hard coating layer and the material for the surface layer are not cured because the hard coating layer is not hardened. The contact time of the coating liquid is long, and it is necessary to use a solvent which does not dissolve or hardly dissolve the aforementioned hard coating agent composition. The hard coating layer is formed in an unhardened or semi-hardened (partially hardened) state, and an unhardened surface layer is formed on the surface. Next, the layer is irradiated with an electron beam to the hard coating layer and hardened or unhardened The surface is then irradiated with ultraviolet rays to harden the two layers. The light-transmitting layer (8) is hardened when the light-transmitting layer (8) using a hardening material is in a semi-hardened state. At this time, the irradiation amount of the electron beam may be For example, 1 to 50 Mr ad, and preferably 3 to 3 OMrad. The acceleration voltage of the electron wire harness may be 20 to 100 kV, and preferably 30 to 70 kV. The irradiation amount and acceleration voltage of the electron wire harness to this extent The hardened surface layer, and at the same time hardened the hard coating layer, especially the hard coating layer near the hardened surface layer to a certain degree, are strongly adhered to the interface-28-200423111 These two layers, moreover, will not cause Damage caused by the electron beams irradiated to the recording layer. Although the amount of ultraviolet radiation irradiated by the electron beams depends on the thickness of the hard coating layer (9), the light transmitting layer (8) using a hardening material is In the hardened state, although it depends on the thickness of the light transmitting layer (8), it may be, for example, 500 to 5000 mJ / cm2, and preferably 100 to 4000 mJ / cm2. The light transmitting layer (8) is semi-hardened In the case of a state, in order to completely harden the light transmitting layer (8), a large amount of ultraviolet radiation is required. By the irradiation of these electron beams, followed by ultraviolet radiation, a completely hardened and strongly adhered hard coating layer is obtained ( 9) and the surface layer (10), and a fully hardened light transmitting layer (8) is obtained at the same time. The electron beam irradiation followed by the ultraviolet irradiation is considered to cause the active energy beams included in the surface layer material to harden efficiently. Reactions between reactive groups of reactive compounds, or reactive energy beam-curable compounds contained in surface layer materials, and active energy beam-curable compounds (including those with modifications) The reaction of the reactive group of the active energy beam reactive group compound on the surface of the inorganic filler, to obtain a completely hardened and strongly adhered hard coating layer (9) and surface layer (1 0). In the case of electron beam irradiation and ultraviolet irradiation, the oxygen concentration in the ambient gas is preferably 500 ppm or less, preferably 200 ppm or less, and preferably 1 Oppm or less, preferably by rinsing with an inert gas such as nitrogen. This is to suppress the hardening of the surface due to oxygen radicals generated in the atmosphere. Alternatively, instead of suppressing the oxygen concentration in the irradiation atmosphere gas, conventionally recognized -29-200423111 various oxygen blocking inhibitors may be added to the hard coating agent composition and / or the material for the surface layer. As the oxygen barrier inhibitors, for example, the oxygen barrier inhibitors described in Japanese Patent Application Laid-Open No. 2000-109828, Japanese Patent Application Laid-Open No. 2000-109828, and Japanese Patent Application Laid-Open No. 2000-144011 can be used. Of course, it is also possible to use the above-mentioned oxygen blocking inhibitor and the oxygen concentration inhibitor in the irradiation atmosphere. By using the manufacturing process according to the present invention, on the hard coating layer (9) with high hardness, a thin surface layer (1 0) having good antifouling and lubricating properties is provided to the extent that the hardness is reflected on the outermost surface. At the same time, good adhesion of the hard coating layer (9) and the surface layer (10) was obtained. Next, a manufacturing method of the present invention for an optical information medium (hereinafter, simply referred to as an optical disc) of another configuration example will be described with reference to FIG. 2. Fig. 2 is a schematic sectional view of another example of the optical disc manufactured in the present invention. The optical disc (3 1) shown in FIG. 2 has an organic pigment layer (25), a reflective layer on the pigment layer (25), and a reflective layer (23) on one side of the light-transmitting supporting substrate (20). Via the supporting substrate (21) bonded to the adhesive layer (28), a light transmissive hard coating layer (29) and a light transmissive surface layer (30) are provided on the other side of the support substrate (20). In this example, the pigment layer (25) and the reflective layer (23) constitute a recording layer. The optical disc (31) is used by passing a laser light for recording or reading through a surface layer (30), a hard coating layer (29), and a supporting substrate (20). These discs have a memory DVD-R. For recording / reading laser light, laser light with a wavelength of 650 nm or 660 nm is used. A blue laser beam (wavelength of about 405 nm) was used. In addition to the memory-type DVD-R shown in Figure 2, various read-only DVD-ROMs, -30-200423111, and rewritable DVD-RAMs are being commercialized as optical information media. The DVD for reading only includes DVD-Video, DVD-ROM, etc. In these optical recording media, when the light-transmitting substrate is formed, the pits called the information signals are formed on the pits. A metal reflective layer such as A1 is formed, and a protective layer is further formed. The protective layer is bonded to other supporting substrates through an adhesive layer to form the final optical information medium. In the case of a rewritable DVD, a recording layer can be formed in the same manner as described for the aforementioned phase change optical disc. In addition, in these constituted media, a method of recording / reading using a blue laser beam is also studied. As for the supporting substrate (20), a light-transmitting substrate is used. In the past, the light-transmissive support substrate (20) was an injection-molded polycarbonate resin, and various information was formed on the surface, such as pre-pits or pre-grooves. The materials used are not limited to these, but also use chain Resins such as olefin resins are preferred. Alternatively, it can be obtained by forming a pre-pit or a pre-groove on the glass plate by the 2P method. On the support substrate (20), an organic pigment dissolved in a solvent is applied by a spin coating method, and an organic pigment layer having a desired thickness is formed by drying. The aspect of the organic pigment layer is selected from various cyanocyanine pigments, diazo pigments, phthalocyanine pigments, and the like. The method for forming the pigment layer is not only a spin coating method but also a spray method, a screen printing method, and a vapor deposition method. The thickness of the formed film is appropriately selected depending on the pigment used. When the spin coating method is applied, the pigment component is dissolved in a solvent and used as an organic pigment solution. The solvent is selected to sufficiently dissolve the pigment and does not adversely affect the transparent substrate. The concentration is about 3%. 200423111 It is preferably about 0. 0 to 1 to 10% by weight. Examples of solvents include methanol, ethanol, isopropenyl alcohol, methyl cellulose, ethyl cellulose, tetrahexane, heptane, octane, decane, cyclohexane, and methylhexyl; Aliphatic or aliphatic cyclic solvents such as methylcyclohexane; aromatic hydrocarbons such as toluene, xylene, and benzene; halogen solvents such as chloroform, tetrachloroethane, and dibromoethane; diethyl ether, dibutyl Ethers, diisopropyl ethers, agents; ketone solvents such as 3-hydroxy-3-methylbutanone; ester solvents such as ethyl ester; water and the like, from which, those who can be used can be used. These may be used alone or may be mixed with two rice organic pigment layers. Although the film thickness is not particularly limited, it is preferably about 60 to 250 nm. The organic pigment layer (25) is provided with a reflective layer (in terms of materials, alone or in an alloy, which is high enough for reading light, such as Au, Ag, Cu, Al, Ni, Pd, etc.) For example, V, Nb, Ru, W, Mn, Re, Fe, Co, Rh, Ir In, Si, Ge, Te, Pb, Po, Sn, Bi, etc. can be mentioned as examples of the formation of a reflective layer. There are sputtering method, ion plating method, vacuum evaporation method, etc., but it is not necessary to provide a recognized inorganic or organic intermediate layer for improving the reflectance on the example plate or under the reflective layer. There are no particular restrictions, but with alcohols such as 10 to 300 nm alcohols, octafluoropentanol, and fluoropropanol: cyclohexane, ethyl cyclic hydrocarbon-based compound-based solvents; tetrachemical hydrocarbons Ethyl ether-soluble acid ethyl esters such as dioxane, and lactic acid methyl ester will not attack the above base plate. (Approximately 1 to 3 OOnm 2 3). The wavelength of the reflective layer is the reflectivity sufficient for Cr, Pt and other elements. Mg, Se, Hf,, Zn, Cd, Ga, semi-metallic, etc. Implantation method, chemical vaporization limitation. Also, in the base or recording characteristics layer The thickness of the reflective layer is preferably about 32-200423111 about 80 to 200 nm. The reflective layer (23) is usually bonded to the supporting substrate via an adhesive layer (28) that also functions as a protective layer ( 2〗). The support substrate (2) is the same as the aforementioned support substrate (20). The material of the bonding layer (28) is' if it can be bonded to the two substrates (21) and (20) and protect the reflective layer from external forces There are no particular restrictions. Examples of the adhesive include thermoplastic resins, thermosetting resins, and UV-curable resins. Thermoplastic resins and thermosetting resins can be dissolved in an appropriate solvent to coat the coating liquid. And is formed by drying. The UV-curable resin can be applied as it is or dissolved in an appropriate solvent to prepare a coating solution, and then cured by irradiating ultraviolet rays. For the UV-curable resin, it can be used For example, acrylic resins such as acrylic urethane, epoxy acrylate, polyester acrylate, etc. These materials can be used alone or in combination, not only single layer but also Multiple layers are used. The method of forming the next layer (2 8) is the same as that of the recording layer using a coating method such as a spin coating method or a casting method. In addition, the adhesive used for bonding is a hot-melt adhesive, UV-curable adhesives, heat-curable adhesives, and adhesive-type adhesives are applicable to individual methods. Examples include roll coating, screen printing, and spin coating. In addition, the UV curing adhesive is used, and the silk screen printing method or the spin coating method is used to judge collectively the productivity and optical disc characteristics. In addition, a hard coating layer (29) is formed on the other surface of the base substrate (20). ) And surface layer (30) of the composite hard coating. Hard coating agent composition containing active energy beam hardening component for hard-33-200423111 coating layer, and active energy beam hardening component containing lubricating and / or antifouling function for surface layer (30) The material for the surface layer is the same as that in the manufacturing of the optical disc described in FIG. 1 individually. The formation of the hard coating layer (29) and the surface layer (30) may be performed in the same manner as in the manufacturing of the optical disc shown in FIG. In the optical disc of FIG. 2, the hard coating layer (29) may be formed to a thickness of 1 // m to 10 // m, and preferably 1 // m to 5 // m. The surface layer (30) can be formed to a thickness of 1 nm to 100 nm. By using the process of the present invention, a thin coating layer (30) with antifouling and lubricating properties is provided on the hard coating layer (29) with high hardness reflecting the hardness to the outermost surface, and a hard coating is obtained at the same time. The good adhesion between the layer (29) and the surface layer (30). By using materials such as the above, film formation, and hardening methods, optical information media with a composite hard coating layer that is excellent in abrasion resistance, abrasion resistance, antifouling, and lubricity, and also excellent in durability are manufactured. [Examples] Although the present invention will be described more specifically with reference to the following examples, the present invention is not limited to those examples. [Example 1]: Light-transmitting layer made of active energy beam hardening material A sample of an optical recording disc having the layer structure shown in Fig. 1 was prepared as follows. 100 nm of Al ^ PtCu! (Atomic ratio) was formed on the surface of the grooved disc-shaped support substrate (2) (made of polycarbonate, 120 mm in diameter and 1.1 mm in thickness) by sputtering. Thick reflective layer (3). The depth of the aforementioned trenches is expressed in terms of wavelength; the optical path length at I = 405 nm is expressed as λ / 6. Groove recording method I 34- 200423111 The pits of the recording track in the formula are 0.32 μm. Next, on the surface of the reflective layer (3), a second dielectric layer (4) with a thickness of 20 nm was formed by using an A1203 rake and a sputtering method. A 12 nm thick recording material layer (5) was formed on the surface of the second dielectric layer (4) by using an alloy target composed of a phase change material and by a sputtering method. The composition (atomic ratio) of the recording material layer (5) was sb74Te18 (Gejn!). On the surface of the recording material layer (5), a ZnS (80 mol%)-Si02 (20 mol%) target was used and a first dielectric layer (6) having a thickness of 130 nm was formed by a sputtering method. Next, on the surface of the first dielectric layer (6), a UV-curable material described below was applied by a spin coating method, and then was partially cured by irradiating ultraviolet rays (irradiation amount: 500 m; T / Cm2). For example, a light-transmitting layer (8) is formed with a thickness of 98 // m after complete hardening. (Light transmission layer: composition of ultraviolet curable material) 50 parts by weight of acrylic urethane oligomer (manufactured by Mitsubishi Chemical Corporation, Great Britain UK6035) isocyanate EO modified tripropionate 10 parts by weight (manufactured by Toa Synthesis Co., Ltd., Aronix M31 5) 5 parts by weight of isocyanate EO modified diacrylate (manufactured by Toa Synthesis Co., Ltd., Aronix M21 5) Tetrahydrofuran propionate 2 5 parts by weight of a photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone) 3 parts by weight 'on the light transmitting layer (8), a UV / electron composition of the following composition is applied by a spin coating method-35-200423111 After the wire harness hardening hard coating agent is heated at 80 ° C in the atmosphere for 3 minutes to remove the diluent solvent inside the coating film, an unhardened hard coating layer is formed (9). (Composition of hard coating agent) Reactive group modified colloidal silica (dispersant: propylene glycol monomethyl ether acetoacetate, non-volatile content: 40% by weight) 1 0 0 parts by weight of dipentaerythritol hexaacrylate 4 8 parts by weight of tetrahydrofuran acrylate 1 2 parts by weight of propylene glycol monomethyl ether acetamyl ester 40 0 parts by weight (non-reactive diluent solvent) Ilkachya 1 84 (polymerization initiator) 5 parts by weight, followed by Spin coating with 0.5% (mass percentage) of perfluoropolyether diacrylate (manufactured by Aodimont, FombrinZDOL, acrylic modified, approximately 2000 molecular weight) fluorospironate FC-77 (manufactured by Sumitomo 3M) ) The solution is dried on the unhardened hard coating layer (9) at 80 ° C for 3 minutes to form an unhardened surface layer (1 0). Secondly, the hard coating layer (9) and the surface layer (10) are simultaneously hardened by irradiating the electron beam under a nitrogen flow. An electron beam irradiating device Min-EB (manufactured by Toyo Ink Manufacturing Co., Ltd.) was used, so that the acceleration voltage of the electron beam was 50 kV, and the irradiation limit was 100 kGy (lOMrad). The oxygen concentration in the irradiation atmosphere was 80 ppm. Furthermore, under a nitrogen stream, ultraviolet rays were irradiated (irradiation: -36- 200423111, irradiation volume: 3 000 m J / cm2), and the light transmitting layer (8) and the hard coating layer (9) were completely hardened. The oxygen concentration of the irradiation atmosphere gas was 80 PPm. The film thickness of the hard coating layer (9) is about 25 nm for the film thickness of the surface layer (10). In addition, the film thickness of the surface layer was measured by a fluorescent X-ray analysis (XRF) using a perfluoropolyether (Dimkin Corporation, Dimnam) as a reference material. In this way, a disc sample is obtained. [Example 2] After the formation of the unhardened hard coating layer (9) and the coating of the surface layer (10), in addition to ultraviolet irradiation (irradiation amount: 80 mJ / cm2) and a partially hardened hard coating layer (9), In the same manner as in Example 1, a disc sample was obtained. The thickness of the hard coating layer (9) is about 25 nm of the thickness of the surface layer (10). [Example 3] In addition to changing the amount of ultraviolet radiation in the formation of the light transmitting layer (8) to 3 00 J / cm2, The light transmitting layer (8) is completely hardened before the hard coating agent is applied, and after the formation of the unhardened hard coating layer (9), the surface layer (10) is subjected to ultraviolet irradiation (irradiation amount: 80 mJ / cm2), Except for the partially cured hard coating layer (9), in the same manner as in Example 1, an optical disk sample was obtained. The thickness of the hard coating layer (9) is 2.1 // m, and the thickness of the surface layer (10) is approximately 25 nm. [Example 4] A light-transmitting layer was formed from a light-transmitting sheet until the first dielectric layer (6) was formed, and it was performed in the same manner as in Example 1. On the surface of the first dielectric layer (6), a radically polymerizable ultraviolet curable resin solution (manufactured by Mitsubishi Electric Corporation, 4x 108E 'solvent: butyl acetate) is applied by a spin coating method, and the thickness after curing is 2.0 Am Terrain-37-200423111 into a resin material layer. Next, a 100 // m-thick polycarbonate sheet was placed on the aforementioned resin material layer in a vacuum (below 0.1 atmosphere). As the polycarbonate sheet, pure S manufactured by Teijin Co., Ltd. manufactured by a casting method was used. Next, the atmosphere is returned to atmospheric pressure, and the resin material layer is cured by irradiating ultraviolet rays, and then the polycarbonate sheet is made a light transmitting layer (8). Subsequent operations are performed in the same manner as in Example 1. That is, an unhardened hard coating layer (9) is formed on the light transmitting layer (8). Next, an unhardened surface layer (1 0) is formed. Then, the hard coating layer (9) is simultaneously hardened by irradiating an electron beam under a nitrogen stream. ) And surface layer (10). The electron beam acceleration voltage was 50 kV, and the irradiation dose was 100 kGy (1 OMrad). The oxygen concentration in the irradiation atmosphere was 8 Oppm. Furthermore, the hard coating layer (9) was completely hardened by irradiating ultraviolet rays (irradiation amount: 3,000 mJ / cm2) under a nitrogen stream. The oxygen concentration in the irradiation atmosphere was 80 ppm. The thickness of the hard coating layer (9) is about 25 nm of the thickness of the surface layer (10). [Comparative Example 1] An optical disc sample was obtained in the same manner as in Example 1 except that the final ultraviolet irradiation (irradiation amount: 3 000 mJ / cm2) was not performed. [Comparative Example 2] The same procedure as in Example i was performed except that the final electron beam irradiation (irradiation amount: 1000 k G y (1 OMrad)) was not performed to obtain a disc sample. [Comparative Example 3] Except after the formation of the unhardened hard coating layer (9) and before the application of the unhardened surface layer (10), ultraviolet irradiation (irradiation amount: 3000mj / cm2), 38-200423111 was completely hardened. Except for the coating layer (9), it was carried out in the same manner as in Example 1 to obtain a sample of the optical disk. (Evaluation of the surface of the optical disk sample) For each optical disk sample produced in Examples 1 to 4, that is, Comparative Examples 1 to 3, the following performance tests were performed. (1) Abrasion resistance Use steel wool # 0000 to determine the degree of scratches generated by sliding the hard coating surface of each optical disc sample back and forth 20 times with a load of 4.9 N / cm2. The judgment criteria are as follows. φ 〇: No scratch generation △: Slight scratch generation X: Scratch generation (2) Antifouling (antifouling durability) The contact angle of pure water on the hard-coated surface of each disc sample was measured. The measurement was performed after sliding the surface of the sample with a weight containing a solvent. The sliding conditions are as follows. That is, a non-woven fabric (manufactured by Asahi Kasei Industries Co., Ltd., CT-Flint-CT-8) was impregnated with acetone and slid back and forth 50 ^ times under a load of 4.9 N / cm2. The contact angle was measured using a contact angle meter CA-D manufactured by Kyowa Interface Science Co., Ltd. at an environment of 20 ° C air temperature and 60% relative humidity. Table 1 Examples Examples Examples Examples Comparative Examples Comparative Examples 1 2 3 4 1 2 3 Abrasion resistance 〇〇〇〇 × 〇〇 Contact angle (degrees) 106 105 106 105 105 59 61 -39- 200423111 The above measurement results are shown in Table 1. As can be seen from Table 1, the optical disk samples of Examples 1 to 4 are excellent in abrasion resistance and have excellent antifouling durability. In Comparative Example 1, since the final ultraviolet irradiation was not performed, the abrasion resistance was significantly deteriorated. In Comparative Example 2, since the electron beam irradiation was not performed, the antifouling property was significantly deteriorated. In Comparative Example 3, since the surface layer was applied after the hardened coating layer was completely cured, the antifouling property was significantly deteriorated. In the above examples, the application of a composite hard coating layer to a phase change optical disc is shown. However, the present invention is not only an optical disc with a phase change recording layer, but also a read-only optical disc or a memory optical disc. Therefore, the foregoing examples are merely exemplified by so-called viewpoints and are not to be interpreted without limitation. In addition, all the changes belonging to the equal scope of the application scope are within the scope of the present invention. (V) Brief Description of Drawings Figure 1 is a schematic sectional view of an example of an optical disc manufactured in the present invention. Fig. 2 is a schematic sectional view of an example of an optical disc manufactured in the present invention. Description of component symbols 1 Optical information media 2 Supporting substrate 3 Reflective layer 4 Second dielectric layer 5 Phase change recording material layer _ 4 0-First dielectric layer recording layer Light transmission layer Hard coating layer Surface layer Light transmittance support Substrate support Substrate reflective layer, organic pigment layer, light-transmissive hard coating layer, light-transmissive surface layer disc

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Claims (1)

200423111 Scope of patent application: 1 · A method for manufacturing optical information media, which is a method for manufacturing an optical information medium with at least a recording layer, a light transmitting layer, a hard coating layer and a surface layer in order on a supporting substrate, including: : Applying a hard coating composition containing an active energy beam hardening component to the light-transmitting layer to form an unhardened hard coating layer. The unhardened hard coating layer contains a lubricant and / or antifouling function. 'The surface layer of the active energy beam hardening component is formed into a film to form an uncured surface layer, and the formed uncured hard coating layer and the uncured surface layer are irradiated with an electron beam', and then the two layers are cured by irradiating ultraviolet rays. To form a hardened hard coating layer and a hardened surface layer. 2. The manufacturing method of the optical information medium according to item 1 of the scope of patent application, wherein the active energy beam hardening component contained in the hard coating composition is a ultraviolet hardening component. 3. The manufacturing method of the optical information medium according to item 1 of the scope of patent application, wherein the active energy beam-hardening component contained in the surface layer material is an electron beam-hardening component. 4 · The manufacturing method of the optical information medium according to item 1 of the scope of patent application, wherein the active energy beam-hardening component contained in the surface material is an electron beam-hardening component, and has a polysiloxane-based substituent and / or a fluorine-based component. Substituent group 05 · The manufacturing method of the optical information medium as described in the first item of the patent application, wherein after forming an unhardened hard coating layer, it can be dried as required, and irradiated with-4 2-200423111 UV to become hardened in a semi-hardened state. The coating layer is then formed on the semi-hardened hard coating layer to form a film of the surface layer material to form an unhardened surface layer. 6. The method for manufacturing an optical information medium according to item 5 of the scope of patent application, wherein the uncured hard coating layer is irradiated with ultraviolet rays and then annealed (thermally tempered). 7 · The manufacturing method of the optical information medium according to item 1 of the scope of patent application, wherein the material for the surface layer is formed by coating and the material for the surface layer is coated, followed by heat treatment. 8 · The manufacturing method of the optical information medium according to item 1 of the patent application scope, wherein the recording layer is coated with an active energy beam hardening material, and is irradiated with ultraviolet rays to form a semi-hardened or hardened light transmission layer, and then semi-hardened Or, a hard coating agent composition is coated on the light-transmitting layer in a hardened state to form an unhardened hard coating layer. 9. The manufacturing method of the optical information medium according to item 8 of the patent application scope, wherein the light transmission layer is irradiated with ultraviolet rays and then subjected to an annealing treatment (heat relaxation treatment). 1 〇 · The manufacturing method of the optical information medium according to item 1 of the patent application scope, wherein a resin sheet is used to form a light transmitting layer on the recording layer, and then a hard coating agent composition is coated on the light transmitting layer to form an unhardened material. Hard coating layer 01. The manufacturing method of the optical information medium according to item 1 of the patent application, wherein the surface layer has a thickness of 1 nm to 100 nm. 1 2. The manufacturing method of the optical information medium according to item 1 of the scope of patent application, wherein a 43-200423111 light transmission layer has a thickness of 10 // m to 300 // m. 1 3 · — A method for manufacturing an optical information medium, which is provided with at least a recording layer on one side of a light-transmitting supporting substrate, and a hard coating layer and a surface layer in order on the other side of the light-transmitting supporting substrate. A method for manufacturing an optical information medium, comprising: coating a hard coating agent composition containing an active energy beam hardening component on the other side of a light-transmitting supporting substrate to form an unhardened hard coating layer; On the coating layer, a material for a surface layer containing an active energy beam hardening component having a lubricating and / or antifouling function is formed into a film to form an unhardened surface layer, and an electron beam is irradiated onto the formed unhardened hard coating layer and The unhardened surface layer is then irradiated with ultraviolet rays to harden the two layers to form a hardened hard coating layer and a hardened surface layer. One 44 one