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WO2010113976A1 - Uv-curable resin composition for use in multi-layer optical disc - Google Patents

Uv-curable resin composition for use in multi-layer optical disc Download PDF

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Publication number
WO2010113976A1
WO2010113976A1 PCT/JP2010/055760 JP2010055760W WO2010113976A1 WO 2010113976 A1 WO2010113976 A1 WO 2010113976A1 JP 2010055760 W JP2010055760 W JP 2010055760W WO 2010113976 A1 WO2010113976 A1 WO 2010113976A1
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WO
WIPO (PCT)
Prior art keywords
acrylate
meth
resin composition
curable resin
ultraviolet curable
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2010/055760
Other languages
French (fr)
Japanese (ja)
Inventor
裕貴 堤
大祐 小林
雄一朗 松尾
聡 小木
正弘 内藤
潤 木戸場
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Kayaku Co Ltd
Original Assignee
Nippon Kayaku Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Kayaku Co Ltd filed Critical Nippon Kayaku Co Ltd
Priority to SG2011071008A priority Critical patent/SG174979A1/en
Priority to CN2010800148704A priority patent/CN102379007A/en
Publication of WO2010113976A1 publication Critical patent/WO2010113976A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/26—Apparatus or processes specially adapted for the manufacture of record carriers
    • G11B7/263—Preparing and using a stamper, e.g. pressing or injection molding substrates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
    • C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
    • C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
    • C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C08L75/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/256—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers improving adhesion between layers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/2403—Layers; Shape, structure or physical properties thereof
    • G11B7/24035—Recording layers
    • G11B7/24038—Multiple laminated recording layers
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
    • G11B7/246—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes
    • G11B7/2467—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes azo-dyes

Definitions

  • the present invention relates to an ultraviolet curable resin composition for optical discs and a cured product thereof, and efficiently produces next-generation high-density optical discs that have high adhesion to a reflective film layer or a dielectric layer and excellent peelability from a stamper.
  • the present invention relates to a resin composition.
  • a DVD disc having two recording layers has a structure in which two recording layers are laminated via a transparent resin intermediate layer.
  • a 0.6 mm first transparent resin substrate, a first recording layer, a first translucent reflective film layer, a transparent resin intermediate layer, a second recording layer, a second reflective film layer, an adhesive It is the structure which laminated
  • the transparent resin intermediate layer is coated with an ultraviolet curable resin composition that forms the transparent resin intermediate layer on the first semi-transparent reflective film layer, and irregularities such as guide grooves for recording / reproducing beams are formed. It is formed by pressing a transparent resin stamper having a pattern to cure the ultraviolet curable resin composition, then peeling the stamper, and transferring irregularities onto the surface of the ultraviolet curable resin composition.
  • a pit-like recording pattern is transferred to one side of a polycarbonate substrate having a diameter of 120 mm and a thickness of 1.1 mm, for example, and a first recording layer is formed on the surface of the substrate.
  • the reflective film layer for example, a silver alloy reflective film layer is formed.
  • a transparent resin intermediate layer having a pit-like recording pattern transferred thereon is formed on the first reflective film layer, and a second reflective film layer that becomes the second recording layer, for example, a silver alloy reflective film, is formed on the intermediate film.
  • a film layer is deposited. And it becomes the structure which laminates
  • a silver alloy reflective film layer is formed into a film in vacuum, for example by sputtering method.
  • a pit-like recording pattern is transferred to one side of a polycarbonate substrate having a diameter of 120 mm and a thickness of 1.1 mm, for example, and a first reflective film layer, a first dielectric layer, A first recording layer and a second dielectric layer are laminated, and further, a transparent resin intermediate layer, a second reflective film layer, a third dielectric layer, a second recording layer, a fourth dielectric layer, a transparent
  • the resin layers are stacked in this order.
  • the transparent resin intermediate layer is coated with an ultraviolet curable resin composition that forms the transparent resin intermediate layer on the reflective film layer or the dielectric layer, and the projections and depressions such as guide grooves for recording / reproducing beams are formed. It is formed by pressing a transparent resin stamper having a pattern to cure the ultraviolet curable resin composition, then peeling the stamper, and transferring irregularities onto the surface of the ultraviolet curable resin composition.
  • the transparent resin intermediate layer is usually composed of a peeling layer adhered to the second reflective film layer and an adhesive layer adhered to the first reflective film layer in the read-only disk, and the first in the recording type disk. 2 is composed of a release layer bonded to the reflective film layer 2 and an adhesive layer bonded to the second dielectric layer.
  • the transfer method is called a 2P (Photo Polymerization) method
  • the ultraviolet curable resin composition used is called a 2P resin.
  • the transparent resin stamper include acrylic resins, methacrylic resins, polycarbonate resins, polyolefin resins (particularly amorphous polyolefins), polyester resins, polystyrene resins, and epoxy resins.
  • amorphous polyolefin is preferable from the viewpoint of peelability after curing 2P resin, low hygroscopicity, shape stability, and the like
  • polycarbonate resin is preferable from the viewpoint of material cost.
  • polycarbonate resin is used for a 0.6 mm resin substrate for DVD and a 1.1 mm resin substrate for Blu-ray Disc.
  • the release of the polycarbonate resin stamper from the cured 2P resin layer is facilitated by using an ultraviolet curable resin different from the 2P resin on the resin substrate side.
  • the peelability from the transparent resin stamper is poor, a part of the transparent resin intermediate layer peels off together with the transparent resin stamper, resulting in a defect. If transferability is poor, an error occurs during recording / reproduction. If the warpage is large after UV curing, the recording layer and the reflective film layer cannot be uniformly formed on the formed concavo-convex pattern, the second substrate cannot be bonded in the case of DVD, or 0 in the case of Blu-ray Disc. A 1 mm light transmission layer cannot be formed uniformly. In addition, when the uneven pattern is deformed under high temperature and high humidity, the recording characteristics (for example, jitter characteristics) of the first and second recording layers are not equivalent.
  • Patent Documents 1 to 4 a metal stamper is used to form an uneven pattern on a glass substrate, and there is no description of forming an uneven pattern using a transparent resin stamper.
  • Patent Documents 5 to 8 describe the 2P resin, but do not describe the resin of the present invention.
  • Japanese Unexamined Patent Publication No. 5-59139 Japanese Patent Laid-Open No. 5-132534 Japanese Unexamined Patent Publication No. 5-140254 Japanese Unexamined Patent Publication No. 5-132506 Japanese Unexamined Patent Publication No. 2003-331463 Japanese Unexamined Patent Publication No. 2004-288242 Japanese Unexamined Patent Publication No. 2004-288264 Japanese Unexamined Patent Publication No. 2005-332564
  • the ultraviolet curable resin used as the 2P agent needs to be easily peeled off from the stamper while holding the pattern from the stamper on which the concave / convex pattern is formed. At that time, if it is difficult to peel off from the stamper, a problem occurs such that the resin adheres to the stamper and does not adhere to the reflective film layer or the dielectric layer, leading to a decrease in production efficiency. Further, even if the resin has high releasability from the stamper, if it is peeled off when placed under high temperature and high humidity, there arises a problem that a reading error occurs.
  • the present invention uses a polyfunctional acrylate-modified urethane acrylate and a (meth) acrylate monomer, so that it is particularly excellent in peeling from a stamper and is also capable of reflecting film layers or dielectrics even under high temperature and high humidity.
  • the object is to provide a resin composition in close contact with the body layer.
  • the present invention can selectively adhere to the reflective film layer or the dielectric layer when the stamper is peeled off, it is possible to omit the adhesive layer of the 2P UV curable resin. is there.
  • a urethane (meth) acrylate ultraviolet curable resin composition obtained by reacting an organic isocyanate and a polyfunctional acrylate having a hydroxyl group
  • the present inventors have improved the peelability from a stamper, under high temperature and high humidity.
  • the present inventors have found a resin composition that adheres firmly to the reflective film layer or the dielectric layer even when placed. This has led to the development of a UV-effect resin composition that has high peelability from the stamper and excellent adhesion to the reflective film layer or the recording film.
  • the present invention relates to the following (1) to (7).
  • (1) A hexafunctional or higher functional urethane (meth) acrylate obtained by reacting an organic isocyanate having two or more isocyanate groups in one molecule with a trifunctional or higher functional (meth) acrylate having a hydroxyl group,
  • C a photopolymerization initiator.
  • urethane (meth) acrylate (A) obtained by reacting an organic isocyanate having two or more isocyanate groups in one molecule with a trifunctional or higher functional (meth) acrylate having a hydroxyl group, the organic isocyanate is isophorone.
  • the ultraviolet curable resin composition for multilayer optical disks according to item (1) which is one or more selected from the group consisting of trifunctional isocyanates represented by: (3) In the urethane (meth) acrylate (A) obtained by reacting an organic isocyanate having two or more isocyanate groups in one molecule with a trifunctional or higher functional (meth) acrylate having a hydroxyl group, a trifunctional group having a hydroxyl group.
  • the above (meth) acrylates are pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri (meth) acrylate of pentaerythritol ⁇ -caprolactone adduct, and ⁇ -caprolactone adduct of dipentaerythritol.
  • Trifunctional or lower (meth) acrylate monomer (B) is modified with isobornyl acrylate, neopentyl glycol diacrylate, propylene oxide modified neopentyl glycol diacrylate, tricyclodecane dimethanol diacrylate, and hydropivalaldehyde
  • the ultraviolet curable resin composition for multilayer optical disks according to any one of (1) to (3), wherein the ultraviolet curable resin composition is one or more selected from the group consisting of trimethylolpropane diacrylate.
  • Items (1) to (4) containing 5 to 80% by weight of component (A), 10 to 80% by weight of component (B), and 1 to 15% by weight of component (C) with respect to the entire resin composition.
  • the ultraviolet curable resin composition for multilayer optical disks according to any one of items 1).
  • (6) A cured product obtained by irradiating the ultraviolet curable resin composition for multilayer optical disks according to any one of (1) to (5) with active energy rays.
  • (7) A multilayer optical disk having the cured product as described in (6) above.
  • the ultraviolet curable resin composition of the present invention and its cured product are excellent as a 2P agent that is excellent in releasability from a stamper and is in close contact with a reflective film layer or a dielectric layer even when placed under high temperature and high humidity. . Further, it is possible to provide an ultraviolet curable resin that can omit the adhesive layer and form the intermediate layer with one liquid.
  • the present invention relates to (A) a hexafunctional or higher functional urethane obtained by reacting (A) an organic isocyanate having two or more isocyanate groups in one molecule with a trifunctional or higher functional (meth) acrylate having a hydroxyl group.
  • the organic isocyanate used in the present invention is a compound having two or more isocyanate groups in the molecule, and any known one can be used without particular limitation.
  • diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, diphenylmethane-4,4′-diisocyanate, or dicyclopentanyl diisocyanate.
  • R is the same as R in the above formula (1).
  • the trifunctional or higher functional (meth) acrylate having a hydroxyl group specifically refers to a tri to octafunctional (meth) acrylate having a hydroxyl group, and any known one can be used without particular limitation. Examples include pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri (meth) acrylate of ⁇ -caprolactone adduct of pentaerythritol, tri, tetra or penta of ⁇ -caprolactone adduct of dipentaerythritol (Meth) acrylate etc. are mentioned. In the present invention, pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are particularly preferable.
  • the reaction is carried out as follows. That is, the organic polyisocyanate is mixed so that the isocyanate group is preferably 1.1 to 2.0 equivalents per one equivalent of the hydroxyl group of the tri- or higher functional (meth) acrylate having a hydroxyl group, and the reaction temperature is preferably 70 to By making it react at 90 degreeC, the target urethane (meth) acrylate (A) can be obtained.
  • the above (A) urethane (meth) acrylate can be used alone or in combination of two or more.
  • the amount of (A) urethane (meth) acrylate used in the composition is 5 to 80% by weight, preferably 15 to 75% by weight, particularly preferably about 20 to 70% by weight.
  • any known monomer can be used without particular limitation.
  • Examples include tricyclodecane (meth) acrylate, benzyl acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, Morpholine (meth) acrylate, neopentyl glycol di (meth) acrylate, propylene oxide modified neopentyl glycol di (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, hydroxypivalaldehyde modified trimethylolpropane di (meta) ) Acrylate, neopentyl glycol di (meth) acrylate hydroxypivalate, and the
  • the (meth) acrylate monomer is isobornyl acrylate, neopentyl glycol diacrylate, propylene oxide-modified neopentyl glycol diacrylate, tricyclodecane dimethanol diacrylate, hydropivalaldehyde-modified tri
  • the amount used in the composition is 10 to 80% by weight, preferably 15 to 75% by weight, more preferably 20 to 70% by weight.
  • Examples of the (C) photopolymerization initiator contained in the ultraviolet curable resin composition of the present invention include 1-hydroxycyclohexyl phenyl ketone (Irgacure 184; manufactured by Ciba Specialty Chemicals), 1- [4- (2- Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (Irgacure 2959; manufactured by Ciba Specialty Chemicals), 2-hydroxy-1- ⁇ 4- [4- (2- Hydroxy-2-methyl-propionyl) -benzyl] -phenyl ⁇ -2-methyl-propan-1-one (Irgacure 127; manufactured by Ciba Specialty Chemicals), 2,2-dimethoxy-2-phenylacetophenone (Irgacure 651) Manufactured by Ciba Specialty Chemicals), oligo [2-hydroxy-2-methyl] 1- [4- (1-methylvinyl) phenyl] propanone] (Esa
  • photopolymerization initiators may be used alone or in combination at any ratio, and may be used in combination with photopolymerization initiation assistants such as amines.
  • the content of the (C) photopolymerization initiator in the ultraviolet curable resin composition of the present invention is 1 to 15% by weight, preferably about 1 to 10% by weight.
  • photopolymerization initiation assistants such as amines that can be used in the present invention include diethanolamine, 2-dimethylaminoethylbenzoate, dimethylaminoacetophenone, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester. Etc.
  • the content in the ultraviolet curable fat composition of the present invention is preferably 0.05 to 5% by weight, particularly preferably about 0.1 to 3% by weight.
  • phosphoric acid (meth) acrylate can be added if necessary.
  • Phosphoric acid (meth) acrylate improves the adhesion between aluminum, silver or a silver alloy and the cured adhesive, but may corrode the metal film, and its amount used is limited.
  • a silane coupling agent, a leveling agent, an antifoaming agent, a polymerization inhibitor, a light stabilizer (such as a hindered amine), an antioxidant, an antistatic agent You may use together additives, such as a surface lubricant and a filler.
  • additives examples include, for example, KBM-502, KBM-503, KBM-5103, KBM-802, KBM-803 manufactured by Shin-Etsu Chemical Co., Ltd. BYK-333, BYK-307 manufactured by BYK Chemie. BYK-3500, BYK-3530, BYK-3570; Z-6062, SH-6062, SH-29PA manufactured by Toray Dow Corning Co., Ltd .; LA-82 manufactured by Adeka Co., Ltd., and the like.
  • the ultraviolet curable resin composition of the present invention can be obtained by mixing and dissolving the above components at room temperature to 80 ° C. and then filtering if necessary.
  • the viscosity of the ultraviolet curable resin composition of the present invention is 10 to 800 mPa ⁇ s, preferably 40 to 500 mPa ⁇ s as measured with a B-type viscometer at 25 ° C.
  • the transparent resin intermediate layer is formed on (1) at least one of the first transparent resin substrate, the first recording layer, the substrate on which the first translucent reflective film layer is laminated, and the transparent resin stamper.
  • the resin composition is applied by a spin coating method, a screen printing method, a roll coating method, or the like, and then bonded together and irradiated with ultraviolet rays from the transparent resin stamper side.
  • the transparent resin stamper is coated with the resin composition of the present invention by the above method and then cured with ultraviolet rays, and the first transparent resin substrate, the first recording layer, and the first translucent reflective film layer are laminated. It is also possible to form the substrate by adhering it with an arbitrary ultraviolet curable resin.
  • the soot formation method is preferable because production efficiency can be omitted and production costs can be reduced.
  • a transparent resin intermediate layer is formed on a Blu-ray disc in the same manner as DVD.
  • polycarbonate resin is used for the 0.6 mm first transparent resin substrate for DVD and HD-DVD and the 1.1 mm resin substrate for Blu-ray Disc.
  • the method (1) is preferred from the viewpoint of peelability.
  • the transparent resin stamper examples include acrylic resins, methacrylic resins, polycarbonate resins, polyolefin resins (particularly amorphous polyolefins), polyester resins, polystyrene resins, and epoxy resins.
  • amorphous polyolefin is preferable from the viewpoint of peelability after curing 2P resin, low hygroscopicity, shape stability, and the like, and polycarbonate resin is preferable from the viewpoint of material cost.
  • Either transparent resin stamper can be used for the 2P curable resin composition of the present invention.
  • the ultraviolet curable resin composition of the present invention gives a cured product by irradiation with active energy rays.
  • Examples of the active energy ray include ultraviolet rays to near ultraviolet rays.
  • ultraviolet rays to near ultraviolet rays For example, low pressure, high pressure, ultra high pressure mercury lamp, metal halide lamp, (pulse) xenon lamp, electrodeless lamp, ultraviolet light emitting diode, and the like can be mentioned.
  • the cured product is also included in the present invention.
  • an organic dye or a phase change material can be used for the recording layer formed on the transparent resin intermediate layer of the cured product.
  • organic dyes include metal-containing azo, polymethine, and phthalocyanine
  • phase change materials include Sb and Te, In, Ag, Au, Bi, Se, Al, P, Ge, H, Si, C, V , W, Ta, Zn, Ti, Ce, Tb, Sn, and Pb are added.
  • the resin composition of the present invention can be used for either an optical disc or a Blu-ray disc having a structure in which a polycarbonate substrate is bonded.
  • Examples of the coating method include a spin coating method, a 2P method, a roll coating method, and a screen printing method.
  • the transmittance at 405 nm is preferably 80% or more in a cured product having a thickness of 90-100 ⁇ m. .
  • Synthesis Example 1 Synthesis of Urethane Acrylate (A-1) In a round bottom flask equipped with a stirrer, a cooling tube and a thermometer, 0.63 parts by weight of isophorone diisocyanate, 93.9 parts by weight of pentaerythritol triacrylate, and a polymerization inhibitor 0.03 part by weight of a certain methoquinone and 0.05 part by weight of dibutyltin dilaurate were charged, mixed at room temperature for 30 minutes, and reacted at 80 ° C. for 5 hours. The reaction was terminated when the isocyanate concentration became 0.1% or less to obtain the intended urethane acrylate.
  • Synthesis Example 3 Synthesis of urethane acrylate (A-3) In a round bottom flask equipped with a stirrer, a condenser tube and a thermometer, 14.8 parts by weight of hexamethylene diisocyanate and 85.1 parts by weight of dipentaerythritol pentaacrylate, polymerization prohibited 0.03 part by weight of methoquinone as an agent and 0.05 part by weight of dibutyltin dilaurate were charged, mixed at room temperature for 30 minutes, and reacted at 80 ° C. for 5 hours. The reaction was terminated when the isocyanate concentration became 0.1% or less to obtain the intended urethane acrylate.
  • Table 1 shows the results of evaluating the constituent materials, the amounts used, and the items of the resin compositions of Examples 1 to 3 and Comparative Examples 1 to 3. In addition, "part" in description shows a weight part.
  • each component shown with the abbreviation in Table 1 is as follows.
  • A-1 Urethane acrylate obtained in Synthesis Example 1
  • A-2 Urethane acrylate obtained in Synthesis Example 2
  • A-3 Urethane acrylate obtained in Synthesis Example 3
  • IBA Isobornyl acrylate, Daiichi Kogyo Kagaku RP-1040: Pentaerythritol ethylene oxide modified tetraacrylate, Nippon Kayaku THE-330: Ethylene oxide modified trimethylolpropane triacrylate, Nippon Kayaku DPHA: Dipentaerythritol hexaacrylate, Nippon Kayaku Irgacure 184: 1-hydroxycyclohexyl phenyl ketone, manufactured by Ciba Specialty Chemicals
  • a sample disk for evaluation was produced by the following methods 1 to 3 using the obtained ultraviolet curable resin composition.
  • Air bubbles are formed on the inner periphery of a polycarbonate substrate (first substrate) having a diameter of 120 mm / 0.6 mm on which an azo dye layer as a recording layer, a reflective film layer, and a ZnS / SiO 2 layer as a dielectric layer are formed.
  • a transparent resin prepared so as not to enter was placed, a stamper was placed on the resin, and spin-coating was performed at 2000 rpm for 4 seconds to bond them together. 2.
  • a high pressure mercury lamp (80 W / cm) was irradiated from the transparent resin stamper side at 400 mJ / cm 2 to cure the second ultraviolet curable resin composition. 3.
  • a disk peeling device (Origin Electric Co., Ltd.), the transparent resin stamper was peeled off to produce a sample disk for evaluation.
  • the ultraviolet curable resin composition of the present invention and Examples 1 to 3, which are cured products thereof, are excellent in adhesion even under conditions of high temperature and humidity as compared with Comparative Example 1. Further, it was confirmed that the resin composition was particularly excellent in peelability as compared with Comparative Examples 2 and 3 using a polyfunctional acrylate monomer.
  • the ultraviolet curable resin composition of the present invention and its cured product are excellent as a peelable and useful as a 2P agent that is in close contact with a reflective film layer or a dielectric layer even when placed under high temperature and high humidity. Further, it is possible to provide an ultraviolet curable resin capable of omitting the adhesive layer and forming the intermediate layer with one liquid.

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Abstract

Disclosed is a base for use in an optical disc which has excellent mass productivity for substrate formation by a 2P method, particularly favorable release properties from a stamper, and high adhesion strength to a reflective film layer or a dielectric layer even under high-temperature and high-humidity conditions. Specifically disclosed is a UV-curable resin composition for use in a multi-layer optical disc, with which such a base for use in an optical disc can be formed. The UV-curable resin composition for use in a multi-layer optical disc contains (A) a hexa- or higher-functional urethane (meth)acrylate obtained by reacting an organic isocyanate having two or more isocyanate groups per molecule with a tri- or higher-functional (meth)acrylate having a hydroxy group, (B) a tri- or lower-functional (meth)acrylate monomer, and (C) a photopolymerization initiator.

Description

多層光ディスク用紫外線硬化型樹脂組成物UV curable resin composition for multilayer optical disk

　本発明は光ディスク用紫外線硬化型樹脂組成物およびその硬化物に関し、反射膜層又は誘電体層との密着力が高く、スタンパからの剥離性に優れた次世代高密度光ディスクを効率的に生産するための樹脂組成物に関する。 The present invention relates to an ultraviolet curable resin composition for optical discs and a cured product thereof, and efficiently produces next-generation high-density optical discs that have high adhesion to a reflective film layer or a dielectric layer and excellent peelability from a stamper. The present invention relates to a resin composition.

　近年、光ディスクに対する大容量化の要求が著しい。光ディスクの記録容量を高める技術としては、記録・再生ビ－ムの短波長化、記録・再生ビ－ム照射光学系における対物レンズの高ＮＡ（開口数）化、記録層の多層化などが挙げられる。これらのうち記録層の多層化による大容量化は、短波長化や高ＮＡ化に比べ、低コストでの大容量化が可能である。
　例えば、２個の記録層を有するＤＶＤディスクは、２つの記録層を、透明樹脂中間層を介して積層した構造をとっている。具体的には、０．６ｍｍの第１の透明樹脂基板、第１の記録層、第１の半透明反射膜層、透明樹脂中間層、第２の記録層、第２の反射膜層、接着層、０．６ｍｍの第２の透明樹脂基板の順に積層した構造である。この場合は、透明樹脂中間層は第１の半透明反射膜層上に透明樹脂中間層を形成する紫外線硬化型樹脂組成物を塗布し、記録・再生ビ－ムのガイド用案内溝などの凹凸パタ－ンのある透明樹脂スタンパに押しつけ、紫外線硬化樹脂組成物を硬化させた後スタンパを剥離し、紫外線硬化型樹脂組成物の表面に凹凸を転写させて形成される。 In recent years, there has been a significant demand for larger capacity for optical disks. Technologies for increasing the recording capacity of optical disks include shortening the recording / reproducing beam, increasing the NA (numerical aperture) of the objective lens in the recording / reproducing beam irradiation optical system, and increasing the number of recording layers. It is done. Among these, the increase in capacity by increasing the number of recording layers can increase the capacity at a lower cost than the reduction in wavelength and the increase in NA.
For example, a DVD disc having two recording layers has a structure in which two recording layers are laminated via a transparent resin intermediate layer. Specifically, a 0.6 mm first transparent resin substrate, a first recording layer, a first translucent reflective film layer, a transparent resin intermediate layer, a second recording layer, a second reflective film layer, an adhesive It is the structure which laminated | stacked in order of the layer and the 2nd transparent resin substrate of 0.6 mm. In this case, the transparent resin intermediate layer is coated with an ultraviolet curable resin composition that forms the transparent resin intermediate layer on the first semi-transparent reflective film layer, and irregularities such as guide grooves for recording / reproducing beams are formed. It is formed by pressing a transparent resin stamper having a pattern to cure the ultraviolet curable resin composition, then peeling the stamper, and transferring irregularities onto the surface of the ultraviolet curable resin composition.

　ブルーレイディスクにおいては、読み取り専用ディスクでは、基板である例えば直径１２０ｍｍ、厚み１．１ｍｍのポリカーボネート基板の片面にピット状の記録パターンが転写され、この基板の表面に第１の記録層となる第１の反射膜層、例えば銀合金反射膜層が成膜される。さらに、第１の反射膜層上にピット状の記録パターンが転写された透明樹脂中間層が形成され、この中間膜上に第２の記録層となる第２の反射膜層、例えば銀合金反射膜層が成膜される。そして、透明樹脂層を積層する構成となっている。尚、銀合金反射膜層は、例えばスパッタリング法により、真空中で成膜される手法が提案されている。
　記録型ディスクでは、基盤である例えば直径１２０ｍｍ、厚み１．１ｍｍのポリカーボネート基板の片面にピット状の記録パターンが転写され、この基盤の表面に第１の反射膜層、第１の誘電体層、第１の記録層、第２の誘電体層が積層され、さらに透明樹脂中間層、第２の反射膜層、第３の誘電体層、第２の記録層、第４の誘電体層、透明樹脂層の順に積層した構造となっている。
　これらの場合において、透明樹脂中間層は反射膜層又は誘電体層上に透明樹脂中間層を形成する紫外線硬化型樹脂組成物を塗布し、記録・再生ビ－ムのガイド用案内溝などの凹凸パタ－ンのある透明樹脂スタンパに押しつけ、紫外線硬化樹脂組成物を硬化させた後スタンパを剥離し、紫外線硬化型樹脂組成物の表面に凹凸を転写させて形成される。ここで、通常、透明樹脂中間層は読み取り専用ディスクでは、第２の反射膜層に接着している剥離層と第１の反射膜層に接着している接着層からなり、記録型ディスクでは第２の反射膜層に接着している剥離層と第２の誘電体層に接着している接着層からなっている。 In a Blu-ray disc, in a read-only disc, a pit-like recording pattern is transferred to one side of a polycarbonate substrate having a diameter of 120 mm and a thickness of 1.1 mm, for example, and a first recording layer is formed on the surface of the substrate. The reflective film layer, for example, a silver alloy reflective film layer is formed. Further, a transparent resin intermediate layer having a pit-like recording pattern transferred thereon is formed on the first reflective film layer, and a second reflective film layer that becomes the second recording layer, for example, a silver alloy reflective film, is formed on the intermediate film. A film layer is deposited. And it becomes the structure which laminates | stacks a transparent resin layer. In addition, the technique with which a silver alloy reflective film layer is formed into a film in vacuum, for example by sputtering method is proposed.
In a recording disk, a pit-like recording pattern is transferred to one side of a polycarbonate substrate having a diameter of 120 mm and a thickness of 1.1 mm, for example, and a first reflective film layer, a first dielectric layer, A first recording layer and a second dielectric layer are laminated, and further, a transparent resin intermediate layer, a second reflective film layer, a third dielectric layer, a second recording layer, a fourth dielectric layer, a transparent The resin layers are stacked in this order.
In these cases, the transparent resin intermediate layer is coated with an ultraviolet curable resin composition that forms the transparent resin intermediate layer on the reflective film layer or the dielectric layer, and the projections and depressions such as guide grooves for recording / reproducing beams are formed. It is formed by pressing a transparent resin stamper having a pattern to cure the ultraviolet curable resin composition, then peeling the stamper, and transferring irregularities onto the surface of the ultraviolet curable resin composition. Here, the transparent resin intermediate layer is usually composed of a peeling layer adhered to the second reflective film layer and an adhesive layer adhered to the first reflective film layer in the read-only disk, and the first in the recording type disk. 2 is composed of a release layer bonded to the reflective film layer 2 and an adhesive layer bonded to the second dielectric layer.

　一般に、該転写法を２Ｐ（Ｐｈｏｔｏ Ｐｏｌｙｍｅｒｉｚａｔｉｏｎ）法といい、使用する紫外線硬化型樹脂組成物を２Ｐ樹脂という。
　透明樹脂スタンパは、アクリル系樹脂、メタクリル系樹脂、ポリカーボネート樹脂、ポリオレフィン系樹脂（特に非晶質ポリオレフィン）、ポリエステル系樹脂、ポリスチレン樹脂、エポキシ樹脂等が挙げられる。これらの中でも、２Ｐ樹脂を硬化させた後の剥離性、低吸湿性、形状安定性等の点から非晶質ポリオレフィンが好ましく、材料コストの点からはポリカーボネート樹脂が好ましい。
　一般に、ＤＶＤの０．６ｍｍの樹脂基板、ブルーレイディスクの１．１ｍｍの樹脂基板はポリカーボネート樹脂が使用される。ポリカーボネート樹脂を透明樹脂スタンパとして使用する場合、２Ｐ樹脂とは別の紫外線硬化型樹脂を樹脂基板側に使用することで、硬化後の２Ｐ樹脂層からポリカーボネート製樹脂スタンパの剥離性を容易にする。 In general, the transfer method is called a 2P (Photo Polymerization) method, and the ultraviolet curable resin composition used is called a 2P resin.
Examples of the transparent resin stamper include acrylic resins, methacrylic resins, polycarbonate resins, polyolefin resins (particularly amorphous polyolefins), polyester resins, polystyrene resins, and epoxy resins. Among these, amorphous polyolefin is preferable from the viewpoint of peelability after curing 2P resin, low hygroscopicity, shape stability, and the like, and polycarbonate resin is preferable from the viewpoint of material cost.
Generally, polycarbonate resin is used for a 0.6 mm resin substrate for DVD and a 1.1 mm resin substrate for Blu-ray Disc. When the polycarbonate resin is used as the transparent resin stamper, the release of the polycarbonate resin stamper from the cured 2P resin layer is facilitated by using an ultraviolet curable resin different from the 2P resin on the resin substrate side.

　透明樹脂スタンパからの剥離性が悪いと透明樹脂中間層の一部が透明樹脂スタンパと共に剥離してしまい欠陥が生じる。転写性が悪いと記録・再生時にエラ－を生じる。紫外線硬化後に反りが大きいと、形成した凹凸パターンに記録層や反射膜層を均一に形成できなかったり、ＤＶＤの場合は第２の基板を貼り合わせることができなかったり、ブルーレイディスクの場合は０．１ｍｍの光透過層を均一に形成できない。また、高温高湿下で凹凸パタ－ンが変形すると、第１、２の記録層の記録特性（例えば、ジッタ特性）が同等にならない。
　特許文献１～４の２Ｐ樹脂は金属製のスタンパを用いてガラス基板上に凹凸パタ－ンを形成しており、透明樹脂スタンパによる凹凸パタ－ン形成についての記載はない。また、特許文献５～８に２Ｐ樹脂の記載はあるが、本発明の樹脂についての記載はない。 If the peelability from the transparent resin stamper is poor, a part of the transparent resin intermediate layer peels off together with the transparent resin stamper, resulting in a defect. If transferability is poor, an error occurs during recording / reproduction. If the warpage is large after UV curing, the recording layer and the reflective film layer cannot be uniformly formed on the formed concavo-convex pattern, the second substrate cannot be bonded in the case of DVD, or 0 in the case of Blu-ray Disc. A 1 mm light transmission layer cannot be formed uniformly. In addition, when the uneven pattern is deformed under high temperature and high humidity, the recording characteristics (for example, jitter characteristics) of the first and second recording layers are not equivalent.
In the 2P resin of Patent Documents 1 to 4, a metal stamper is used to form an uneven pattern on a glass substrate, and there is no description of forming an uneven pattern using a transparent resin stamper. Patent Documents 5 to 8 describe the 2P resin, but do not describe the resin of the present invention.

日本特開平５－５９１３９号公報Japanese Unexamined Patent Publication No. 5-59139 日本特開平５－１３２５３４号公報Japanese Patent Laid-Open No. 5-132534 日本特開平５－１４０２５４号公報Japanese Unexamined Patent Publication No. 5-140254 日本特開平５－１３２５０６号公報Japanese Unexamined Patent Publication No. 5-132506 日本特開２００３－３３１４６３号公報Japanese Unexamined Patent Publication No. 2003-331463 日本特開２００４－２８８２４２号公報Japanese Unexamined Patent Publication No. 2004-288242 日本特開２００４－２８８２６４号公報Japanese Unexamined Patent Publication No. 2004-288264 日本特開２００５－３３２５６４号公報Japanese Unexamined Patent Publication No. 2005-332564

　通常、２Ｐ剤として用いられる紫外線硬化型樹脂は凹凸パターンが形成されたスタンパから、当該パターンを保持したままで、スタンパから剥がしやすくする必要がある。その際、スタンパから剥離しにくいと、樹脂がスタンパに付着して、反射膜層又は誘電体層に接着しない等の問題が生じ、生産効率の低下を招くこととなる。また、スタンパからの剥離性が高い樹脂であっても、高温多湿下におかれた時に剥離すれば、読み取りエラーが生じてしまうという問題が生じてしまう。 Usually, the ultraviolet curable resin used as the 2P agent needs to be easily peeled off from the stamper while holding the pattern from the stamper on which the concave / convex pattern is formed. At that time, if it is difficult to peel off from the stamper, a problem occurs such that the resin adheres to the stamper and does not adhere to the reflective film layer or the dielectric layer, leading to a decrease in production efficiency. Further, even if the resin has high releasability from the stamper, if it is peeled off when placed under high temperature and high humidity, there arises a problem that a reading error occurs.

　そこで、本発明はこのような実情に鑑みて、多官能アクリレート変性ウレタンアクリレートと（メタ）アクリレートモノマーを用いることで、スタンパからの剥離に特に優れ、かつ、高温多湿下においても反射膜層又は誘電体層に密着している樹脂組成を提供することにある。 Accordingly, in view of such circumstances, the present invention uses a polyfunctional acrylate-modified urethane acrylate and a (meth) acrylate monomer, so that it is particularly excellent in peeling from a stamper and is also capable of reflecting film layers or dielectrics even under high temperature and high humidity. The object is to provide a resin composition in close contact with the body layer.

　さらに、本発明はスタンパを剥離させる際に選択的に反射膜層又は誘電体層に接着させることができるため、２Ｐ剤の紫外線硬化型樹脂の接着剤層を省略することを可能にするものである。 Furthermore, since the present invention can selectively adhere to the reflective film layer or the dielectric layer when the stamper is peeled off, it is possible to omit the adhesive layer of the 2P UV curable resin. is there.

　本発明者らは、有機イソシアネートと水酸基を有する多官能アクリレートを反応させて得られるウレタン（メタ）アクリレート紫外線硬化型樹脂組成物を使用することで、スタンパからの剥離性を高め、高温多湿下で置かれても反射膜層又は誘電体層にしっかり密着する樹脂組成を見出した。これにより、スタンパからの剥離性が高く、反射膜層又は記録膜に対する密着性に優れた紫外線効果型樹脂組成物を開発するに至ったのである。 By using a urethane (meth) acrylate ultraviolet curable resin composition obtained by reacting an organic isocyanate and a polyfunctional acrylate having a hydroxyl group, the present inventors have improved the peelability from a stamper, under high temperature and high humidity. The present inventors have found a resin composition that adheres firmly to the reflective film layer or the dielectric layer even when placed. This has led to the development of a UV-effect resin composition that has high peelability from the stamper and excellent adhesion to the reflective film layer or the recording film.

　本発明は、次の（１）～（７）に関する。
（１）（Ａ）１分子中に２個以上のイソシアネート基を有する有機イソシアネートと水酸基を有する３官能以上の（メタ）アクリレートを反応させて得られる６官能以上のウレタン（メタ）アクリレート、（Ｂ）３官能以下の（メタ）アクリレートモノマー、及び（Ｃ）光重合開始剤を含有する、多層光ディスク用紫外線硬化型樹脂組成物。
（２）１分子中に２個以上のイソシアネート基を有する有機イソシアネートと水酸基を有する３官能以上の（メタ）アクリレートを反応させて得られるウレタン（メタ）アクリレート（Ａ）において、有機イソシアネートが、イソホロンジイソシアネート、ヘキサメチレンジイソシアネート、トリレンジイソシアネート、キシレンジイソシアネート、ジフェニルメタン－４，４’－ジイソシアネート、ジシクロペンタニルジイソシアネート、及び下記式（１） The present invention relates to the following (1) to (7).
(1) (A) A hexafunctional or higher functional urethane (meth) acrylate obtained by reacting an organic isocyanate having two or more isocyanate groups in one molecule with a trifunctional or higher functional (meth) acrylate having a hydroxyl group, (B An ultraviolet curable resin composition for a multilayer optical disk, comprising a trifunctional (meth) acrylate monomer and (C) a photopolymerization initiator.
(2) In urethane (meth) acrylate (A) obtained by reacting an organic isocyanate having two or more isocyanate groups in one molecule with a trifunctional or higher functional (meth) acrylate having a hydroxyl group, the organic isocyanate is isophorone. Diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, diphenylmethane-4,4′-diisocyanate, dicyclopentanyl diisocyanate, and the following formula (1)

Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007

（式中、Ｒは、

Figure JPOXMLDOC01-appb-C000008
、
Figure JPOXMLDOC01-appb-C000009
 、
Figure JPOXMLDOC01-appb-C000010
 、
Figure JPOXMLDOC01-appb-C000011
 又は
Figure JPOXMLDOC01-appb-C000012
 (Wherein R is
Figure JPOXMLDOC01-appb-C000008
 ,
Figure JPOXMLDOC01-appb-C000009
 ,
Figure JPOXMLDOC01-appb-C000010
 ,
Figure JPOXMLDOC01-appb-C000011
 Or
Figure JPOXMLDOC01-appb-C000012

を示す。）で表わされる３官能イソシアネートからなる群から選択される１種もしくは２種以上である、前記（１）項に記載の多層光ディスク用紫外線硬化型樹脂組成物。
（３）１分子中に２個以上のイソシアネート基を有する有機イソシアネートと水酸基を有する３官能以上の（メタ）アクリレートを反応させて得られるウレタン（メタ）アクリレート（Ａ）において、水酸基を有する３官能以上の（メタ）アクリレートがペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ペンタエリスリトールのε－カプロラクトン付加物のトリ（メタ）アクリレート、及びジペンタエリスリトールのε－カプロラクトン付加物のトリ、テトラ又はペンタ（メタ）アクリレートからなる群から選択される１種もしくは２種以上である、前記（１）項又は（２）項に記載の多層光ディスク用紫外線硬化型樹脂組成物。
（４）３官能以下の（メタ）アクリレートモノマー（Ｂ）がイソボルニルアクリレート、ネオペンチルグリコールジアクリレート、プロピレンオキサイド変性ネオペンチルグリコールジアクリレート、トリシクロデカンジメタノールジアクリレート、及びヒドロピバルアルデヒド変性トリメチロールプロパンジアクリレートからなる群から選択される１種もしくは２種以上である、前記（１）項乃至（３）項のいずれか一項に記載の多層光ディスク用紫外線硬化型樹脂組成物。
（５）樹脂組成物全体に対し、（Ａ）成分５～８０重量％、（Ｂ）成分１０～８０重量％、（Ｃ）成分１～１５重量％を含有する前記（１）項乃至（４）項のいずれか一項に記載の多層光ディスク用紫外線硬化型樹脂組成物。
（６）前記（１）項乃至（５）項のいずれか一項に記載の多層光ディスク用紫外線硬化型樹脂組成物に活性エネルギー線を照射して得られる硬化物。
（７）前記（６）項記載の硬化物を有する多層光ディスク。 Indicates. The ultraviolet curable resin composition for multilayer optical disks according to item (1), which is one or more selected from the group consisting of trifunctional isocyanates represented by:
(3) In the urethane (meth) acrylate (A) obtained by reacting an organic isocyanate having two or more isocyanate groups in one molecule with a trifunctional or higher functional (meth) acrylate having a hydroxyl group, a trifunctional group having a hydroxyl group. The above (meth) acrylates are pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri (meth) acrylate of pentaerythritol ε-caprolactone adduct, and ε-caprolactone adduct of dipentaerythritol. The ultraviolet curable resin composition for multilayer optical disks according to (1) or (2), which is one or more selected from the group consisting of tri, tetra, or penta (meth) acrylates.
(4) Trifunctional or lower (meth) acrylate monomer (B) is modified with isobornyl acrylate, neopentyl glycol diacrylate, propylene oxide modified neopentyl glycol diacrylate, tricyclodecane dimethanol diacrylate, and hydropivalaldehyde The ultraviolet curable resin composition for multilayer optical disks according to any one of (1) to (3), wherein the ultraviolet curable resin composition is one or more selected from the group consisting of trimethylolpropane diacrylate.
(5) Items (1) to (4) containing 5 to 80% by weight of component (A), 10 to 80% by weight of component (B), and 1 to 15% by weight of component (C) with respect to the entire resin composition. The ultraviolet curable resin composition for multilayer optical disks according to any one of items 1).
(6) A cured product obtained by irradiating the ultraviolet curable resin composition for multilayer optical disks according to any one of (1) to (5) with active energy rays.
(7) A multilayer optical disk having the cured product as described in (6) above.

　本発明の紫外線硬化型樹脂組成物及びその硬化物は、スタンパからの剥離性に優れ、かつ高温多湿下に置かれても反射膜層又は誘電体層に密着している２Ｐ剤として有用である。また、接着層を省略して１液で中間層を形成させることを可能とする紫外線硬化型樹脂を提供することができる。 The ultraviolet curable resin composition of the present invention and its cured product are excellent as a 2P agent that is excellent in releasability from a stamper and is in close contact with a reflective film layer or a dielectric layer even when placed under high temperature and high humidity. . Further, it is possible to provide an ultraviolet curable resin that can omit the adhesive layer and form the intermediate layer with one liquid.

　本発明は、樹脂組成物中に、（Ａ）１分子中に２個以上のイソシアネート基を有する有機イソシアネートと水酸基を有する３官能以上の（メタ）アクリレートを反応させて得られる６官能以上のウレタン（メタ）アクリレートと、（Ｂ）３官能以下の（メタ）アクリレートモノマー、及び（Ｃ）光重合開始剤を含有する光ディスク用紫外線硬化型樹脂組成物である。 The present invention relates to (A) a hexafunctional or higher functional urethane obtained by reacting (A) an organic isocyanate having two or more isocyanate groups in one molecule with a trifunctional or higher functional (meth) acrylate having a hydroxyl group. An ultraviolet curable resin composition for an optical disk containing (meth) acrylate, (B) a trifunctional or lower (meth) acrylate monomer, and (C) a photopolymerization initiator.

　本発明の紫外線硬化型樹脂組成物では、（Ａ）１分子中に２個以上のイソシアネート基を有する有機イソシアネートとヒドロキシ変性多官能アクリレートを反応させて得られる６官能以上のウレタン（メタ）アクリレートを使用する。
　本発明に用いられる有機イソシアネートは分子内に２個以上のイソシアネート基を有する化合物であり、公知のものであれば特に限定なく使用することができる。例としてイソホロンジイソシアネート、ヘキサメチレンジイソシアネート、トリレンジイソシアネート、キシレンジイソシアネート、ジフェニルメタン－４，４’－ジイソシアネート、又はジシクロペンタニルジイソシアネート等のジイソシアネート類が挙げられる。 In the ultraviolet curable resin composition of the present invention, (A) a hexafunctional or higher functional urethane (meth) acrylate obtained by reacting an organic isocyanate having two or more isocyanate groups in one molecule with a hydroxy-modified polyfunctional acrylate use.
The organic isocyanate used in the present invention is a compound having two or more isocyanate groups in the molecule, and any known one can be used without particular limitation. Examples include diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, diphenylmethane-4,4′-diisocyanate, or dicyclopentanyl diisocyanate.

　さらに、本発明においては、変性イソシアネートとして、ジイソシアネートモノマーをイソシアヌレート変性させた下記式（１） Furthermore, in the present invention, the following formula (1) in which a diisocyanate monomer is isocyanurate-modified as a modified isocyanate:

Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013

（式中、Ｒは、

Figure JPOXMLDOC01-appb-C000014
、
Figure JPOXMLDOC01-appb-C000015
 、
Figure JPOXMLDOC01-appb-C000016
、
Figure JPOXMLDOC01-appb-C000017
又は
Figure JPOXMLDOC01-appb-C000018
 (Wherein R is
Figure JPOXMLDOC01-appb-C000014
 ,
Figure JPOXMLDOC01-appb-C000015
 ,
Figure JPOXMLDOC01-appb-C000016
,
Figure JPOXMLDOC01-appb-C000017
Or
Figure JPOXMLDOC01-appb-C000018

を示す。）で表される３官能イソシアネートが用いられる。 Indicates. ) Is used.

　これらの化合物は適宜公知の方法で合成して得られるが、市場品としては、例えば、武田薬品工業社製　タケネートＤ－１７０Ｎ；住化バイエルウレタン社製　スミジュールＮ－３３００、デスモジュールＬ、デスモジュールＨＬ；デグッサ社製　Ｔ－１８９０が挙げられる。
　有機イソシアネートとして本願では式（１）で表される３官能イソシアネートが好ましく、特にヘキサメチレンジイソシアネートイソシアヌレート３量体（Ｒ＝－（ＣＨ２）６－）の化合物が好ましい。 These compounds can be obtained by appropriately synthesizing by known methods. Examples of commercially available products include Takenate D-170N manufactured by Takeda Pharmaceutical Co., Ltd .; Sumidur N-3300 manufactured by Sumika Bayer Urethane Co., Module HL; Degussa T-1890
In the present application, a trifunctional isocyanate represented by the formula (1) is preferable as the organic isocyanate, and a hexamethylene diisocyanate isocyanurate trimer (R = — (CH 2 ) 6 —) compound is particularly preferable.

  また更に、変性イソシアネートとしてジイソシアネートモノマーをビウレット反応させた、下記式（２） Furthermore, a diisocyanate monomer is biuret-reacted as a modified isocyanate, and the following formula (2)

Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019

（式中、Ｒは、上記式（1）のＲと同様である）で表されるイソシアネートでも可能である。 (In the formula, R is the same as R in the above formula (1)).

　水酸基を有する３官能以上の（メタ）アクリレートとしては、具体的には水酸基を有する３～８官能の（メタ）アクリレートを指し、公知ものであれば特に限定なく使用できる。例として、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ペンタエリスリトールのε－カプロラクトン付加物のトリ（メタ）アクリレート、ジペンタエリスリトールのε－カプロラクトン付加物のトリ、テトラ又はペンタ（メタ）アクリレート等が挙げられる。本発明では特に、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレートが好ましい。 The trifunctional or higher functional (meth) acrylate having a hydroxyl group specifically refers to a tri to octafunctional (meth) acrylate having a hydroxyl group, and any known one can be used without particular limitation. Examples include pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri (meth) acrylate of ε-caprolactone adduct of pentaerythritol, tri, tetra or penta of ε-caprolactone adduct of dipentaerythritol (Meth) acrylate etc. are mentioned. In the present invention, pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are particularly preferable.

　反応は以下のようにして行う。即ち、水酸基を有する３官能以上の（メタ）アクリレートの水酸基１当量あたり有機ポリイソシアネートをそのイソシアネート基が好ましくは１．１～２．０当量になるように混合し、反応温度を好ましくは７０～９０℃で反応させることで、目的とするウレタン（メタ）アクリレート（Ａ）を得ることができる。
　上記（Ａ）ウレタン（メタ）アクリレートは１種又は２種以上を任意割合で混合使用することができる。（Ａ）ウレタン（メタ）アクリレートの組成物中の使用量としては内割で、５～８０重量％、好ましくは１５～７５重量％、特に好ましくは２０～７０重量％程度である。 The reaction is carried out as follows. That is, the organic polyisocyanate is mixed so that the isocyanate group is preferably 1.1 to 2.0 equivalents per one equivalent of the hydroxyl group of the tri- or higher functional (meth) acrylate having a hydroxyl group, and the reaction temperature is preferably 70 to By making it react at 90 degreeC, the target urethane (meth) acrylate (A) can be obtained.
The above (A) urethane (meth) acrylate can be used alone or in combination of two or more. The amount of (A) urethane (meth) acrylate used in the composition is 5 to 80% by weight, preferably 15 to 75% by weight, particularly preferably about 20 to 70% by weight.

　本発明で用いられる（Ｂ）３官能以下の（メタ）アクリレートモノマーとしては、公知のものであれば、特に限定することなく使用できる。例としては、トリシクロデカン（メタ）アクリレート、ベンジルアクリレート、ジシクロペンタニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、アダマンチル（メタ）アクリレート、ベンジル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、モルフォリン（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、プロピレンオキサイド変性ネオペンチルグリコールジ（メタ）アクリレート、トリシクロデカンジメチロールジ（メタ）アクリレート、ヒドロキシピバルアルデヒド変性トリメチロールプロパンジ（メタ）アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジ（メタ）アクリレート、等が挙げられる。
　ここで、剥離性を向上させるため、（メタ）アクリレートモノマーがイソボルニルアクリレート、ネオペンチルグリコールジアクリレート、プロピレンオキサイド変性ネオペンチルグリコールジアクリレート、トリシクロデカンジメタノールジアクリレート、ヒドロピバルアルデヒド変性トリメチロールプロパンジアクリレートを使用することが好ましい。組成物中の使用量としては、内割で１０～８０重量％で、好ましくは１５～７５重量％であり、より好ましくは２０～７０重量％である。 As the (B) trifunctional or lower (meth) acrylate monomer used in the present invention, any known monomer can be used without particular limitation. Examples include tricyclodecane (meth) acrylate, benzyl acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, Morpholine (meth) acrylate, neopentyl glycol di (meth) acrylate, propylene oxide modified neopentyl glycol di (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, hydroxypivalaldehyde modified trimethylolpropane di (meta) ) Acrylate, neopentyl glycol di (meth) acrylate hydroxypivalate, and the like.
Here, in order to improve releasability, the (meth) acrylate monomer is isobornyl acrylate, neopentyl glycol diacrylate, propylene oxide-modified neopentyl glycol diacrylate, tricyclodecane dimethanol diacrylate, hydropivalaldehyde-modified tri Preference is given to using methylolpropane diacrylate. The amount used in the composition is 10 to 80% by weight, preferably 15 to 75% by weight, more preferably 20 to 70% by weight.

　本発明の紫外線硬化型樹脂組成物に含有される（Ｃ）光重合開始剤としては、１－ヒドロキシシクロヘキシルフェニルケトン（イルガキュアー１８４；チバ・スペシャリティ・ケミカルズ製）、１－[４－（２－ヒドロキシエトキシ）－フェニル]－２－ヒドロキシ－２－メチル－１－プロパン－１－オン（イルガキュアー２９５９；チバ・スペシャリティ・ケミカルズ製）、２－ヒドロキシ－１－｛４－［４－（２－ヒドロキシ－２－メチル－プロピオニル）－ベンジル]－フェニル｝－２－メチル－プロパン－１－オン（イルガキュアー１２７；チバ・スペシャリティ・ケミカルズ製）、２，２－ジメトキシ－２－フェニルアセトフェノン（イルガキュア６５１；チバ・スペシャリティ・ケミカルズ製）、オリゴ[２－ヒドロキシ－２－メチル－１－[４－（１－メチルビニル）フェニル]プロパノン]（エサキュアONE；ランバルティ製）、２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン（ダロキュア１１７３；チバ・スペシャリティ・ケミカルズ製）、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノプロパン－１－オン（イルガキュアー９０７；チバスペシャリティーケミカルズ製）、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）－ブタン－１－オン、２－クロロチオキサントン、２，４－ジメチルチオキサントン、２，４－ジイソプロピルチオキサントン、イソプロピルチオキサントン、２，４，６－トリメチルベンゾイルジフェニルフォスフィンオキサイド（ルシリンTPO：BASF製）、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド（イルガキュアー８１９；チバ・スペシャリティ・ケミカルズ製）、ビス（２，６－ジメトキシベンゾイル）－２，４，４－トリメチルペンチルフォスフィンオキサイド等が挙げられる。 Examples of the (C) photopolymerization initiator contained in the ultraviolet curable resin composition of the present invention include 1-hydroxycyclohexyl phenyl ketone (Irgacure 184; manufactured by Ciba Specialty Chemicals), 1- [4- (2- Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (Irgacure 2959; manufactured by Ciba Specialty Chemicals), 2-hydroxy-1- {4- [4- (2- Hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one (Irgacure 127; manufactured by Ciba Specialty Chemicals), 2,2-dimethoxy-2-phenylacetophenone (Irgacure 651) Manufactured by Ciba Specialty Chemicals), oligo [2-hydroxy-2-methyl] 1- [4- (1-methylvinyl) phenyl] propanone] (Esacure ONE; manufactured by Lamberti), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur 1173; Ciba Specialty) Chemicals), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907; manufactured by Ciba Specialty Chemicals), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (lucillin TPO) : BASF), screw (2,4,6-trimethyl) Rubenzoyl) -phenylphosphine oxide (Irgacure 819; manufactured by Ciba Specialty Chemicals), bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, and the like.

　これらの光重合開始剤は１種類でも複数でも任意の割合で混合して使用することができ、アミン類等の光重合開始助剤と併用することも可能である。
　本発明の紫外線硬化型樹脂組成物中の（Ｃ）光重合開始剤の含有量としては１～１５重量％が用いられ、好ましくは１～１０重量％程度である。
　本発明で使用しうるアミン類等の光重合開始助剤としては、例えば、ジエタノールアミン、２－ジメチルアミノエチルベンゾエート、ジメチルアミノアセトフェノン、ｐ－ジメチルアミノ安息香酸エチルエステル、ｐ－ジメチルアミノ安息香酸イソアミルエステル等が挙げられる。光重合開始助剤を併用する場合、本発明の紫外線硬化型脂組組成物中の含有量としては０．０５～５重量％が好ましく、特に好ましくは０．１～３重量％程度である。 These photopolymerization initiators may be used alone or in combination at any ratio, and may be used in combination with photopolymerization initiation assistants such as amines.
The content of the (C) photopolymerization initiator in the ultraviolet curable resin composition of the present invention is 1 to 15% by weight, preferably about 1 to 10% by weight.
Examples of photopolymerization initiation assistants such as amines that can be used in the present invention include diethanolamine, 2-dimethylaminoethylbenzoate, dimethylaminoacetophenone, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester. Etc. When a photopolymerization initiation aid is used in combination, the content in the ultraviolet curable fat composition of the present invention is preferably 0.05 to 5% by weight, particularly preferably about 0.1 to 3% by weight.

　本発明の紫外線硬化型樹脂組成物においては、必要によりリン酸（メタ）アクリレートを加えることができる。リン酸（メタ）アクリレートは、アルミニウム、銀または銀合金と接着剤硬化物との接着性を向上させるが、金属膜を腐食させる恐れがありその使用量は制限される。
　更に、本発明には、上記の成分に加え、必要によりシランカップリング剤、レベリング剤、消泡剤、重合禁止剤、光安定剤（ヒンダ－ドアミン系等）、酸化防止剤、帯電防止剤、表面潤滑剤、充填剤などの添加剤を併用してもよい。このような添加剤の例としては、例えば、信越化学（株）社製　ＫＢＭ－５０２、ＫＢＭ－５０３、ＫＢＭ－５１０３、ＫＢＭ－８０２、ＫＢＭ－８０３；ビックケミー社製　ＢＹＫ－３３３、ＢＹＫ－３０７、ＢＹＫ－３５００、ＢＹＫ－３５３０、ＢＹＫ－３５７０；東レ・ダウコーニング（株）社製　Ｚ－６０６２、ＳＨ－６０６２、ＳＨ－２９ＰＡ；（株）アデカ社製　ＬＡ－８２等が挙げられる。 In the ultraviolet curable resin composition of the present invention, phosphoric acid (meth) acrylate can be added if necessary. Phosphoric acid (meth) acrylate improves the adhesion between aluminum, silver or a silver alloy and the cured adhesive, but may corrode the metal film, and its amount used is limited.
Further, in the present invention, in addition to the above components, if necessary, a silane coupling agent, a leveling agent, an antifoaming agent, a polymerization inhibitor, a light stabilizer (such as a hindered amine), an antioxidant, an antistatic agent, You may use together additives, such as a surface lubricant and a filler. Examples of such additives include, for example, KBM-502, KBM-503, KBM-5103, KBM-802, KBM-803 manufactured by Shin-Etsu Chemical Co., Ltd. BYK-333, BYK-307 manufactured by BYK Chemie. BYK-3500, BYK-3530, BYK-3570; Z-6062, SH-6062, SH-29PA manufactured by Toray Dow Corning Co., Ltd .; LA-82 manufactured by Adeka Co., Ltd., and the like.

　本発明の紫外線硬化型樹脂組成物は、前記各成分を常温～８０℃で混合溶解後、必要により濾過して得ることができる。
　本発明の紫外線硬化型樹脂組成物の粘度は、Ｂ型粘度計で２５℃での測定で１０～８００ｍＰａ・ｓ、好ましくは４０～５００ｍＰａ・ｓである。 The ultraviolet curable resin composition of the present invention can be obtained by mixing and dissolving the above components at room temperature to 80 ° C. and then filtering if necessary.
The viscosity of the ultraviolet curable resin composition of the present invention is 10 to 800 mPa · s, preferably 40 to 500 mPa · s as measured with a B-type viscometer at 25 ° C.

　ＤＶＤの場合、透明樹脂中間層は、(1) 第１の透明樹脂基板、第１の記録層、第１の半透明反射膜層が積層された基板と透明樹脂スタンパの少なくとも一方に、本発明の樹脂組成物をスピンコ－ト法、スクリ－ン印刷法、ロールコート法等方法により塗工後、貼り合わせて透明樹脂スタンパ側から紫外線を照射して形成される。または、(2) 透明樹脂スタンパに前記方法により本発明の樹脂組成物を塗工後、紫外線硬化させ、第１の透明樹脂基板、第１の記録層、第１の半透明反射膜層が積層された基板と任意の紫外線硬化型樹脂で貼り合わせて形成させることもできる。(1) の形成方法は生産効率を省略できる点で、生産コストの低減が望めるため、好ましい。また、ブルーレイディスクもＤＶＤと同様の方法で透明樹脂中間層を形成する。一般に、ＤＶＤやＨＤ－ＤＶＤの０．６ｍｍの第１の透明樹脂基板、ブルーレイディスクの１．１ｍｍの樹脂基板はポリカーボネート樹脂が使用される。ポリカーボネート製透明樹脂スタンパを使用する場合も、剥離性の点から(1) の方法が好ましい。 In the case of DVD, the transparent resin intermediate layer is formed on (1) at least one of the first transparent resin substrate, the first recording layer, the substrate on which the first translucent reflective film layer is laminated, and the transparent resin stamper. The resin composition is applied by a spin coating method, a screen printing method, a roll coating method, or the like, and then bonded together and irradiated with ultraviolet rays from the transparent resin stamper side. Or (2) the transparent resin stamper is coated with the resin composition of the present invention by the above method and then cured with ultraviolet rays, and the first transparent resin substrate, the first recording layer, and the first translucent reflective film layer are laminated. It is also possible to form the substrate by adhering it with an arbitrary ultraviolet curable resin. (1) The soot formation method is preferable because production efficiency can be omitted and production costs can be reduced. In addition, a transparent resin intermediate layer is formed on a Blu-ray disc in the same manner as DVD. Generally, polycarbonate resin is used for the 0.6 mm first transparent resin substrate for DVD and HD-DVD and the 1.1 mm resin substrate for Blu-ray Disc. When using a polycarbonate transparent resin stamper, the method (1) is preferred from the viewpoint of peelability.

　透明樹脂スタンパとしては、例えば、アクリル系樹脂、メタクリル系樹脂、ポリカーボネート樹脂、ポリオレフィン系樹脂（特に非晶質ポリオレフィン）、ポリエステル系樹脂、ポリスチレン樹脂、エポキシ樹脂等が挙げられる。これらの中でも、２Ｐ樹脂を硬化させた後の剥離性、低吸湿性、形状安定性等の点から非晶質ポリオレフィンが好ましく、材料コストの点からはポリカーボネート樹脂が好ましい。本発明の２Ｐ硬化型樹脂組成物はどちらの透明樹脂スタンパも使用できる。
　本発明の紫外線硬化型樹脂組成物は、活性エネルギー線の照射により硬化物を与える。該活性エネルギー線をしては、例えば、紫外～近紫外の光線が挙げられる。例えば、低圧、高圧、超高圧水銀灯、メタルハライドランプ、（パルス）キセノンランプ、無電極ランプ、紫外線発光ダイオ－ド等があげられる。前記硬化物も本発明に含まれる。 Examples of the transparent resin stamper include acrylic resins, methacrylic resins, polycarbonate resins, polyolefin resins (particularly amorphous polyolefins), polyester resins, polystyrene resins, and epoxy resins. Among these, amorphous polyolefin is preferable from the viewpoint of peelability after curing 2P resin, low hygroscopicity, shape stability, and the like, and polycarbonate resin is preferable from the viewpoint of material cost. Either transparent resin stamper can be used for the 2P curable resin composition of the present invention.
The ultraviolet curable resin composition of the present invention gives a cured product by irradiation with active energy rays. Examples of the active energy ray include ultraviolet rays to near ultraviolet rays. For example, low pressure, high pressure, ultra high pressure mercury lamp, metal halide lamp, (pulse) xenon lamp, electrodeless lamp, ultraviolet light emitting diode, and the like can be mentioned. The cured product is also included in the present invention.

　前記硬化物による透明樹脂中間層上に形成される記録層は有機色素や相変化材料のいずれも使用できる。例えば、有機色素は含金属アゾ系、ポリメチン系、フタロシアニン系が挙げられ、相変化材料はＳｂおよびＴｅにＩｎ、Ａｇ、Ａｕ、Ｂｉ、Ｓｅ、Ａｌ、Ｐ、Ｇｅ、Ｈ、Ｓｉ、Ｃ、Ｖ、Ｗ、Ｔａ、Ｚｎ、Ｔｉ、Ｃｅ、Ｔｂ、Ｓｎ、Ｐｂのいずれか一種以上を添加したものがあげられる。
　また、本発明の樹脂組成物はポリカーボネート製基板を貼り合わせた構造の光ディスクやブルーレイディスクのいずれにも使用できる。 For the recording layer formed on the transparent resin intermediate layer of the cured product, either an organic dye or a phase change material can be used. For example, organic dyes include metal-containing azo, polymethine, and phthalocyanine, and phase change materials include Sb and Te, In, Ag, Au, Bi, Se, Al, P, Ge, H, Si, C, V , W, Ta, Zn, Ti, Ce, Tb, Sn, and Pb are added.
In addition, the resin composition of the present invention can be used for either an optical disc or a Blu-ray disc having a structure in which a polycarbonate substrate is bonded.

　塗工方法として、例えば、スピンコート法、２Ｐ法、ロールコート法、スクリーン印刷法等が挙げられる。 Examples of the coating method include a spin coating method, a 2P method, a roll coating method, and a screen printing method.

　また、次世代の高密度光ディスクには読み取り及び／又は書き込みに４００ｎｍ前後の青色レーザーが使用されることから、膜厚９０－１００μｍの硬化物において４０５ｎｍの透過率が８０％以上であることが好ましい。 In addition, since a blue laser having a wavelength of about 400 nm is used for reading and / or writing in the next-generation high-density optical disc, the transmittance at 405 nm is preferably 80% or more in a cured product having a thickness of 90-100 μm. .

　以下、本発明について実施例を用いて詳細に説明する。
合成例１：ウレタンアクリレート（Ａ－１）の合成
　攪拌装置、冷却管及び温度計のついた丸底フラスコにイソホロンジイソシアネート０．６３重量部とペンタエリスリトールトリアクリレート９３．９重量部、重合禁止剤であるメトキノンを０．０３重量部及びジブチル錫ジラウレート０．０５重量部を仕込み、室温で３０分間混合させ、８０℃で５時間反応させた。イソシアネート濃度が０．１％以下になった所で反応を終了し、目的とするウレタンアクリレートを得た。
合成例２：ウレタンアクリレート（Ａ－２）の合成
　攪拌装置、冷却管及び温度計のついた丸底フラスコにヘキサメチレンジイソシアネートのイソシアヌレート変性タイプ（武田薬品工業社製タケネートＤ－１７０Ｎ；式（１）Ｒ＝－（ＣＨ２）６－）１１．６重量部とジペンタエリスリトールペンタアクリレート８８．４重量部、重合禁止剤であるメトキノンを０．０５重量部及びジブチル錫ジラウレート０．０５重量部を仕込み、室温で３０分間混合させ、８０℃で５時間反応させた。イソシアネート濃度が０．１％以下になった所で反応を終了し、目的とするウレタンアクリレートを得た。
合成例３：ウレタンアクリレート（Ａ－３）の合成
　攪拌装置、冷却管及び温度計のついた丸底フラスコにヘキサメチレンジイソシアネート１４．８重量部とジペンタエリスリトールペンタアクリレート８５．１重量部、重合禁止剤であるメトキノンを０．０３重量部及びジブチル錫ジラウレート０．０５重量部を仕込み、室温で３０分間混合させ、８０℃で５時間反応させた。イソシアネート濃度が０．１％以下になった所で反応を終了し、目的とするウレタンアクリレートを得た。
実施例及び試験例
　実施例１～３及び比較例１～３の樹脂組成物につき、構成材料及び使用量と記項目を評価したその結果を表１に示した。なお、記載中の「部」は重量部を示す。 Hereinafter, the present invention will be described in detail with reference to examples.
Synthesis Example 1 Synthesis of Urethane Acrylate (A-1) In a round bottom flask equipped with a stirrer, a cooling tube and a thermometer, 0.63 parts by weight of isophorone diisocyanate, 93.9 parts by weight of pentaerythritol triacrylate, and a polymerization inhibitor 0.03 part by weight of a certain methoquinone and 0.05 part by weight of dibutyltin dilaurate were charged, mixed at room temperature for 30 minutes, and reacted at 80 ° C. for 5 hours. The reaction was terminated when the isocyanate concentration became 0.1% or less to obtain the intended urethane acrylate.
Synthesis Example 2 Synthesis of Urethane Acrylate (A-2) Isocyanurate-modified type of hexamethylene diisocyanate (Takenate D-170N, Takeda Pharmaceutical Company Limited; formula (1) ) R =-(CH 2 ) 6- ) 11.6 parts by weight, 88.4 parts by weight of dipentaerythritol pentaacrylate, 0.05 parts by weight of methoquinone as a polymerization inhibitor and 0.05 parts by weight of dibutyltin dilaurate The mixture was charged, mixed at room temperature for 30 minutes, and reacted at 80 ° C. for 5 hours. The reaction was terminated when the isocyanate concentration became 0.1% or less to obtain the intended urethane acrylate.
Synthesis Example 3: Synthesis of urethane acrylate (A-3) In a round bottom flask equipped with a stirrer, a condenser tube and a thermometer, 14.8 parts by weight of hexamethylene diisocyanate and 85.1 parts by weight of dipentaerythritol pentaacrylate, polymerization prohibited 0.03 part by weight of methoquinone as an agent and 0.05 part by weight of dibutyltin dilaurate were charged, mixed at room temperature for 30 minutes, and reacted at 80 ° C. for 5 hours. The reaction was terminated when the isocyanate concentration became 0.1% or less to obtain the intended urethane acrylate.
Examples and Test Examples Table 1 shows the results of evaluating the constituent materials, the amounts used, and the items of the resin compositions of Examples 1 to 3 and Comparative Examples 1 to 3. In addition, "part" in description shows a weight part.

Figure JPOXMLDOC01-appb-T000020
Figure JPOXMLDOC01-appb-T000020

  なお、表１中に略称で示した各成分は下記の通りである。
　Ａ－１：合成例１で得られたウレタンアクリレート
　Ａ－２：合成例２で得られたウレタンアクリレート
　Ａ－３：合成例３で得られたウレタンアクリレート
　ＩＢＡ：イソボルニルアクリレート、第一工業化学社製
　ＲＰ－１０４０：ペンタエリスリトールエチレンオキサイド変性テトラアクリレート、日本化薬社製
　ＴＨＥ－３３０：エチレンオキサイド変性トリメチロールプロパントリアクリレート、日本化薬社製
　ＤＰＨＡ：ジペンタエリスリトールヘキサアクリレート、日本化薬社製
　イルガキュアー１８４：１－ヒドロキシシクロヘキシルフェニルケトン、チバ・スペシャルティーケミカル社製 In addition, each component shown with the abbreviation in Table 1 is as follows.
A-1: Urethane acrylate obtained in Synthesis Example 1 A-2: Urethane acrylate obtained in Synthesis Example 2 A-3: Urethane acrylate obtained in Synthesis Example 3 IBA: Isobornyl acrylate, Daiichi Kogyo Kagaku RP-1040: Pentaerythritol ethylene oxide modified tetraacrylate, Nippon Kayaku THE-330: Ethylene oxide modified trimethylolpropane triacrylate, Nippon Kayaku DPHA: Dipentaerythritol hexaacrylate, Nippon Kayaku Irgacure 184: 1-hydroxycyclohexyl phenyl ketone, manufactured by Ciba Specialty Chemicals

（評価用サンプルの作製）
　得られた紫外線硬化型樹脂組成物を用い、以下１～３の方法にて評価用サンプルディスクを作製した。
１．記録層としてのアゾ系色素層、反射膜層、誘電体層としてのＺｎＳ・ＳｉＯ２層が形成された直径１２０ｍｍ／０．６ｍｍ厚のポリカーボネート製基板（第１の基板）内周上に、気泡が入らないように作製した透明樹脂を載せ、当該樹脂の上にスタンパを載せて２０００ｒｐｍ、４秒間スピンコートして貼り合わせた。
２．高圧水銀灯（８０Ｗ／ｃｍ）を透明樹脂スタンパ側から４００ｍJ／ｃｍ２照射し、第２の紫外線硬化型樹脂組成物を硬化させた。
３．ディスク剥離装置（オリジン電機（株）製）を用いて、透明樹脂スタンパを剥離し、評価用サンプルディスクを作製した。 (Preparation of sample for evaluation)
A sample disk for evaluation was produced by the following methods 1 to 3 using the obtained ultraviolet curable resin composition.
1. Air bubbles are formed on the inner periphery of a polycarbonate substrate (first substrate) having a diameter of 120 mm / 0.6 mm on which an azo dye layer as a recording layer, a reflective film layer, and a ZnS / SiO 2 layer as a dielectric layer are formed. A transparent resin prepared so as not to enter was placed, a stamper was placed on the resin, and spin-coating was performed at 2000 rpm for 4 seconds to bond them together.
2. A high pressure mercury lamp (80 W / cm) was irradiated from the transparent resin stamper side at 400 mJ / cm 2 to cure the second ultraviolet curable resin composition.
3. Using a disk peeling device (Origin Electric Co., Ltd.), the transparent resin stamper was peeled off to produce a sample disk for evaluation.

（ａ）剥離性テスト
　ディスク剥離装置（オリジン電機（株）製）を使用して剥離性が悪い内径６０ｍｍでの剥離強度を計測器（ＦＧＣ－５Ｂ、日本電産シンボ（株）製）で測定することにより行った。剥離良好性の判断は下記基準で行った。
　　○・・・剥離強度１．５kgf以下　　
　　×・・・剥離強度１．５kgf超 (A) Peelability test Using a disk peeler (Origin Electric Co., Ltd.), measure the peel strength at an inner diameter of 60 mm with poor peelability using a measuring instrument (FGC-5B, Nidec Symbo Co., Ltd.). It was done by doing. Judgment of good peeling was made according to the following criteria.
○ ・ ・ ・ Peel strength 1.5kgf or less
× ・ ・ ・ Peel strength over 1.5kgf

（ｂ）耐久性（耐湿性）テスト
　耐湿性テストとしては、前記の工程で作製した剥離後のサンプルディスクを８０℃８５％の高温多湿下の条件で９６時間放置した後、２４時間室温で保存し、高温多湿下に置く前と室温で保存した後で記録膜から剥離していないか否かで判定した。
　　○・・・密着　　
　　×・・・剥離 (B) Durability (moisture resistance) test As a moisture resistance test, the peeled sample disk produced in the above-mentioned process was allowed to stand for 96 hours under conditions of high temperature and high humidity of 80 ° C and 85%, and then stored at room temperature for 24 hours. Then, it was judged whether or not it was peeled off from the recording film before being placed under high temperature and high humidity and after being stored at room temperature.
○ ・ ・ ・ Close contact
× ・ ・ ・ Peeling

　表１から明らかなように本発明の紫外線硬化型樹脂組成物及びその硬化物である実施例１～３は、比較例１と比較して高温多湿下の状況でも密着力に優れている。また、多官能のアクリレートモノマーを用いた比較例２、比較例３に比べ特に剥離性にすぐれている樹脂組成物となっていることが確認された。 As is clear from Table 1, the ultraviolet curable resin composition of the present invention and Examples 1 to 3, which are cured products thereof, are excellent in adhesion even under conditions of high temperature and humidity as compared with Comparative Example 1. Further, it was confirmed that the resin composition was particularly excellent in peelability as compared with Comparative Examples 2 and 3 using a polyfunctional acrylate monomer.

　本発明の紫外線硬化型樹脂組成物及びその硬化物は、剥離性に優れ、かつ高温多湿下に置かれても反射膜層又は誘電体層に密着している２Ｐ剤として有用である。また、接着層を省略して１液で中間層を形成させることを可能とする、紫外線硬化型樹脂を提供することができる。 The ultraviolet curable resin composition of the present invention and its cured product are excellent as a peelable and useful as a 2P agent that is in close contact with a reflective film layer or a dielectric layer even when placed under high temperature and high humidity. Further, it is possible to provide an ultraviolet curable resin capable of omitting the adhesive layer and forming the intermediate layer with one liquid.

　本発明を特定の態様を参照して詳細に説明したが、本発明の精神と範囲を離れることなく様々な変更および修正が可能であることは、当業者にとって明らかである。
　なお、本出願は、２００９年３月３１日付で出願された日本特許出願（特願２００９－０８４５３４）に基づいており、その全体が引用により援用される。また、ここに引用されるすべての参照は全体として取り込まれる。 Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on March 31, 2009 (Japanese Patent Application No. 2009-084534), which is incorporated by reference in its entirety. Also, all references cited herein are incorporated as a whole.

Claims (7)

　（Ａ）１分子中に２個以上のイソシアネート基を有する有機イソシアネートと水酸基を有する３官能以上の（メタ）アクリレートを反応させて得られる６官能以上のウレタン（メタ）アクリレート、（Ｂ）３官能以下の（メタ）アクリレートモノマー、及び（Ｃ）光重合開始剤を含有する多層光ディスク用紫外線硬化型樹脂組成物。 (A) A hexafunctional or higher functional urethane (meth) acrylate obtained by reacting an organic isocyanate having two or more isocyanate groups in one molecule with a trifunctional or higher functional (meth) acrylate having a hydroxyl group, (B) trifunctional The ultraviolet curable resin composition for multilayer optical disks containing the following (meth) acrylate monomers and (C) a photoinitiator. 　１分子中に２個以上のイソシアネート基を有する有機イソシアネートと水酸基を有する３官能以上の（メタ）アクリレートを反応させて得られる６官能以上のウレタン（メタ）アクリレート（Ａ）において、有機イソシアネートが、イソホロンジイソシアネート、ヘキサメチレンジイソシアネート、トリレンジイソシアネート、キシレンジイソシアネート、ジフェニルメタン－４，４’－ジイソシアネート、ジシクロペンタニルジイソシアネート、及び式（１）
Figure JPOXMLDOC01-appb-C000001
（式中、Ｒは、
Figure JPOXMLDOC01-appb-C000002
、
Figure JPOXMLDOC01-appb-C000003
、
Figure JPOXMLDOC01-appb-C000004
、
Figure JPOXMLDOC01-appb-C000005
又は
Figure JPOXMLDOC01-appb-C000006
 を示す。）で表わされる３官能イソシアネートからなる群から選択される１種もしくは２種以上である、請求項１記載の多層光ディスク用紫外線硬化型樹脂組成物。 In the hexafunctional or higher urethane (meth) acrylate (A) obtained by reacting an organic isocyanate having two or more isocyanate groups in one molecule with a trifunctional or higher functional (meth) acrylate having a hydroxyl group, the organic isocyanate is Isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, diphenylmethane-4,4′-diisocyanate, dicyclopentanyl diisocyanate, and formula (1)
Figure JPOXMLDOC01-appb-C000001
(Wherein R is
Figure JPOXMLDOC01-appb-C000002
,
Figure JPOXMLDOC01-appb-C000003
,
Figure JPOXMLDOC01-appb-C000004
,
Figure JPOXMLDOC01-appb-C000005
Or
Figure JPOXMLDOC01-appb-C000006
 Indicates. The ultraviolet curable resin composition for multilayer optical disks according to claim 1, which is one or more selected from the group consisting of trifunctional isocyanates represented by: 　１分子中に２個以上のイソシアネート基を有する有機イソシアネートと水酸基を有する３官能以上の（メタ）アクリレートを反応させて得られるウレタン（メタ）アクリレート（Ａ）において、水酸基を有する３官能以上の（メタ）アクリレートがペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ペンタエリスリトールのε－カプロラクトン付加物のトリ（メタ）アクリレート、及びジペンタエリスリトールのε－カプロラクトン付加物のトリ、テトラ又はペンタ（メタ）アクリレートからなる群から選択される１種もしくは２種以上である、請求項１又は請求項２記載の多層光ディスク用紫外線硬化型樹脂組成物。 In urethane (meth) acrylate (A) obtained by reacting an organic isocyanate having two or more isocyanate groups in one molecule with a trifunctional or higher functional (meth) acrylate having a hydroxyl group, a trifunctional or higher functional group having a hydroxyl group ( (Meth) acrylate is pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri (meth) acrylate of ε-caprolactone adduct of pentaerythritol, and tri, tetra of ε-caprolactone adduct of dipentaerythritol Or the ultraviolet curable resin composition for multilayer optical disks of Claim 1 or Claim 2 which is 1 type (s) or 2 or more types selected from the group which consists of a penta (meth) acrylate. 　３官能以下の（メタ）アクリレートモノマー（Ｂ）がイソボルニルアクリレート、ネオペンチルグリコールジアクリレート、プロピレンオキサイド変性ネオペンチルグリコールジアクリレート、トリシクロデカンジメタノールジアクリレート、及びヒドロピバルアルデヒド変性トリメチロールプロパンジアクリレートからなる群から選択される１種もしくは２種以上である、請求項１乃至請求項３のいずれか一項に記載の多層光ディスク用紫外線硬化型樹脂組成物。 Trifunctional or lower (meth) acrylate monomer (B) is isobornyl acrylate, neopentyl glycol diacrylate, propylene oxide modified neopentyl glycol diacrylate, tricyclodecane dimethanol diacrylate, and hydropivalaldehyde modified trimethylolpropane The ultraviolet curable resin composition for multilayer optical disks according to any one of claims 1 to 3, wherein the ultraviolet curable resin composition is one or more selected from the group consisting of diacrylates. 　樹脂組成物全体に対し、（Ａ）成分５～８０重量％、（Ｂ）成分１０～８０重量％、（Ｃ）成分１～１５重量％を含有する請求項１乃至請求項４のいずれか一項に記載の多層光ディスク用紫外線硬化型樹脂組成物。 5. The resin composition according to claim 1, comprising 5 to 80% by weight of component (A), 10 to 80% by weight of component (B), and 1 to 15% by weight of component (C) with respect to the entire resin composition. Item 4. The ultraviolet curable resin composition for multilayer optical disks according to the item. 　請求項１乃至請求項５のいずれか一項に記載の多層光ディスク用紫外線硬化型樹脂組成物に活性エネルギー線を照射して得られる硬化物。 Hardened | cured material obtained by irradiating an active energy ray to the ultraviolet curable resin composition for multilayer optical disks as described in any one of Claims 1 thru | or 5. 　請求項６記載の硬化物を有する多層光ディスク。 A multilayer optical disk having the cured product according to claim 6.
PCT/JP2010/055760 2009-03-31 2010-03-30 Uv-curable resin composition for use in multi-layer optical disc Ceased WO2010113976A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0559139A (en) * 1991-09-04 1993-03-09 Dainippon Ink & Chem Inc UV curable resin composition
JP2003096146A (en) * 2001-07-18 2003-04-03 Mitsubishi Rayon Co Ltd Active energy ray curable composition, and optical disk
JP4193916B2 (en) * 2007-03-23 2008-12-10 Ｄｉｃ株式会社 Ultraviolet curable composition for optical disc intermediate layer and optical disc

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CN1160431C (en) * 1998-08-20 2004-08-04 Dsm有限公司 adhesive for optical disk

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0559139A (en) * 1991-09-04 1993-03-09 Dainippon Ink & Chem Inc UV curable resin composition
JP2003096146A (en) * 2001-07-18 2003-04-03 Mitsubishi Rayon Co Ltd Active energy ray curable composition, and optical disk
JP4193916B2 (en) * 2007-03-23 2008-12-10 Ｄｉｃ株式会社 Ultraviolet curable composition for optical disc intermediate layer and optical disc

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