WO2010143568A1 - Optical disc and ultraviolet-curable composition for intermediate layer of optical disc - Google Patents

Optical disc and ultraviolet-curable composition for intermediate layer of optical disc Download PDF

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Publication number
WO2010143568A1
WO2010143568A1 PCT/JP2010/059329 JP2010059329W WO2010143568A1 WO 2010143568 A1 WO2010143568 A1 WO 2010143568A1 JP 2010059329 W JP2010059329 W JP 2010059329W WO 2010143568 A1 WO2010143568 A1 WO 2010143568A1
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ultraviolet curable
layer
curable composition
meth
intermediate layer
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PCT/JP2010/059329
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French (fr)
Japanese (ja)
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直明 飯岡
伊藤 大介
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Dic株式会社
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Priority to JP2011518468A priority Critical patent/JPWO2010143568A1/en
Publication of WO2010143568A1 publication Critical patent/WO2010143568A1/en

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    • GPHYSICS
    • G11INFORMATION STORAGE
    • G11BINFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00Recording 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
    • G11B7/24Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252Record 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
    • GPHYSICS
    • G11INFORMATION STORAGE
    • G11BINFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00Recording 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
    • G11B7/24Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/2403Layers; Shape, structure or physical properties thereof
    • G11B7/24035Recording layers
    • G11B7/24038Multiple laminated recording layers
    • GPHYSICS
    • G11INFORMATION STORAGE
    • G11BINFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00Recording 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
    • G11B7/24Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/26Apparatus or processes specially adapted for the manufacture of record carriers

Definitions

  • the present invention provides an optical disc that has at least two or more light reflecting layers and performs recording or reproduction with a semiconductor laser (hereinafter referred to as a blue laser) having an oscillation wavelength in the range of 370 nm to 430 nm, and the light reflecting layer.
  • a semiconductor laser hereinafter referred to as a blue laser
  • the present invention relates to an ultraviolet curable composition suitable for an intermediate layer.
  • a DVD Digital Versatile Disc
  • CD Compact Disc
  • High-density recording methods and optical discs for the next generation of DVD have been studied, and high-density recording using a new optical disc structure using a blue laser with a shorter wavelength and a high numerical aperture optical system than DVD.
  • a scheme has been proposed. Even in such a high-density recording type optical disk, a multilayer optical disk having two or more information recording portions is required in order to realize further higher density.
  • a concavo-convex pattern such as pits and grooves is usually formed on a substrate, and a light reflecting layer is laminated on the substrate to form a first information recording portion.
  • An intermediate layer is provided on the recording layer with a cured film of an ultraviolet curable composition or the like, and a second unevenness pattern is formed on the intermediate layer to provide a second information recording portion.
  • the intermediate layer on which the concave / convex pattern is provided is composed of, for example, an ultraviolet curable composition containing a trifunctional or higher functional urethane (meth) acrylate and a tetrafunctional or higher functional polyfunctional (meth) acrylate.
  • an ultraviolet curable composition containing a specific amount of polyfunctional (meth) acrylate, monofunctional (meth) acrylate, alicyclic (meth) acrylate and methacrylate (refer to Patent Document 2) Is disclosed.
  • the intermediate layer made of these ultraviolet curable compositions has a very good releasability and is preferably a composition capable of forming an uneven pattern such as pits and grooves, and is formed from the intermediate layer made of the composition.
  • An optical disk exhibits suitable signal characteristics. However, when applied to an optical disk that is recorded or reproduced by a blue laser, the signal characteristics may be deteriorated in a high temperature environment.
  • the problem to be solved by the present invention is to provide an optical disc capable of suitably maintaining signal characteristics even in a high temperature environment.
  • an ultraviolet curable composition capable of suppressing the generation of volatile components even in a high temperature environment, providing an optical disc capable of suitably maintaining signal characteristics, and capable of forming an intermediate layer having good peelability from a stamper. It is in.
  • the substrate has at least a first light reflection layer, an intermediate layer composed of a cured film of an ultraviolet curable composition, a second light reflective layer, and a light transmission layer in this order, and the ultraviolet curable composition
  • An optical disc in which an intermediate layer composed of a cured film of an object is directly laminated with the second light reflecting layer and reproduces information by entering a blue laser from the light transmitting layer side, wherein the second light reflecting layer
  • the cured film of the ultraviolet curable composition forming the intermediate layer on which is laminated has a weight reduction rate of 3.5% by mass or less when left in an environment of 110 ° C. for 1 hour after ultraviolet curing.
  • An optical disc is provided.
  • the present invention further includes, on the substrate, at least a first light reflection layer, an intermediate layer composed of a cured film of an ultraviolet curable composition, a second light reflection layer, and a light transmission layer in this order.
  • An intermediate layer made of a cured film of a curable composition is directly laminated with the second light reflecting layer, and the second cured film of the optical disc that reproduces information by injecting a blue laser from the light transmitting layer side.
  • An ultraviolet curable composition to be formed comprising an ultraviolet curable compound and a polymerization initiator, wherein the content of the polymerization initiator with respect to 100 parts by mass of the ultraviolet curable compound is 2 to 10 parts by mass, and the molecular weight is Provided is an ultraviolet curable composition for an optical disc intermediate layer, wherein the content of a polymerization initiator of 215 or less is 5% by mass or less.
  • the optical disc of the present invention hardly deteriorates signal characteristics even in a high temperature environment, and can suitably reproduce a signal.
  • the ultraviolet curable composition for an optical disc intermediate layer of the present invention since generation of volatile components can be suppressed even under a high temperature environment, there is little pollution to the environment and the releasability from the stamper is good. Furthermore, since the weight loss due to the generation of volatile components can be suppressed, it is possible to realize an optical disc that can suitably maintain signal characteristics even in a high temperature environment.
  • the optical disk of the present invention comprises, on the substrate, at least a first light reflecting layer, an intermediate layer composed of a cured film of an ultraviolet curable composition, a second light reflecting layer and a light transmitting layer in this order, and the ultraviolet curable type
  • An intermediate layer made of a cured film of the composition is directly laminated with the second light reflecting layer, and is an optical disc that reproduces information by injecting a blue laser from the light transmitting layer side, and the second light reflecting layer
  • the cured film of the ultraviolet curable composition forming the intermediate layer on which is laminated is an optical disc having a weight reduction rate of 3.5% by mass or less when left in a 110 ° C. environment for 1 hour after ultraviolet curing.
  • (meth) acrylate refers to acrylate or methacrylate
  • (meth) acryloyl group refers to acryloyl group or methacryloyl group.
  • the intermediate layer is a layer that is provided in a portion other than the surface layer of the optical disc and has other layers on the front and back surfaces.
  • a disk-shaped circular resin substrate can be used, and polycarbonate can be preferably used as the resin.
  • the optical disk is read-only, pits for recording information on the substrate are formed on the surface laminated with the light reflecting layer.
  • a substrate having a thickness of about 1.1 mm can be used.
  • both the first light reflecting layer and the second light reflecting layer may be any one that can reflect a laser beam and form an optical disk that can be recorded and reproduced.
  • a metal such as gold, copper, or aluminum or an alloy thereof, or an inorganic compound such as silicon can be used.
  • silver or an alloy containing silver as a main component is preferably used because of the high reflectance of light in the vicinity of 400 nm.
  • the thickness of the light reflecting layer is preferably about 10 to 60 nm.
  • the same light reflecting layer can be suitably used.
  • a cured film of an ultraviolet curable composition is provided as an intermediate layer provided between the first light reflecting layer and the second light reflecting layer and directly laminated with the second light reflecting layer. Having an intermediate layer.
  • the intermediate layer on which the second light reflecting layer is laminated is an intermediate layer on which a concave and convex pattern such as pits and grooves is formed on the surface, and is a layer that forms an information recording site together with the second light reflecting layer. .
  • pits for recording information are provided on the surface of the intermediate layer.
  • the weight reduction rate when left in a 110 ° C. environment for 1 hour after ultraviolet curing is 3.5% by mass or less, preferably 3.
  • a cured film of an ultraviolet curable composition of 0% by mass or less, more preferably 2.5% by mass or less is used.
  • the weight reduction rate after standing for 1 hour in a 110 ° C. environment after UV curing can be measured according to ASTM Designation: D5403.
  • ASTM D5403 the weight loss rate after standing for 1 hour in a 110 ° C. environment after UV curing is expressed as Potential Volatiles, and is determined from the following equation.
  • Potential Volatiles 100 [(CD) / (BA)]
  • C glass substrate + intermediate layer after curing
  • D glass substrate + intermediate layer after standing for 1 hour in 110 ° C. environment .
  • the cured film of the ultraviolet curable composition forming the intermediate layer on which the second light reflecting layer is laminated preferably has an elastic modulus at 25 ° C. of 800 to 3000 MPa, and more preferably 1500 to 2500 MPa.
  • the ultraviolet curable composition used for the intermediate layer on which the second light reflecting layer is laminated a composition containing an ultraviolet curable compound and a polymerization initiator and capable of obtaining a cured film having the above characteristics.
  • the UV-curable compound may be used as a UV-curable compound (meth) acrylate having three or more (meth) acryloyl groups in one molecule (hereinafter abbreviated as trifunctional (meth) acrylate) or in one molecule.
  • (Meth) acrylate having two (meth) acryloyl groups hereinafter abbreviated as bifunctional (meth) acrylate
  • (meth) acrylate having one (meth) acryloyl group in one molecule (Meth) acrylate monomers such as monofunctional (meth) acrylate), and (meth) such as epoxy (meth) acrylate and urethane (meth) acrylate
  • the chestnut rate oligomers can be used.
  • Examples of the tri- or higher functional (meth) acrylate used in the present invention include bis (2-acryloyloxyethyl) hydroxyethyl isocyanurate, bis (2-acryloyloxypropyl) hydroxypropyl isocyanurate, and bis (2-acryloyloxy).
  • trifunctional (meth) acrylate can be preferably used, and triol di- or tri (meth) acrylate obtained by adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of trimethylolpropane is an elastic property after curing. It is more preferable because the rate can be adjusted high.
  • bifunctional (meth) acrylate examples include 1,4-butanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate.
  • dipropylene glycol di (meth) acrylate is particularly preferable.
  • ultraviolet curable compounds such as N-vinyl pyrrolidone, N-vinyl caprolactam, vinyl ether monomer, and phosphate group-containing (meth) acrylate can be used as necessary.
  • Examples of monofunctional (meth) acrylates include ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, tridecyl (meth) acrylate, hexadecyl (meth) acrylate, and octadecyl.
  • (Meth) acrylate isoamyl (meth) acrylate, isodecyl (meth) acrylate, isostearyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-chloro-2-hydroxypropyl ( Aliphatic (meth) acrylates such as (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, nonylphenoxyethyl (meth) acrylate, 2- Roxy-3-phenoxypropyl (meth) acrylate, phenoxyethyl (meth) acrylate, aromatic (meth) acrylate such as benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, di Cyclopentenyloxyethyl (me
  • a (meth) acrylate monomer having three or more (meth) acryloyl groups in one molecule is ultraviolet.
  • the product is preferable because it is easy to adjust the weight reduction rate, elastic modulus, or viscosity range.
  • the content of trifunctional (meth) acrylate is more preferably 50 to 70% by mass. Further, the content of the monofunctional (meth) acrylate is more preferably 5% by mass or less, and particularly preferably 1% by mass or less.
  • a (meth) acrylate oligomer may be used in combination with these monomer components.
  • the (meth) acrylate oligomer is not particularly limited, and various urethane (meth) acrylates, epoxy (meth) acrylates, polyester (meth) acrylates, and polyether (meth) acrylates can be used.
  • urethane (meth) acrylate and epoxy (meth) acrylate can be preferably used because the (meth) acryloyl group concentration of the ultraviolet curable composition and the elastic modulus after curing are easily adjusted to a suitable range.
  • the number of cross-linking points, distance between cross-linking points, and cross-linking structure of the cured film can be suitably controlled, and curing with less change in shape such as warping can be achieved by imparting appropriate flexibility to the cured film.
  • a film can be formed.
  • the urethane (meth) acrylate used in the present invention includes a compound having two or more isocyanate groups in the molecule, a compound having a hydroxyl group and a (meth) acryloyl group, and two or more hydroxyl groups in the molecule.
  • a urethane (meth) acrylate obtained from a compound having a diol can be preferably used.
  • urethane (meth) acrylate obtained by reacting a compound having a hydroxyl group and a (meth) acryloyl group with a compound having two isocyanate groups in the molecule can also be preferably used.
  • Examples of compounds having two or more isocyanate groups in the molecule include tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, bis (isocyanatomethyl) cyclohexane, cyclohexane diisocyanate, bis (isocyanatocyclohexyl) methane, and isophorone.
  • Examples thereof include polyisocyanates such as diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, and m-phenylene diisocyanate.
  • a diisocyanate compound having two isocyanate groups in the molecule can be preferably used, and tolylene diisocyanate is particularly preferable because it does not deteriorate the hue and does not decrease the light transmittance.
  • Examples of the compound having a hydroxyl group and a (meth) acryloyl group include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and these (meth) acrylates and 2
  • a compound obtained by reacting with a compound having at least one hydroxyl group may also be used.
  • it may be a compound obtained by reacting a compound having two or more hydroxyl groups with (meth) acrylic acid.
  • Polyols are preferably used as the compound having two or more hydroxyl groups, and specific examples thereof include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3- Propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, eopentyl glycol, 3-methyl-1,5-pentanediol, 2,3,5-trimethyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1, 8-octanediol, trimethylolpropane, pentaerythritol, sorbitol, mannitol, glycerin,
  • polyether polyols having ether bonds polyether polyols having ether bonds
  • polyester polyols having ester bonds obtained by reaction with polybasic acids and ring-opening polymerization of cyclic esters or polycarbonate polyols having carbonate bonds obtained by reaction with carbonates.
  • At least a part of these polyols preferably 15 mol% or more in the total amount of polyols, more preferably 30 mol% or more in the total amount of polyols, preferably has a molecular weight of 500-2500.
  • polyether polyol examples include polytetramethylene glycol as a ring-opening polymer of a cyclic ether such as tetrahydrofuran, in addition to the multimers of the polyols, and ethylene polyol, propylene oxide, 1 , 2-butylene oxide, 1,3-butylene oxide, 2,3-butylene oxide, tetrahydrofuran, styrene oxide, an adduct of alkylene oxide such as epichlorohydrin, and the like.
  • polyester polyol examples include a reaction product of the above polyols with a polybasic acid such as maleic acid, fumaric acid, adipic acid, sebacic acid, and phthalic acid, and a ring-opening polymer of a cyclic ester such as caprolactone.
  • a polybasic acid such as maleic acid, fumaric acid, adipic acid, sebacic acid, and phthalic acid
  • a ring-opening polymer of a cyclic ester such as caprolactone.
  • polycarbonate polyol examples include the above polyols and alkylene carbonates such as ethylene carbonate, 1,2-propylene carbonate, and 1,2-butylene carbonate, or diphenyl carbonate, 4-methyldiphenyl carbonate, 4-ethyldiphenyl carbonate, 4-propyldiphenyl carbonate, 4,4'-dimethyldiphenyl carbonate, 2-tolyl-4-tolyl carbonate, 4,4'-diethyldiphenyl carbonate, 4,4'-dipropyldiphenyl carbonate, phenyltoluyl carbonate, bischlorophenyl carbonate Diaryl carbonates such as phenyl chlorophenyl carbonate, phenyl naphthyl carbonate, dinaphthyl carbonate, etc.
  • alkylene carbonates such as ethylene carbonate, 1,2-propylene carbonate, and 1,2-butylene carbonate, or diphenyl carbonate
  • 4-methyldiphenyl carbonate 4-e
  • Dialkyl carbonate such as dicarbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, di-t-butyl carbonate, di-n-amyl carbonate, diisoamyl carbonate, etc.
  • Examples include reactants.
  • the polyol to be used may be one kind or two or more kinds may be used in combination, but urethane (meth) acrylate using two or more kinds of polyether polyol, polyester polyol and polycarbonate polyol is preferable, and two kinds are used in combination. More preferably.
  • urethane (meth) acrylate using two or more kinds of polyether polyol, polyester polyol and polycarbonate polyol is preferable, and two kinds are used in combination. More preferably.
  • the content of each polyol when used in combination with the polyol is preferably 20 to 90% by mass, more preferably 30 to 80% by mass, based on the total amount of polyol used.
  • the polyester polyol content is preferably 10 to 70% by mass, more preferably 20 to 60% by mass.
  • the urethane (meth) acrylate used in the present invention is preferably a structure having no aromatic ring, since the transparency becomes high.
  • urethane (meth) acrylate used in the present invention, polyether skeleton urethane acrylate, DIC Corporation FAU-742TP, FAU-306, polyester skeleton urethane acrylate, Cognis Japan Co., Ltd.
  • Photomer Preferred examples include -6892 and Ebecryl-8405 manufactured by Daicel Cytec Co., Ltd.
  • the content of urethane (meth) acrylate in the ultraviolet curable composition of the present invention is preferably 20% by mass or less in the ultraviolet curable compound contained in the ultraviolet curable composition, and is preferably 5 to 15% by mass. It is particularly preferred.
  • the molecular weight (Mw) measured by gel permeation chromatography (GPC) of urethane (meth) acrylate used in the present invention is preferably 1000 to 20000, and more preferably 1500 to 10,000. Thereby, the durability and light resistance of the optical disk using the ultraviolet curable composition of the present invention are further improved. If the molecular weight is high, the viscosity becomes high and handling becomes difficult. On the other hand, when the molecular weight is low, the distance between cross-linking points is shortened, so that the curing shrinkage is increased.
  • the GPC uses HLC-8020 manufactured by Tosoh Corporation, the column uses GMHxl-GMHxl-G200Hxl-G1000Hxlw, the solvent uses THF, and the column temperature is 40 ° C. at a flow rate of 1.0 ml / min.
  • the detector temperature is 30 ° C., and the molecular weight is measured in terms of standard polystyrene.
  • the urethane (meth) acrylate When the urethane (meth) acrylate is used, it is used at 40% by mass or less in the ultraviolet curable compound contained in the ultraviolet curable composition used for the intermediate layer on which the second light reflecting layer is laminated. It is particularly preferable that the content is 20% by mass or less.
  • epoxy (meth) acrylate used in the present invention any epoxy (meth) acrylate having the above characteristics can be used.
  • bisphenol type epoxy (meth) acrylate represented by the following formula (1) can be used.
  • Y represents —SO 2 —, —CH 2 —, —CH (CH 3 ) — or —C (CH 3 ) 2 —, and each Z independently represents a hydrogen atom or —CH 3 .
  • N represents 0 or an integer of 1 or more.
  • bisphenol type epoxy (meth) acrylate examples include bisphenol A type epoxy resins such as Epicoat 802, 1001, and 1004 manufactured by Yuka Shell Epoxy, and bisphenol F type epoxy resins such as Epicoat 4001P, 4002P, and 4003P, ) Epoxy acrylate obtained by reaction with acrylic acid.
  • Y is -C (CH 3) 2 - a, more that n is bisphenol A type epoxy (meth) acrylate to the addition polymer of the structure is an integer of 0 or 1 to 6 and the main constituent preferable.
  • epoxy (meth) acrylates such as hydrogenated bisphenol A type and bisphenol F type can also be suitably used.
  • the molecular weight (Mw) measured by gel permeation chromatography (GPC) of the epoxy (meth) acrylate used in the present invention is preferably 500 to 3000, more preferably 800 to 1500.
  • GPC gel permeation chromatography
  • the GPC used was Sakai HLC-8020 manufactured by Tosoh Corporation, and the column used was GMHxl-GMHxl-G200Hxl-G1000Hxlw.
  • the solvent used was THF, the column temperature was 40 ° C., the detector temperature was 30 ° C., and the molecular weight was measured in terms of standard polystyrene at a flow rate of 1.0 ml / min.
  • the ultraviolet curable composition used for the intermediate layer on which the second light reflecting layer is laminated preferably has a B-type viscosity at 25 ° C. of 1000 mPa or less, particularly preferably 50 to 500 mPa.
  • the thickness of the intermediate layer between the reflective films in the optical disk is formed with a thickness of about 5 to 30 ⁇ m. By setting the viscosity range, the intermediate layer with the thickness can be suitably formed.
  • the (meth) acryloyl group concentration of the ultraviolet curable composition is preferably 4 to 10 mmol / g.
  • the content of the polymerization initiator used with respect to 100 parts by mass of the ultraviolet curable compound contained in the ultraviolet curable composition Is preferably 2 to 10 parts by mass, and more preferably 3 to 8 parts by mass.
  • content of the polymerization initiator whose molecular weight is 215 or less into the said polymerization initiator into 5 mass parts or less, and it is still more preferable to set it as 4 mass parts or less.
  • the polymerization initiator having a molecular weight exceeding 215 is preferably contained in an amount of 1 part by mass or more, more preferably 1 to 5 parts by mass, and more preferably 1 to 3 parts by mass with respect to 100 parts by mass of the ultraviolet curable compound. It is particularly preferred.
  • a polymerization initiator having a molecular weight of 215 or less may not be contained, but it is preferable to use 1 part by mass or more in combination with a polymerization initiator having a molecular weight exceeding 215 because stable signal characteristics can be easily obtained.
  • by adjusting the polymerization initiator in the ultraviolet curable composition forming the intermediate layer on which the second light reflecting layer is laminated as described above when exposed to high temperatures during the production process. However, it is difficult to reduce the weight of the optical disk, and stable signal characteristics can be obtained even in a high temperature and high humidity environment when the optical disk is formed. Further, it is possible to reduce the contamination of the exhaust equipment due to volatile components during the production of the optical disk.
  • Examples of the polymerization initiator having a molecular weight exceeding 215 include benzoin isobutyl ether, benzyl, 1-hydroxycyclohexyl phenyl ketone, benzoin ethyl ether, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one.
  • 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone And at least one selected from 2,4,6-trimethylbenzoyldiphenylphosphine can be preferably used.
  • oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone and 2,4,6-trimethylbenzoyldiphenylphosphine It is preferable to use these, and it is particularly preferable to use these in combination.
  • Examples of the polymerization initiator having a molecular weight of 215 or less include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, benzoin methyl ether, benzophenone, benzyl, phenyl Examples include glyoxylic acid methyl ester. Of these, 1-hydroxy-cyclohexyl-phenyl-ketone is preferably used in combination with a polymerization initiator having a molecular weight exceeding 215.
  • a surfactant in the ultraviolet curable composition used for the intermediate layer on which the second light reflecting layer is laminated, as necessary, a surfactant, a leveling agent, a thermal polymerization inhibitor, a hindered phenol, a phosphate, Antioxidants such as phyto, and light stabilizers such as hindered amines can also be used.
  • sensitizers include trimethylamine, methyldimethanolamine, triethanolamine, p-dimethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N-dimethylbenzylamine and 4,4′-bis (diethylamino) benzophenone or the like can be used, and further, an amine that does not cause an addition reaction can be used in combination with the photopolymerizable compound.
  • the intermediate layer made of the cured film of the ultraviolet curable composition on which the second light reflecting layer is laminated may be directly laminated with the first light reflecting layer.
  • the intermediate layer on which the second light reflecting layer is laminated it has a second intermediate layer laminated on the first light reflecting layer, so that suitable pit formation and light reflecting layer and field adhesion can be achieved. Or, it becomes easy to suitably adjust a plurality of required characteristics such as suppression of warpage of the optical disk.
  • an intermediate layer formed from a cured film of an ultraviolet curable composition as the second intermediate layer laminated with the first light reflecting layer.
  • the cured film of the ultraviolet curable composition used for the first intermediate layer preferably has an elastic modulus at 25 ° C. of 500 to 3000 MPa, more preferably 1000 to 2000 MPa.
  • the second intermediate layer is preferably 300 MPa or more, preferably 500 MPa or more lower than the intermediate layer on which the second light reflecting layer is laminated.
  • the thickness of the intermediate layer between the reflective films in the optical disk is formed with a thickness of about 5 to 30 ⁇ m.
  • the second intermediate layer is By forming the second light reflection layer to be thicker than the intermediate layer on which the second light reflection layer is laminated, it becomes easy to reduce the warp suitably. Therefore, the thickness of the intermediate layer on which the second light reflecting layer is laminated is set to 10 ⁇ m or less, preferably 2 to 5 ⁇ m, and the thickness of the second intermediate layer is set to about 3 to 25 ⁇ m thicker than this. It is preferable.
  • the ultraviolet curable composition used for the second intermediate layer preferably has a B-type viscosity at 25 ° C. of 1000 mPa or less, particularly preferably 50 to 600 mPa. By setting the viscosity within the above range, an intermediate layer on which the second light reflecting layer is laminated can be suitably laminated on the second intermediate layer.
  • the second intermediate layer has a higher surface tension than the intermediate layer on which the second light reflecting layer is laminated.
  • the intermediate layer in which the second light reflection layer is laminated on the first intermediate layer can be suitably applied.
  • the UV curable composition used for the second intermediate layer can be suitably used from the UV curable compounds listed as the UV curable compounds used for the intermediate layer on which the second light reflecting layer is laminated.
  • the ultraviolet curable compound contains 40 to 80% by mass of a (meth) acrylate monomer having three or more (meth) acryloyl groups in one molecule and urethane (meth) acrylate is used, It is preferable that it is below mass%.
  • the polymerization initiator to be used is not particularly limited, and various polymerization initiators listed as polymerization initiators used for the intermediate layer on which the second light reflecting layer is laminated can be used.
  • the content of the polymerization initiator is preferably 2 to 10% by mass.
  • additives used for the intermediate layer on which the second light reflecting layer is laminated can be suitably used.
  • a light transmission layer is formed directly on the second light reflection layer on the intermediate layer on which the second light reflection layer is laminated or via another layer.
  • the light transmission layer it is preferable to efficiently transmit a blue laser having an oscillation wavelength of laser light of 370 to 430 nm, and a transmittance of 405 nm light is preferably 85% or more at a thickness of 100 ⁇ m. 90% or more is particularly preferable.
  • the thickness of the light transmission layer in the optical disk of the present invention may be appropriately adjusted according to the structure of the optical disk, and the total thickness of the intermediate layer and the light transmission layer formed in the optical disk is preferably 70 to 110 ⁇ m.
  • the thickness of the light transmission layer is usually set to about 100 ⁇ m, but the thickness greatly affects the light transmittance and signal reading and recording, and therefore needs to be sufficiently managed.
  • the light transmission layer may be formed of a single cured layer having the thickness or a plurality of layers may be laminated.
  • the light-transmitting layer in the optical disk of the present invention is less likely to warp during curing, and the error of the reproduction signal does not increase easily even when a load is applied for a long time, and the signal can be suitably reproduced by recovering the error over time. It is preferable to provide a simple optical disc.
  • an elastic modulus (25 ° C.) obtained by pressing with a load of 100 mN using a Vickers indenter with a ridge angle of 136 ° is 1500 MPa or less, preferably 50 to 1300 MPa, more preferably 400.
  • a light-transmitting layer having a pressure of ⁇ 900 MPa, most preferably 400-600 MPa can be preferably used.
  • the light transmission layer is less likely to warp during UV curing, and deformation is easily recovered even with a long-time load, so that information can be recorded / reproduced satisfactorily.
  • the elastic modulus using a Vickers indenter can be measured according to ISO standard ISO14577.
  • ISO14577 the elastic modulus obtained by pressing a Vickers indenter with a ridge-to-ridge angle of 136 ° is expressed as indentation elastic modulus EIT .
  • the plastic deformation rate is expressed as indentation creep CIT and is obtained from the following equation.
  • h1 indentation depth when the load reaches 100 mN
  • h2 indentation depth when the load is held for 60 seconds after reaching the load of 100 mN.
  • measurement can be performed using a Fisherscope HM2000 manufactured by Fischer Instruments.
  • the light transmission layer used in the present invention preferably has a plastic deformation rate of 30 to 90% when pressed with a load of 100 mN and held for 60 seconds using a Vickers indenter with a ridge angle of 136 °, and 40 to It is more preferably 90%, particularly preferably 40 to 60%.
  • the loss elastic modulus (E ′′) at 60 ° C. in the dynamic viscoelastic spectrum measured at a frequency of 3.5 Hz of the light transmission layer is preferably 10 MPa or less, and preferably 0.1 to 7 MPa. More preferred is 1-7 MPa. .
  • the loss elastic modulus at 60 ° C. is in this range, the error of the reproduction signal hardly increases even when a load is applied for a long time, and the signal is preferably easily reproduced by recovering the error with time.
  • the light transmission layer was punched into a JIS K 7127 test piece type 5 shape with a dumbbell cutter, and this test piece was used to measure dynamic viscoelasticity manufactured by Rheometrics. It can be measured with an apparatus RSA-II (frequency 3.5 Hz, temperature rising rate 3 ° C./min).
  • the loss tangent (tan ⁇ ) at 60 ° C. in the dynamic viscoelasticity spectrum measured above is preferably a light transmission layer of 0.25 or less, and preferably 0.01 to 0.20 or less. Particularly preferred.
  • the loss tangent at 60 ° C. is within this range, even when a load is applied for a long time, the error of the reproduction signal hardly increases, and the error is recovered over time, so that the signal reproduction is easily facilitated.
  • the intermediate layer and the light transmission layer of the optical disk of the present invention preferably efficiently transmit a blue laser having a laser light oscillation wavelength of 370 to 430 nm, and have a light transmittance of 405 nm at a thickness of 100 ⁇ m of 85. % Or more is preferable, and 90% or more is particularly preferable.
  • the optical disk of the present invention comprises, on the substrate, at least a first light reflecting layer, an intermediate layer composed of a cured film of an ultraviolet curable composition, a second light reflecting layer and a light transmitting layer in this order, and the ultraviolet curable type
  • the optical disc of the present invention may be either a reproduction-only disc or a recordable / reproducible disc.
  • information recording pits are provided on the substrate and an intermediate layer on which the second light reflecting layer is laminated.
  • a guide groove for tracking a laser beam called a recording track (groove), which is an information recording portion, is provided when a single circular resin substrate is injection-molded, and then on the substrate having the recording track.
  • the first light reflecting layer, the intermediate layer composed of the cured film of the ultraviolet curable composition, and the second light reflecting layer are sequentially laminated, and at least the light transmitting layer is provided on the second light reflecting layer.
  • pits are formed on the second intermediate layer.
  • a configuration in which a second intermediate layer made of a cured film of an ultraviolet curable composition is further provided between the first light reflecting layer and the intermediate layer made of a cured film of the ultraviolet curable composition is also preferable. Can be used.
  • the recordable / reproducible disc has a configuration in which an information recording layer is provided between the substrate and the first light reflecting layer and between the second intermediate layer and the second light reflecting layer.
  • a first light reflecting layer is formed on one circular resin substrate, then a first information recording layer such as a phase change film or a magneto-optical recording film is provided, and the first light reflecting layer is further provided.
  • an intermediate layer composed of a cured film of an ultraviolet curable composition on the layer, a second light reflecting layer, and a second information recording layer, and further forming a light transmitting layer on the layer, It can be set as the structure which has two layers of information recording layers.
  • both the read-only disc and the recordable / reproducible disc may have a structure in which three or more layers of information recording portions and information recording layers are further laminated.
  • the ultraviolet curable composition applied in forming the intermediate layer or the light transmitting layer by irradiating with ultraviolet rays for example, it can be performed by a continuous light irradiation method using a metal halide lamp, a high pressure mercury lamp, or the like, and described in US Pat. No. 5,904,795. It can also be performed by the flash irradiation method.
  • the flash irradiation method is more preferable in that it can be cured efficiently.
  • the accumulated light amount When irradiating with ultraviolet rays, it is preferable to control the accumulated light amount to be 0.05 to 1 J / cm 2 . More preferably accumulated light amount is 0.05 ⁇ 0.8J / cm 2, particularly preferably 0.05 ⁇ 0.6J / cm 2.
  • the ultraviolet curable composition used for the optical disk of the present invention is sufficiently cured even when the integrated light quantity is small, and does not cause tacking of the end face or surface of the optical disk, and further does not cause warping or distortion of the optical disk.
  • an information recording layer is provided on the light reflecting layer.
  • the information recording layer only needs to be capable of recording / reproducing information, and may be any of a phase change recording layer, a magneto-optical recording layer, and an organic dye recording layer.
  • the information recording layer is usually composed of a dielectric layer and a phase change film.
  • the dielectric layer is required to have a function of buffering heat generated in the phase change layer and a function of adjusting the reflectivity of the disk, and a mixed composition of ZnS and SiO 2 is used.
  • the phase change film causes a difference in reflectance between the amorphous state and the crystalline state due to the phase change of the film, and uses a Ge—Sb—Te, Sb—Te, or Ag—In—Sb—Te alloy. Can do.
  • the light transmission layer may be the outermost layer, but a hard coat layer may be further provided on the surface layer.
  • the hard coat layer is preferably thin from the viewpoint of warping of the optical disc, and is preferably 5 ⁇ m or less.
  • the signal error SER after applying a load to the surface of the light transmission layer is 10 ⁇ 2 or less because there are few signal reproduction failures.
  • a first light reflecting layer 2 and an intermediate layer 3 made of a cured film of an ultraviolet curable composition are formed on a substrate 1.
  • a two-layer type optical disc in which a second light reflecting layer 4 and a light transmitting layer 5 are stacked thereon, and a blue laser is incident from the light transmitting layer 5 side to record or reproduce information.
  • the configuration can be exemplified.
  • the thickness of the layer the sum of the thickness of the light transmission layer 5 and the thickness of the intermediate layer 3 is in the range of 100 ⁇ 10 ⁇ m.
  • the thickness of the substrate 1 is about 1.1 mm, and the light reflecting film is a thin film such as silver.
  • a hard coat layer 6 may be provided as the outermost layer.
  • the hard coat layer 6 is preferably a layer having high hardness and excellent wear resistance.
  • the thickness of the hard coat layer is preferably 1 to 5 ⁇ m, and more preferably 3 to 5 ⁇ m.
  • a configuration in which the layer 3 and the second intermediate layer 7 laminated with the first light reflection layer 2 are also preferable.
  • a substrate 1 having a guide groove for tracking a laser beam called a recording track is manufactured by injection molding a polycarbonate resin.
  • the first light reflecting layer 2 is formed on the surface of the substrate 1 on the recording track side by sputtering or vapor-depositing a silver alloy or the like.
  • An ultraviolet curable composition for forming the intermediate layer 3 having a recording track is applied thereon, and a mold for forming a recording track (groove) is bonded thereon, from one or both sides of the bonded disk.
  • the ultraviolet curable composition is cured by irradiating with ultraviolet rays.
  • the mold is peeled off, and the second light reflecting layer 4 is formed on the surface of the intermediate layer 3 on the side having the recording track (groove) by sputtering or vapor deposition of silver alloy or the like.
  • the ultraviolet curable composition After applying the ultraviolet curable composition, it is cured by ultraviolet irradiation to form the light transmission layer 5, thereby producing the optical disk of FIG.
  • a hard coat layer 6 is further formed thereon by spin coating or the like.
  • a substrate 1 having a guide groove for tracking laser light called a recording track (groove) is manufactured by injection molding polycarbonate resin.
  • the first light reflecting layer 2 is formed on the surface of the substrate 1 on the recording track side by sputtering or vapor-depositing a silver alloy or the like.
  • An intermediate layer is formed thereon.
  • a second intermediate layer 7 for laminating an intermediate layer 3 having a recording track is formed on the first light reflecting layer 2 formed on the substrate 1.
  • the second intermediate layer 7 is formed by applying an ultraviolet curable composition, irradiating ultraviolet rays from one or both sides of the disk, curing or semi-curing the ultraviolet curable composition, and having a recording track thereon.
  • An ultraviolet curable composition for forming the layer 3 is applied, a mold for forming a recording track (groove) is bonded thereon, and ultraviolet light is irradiated from one or both surfaces of the bonded disk, The ultraviolet curable composition is cured.
  • the mold is peeled off, and the second light reflecting layer 4 is formed on the surface of the intermediate layer 3 on the side having the recording track (groove) by sputtering or vapor deposition of silver alloy or the like.
  • the optical disk shown in FIG. 3 can be produced by applying the ultraviolet curable composition and then curing it by ultraviolet irradiation to form the light transmission layer 5. Even when a phase change recording layer is used for the light reflection layer, an optical disc can be produced by the same method as described above.
  • ⁇ Test method Method for measuring viscosity> About the ultraviolet curable composition, the viscosity in 25 degreeC was measured using the B-type viscosity meter (the Tokyo Keiki make, BM type
  • ⁇ Test method Measurement method of elastic modulus>
  • the UV curable composition was applied on a glass plate so that the cured coating film was 100 ⁇ 10 ⁇ m, and then 500 mJ / cm 2 in a nitrogen atmosphere using a metal halide lamp (with a cold mirror, lamp output 120 W / cm). And cured.
  • the elastic modulus of this cured coating film was measured with an automatic dynamic viscoelasticity measuring apparatus manufactured by TA Instruments Inc., and the dynamic elastic modulus E ′ at 25 ° C. was defined as the elastic modulus.
  • ⁇ Test method optical disk durability test>
  • the recording disk (groove) is formed and applied to the polycarbonate disk on which the reflective film made of an alloy containing silver as a main component is laminated with the ultraviolet curable composition dispenser of each example and each comparative example, and the transparent polycarbonate disk is stacked. Combined. Subsequently, it was rotated with a spin coater so that the film thickness of the cured coating film became 10 to 20 ⁇ m. Next, using a “flash irradiation device RC-800” manufactured by XENON, 15-shot ultraviolet rays were irradiated in air from the transparent substrate side to prepare optical disk samples using the respective compositions.
  • the number of PI errors of each obtained sample was measured, and then an environmental test was performed at 80 ° C. and 85% RH 96 hours using “Etac constant temperature and high humidity device SD01” manufactured by Espec. After the test, the number of PI errors in each sample was measured.
  • PI error ratio was measured by “SA300” manufactured by Audio Dev Co., Ltd.
  • the PI error ratio (number of PI errors after the environmental test / number of PI errors before the environmental test) was determined from the number of PI errors before and after the environmental test.
  • the oligomers in the table are as follows.
  • FAU-742TP urethane acrylate (urethane acrylate obtained by reacting tolylene diisocyanate / hydroxyethyl acrylate on both ends of polytetramethylene glycol having a molecular weight of 850)
  • Molecular weight Mw 3700, manufactured by DIC Corporation V5530: Bisphenol A type epoxy acrylate (epoxy acrylate in which acrylic acid is reacted on both ends of bisphenol A type epoxy resin having a molecular weight of 850)
  • DPGDA Dipropylene glycol diacrylate
  • Photor 4094 Glyceryl [4PO] triacrylate Cognis Japan Co., Ltd.
  • Photomer 4017 Hexadidiol diacrylate Cognis Japan Co., Ltd.
  • THFA Tetrahydrofurfuryl acrylate -Hydroxy-cyclohexyl-phenyl-ketone (molecular weight: 204.3)
  • Ciba Specialte Initiator B 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (molecular weight: 279.4) Ciba Specialty Chemicals Co., Ltd.
  • R represents a hydrogen atom or a methyl group, and m is 2 to 3.
  • Initiator D 2,4,6-trimethylbenzoyldiphenylphosphine oxide (molecular weight: 348)
  • Initiator E 2-hydroxy-2-methyl-1-phenyl-propan-1-one (molecular weight: 164.2) Ciba Specialty Chemicals Co., gallic acid: (Dainippon Sumitomo Pharma Co., Ltd.)
  • the optical discs of Examples 1 to 10 having a low weight loss rate of the intermediate layer had a small PI error ratio and good durability under a high temperature and high humidity environment.
  • Comparative Examples 1 to 4 had a large PI error ratio and were not durable in a high temperature and high humidity environment.

Abstract

Disclosed is an optical disc comprising a substrate and, successively formed thereon, at least a first light-reflecting layer, an intermediate layer comprising a cured film formed of a ultraviolet-curable composition, a second light-reflecting layer and a light-transmitting layer, wherein the intermediate layer comprising a cured film formed of a ultraviolet-curable composition is laminated directly on the second light-reflecting layer and a blue laser beam is inputted from the light-transmitting layer side to regenerate data. By this optical disc, wherein the cured film of the ultraviolet-curable composition constituting the intermediate layer, that is equipped with the second light-reflecting layer laminated thereon, shows a weight loss of 3.5 mass% or less when cured with ultraviolet light and then allowed to stand in an environment at 110°C for 1 hour, appropriate signal characteristics can be maintained even in a high-temperature environment.

Description

光ディスク及び光ディスク中間層用紫外線硬化型組成物Optical disk and ultraviolet curable composition for optical disk intermediate layer
 本発明は、少なくとも二以上の光反射層を有し、370nm~430nmの範囲内に発振波長を有する半導体レーザー(以下ブルーレーザーと称す)により記録又は再生を行う光ディスク、及び当該光反射層間に設けられる中間層に適した紫外線硬化型組成物に関する。 The present invention provides an optical disc that has at least two or more light reflecting layers and performs recording or reproduction with a semiconductor laser (hereinafter referred to as a blue laser) having an oscillation wavelength in the range of 370 nm to 430 nm, and the light reflecting layer. The present invention relates to an ultraviolet curable composition suitable for an intermediate layer.
 高密度記録可能な光ディスクとして主流となっているDVD(Digital Versatile Disc)は厚さ0.6mmの2枚の基板を接着剤で貼り合わせた構造を有している。DVDにおいては高密度化を達成するため、CD(Compact Disc)に比べ短波長の650nmのレーザーを用い、光学系も高開口数化している。 A DVD (Digital Versatile Disc), which is the mainstream as an optical disk capable of high density recording, has a structure in which two substrates with a thickness of 0.6 mm are bonded together with an adhesive. In order to achieve high density in a DVD, a 650 nm laser having a shorter wavelength is used compared to a CD (Compact Disc), and the optical system has a high numerical aperture.
 しかし、HDTV(high definition television)に対応した高画質の映像等を記録または再生する為には更なる高密度化が必要となる。DVDの次世代に位置する更なる高密度記録の方法及びその光ディスクの検討が行われており、DVDよりも更に短波長のブルーレーザー及び高開口数の光学系を用いる新しい光ディスク構造による高密度記録方式が提案されている。このような高密度記録方式の光ディスクにおいても更なる高密度化を実現するため、情報記録部位を二層以上設けた多層の光ディスクが求められている。 However, it is necessary to further increase the density in order to record or reproduce high-definition video or the like corresponding to HDTV (high definition television). High-density recording methods and optical discs for the next generation of DVD have been studied, and high-density recording using a new optical disc structure using a blue laser with a shorter wavelength and a high numerical aperture optical system than DVD. A scheme has been proposed. Even in such a high-density recording type optical disk, a multilayer optical disk having two or more information recording portions is required in order to realize further higher density.
 高密度記録方式の多層光ディスクにおいては、通常、基板上にピットやグルーブ等の凹凸パターンが形成され、当該基板上に光反射層を積層して第一の情報記録部位とし、当該第一の情報記録層上に紫外線硬化型組成物の硬化膜等により中間層を設け、当該中間層に二層目の凹凸パターンを形成して第二の情報記録部位が設けられる。 In a high-density recording type multi-layer optical disc, a concavo-convex pattern such as pits and grooves is usually formed on a substrate, and a light reflecting layer is laminated on the substrate to form a first information recording portion. An intermediate layer is provided on the recording layer with a cured film of an ultraviolet curable composition or the like, and a second unevenness pattern is formed on the intermediate layer to provide a second information recording portion.
 このような多層光ディスクにおいて凹凸パターンが設けられる中間層としては、例えば、3官能以上のウレタン(メタ)アクリレートと、4官能以上の多官能(メタ)アクリレートを含有する紫外線硬化型組成物からなるもの(特許文献1参照)や、多官能(メタ)アクリレート、単官能(メタ)アクリレート、脂環式(メタ)アクリレート及びメタクリレートを特定量含有する紫外線硬化型組成物からなるもの(特許文献2参照)が開示されている。 In such a multilayer optical disc, the intermediate layer on which the concave / convex pattern is provided is composed of, for example, an ultraviolet curable composition containing a trifunctional or higher functional urethane (meth) acrylate and a tetrafunctional or higher functional polyfunctional (meth) acrylate. (Refer to Patent Document 1), or composed of an ultraviolet curable composition containing a specific amount of polyfunctional (meth) acrylate, monofunctional (meth) acrylate, alicyclic (meth) acrylate and methacrylate (refer to Patent Document 2) Is disclosed.
 これら紫外線硬化型組成物からなる中間層は、極めて良好な剥離性を有し、好適にピットやグルーブ等の凹凸パターンを形成可能な組成物であり、当該組成物からなる中間層から形成される光ディスクは好適な信号特性を示すものである。しかし、ブルーレーザーにより記録又は再生する光ディスクに適用した場合に、高温環境下で信号特性が低下する場合があった。 The intermediate layer made of these ultraviolet curable compositions has a very good releasability and is preferably a composition capable of forming an uneven pattern such as pits and grooves, and is formed from the intermediate layer made of the composition. An optical disk exhibits suitable signal characteristics. However, when applied to an optical disk that is recorded or reproduced by a blue laser, the signal characteristics may be deteriorated in a high temperature environment.
特許4193916号公報Japanese Patent No. 4193916 特許4247696号公報Japanese Patent No. 4247696
 本発明が解決しようとする課題は、高温環境下においても信号特性を好適に保持できる光ディスクを提供することにある。 The problem to be solved by the present invention is to provide an optical disc capable of suitably maintaining signal characteristics even in a high temperature environment.
 さらに、高温環境下においても揮発成分の発生を抑制でき、信号特性を好適に保持できる光ディスクを与え、かつ、スタンパとの剥離性が良好な中間層を形成できる紫外線硬化型組成物を提供することにある。 Furthermore, it is possible to provide an ultraviolet curable composition capable of suppressing the generation of volatile components even in a high temperature environment, providing an optical disc capable of suitably maintaining signal characteristics, and capable of forming an intermediate layer having good peelability from a stamper. It is in.
 本発明においては、基板上に、少なくとも第一の光反射層、紫外線硬化型組成物の硬化膜からなる中間層、第二の光反射層及び光透過層を順に有し、前記紫外線硬化型組成物の硬化膜からなる中間層が前記第二の光反射層と直接積層され、前記光透過層側からブルーレーザーを入射して情報の再生を行う光ディスクであって、前記第二の光反射層が積層される中間層を形成する紫外線硬化型組成物の硬化膜が、紫外線硬化後に110℃環境下に1時間静置した際の重量減少率が3.5質量%以下であることを特徴とする光ディスクを提供する。 In the present invention, the substrate has at least a first light reflection layer, an intermediate layer composed of a cured film of an ultraviolet curable composition, a second light reflective layer, and a light transmission layer in this order, and the ultraviolet curable composition An optical disc in which an intermediate layer composed of a cured film of an object is directly laminated with the second light reflecting layer and reproduces information by entering a blue laser from the light transmitting layer side, wherein the second light reflecting layer The cured film of the ultraviolet curable composition forming the intermediate layer on which is laminated has a weight reduction rate of 3.5% by mass or less when left in an environment of 110 ° C. for 1 hour after ultraviolet curing. An optical disc is provided.
 また、本発明は、さらに、基板上に、少なくとも第一の光反射層、紫外線硬化型組成物の硬化膜からなる中間層、第二の光反射層及び光透過層を順に有し、前記紫外線硬化型組成物の硬化膜からなる中間層が前記第二の光反射層と直接積層され、前記光透過層側からブルーレーザーを入射して情報の再生を行う光ディスクの前記第二の硬化膜を形成する紫外線硬化型組成物であって、紫外線硬化性化合物と重合開始剤とを含有し、前記紫外線硬化性化合物100質量部に対する重合開始剤の含有量が2~10質量部であり、分子量が215以下の重合開始剤の含有量が、5質量%以下であることを特徴とする光ディスク中間層用紫外線硬化型組成物を提供する。 The present invention further includes, on the substrate, at least a first light reflection layer, an intermediate layer composed of a cured film of an ultraviolet curable composition, a second light reflection layer, and a light transmission layer in this order. An intermediate layer made of a cured film of a curable composition is directly laminated with the second light reflecting layer, and the second cured film of the optical disc that reproduces information by injecting a blue laser from the light transmitting layer side. An ultraviolet curable composition to be formed, comprising an ultraviolet curable compound and a polymerization initiator, wherein the content of the polymerization initiator with respect to 100 parts by mass of the ultraviolet curable compound is 2 to 10 parts by mass, and the molecular weight is Provided is an ultraviolet curable composition for an optical disc intermediate layer, wherein the content of a polymerization initiator of 215 or less is 5% by mass or less.
 本発明の光ディスクは、高温環境下においても信号特性の悪化が生じ難く、好適に信号再生が可能となる。また、本発明の光ディスク中間層用紫外線硬化型組成物によれば、高温環境下においても揮発成分の発生を抑制できるため、環境への汚染が少なく、また、スタンパとの剥離性が良好であり、さらに、揮発成分の発生による重量減少を抑制できるため高温環境下でも信号特性を好適に保持できる光ディスクを実現できる。 The optical disc of the present invention hardly deteriorates signal characteristics even in a high temperature environment, and can suitably reproduce a signal. In addition, according to the ultraviolet curable composition for an optical disc intermediate layer of the present invention, since generation of volatile components can be suppressed even under a high temperature environment, there is little pollution to the environment and the releasability from the stamper is good. Furthermore, since the weight loss due to the generation of volatile components can be suppressed, it is possible to realize an optical disc that can suitably maintain signal characteristics even in a high temperature environment.
 本発明の光ディスクは、基板上に、少なくとも第一の光反射層、紫外線硬化型組成物の硬化膜からなる中間層、第二の光反射層及び光透過層を順に有し、前記紫外線硬化型組成物の硬化膜からなる中間層が前記第二の光反射層と直接積層され、前記光透過層側からブルーレーザーを入射して情報の再生を行う光ディスクであり、前記第二の光反射層が積層される中間層を形成する紫外線硬化型組成物の硬化膜が、紫外線硬化後に110℃環境下に1時間静置した際の重量減少率が3.5質量%以下の光ディスクである。なお、本明細書中で(メタ)アクリレートとは、アクリレート又はメタクリレートをいい、同様に(メタ)アクリロイル基とは、アクリロイル基又はメタクリロイル基をいう。また、中間層とは、光ディスクの表層以外の部分に設けられ、表裏に他の層を有する層をいう。 The optical disk of the present invention comprises, on the substrate, at least a first light reflecting layer, an intermediate layer composed of a cured film of an ultraviolet curable composition, a second light reflecting layer and a light transmitting layer in this order, and the ultraviolet curable type An intermediate layer made of a cured film of the composition is directly laminated with the second light reflecting layer, and is an optical disc that reproduces information by injecting a blue laser from the light transmitting layer side, and the second light reflecting layer The cured film of the ultraviolet curable composition forming the intermediate layer on which is laminated is an optical disc having a weight reduction rate of 3.5% by mass or less when left in a 110 ° C. environment for 1 hour after ultraviolet curing. In the present specification, (meth) acrylate refers to acrylate or methacrylate, and similarly, (meth) acryloyl group refers to acryloyl group or methacryloyl group. The intermediate layer is a layer that is provided in a portion other than the surface layer of the optical disc and has other layers on the front and back surfaces.
[基板]
 本発明の光ディスクに使用する基板としては、ディスク形状の円形樹脂基板を使用でき、当該樹脂としてはポリカーボネートを好ましく使用できる。光ディスクが再生専用の場合には、基板上に情報記録を担うピットが光反射層と積層される表面に形成される。レーザー光の発振波長が370~430nmであるブルーレーザーにより情報の読み取りを行うブルーレイディスクとして使用する際には、1.1mm程度の厚さの基板が使用できる。
[substrate]
As the substrate used in the optical disk of the present invention, a disk-shaped circular resin substrate can be used, and polycarbonate can be preferably used as the resin. When the optical disk is read-only, pits for recording information on the substrate are formed on the surface laminated with the light reflecting layer. When used as a Blu-ray disc for reading information with a blue laser having a laser light oscillation wavelength of 370 to 430 nm, a substrate having a thickness of about 1.1 mm can be used.
[光反射層]
 本発明の光ディスクに使用する光反射層としては、第一の光反射層及び第二の光反射層共に、レーザー光を反射し、記録・再生が可能な光ディスクを形成できるものであればよく、例えば、金、銅、アルミニウムなどの金属又はその合金、シリコンなどの無機化合物を使用できる。なかでも、400nm近傍の光の反射率が高いことから銀又は銀を主成分とする合金を使用することが好ましい。光反射層の厚さは、10~60nm程度の厚さとすることが好ましい。また、光ディスクの更なる多層化により、第三、第四等の光反射層を設ける場合には、同様の光反射層を好適に用いることができる。
[Light reflection layer]
As the light reflecting layer used in the optical disk of the present invention, both the first light reflecting layer and the second light reflecting layer may be any one that can reflect a laser beam and form an optical disk that can be recorded and reproduced. For example, a metal such as gold, copper, or aluminum or an alloy thereof, or an inorganic compound such as silicon can be used. Of these, silver or an alloy containing silver as a main component is preferably used because of the high reflectance of light in the vicinity of 400 nm. The thickness of the light reflecting layer is preferably about 10 to 60 nm. In addition, when a third, fourth, etc. light reflecting layer is provided by further multilayering of the optical disk, the same light reflecting layer can be suitably used.
[中間層]
 本発明の光ディスクにおいては、第一の光反射層と第二の光反射層との間に設けられ、第二の光反射層と直接積層する中間層として、紫外線硬化型組成物の硬化膜からなる中間層を有する。当該第二の光反射層が積層される中間層は、表面にピットやグルーブ等の凹凸パターンが形成される中間層であり、当該第二の光反射層と共に情報記録部位を形成する層である。光ディスクが再生専用の場合には、当該中間層表面に情報記録を担うピットが設けられる。
[Middle layer]
In the optical disk of the present invention, a cured film of an ultraviolet curable composition is provided as an intermediate layer provided between the first light reflecting layer and the second light reflecting layer and directly laminated with the second light reflecting layer. Having an intermediate layer. The intermediate layer on which the second light reflecting layer is laminated is an intermediate layer on which a concave and convex pattern such as pits and grooves is formed on the surface, and is a layer that forms an information recording site together with the second light reflecting layer. . When the optical disc is read-only, pits for recording information are provided on the surface of the intermediate layer.
 本発明においては、前記第二の光反射層が積層される中間層として、紫外線硬化後に110℃環境下に1時間静置した際の重量減少率が3.5質量%以下、好ましくは3.0質量%以下、更に好ましくは2.5質量%以下である紫外線硬化型組成物の硬化膜を使用する。当該中間層に使用する紫外線硬化型組成物の硬化膜の重量減少率を当該範囲とすることにより、高温環境下においても信号特性の悪化が生じ難く、好適に信号再生が可能となる。 In the present invention, as the intermediate layer on which the second light reflection layer is laminated, the weight reduction rate when left in a 110 ° C. environment for 1 hour after ultraviolet curing is 3.5% by mass or less, preferably 3. A cured film of an ultraviolet curable composition of 0% by mass or less, more preferably 2.5% by mass or less is used. By setting the weight reduction rate of the cured film of the ultraviolet curable composition used for the intermediate layer in this range, signal characteristics are hardly deteriorated even in a high temperature environment, and signal reproduction can be suitably performed.
 紫外線硬化後に110℃環境下1時間静置した際の重量減少率は、ASTM規格のDesignation:D5403に従って測定することができる。
 ASTMのD5403において、紫外線硬化後に110℃環境下に1時間静置した際の重量減少率は、Potential Volatilesとして表され、次の式から求められる。
 Potential Volatiles=100[(C-D)/(B-A)]
 ここで、A:ガラス基板の重さ、B:ガラス基板+硬化前の中間層、C:ガラス基板+硬化後の中間層、D:ガラス基板+110℃環境下に1時間静置後の中間層、である。
The weight reduction rate after standing for 1 hour in a 110 ° C. environment after UV curing can be measured according to ASTM Designation: D5403.
In ASTM D5403, the weight loss rate after standing for 1 hour in a 110 ° C. environment after UV curing is expressed as Potential Volatiles, and is determined from the following equation.
Potential Volatiles = 100 [(CD) / (BA)]
Here, A: weight of glass substrate, B: glass substrate + intermediate layer before curing, C: glass substrate + intermediate layer after curing, D: glass substrate + intermediate layer after standing for 1 hour in 110 ° C. environment .
 第二の光反射層が積層される中間層を形成する紫外線硬化型組成物の硬化膜は、25℃における弾性率が800~3000MPaであることが好ましく、1500~2500MPaであることがより好ましい。当該中間層に使用する硬化膜の弾性率を当該範囲とすることにより、スタンパーから剥離しやすく、また硬化時の反りが小さいディスクとなる。 The cured film of the ultraviolet curable composition forming the intermediate layer on which the second light reflecting layer is laminated preferably has an elastic modulus at 25 ° C. of 800 to 3000 MPa, and more preferably 1500 to 2500 MPa. By setting the elastic modulus of the cured film used for the intermediate layer within the above range, the disk can be easily peeled off from the stamper and has a small warpage during curing.
 前記第二の光反射層が積層される中間層に使用する紫外線硬化型組成物としては、紫外線硬化性化合物と重合開始剤とを含有し、上記特性の硬化膜を得ることができる組成物を使用すればよく、紫外線硬化性化合物としては、一分子中に三以上の(メタ)アクリロイル基を有する(メタ)アクリレート(以下、三官能の(メタ)アクリレートと略記する。)や、一分子中に二個の(メタ)アクリロイル基を有する(メタ)アクリレート(以下、二官能の(メタ)アクリレートと略記する。)、一分子中に一の(メタ)アクリロイル基を有する(メタ)アクリレート(以下、単官能(メタ)アクリレートと略記する)等の(メタ)アクリレートモノマー、更には、エポキシ(メタ)アクリレートやウレタン(メタ)アクリレート等の(メタ)アクリレートオリゴマーを使用できる。 As the ultraviolet curable composition used for the intermediate layer on which the second light reflecting layer is laminated, a composition containing an ultraviolet curable compound and a polymerization initiator and capable of obtaining a cured film having the above characteristics. The UV-curable compound may be used as a UV-curable compound (meth) acrylate having three or more (meth) acryloyl groups in one molecule (hereinafter abbreviated as trifunctional (meth) acrylate) or in one molecule. (Meth) acrylate having two (meth) acryloyl groups (hereinafter abbreviated as bifunctional (meth) acrylate), (meth) acrylate having one (meth) acryloyl group in one molecule (Meth) acrylate monomers such as monofunctional (meth) acrylate), and (meth) such as epoxy (meth) acrylate and urethane (meth) acrylate The chestnut rate oligomers can be used.
 本発明に使用する三官能以上の(メタ)アクリレートとしては、例えば、ビス(2-アクリロイルオキシエチル)ヒドロキシエチルイソシアヌレート、ビス(2-アクリロイルオキシプロピル)ヒドロキシプロピルイソシアヌレート、ビス(2-アクリロイルオキシブチル)ヒドロキシブチルイソシアヌレート、ビス(2-メタクリロイルオキシエチル)ヒドロキシエチルイソシアヌレート、ビス(2-メタクリロイルオキシプロピル)ヒドロキシプロピルイソシアヌレート、ビス(2-メタクリロイルオキシブチル)ヒドロキシブチルイソシアヌレート、トリス(2-アクリロイルオキシエチル)イソシアヌレート、トリス(2-アクリロイルオキシプロピル)イソシアヌレート、トリス(2-アクリロイルオキシブチル)イソシアヌレート、トリス(2-メタクリロイルオキシエチル)イソシアヌレート、トリス(2-メタクリロイルオキシプロピル)イソシアヌレート、トリス(2-メタクリロイルオキシブチル)イソシアヌレート、トリメチロールプロパントリ(メタ)アクリレート、ジトリメチロールプロパンテトラ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(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、ジペンタエリスリトールヘキサ(メタ)アクリレート、トリメチロールプロパン1モルに3モル以上のエチレンオキサイドもしくはプロピレンオキサイドを付加して得たトリオールのジ又はトリ(メタ)アクリレート、ジペンタエリスリトールのポリ(メタ)アクリレート等の多官能(メタ)アクリレート、等を使用できる。 Examples of the tri- or higher functional (meth) acrylate used in the present invention include bis (2-acryloyloxyethyl) hydroxyethyl isocyanurate, bis (2-acryloyloxypropyl) hydroxypropyl isocyanurate, and bis (2-acryloyloxy). Butyl) hydroxybutyl isocyanurate, bis (2-methacryloyloxyethyl) hydroxyethyl isocyanurate, bis (2-methacryloyloxypropyl) hydroxypropyl isocyanurate, bis (2-methacryloyloxybutyl) hydroxybutyl isocyanurate, tris (2- Acryloyloxyethyl) isocyanurate, tris (2-acryloyloxypropyl) isocyanurate, tris (2-acryloyloxybutyl) isocyanurate Tris (2-methacryloyloxyethyl) isocyanurate, tris (2-methacryloyloxypropyl) isocyanurate, tris (2-methacryloyloxybutyl) isocyanurate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropanetetra (meth) ) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 3 moles of ethylene oxide per mole of trimethylolpropane or Diol or tri (meth) acrylate of triol obtained by adding propylene oxide, poly (meth) acrylate of dipentaerythritol Polyfunctional (meth) acrylates such as bets, and the like can be used.
 なかでも、三官能(メタ)アクリレートを好ましく使用でき、トリメチロールプロパン1モルに3モル以上のエチレンオキサイドもしくはプロピレンオキサイドを付加して得たトリオールのジ又はトリ(メタ)アクリレートは、硬化後の弾性率を高く調整することができるので更に好ましい。 Among them, trifunctional (meth) acrylate can be preferably used, and triol di- or tri (meth) acrylate obtained by adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of trimethylolpropane is an elastic property after curing. It is more preferable because the rate can be adjusted high.
 二官能(メタ)アクリレートとしては、例えば、1,4-ブタンジオールジ(メタ)アクリレート、3-メチル-1,5-ペンタンジオールジ(メタ)アクリレート、1,6-ヘキサンジオールジ(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、2-メチル-1,8-オクタンジオールジ(メタ)アクリレート、2-ブチル-2-エチル-1,3-プロパンジオールジ(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、トリメチロールプロパンジ(メタ)アクリレート、ペンタエリスリトールジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、ネオペンチルグリコール1モルに4モル以上のエチレンオキサイドもしくはプロピレンオキサイドを付加して得たジオールのジ(メタ)アクリレート、エチレンオキサイド変性リン酸(メタ)アクリレート、エチレンオキサイド変性アルキル化リン酸ジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、ジプロピレングリコールジ(メタ)アクリレート、トリプロピレングリコールジ(メタ)アクリレート、ポリエーテル(メタ)アクリレート、ジエチルアミノエチル(メタ)アクリレート、脂環式構造を有する(メタ)アクリレートとしては、脂環式の二官能(メタ)アクリレートとして、ノルボルナンジメタノールジ(メタ)アクリレート、ノルボルナンジエタノールジ(メタ)アクリレート、ノルボルナンジメタノールにエチレンオキサイド又はプロピレンオキサイド2モル付加して得たジオールのジ(メタ)アクリレート、トリシクロデカンジメタノールジ(メタ)アクリレート、トリシクロデカンジエタノールジ(メタ)アクリレート、トリシクロデカンジメタノールにエチレンオキサイド又はプロピレンオキサイド2モル付加して得たジオールのジ(メタ)アクリレート、ペンタシクロペンタデカンジメタノールジ(メタ)アクリレート、ペンタシクロペンタデカンジエタノールジ(メタ)アクリレート、ペンタシクロペンタデカンジメタノールにエチレンオキサイド又はプロピレンオキサイド2モル付加して得たジオールのジ(メタ)アクリレート、ペンタシクロペンタデカンジエタノールにエチレンオキサイド又はプロピレンオキサイド2モル付加して得たジオールのジ(メタ)アクリレート、ジメチロールジシクロペンタンジ(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、エチレンオキサイド変性ビスフェノールAジ(メタ)アクリレート、プロピレンオキサイド変性ビスフェノールAジ(メタ)アクリレート等を使用できる。 Examples of the bifunctional (meth) acrylate include 1,4-butanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate. Neopentyl glycol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, ethylene glycol di ( Obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol Gio Di (meth) acrylate, ethylene oxide modified phosphoric acid (meth) acrylate, ethylene oxide modified alkyl phosphate di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (Meth) acrylate, polyether (meth) acrylate, diethylaminoethyl (meth) acrylate, and (meth) acrylate having an alicyclic structure include alicyclic bifunctional (meth) acrylate, norbornane dimethanol di (meth) ) Acrylate, norbornane diethanol di (meth) acrylate, norbornane dimethanol, 2 mol of ethylene oxide or propylene oxide, di (meth) acrylate Didecane (meth) acrylate, pentacyclopentadecane dimethanol obtained by adding 2 mol of ethylene oxide or propylene oxide to rhodecane dimethanol di (meth) acrylate, tricyclodecane diethanol di (meth) acrylate, tricyclodecane dimethanol Di (meth) acrylate, pentacyclopentadecanediethanol di (meth) acrylate, di (meth) acrylate of diol obtained by adding 2 moles of ethylene oxide or propylene oxide to pentacyclopentadecanedimethanol, ethylene oxide or pentacyclopentadecanediethanol Di (meth) acrylate of diol obtained by adding 2 mol of propylene oxide, dimethylol dicyclopentane di (meth) acrylate, hydroxy Pivalaldehyde modified trimethylolpropane di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, propylene oxide modified bisphenol A di (meth) acrylate, etc. can be used. .
 なかでもジプロピレングリコールジ(メタ)アクリレートが特に好ましい。 Of these, dipropylene glycol di (meth) acrylate is particularly preferable.
 また、N-ビニルピロリドン、N-ビニルカプロラクタム、ビニルエーテルモノマー、リン酸基含有(メタ)アクリレート等の紫外線硬化性化合物も必要に応じて使用できる。 Further, ultraviolet curable compounds such as N-vinyl pyrrolidone, N-vinyl caprolactam, vinyl ether monomer, and phosphate group-containing (meth) acrylate can be used as necessary.
 単官能(メタ)アクリレートとしては、例えば、エチル(メタ)アクリレート、ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、ノニル(メタ)アクリレート、トリデシル(メタ)アクリレート、ヘキサデシル(メタ)アクリレート、オクタデシル(メタ)アクリレート、イソアミル(メタ)アクリレート、イソデシル(メタ)アクリレート、イソステアリル(メタ)アクリレート、エトキシエトキシエチル(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリレート、3-クロロ-2-ヒドロキシプロピル(メタ)アクリレート、メトキシエチル(メタ)アクリレート、ブトキシエチル(メタ)アクリレート、等の脂肪族(メタ)アクリレート、ノニルフェノキシエチル(メタ)アクリレート、2-ヒドロキシ-3-フェノキシプロピル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、ベンジル(メタ)アクリレート等の芳香族(メタ)アクリレート、ジシクロペンテニル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、ジシクロペンテニルオキシエチル(メタ)アクリレート、テトラシクロドデカニル(メタ)アクリレート、シクロヘキシル(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、グリシジル(メタ)アクリレート等の脂環式(メタ)アクリレート、カプロラクトン変性テトラヒドロフルフリル(メタ)アクリレート、アクリロイルモルフォリン、イソボルニル(メタ)アクリレート、ノルボルニル(メタ)アクリレート、2-(メタ)アクリロイルオキシメチル-2-メチルビシクロヘプタンアダマンチル(メタ)アクリレート、などを使用できる。 Examples of monofunctional (meth) acrylates include ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, tridecyl (meth) acrylate, hexadecyl (meth) acrylate, and octadecyl. (Meth) acrylate, isoamyl (meth) acrylate, isodecyl (meth) acrylate, isostearyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-chloro-2-hydroxypropyl ( Aliphatic (meth) acrylates such as (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, nonylphenoxyethyl (meth) acrylate, 2- Roxy-3-phenoxypropyl (meth) acrylate, phenoxyethyl (meth) acrylate, aromatic (meth) acrylate such as benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, di Cyclopentenyloxyethyl (meth) acrylate, tetracyclododecanyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, alicyclic (meth) acrylate such as glycidyl (meth) acrylate, caprolactone modified tetrahydro Furfuryl (meth) acrylate, acryloylmorpholine, isobornyl (meth) acrylate, norbornyl (meth) acrylate, 2- (meth) acryloyloxymethyl-2 Methyl Bicycloheptane adamantyl (meth) acrylate, and the like can be used.
 第二の光反射層が積層される中間層に使用する紫外線硬化型組成物中の紫外線硬化性化合物としては、一分子中に三以上の(メタ)アクリロイル基を有する(メタ)アクリレートモノマーを紫外線硬化型組成物に含まれる紫外線硬化性化合物中の40~80質量%含有し、一分子中に一の(メタ)アクリロイル基を有する(メタ)アクリレートモノマーの含有量が10質量%以下含有する組成物が、上記好適な重量減少率や弾性率、あるいは粘度の範囲に調整し易いため好ましい。 As an ultraviolet curable compound in the ultraviolet curable composition used for the intermediate layer on which the second light reflecting layer is laminated, a (meth) acrylate monomer having three or more (meth) acryloyl groups in one molecule is ultraviolet. A composition containing 40 to 80% by mass in the ultraviolet curable compound contained in the curable composition and containing 10% by mass or less of a (meth) acrylate monomer having one (meth) acryloyl group in one molecule. The product is preferable because it is easy to adjust the weight reduction rate, elastic modulus, or viscosity range.
 三官能(メタ)アクリレートの含有量は、50~70質量%であることが更に好ましい。また、単官能(メタ)アクリレートの含有量は5質量%以下であることが更に好ましく、1質量%以下であることが特に好ましい。 The content of trifunctional (meth) acrylate is more preferably 50 to 70% by mass. Further, the content of the monofunctional (meth) acrylate is more preferably 5% by mass or less, and particularly preferably 1% by mass or less.
 また、これらモノマー成分に併用して、(メタ)アクリレートオリゴマーを使用しても良い。(メタ)アクリレートオリゴマーとしては、特に制限されず、各種のウレタン(メタ)アクリレート、エポキシ(メタ)アクリレート、ポリエステル(メタ)アクリレート、ポリエーテル(メタ)アクリレートを使用できる。なかでも紫外線硬化型組成物の(メタ)アクリロイル基濃度と硬化後の弾性率を好適な範囲に調整しやすいことから、ウレタン(メタ)アクリレート及びエポキシ(メタ)アクリレートを好ましく使用できる。中でも、ウレタン(メタ)アクリレートを使用すると、硬化膜の架橋点数や架橋点間距離、架橋構造を好適に制御でき、硬化膜に適度な柔軟性を付与することにより反り等の形状変化の少ない硬化膜を形成できる。 Further, a (meth) acrylate oligomer may be used in combination with these monomer components. The (meth) acrylate oligomer is not particularly limited, and various urethane (meth) acrylates, epoxy (meth) acrylates, polyester (meth) acrylates, and polyether (meth) acrylates can be used. Among these, urethane (meth) acrylate and epoxy (meth) acrylate can be preferably used because the (meth) acryloyl group concentration of the ultraviolet curable composition and the elastic modulus after curing are easily adjusted to a suitable range. Among these, when urethane (meth) acrylate is used, the number of cross-linking points, distance between cross-linking points, and cross-linking structure of the cured film can be suitably controlled, and curing with less change in shape such as warping can be achieved by imparting appropriate flexibility to the cured film. A film can be formed.
 本発明に使用するウレタン(メタ)アクリレートとしては、分子内に2個以上のイソシアネート基を有する化合物と、ヒドロキシル基と(メタ)アクリロイル基とを有する化合物と、分子内に2個以上のヒドロキシル基を有する化合物とから得られるウレタン(メタ)アクリレートを好ましく使用できる。また、ヒドロキシル基と(メタ)アクリロイル基とを有する化合物と、分子内に2個のイソシアネート基を有する化合物とを反応させて得られるウレタン(メタ)アクリレートも好ましく使用できる。 The urethane (meth) acrylate used in the present invention includes a compound having two or more isocyanate groups in the molecule, a compound having a hydroxyl group and a (meth) acryloyl group, and two or more hydroxyl groups in the molecule. A urethane (meth) acrylate obtained from a compound having a diol can be preferably used. Further, urethane (meth) acrylate obtained by reacting a compound having a hydroxyl group and a (meth) acryloyl group with a compound having two isocyanate groups in the molecule can also be preferably used.
 分子内に2個以上のイソシアネート基を有する化合物としては、例えば、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、ビス(イソシアナトメチル)シクロヘキサン、シクロヘキサンジイソシアネート、ビス(イソシアナトシクロヘキシル)メタン、イソホロンジイソシアネート、トリレンジイソシアネート、キシリレンジイソシアネート、ジフェニルメタンジイソシアネート、m-フェニレンジイソシアネートなどのポリイソシアネート類が挙げられる。なかでも、分子内に2個のイソシアネート基を有するジイソシアネート化合物を好ましく使用でき、特にトリレンジイソシアネートは、色相の悪化が無く、かつ光線透過性も低下することがないため特に好ましい。 Examples of compounds having two or more isocyanate groups in the molecule include tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, bis (isocyanatomethyl) cyclohexane, cyclohexane diisocyanate, bis (isocyanatocyclohexyl) methane, and isophorone. Examples thereof include polyisocyanates such as diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, and m-phenylene diisocyanate. Among them, a diisocyanate compound having two isocyanate groups in the molecule can be preferably used, and tolylene diisocyanate is particularly preferable because it does not deteriorate the hue and does not decrease the light transmittance.
 ヒドロキシル基と(メタ)アクリロイル基とを有する化合物としては、例えば、ヒドロキシエチル(メタ)アクリレート、ヒドロキシプロピル(メタ)アクリレート、ヒドロキシブチル(メタ)アクリレート等があり、さらにこれらの(メタ)アクリレートと2個以上のヒドロキシル基を有する化合物とを反応させて得られる化合物でも良い。あるいは2個以上のヒドロキシキル基を有する化合物と(メタ)アクリル酸とを反応させて得られる化合物でも良く、例えばグリシジルエーテル化合物と(メタ)アクリル酸との付加反応物、グリコール化合物のモノ(メタ)アクリレート体等が挙げられる。 Examples of the compound having a hydroxyl group and a (meth) acryloyl group include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and these (meth) acrylates and 2 A compound obtained by reacting with a compound having at least one hydroxyl group may also be used. Alternatively, it may be a compound obtained by reacting a compound having two or more hydroxyl groups with (meth) acrylic acid. For example, an addition reaction product of a glycidyl ether compound and (meth) acrylic acid, or a mono (meth) glycol compound (meta) ) Acrylate and the like.
 2個以上のヒドロキシル基を有する化合物としては、ポリオール類が好ましく用いられ、その具体例としては、エチレングリコール、1,2-プロパンジオール、1,3-プロパンジオール、2-メチル-1,3-プロパンジオール、1,3-ブタンジオール、1,4-ブタンジオール、1,5-ペンタンジオール、2-メチル-1,5-ペンタンジオール、エオペンチルグリコール、3-メチル-1,5-ペンタンジオール、2,3,5-トリメチル-1,5-ペンタンジオール、1,6-ヘキサンジオール、2-エチル-1,6-ヘキサンジオール、2,2,4-トリメチル-1,6-ヘキサンジオール、1,8-オクタンジオール、トリメチロールプロパン、ペンタエリスリトール、ソルビトール、マンニトール、グリセリン、1,2-ジメチロールシクロヘキサン、1,3-ジメチロールシクロヘキサン、1,4-ジメチロールシクロヘキサン等のアルキレンポリオール類等の多量体としての高分子ポリオールが挙げられる。 Polyols are preferably used as the compound having two or more hydroxyl groups, and specific examples thereof include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3- Propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, eopentyl glycol, 3-methyl-1,5-pentanediol, 2,3,5-trimethyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1, 8-octanediol, trimethylolpropane, pentaerythritol, sorbitol, mannitol, glycerin, 1, - dimethylolcyclohexane, 1,3-dimethylolcyclohexane, polymer polyol as multimers such as alkylene polyols such as 1,4-dimethylol cyclohexane.
 なかでも、エーテル結合を有するポリエーテルポリオール、多塩基酸との反応や環状エステルの開環重合により得られるエステル結合を有するポリエステルポリオール、又は、カーボネートとの反応により得られるカーボネート結合を有するポリカーボネートポリオールであることが好ましい。これらポリオール類の少なくとも一部、好ましくはポリオール類全量中の15モル%以上、更に好ましくはポリオール類全量中の30モル%以上は、分子量500~2500であるのが好ましい。 Among them, polyether polyols having ether bonds, polyester polyols having ester bonds obtained by reaction with polybasic acids and ring-opening polymerization of cyclic esters, or polycarbonate polyols having carbonate bonds obtained by reaction with carbonates. Preferably there is. At least a part of these polyols, preferably 15 mol% or more in the total amount of polyols, more preferably 30 mol% or more in the total amount of polyols, preferably has a molecular weight of 500-2500.
 ポリエーテルポリオールとしては、例えば、前記ポリオール類の多量体のほかに、テトラヒドロフラン等の環状エーテルの開環重合体としてのポリテトラメチレングリコール等、及び、前記ポリオール類の、エチレンオキサイド、プロピレンオキサイド、1,2-ブチレンオキサイド、1,3-ブチレンオキサイド、2,3-ブチレンオキサイド、テトラヒドロフラン、スチレンオキサイド、エピクロルヒドリン等のアルキレンオキサイドの付加物等が挙げられる。 Examples of the polyether polyol include polytetramethylene glycol as a ring-opening polymer of a cyclic ether such as tetrahydrofuran, in addition to the multimers of the polyols, and ethylene polyol, propylene oxide, 1 , 2-butylene oxide, 1,3-butylene oxide, 2,3-butylene oxide, tetrahydrofuran, styrene oxide, an adduct of alkylene oxide such as epichlorohydrin, and the like.
 ポリエステルポリオールとしては、例えば、前記ポリオール類と、マレイン酸、フマール酸、アジピン酸、セバシン酸、フタル酸等の多塩基酸との反応物、及び、カプロラクトン等の環状エステルの開環重合体としてのポリカプロラクトン等が挙げられる。 Examples of the polyester polyol include a reaction product of the above polyols with a polybasic acid such as maleic acid, fumaric acid, adipic acid, sebacic acid, and phthalic acid, and a ring-opening polymer of a cyclic ester such as caprolactone. Examples include polycaprolactone.
 ポリカーボネートポリオールとしては、例えば、前記ポリオール類と、エチレンカーボネート、1,2-プロピレンカーボネート、1,2-ブチレンカーボネート等のアルキレンカーボネート、又は、ジフェニルカーボネート、4-メチルジフェニルカーボネート、4-エチルジフェニルカーボネート、4-プロピルジフェニルカーボネート、4,4’-ジメチルジフェニルカーボネート、2-トリル-4-トリルカーボネート、4,4’-ジエチルジフェニルカーボネート、4,4’-ジプロピルジフェニルカーボネート、フェニルトルイルカーボネート、ビスクロロフェニルカーボネート、フェニルクロロフェニルカーボネート、フェニルナフチルカーボネート、ジナフチルカーボネート等のジアリールカーボネート、あるいは、ジメチルカーボネート、ジエチルカーボネート、ジ-n-プロピルカーボネート、ジイソプロピルカーボネート、ジ-n-ブチルカーボネート、ジイソブチルカーボネート、ジ-t-ブチルカーボネート、ジ-n-アミルカーボネート、ジイソアミルカーボネート等のジアルキルカーボネート等との反応物等が挙げられる。 Examples of the polycarbonate polyol include the above polyols and alkylene carbonates such as ethylene carbonate, 1,2-propylene carbonate, and 1,2-butylene carbonate, or diphenyl carbonate, 4-methyldiphenyl carbonate, 4-ethyldiphenyl carbonate, 4-propyldiphenyl carbonate, 4,4'-dimethyldiphenyl carbonate, 2-tolyl-4-tolyl carbonate, 4,4'-diethyldiphenyl carbonate, 4,4'-dipropyldiphenyl carbonate, phenyltoluyl carbonate, bischlorophenyl carbonate Diaryl carbonates such as phenyl chlorophenyl carbonate, phenyl naphthyl carbonate, dinaphthyl carbonate, etc. Dialkyl carbonate such as dicarbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, di-t-butyl carbonate, di-n-amyl carbonate, diisoamyl carbonate, etc. Examples include reactants.
 使用するポリオールは、1種であっても2種以上を併用してもよいが、ポリエーテルポリオール、ポリエステルポリオール及びポリカーボネートポリオールの2種以上を併用したウレタン(メタ)アクリレートが好ましく、2種を併用することがより好ましい。これらポリオールを併用することで、得られる硬化膜の高温高湿環境下における耐変形性や、表面硬度を好適に調整しやすくなる。2種の併用の例としては、表面硬度を高くする場合には、ポリエステルポリオールとポリカーボネートポリオールとの併用が好ましく、耐湿熱変形性を向上させる場合には、ポリエーテルポリオールとを併用させることが好ましい。これらの中間的な特性とする場合には、ポリエーテルポリオールとポリカーボネートポリオールとを併用することが好ましい。 The polyol to be used may be one kind or two or more kinds may be used in combination, but urethane (meth) acrylate using two or more kinds of polyether polyol, polyester polyol and polycarbonate polyol is preferable, and two kinds are used in combination. More preferably. By using these polyols in combination, it becomes easy to suitably adjust the deformation resistance and surface hardness of the obtained cured film in a high temperature and high humidity environment. As an example of two types of combined use, in the case of increasing the surface hardness, the combined use of polyester polyol and polycarbonate polyol is preferable, and in the case of improving the heat and humidity resistance, it is preferable to use a polyether polyol in combination. . In order to achieve these intermediate characteristics, it is preferable to use a polyether polyol and a polycarbonate polyol in combination.
 ポリオール併用時における各ポリオールの含有量としては、使用するポリオールの全量に対して、ポリエーテルポリオールは20~90質量%であることが好ましく30~80質量%であることがより好ましい。ポリエステルポリオールの含有量としては、10~70質量%であることが好ましく、20~60質量%とすることがより好ましい。ポリエーテルポリオールやポリエステルポリオールの含有量を当該範囲とすることで、硬化物の表面硬度や耐湿熱特性が得られやすい。 The content of each polyol when used in combination with the polyol is preferably 20 to 90% by mass, more preferably 30 to 80% by mass, based on the total amount of polyol used. The polyester polyol content is preferably 10 to 70% by mass, more preferably 20 to 60% by mass. By making content of polyether polyol or polyester polyol into the said range, the surface hardness and heat-and-moisture resistant property of hardened | cured material are easy to be obtained.
 また、本発明に使用するウレタン(メタ)アクリレートは、芳香環を有さない構造のものであると透明性が高くなるため好ましい。 In addition, the urethane (meth) acrylate used in the present invention is preferably a structure having no aromatic ring, since the transparency becomes high.
 本発明に使用するウレタン(メタ)アクリレートとしては、ポリエーテル骨格のウレタンアクリレートとして、DIC(株)社製FAU-742TP、FAU-306、ポリエステル骨格のウレタンアクリレートとして、コグニスジャパン(株)社製Photomer-6892、ダイセルサイテック(株)社製Ebecryl-8405等が好ましく例示できる。 As urethane (meth) acrylate used in the present invention, polyether skeleton urethane acrylate, DIC Corporation FAU-742TP, FAU-306, polyester skeleton urethane acrylate, Cognis Japan Co., Ltd. Photomer Preferred examples include -6892 and Ebecryl-8405 manufactured by Daicel Cytec Co., Ltd.
 本発明の紫外線硬化型組成物中のウレタン(メタ)アクリレートの含有量は、紫外線硬化型組成物に含まれる紫外線硬化性化合物中の20質量%以下であることが好ましく、5~15質量%であることが特に好ましい。ウレタン(メタ)アクリレート含有量を当該範囲とすることで硬化膜に適度な柔軟性を付与することが可能となり、特に湿度ショックを与えたときの反り変化が小さくなる。 The content of urethane (meth) acrylate in the ultraviolet curable composition of the present invention is preferably 20% by mass or less in the ultraviolet curable compound contained in the ultraviolet curable composition, and is preferably 5 to 15% by mass. It is particularly preferred. By setting the urethane (meth) acrylate content in the above range, it is possible to impart an appropriate flexibility to the cured film, and in particular, a change in warp when a humidity shock is applied becomes small.
 本発明で使用するウレタン(メタ)アクリレートのゲルパーミエーションクロマトグラフィー(GPC)で測定した分子量(Mw)としては、1000~20000であることが好ましく、1500~10000であることがより好ましい。これにより、本発明の紫外線硬化型組成物を使用した光ディスクの耐久性及び耐光性がより優れたものとなる。分子量が高いと高粘度となり取り扱いが困難となる。一方、分子量が低いと架橋点間距離が短くなるため硬化収縮が大きくなる。なお、GPCは東ソー(株)社製 HLC-8020を用い、カラムはGMHxl-GMHxl-G200Hxl-G1000Hxlwを使用するものとし、溶媒はTHFを用い、1.0ml/minの流量でカラム温度が40℃、検出器温度が30℃、分子量は標準ポリスチレン換算で測定を行うものとする。 The molecular weight (Mw) measured by gel permeation chromatography (GPC) of urethane (meth) acrylate used in the present invention is preferably 1000 to 20000, and more preferably 1500 to 10,000. Thereby, the durability and light resistance of the optical disk using the ultraviolet curable composition of the present invention are further improved. If the molecular weight is high, the viscosity becomes high and handling becomes difficult. On the other hand, when the molecular weight is low, the distance between cross-linking points is shortened, so that the curing shrinkage is increased. The GPC uses HLC-8020 manufactured by Tosoh Corporation, the column uses GMHxl-GMHxl-G200Hxl-G1000Hxlw, the solvent uses THF, and the column temperature is 40 ° C. at a flow rate of 1.0 ml / min. The detector temperature is 30 ° C., and the molecular weight is measured in terms of standard polystyrene.
 上記ウレタン(メタ)アクリレートを使用する場合には、前記第二の光反射層が積層される中間層に使用する紫外線硬化型組成物に含まれる紫外線硬化性化合物中の40質量%以下で使用することが好ましく、20質量%以下であることが特に好ましい。ウレタン(メタ)アクリレートの含有量を当該範囲とすることで硬化膜に適度な柔軟性を付与することが可能となり、特に湿熱環境変化時における反りの少ない硬化膜を実現できる。 When the urethane (meth) acrylate is used, it is used at 40% by mass or less in the ultraviolet curable compound contained in the ultraviolet curable composition used for the intermediate layer on which the second light reflecting layer is laminated. It is particularly preferable that the content is 20% by mass or less. By setting the content of urethane (meth) acrylate within the above range, it is possible to impart appropriate flexibility to the cured film, and in particular, it is possible to realize a cured film with less warpage when the wet heat environment changes.
 本発明で使用するエポキシ(メタ)アクリレートとしては、上記特性を有するものであればよく、例えば、下記式(1)で表されるビスフェノール型エポキシ(メタ)アクリレートを使用できる。 As the epoxy (meth) acrylate used in the present invention, any epoxy (meth) acrylate having the above characteristics can be used. For example, bisphenol type epoxy (meth) acrylate represented by the following formula (1) can be used.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
(式中、Yは-SO-、-CH-、-CH(CH)-又は-C(CH-を表し、Zは各々独立的に、水素原子又は-CHを表し、nは0又は1以上の整数を表す。) (In the formula, Y represents —SO 2 —, —CH 2 —, —CH (CH 3 ) — or —C (CH 3 ) 2 —, and each Z independently represents a hydrogen atom or —CH 3 . , N represents 0 or an integer of 1 or more.
 このようなビスフェノール型エポキシ(メタ)アクリレートとしては、油化シェルエポキシ社製エピコート802、1001、1004等のビスフェノールA型エポキシ樹脂、及びエピコート4001P、4002P、4003P等のビスフェノールF型エポキシ樹脂と(メタ)アクリル酸との反応によって得られるエポキシアクリレート等が挙げられる。 Examples of such bisphenol type epoxy (meth) acrylate include bisphenol A type epoxy resins such as Epicoat 802, 1001, and 1004 manufactured by Yuka Shell Epoxy, and bisphenol F type epoxy resins such as Epicoat 4001P, 4002P, and 4003P, ) Epoxy acrylate obtained by reaction with acrylic acid.
 中でもYが-C(CH-であり、nが0又は1~6の整数である構造の付加重合体を主構成成分とするビスフェノールA型のエポキシ(メタ)アクリレートであることがより好ましい。 Among them, Y is -C (CH 3) 2 - a, more that n is bisphenol A type epoxy (meth) acrylate to the addition polymer of the structure is an integer of 0 or 1 to 6 and the main constituent preferable.
 また、水添ビスフェノールA型、ビスフェノールF型等のエポキシ(メタ)アクリレートも好適に使用できる。 Moreover, epoxy (meth) acrylates such as hydrogenated bisphenol A type and bisphenol F type can also be suitably used.
 本発明で使用するエポキシ(メタ)アクリレートのゲルパーミエーションクロマトグラフィー(GPC)で測定した分子量(Mw)としては、500~3000であることが好ましく、800~1500であることがより好ましい。エポキシ(メタ)アクリレートの構造、及び分子量を上記の範囲とすることにより、本発明の紫外線硬化型組成物を使用した光ディスクの耐久性及び耐光性がより優れたものとなる。なお、GPCは東ソー(株)社製 HLC-8020を用い、カラムはGMHxl-GMHxl-G200Hxl-G1000Hxlwを使用した。溶媒はTHFを用い、1.0ml/minの流量でカラム温度が40℃、検出器温度が30℃、分子量は標準ポリスチレン換算で測定を行った。 The molecular weight (Mw) measured by gel permeation chromatography (GPC) of the epoxy (meth) acrylate used in the present invention is preferably 500 to 3000, more preferably 800 to 1500. By setting the structure and molecular weight of the epoxy (meth) acrylate within the above ranges, the durability and light resistance of the optical disk using the ultraviolet curable composition of the present invention are further improved. The GPC used was Sakai HLC-8020 manufactured by Tosoh Corporation, and the column used was GMHxl-GMHxl-G200Hxl-G1000Hxlw. The solvent used was THF, the column temperature was 40 ° C., the detector temperature was 30 ° C., and the molecular weight was measured in terms of standard polystyrene at a flow rate of 1.0 ml / min.
 第二の光反射層が積層される中間層に使用する紫外線硬化型組成物は、25℃におけるB型粘度が1000mPa以下であることが好ましく、50~500mPaであることが特に好ましい。光ディスク中の反射膜間の中間層の厚さは、5~30μm程度の厚さで形成されるが、当該粘度範囲とすることで、当該厚さの中間層を好適に形成できる。 The ultraviolet curable composition used for the intermediate layer on which the second light reflecting layer is laminated preferably has a B-type viscosity at 25 ° C. of 1000 mPa or less, particularly preferably 50 to 500 mPa. The thickness of the intermediate layer between the reflective films in the optical disk is formed with a thickness of about 5 to 30 μm. By setting the viscosity range, the intermediate layer with the thickness can be suitably formed.
 また、当該紫外線硬化型組成物の(メタ)アクリロイル基濃度は4~10mmol/gとすることが好ましい。 Further, the (meth) acryloyl group concentration of the ultraviolet curable composition is preferably 4 to 10 mmol / g.
[開始剤]
 第二の光反射層が積層される中間層に使用する紫外線硬化型組成物においては、当該紫外線硬化型組成物に含まれる紫外線硬化性化合物100質量部に対し、使用する重合開始剤の含有量を2~10質量部とすることが好ましく、3~8質量部とすることが更に好ましい。また、当該重合開始剤のうち、分子量が215以下の重合開始剤の含有量を、5質量部以下とすることが好ましく、4質量部以下とすることが更に好ましい。また、分子量が215を越える重合開始剤を、紫外線硬化性化合物100質量部に対し1質量部以上含有することが好ましく、1~5質量部含有することが更に好ましく、1~3質量部含有することが特に好ましい。分子量が215以下の重合開始剤は含有しなくとも良いが1質量部以上を、分子量が215を越える重合開始剤と併用することで、安定な信号特性が得られやすくなるため好ましい。本発明においては、第二の光反射層が積層される中間層を形成する紫外線硬化型組成物中の重合開始剤を上記のとおり調整することにより、製造工程中に高温下にさらされる場合においても光ディスクの重量減少が生じ難くなり、光ディスクを形成した際の高温高湿環境下においても安定な信号特性を得ることができる。また、光ディスク製造時に揮発成分による排気設備の汚染を低減できる。
[Initiator]
In the ultraviolet curable composition used for the intermediate layer on which the second light reflecting layer is laminated, the content of the polymerization initiator used with respect to 100 parts by mass of the ultraviolet curable compound contained in the ultraviolet curable composition. Is preferably 2 to 10 parts by mass, and more preferably 3 to 8 parts by mass. Moreover, it is preferable to make content of the polymerization initiator whose molecular weight is 215 or less into the said polymerization initiator into 5 mass parts or less, and it is still more preferable to set it as 4 mass parts or less. The polymerization initiator having a molecular weight exceeding 215 is preferably contained in an amount of 1 part by mass or more, more preferably 1 to 5 parts by mass, and more preferably 1 to 3 parts by mass with respect to 100 parts by mass of the ultraviolet curable compound. It is particularly preferred. A polymerization initiator having a molecular weight of 215 or less may not be contained, but it is preferable to use 1 part by mass or more in combination with a polymerization initiator having a molecular weight exceeding 215 because stable signal characteristics can be easily obtained. In the present invention, by adjusting the polymerization initiator in the ultraviolet curable composition forming the intermediate layer on which the second light reflecting layer is laminated as described above, when exposed to high temperatures during the production process. However, it is difficult to reduce the weight of the optical disk, and stable signal characteristics can be obtained even in a high temperature and high humidity environment when the optical disk is formed. Further, it is possible to reduce the contamination of the exhaust equipment due to volatile components during the production of the optical disk.
 分子量が215を越える重合開始剤としては、例えば、ベンゾインイソブチルエーテル、ベンジル、1-ヒドロキシシクロヘキシルフェニルケトン、ベンゾインエチルエーテル、ベンジルジメチルケタール、2-ヒドロキシ-2-メチル-1-フェニルプロパン-1-オン、1-(4-イソプロピルフェニル)-2-ヒドロキシ-2-メチルプロパン-1-オン、2-メチル-1-(4-メチルチオフェニル)-2-モルフォリノプロパン-1-オン、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、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、フェニルグリオキシリックアシッドメチルエステル、2,4,6-トリメチルベンゾイル-ジフェニルホスフィンオキサイド、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]プロパノン等の分子開裂型や、ベンゾフェノン、4-フェニルベンゾフェノン、イソフタルフェノン、4-ベンゾイル-4’-メチル-ジフェニルスルフィド、2,4-ジエチルチオキサントン、2-イソプロピルチオキサントン、等の水素引き抜き型の光重合開始剤等がある。 Examples of the polymerization initiator having a molecular weight exceeding 215 include benzoin isobutyl ether, benzyl, 1-hydroxycyclohexyl phenyl ketone, benzoin ethyl ether, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one. 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-hydroxy- 1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-Hydroxy-2-methyl-1-propan-1-one, phenylglyoxyl Molecular cleavage types such as acid methyl ester, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone, benzophenone, Examples include hydrogen abstraction-type photopolymerization initiators such as 4-phenylbenzophenone, isophthalphenone, 4-benzoyl-4′-methyl-diphenyl sulfide, 2,4-diethylthioxanthone, and 2-isopropylthioxanthone.
 なかでも、2-メチル-1-(4-メチルチオフェニル)-2-モルフォリノプロパン-1-オン、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、および、2,4,6-トリメチルベンゾイルジフェニルフォスフィンから選ばれる少なくとも一種を好ましく使用できる。また、硬化性が特に良好となることから、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、および、2,4,6-トリメチルベンゾイルジフェニルフォスフィンを使用することが好ましく、これらを併用することが特に好ましい。 Among them, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone And at least one selected from 2,4,6-trimethylbenzoyldiphenylphosphine can be preferably used. Also, since the curability is particularly good, oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone and 2,4,6-trimethylbenzoyldiphenylphosphine It is preferable to use these, and it is particularly preferable to use these in combination.
 また、分子量が215以下の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、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン、ベンゾインメチルエーテル、ベンゾフェノン、ベンジル、フェニルグリオキシリックアシッドメチルエステルなどが例示できる。なかでも、1-ヒドロキシ-シクロヘキシル-フェニル-ケトンを上記分子量が215を越えるの重合開始剤と併用して使用することが好ましい。 Examples of the polymerization initiator having a molecular weight of 215 or less include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, benzoin methyl ether, benzophenone, benzyl, phenyl Examples include glyoxylic acid methyl ester. Of these, 1-hydroxy-cyclohexyl-phenyl-ketone is preferably used in combination with a polymerization initiator having a molecular weight exceeding 215.
[添加剤]
 前記第二の光反射層が積層される中間層に使用する紫外線硬化型組成物には、必要に応じて、添加剤として、界面活性剤、レベリング剤、熱重合禁止剤、ヒンダードフェノール、ホスファイト等の酸化防止剤、ヒンダードアミン等の光安定剤を使用することもできる。また、増感剤として、例えば、トリメチルアミン、メチルジメタノールアミン、トリエタノールアミン、p-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、p-ジメチルアミノ安息香酸イソアミル、N,N-ジメチルベンジルアミン及び4,4’-ビス(ジエチルアミノ)ベンゾフェノン等が使用でき、更に、前記の光重合性化合物と付加反応を起こさないアミン類を併用することもできる。
[Additive]
In the ultraviolet curable composition used for the intermediate layer on which the second light reflecting layer is laminated, as necessary, a surfactant, a leveling agent, a thermal polymerization inhibitor, a hindered phenol, a phosphate, Antioxidants such as phyto, and light stabilizers such as hindered amines can also be used. Examples of sensitizers include trimethylamine, methyldimethanolamine, triethanolamine, p-dimethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N-dimethylbenzylamine and 4,4′-bis (diethylamino) benzophenone or the like can be used, and further, an amine that does not cause an addition reaction can be used in combination with the photopolymerizable compound.
 本発明の光ディスクにおいては、上記第二の光反射層が積層される紫外線硬化型組成物の硬化膜からなる中間層が、第一の光反射層と直接積層されていても良いが、第二の光反射層が積層される紫外線硬化型組成物の硬化膜からなる中間層と、第一の光反射層の間にさらに、紫外線硬化型組成物の硬化膜からなる第二の中間層が第一の光反射層と直接積層されるよう設けられていても良い。上記第二の光反射層が積層される中間層とは別に、第一の光反射層と積層される第二の中間層を有することで、好適なピット形成や、光反射層と野接着性、あるいは光ディスクの反りの抑制等の複数の要求特性を好適に調整しやすくなる。 In the optical disc of the present invention, the intermediate layer made of the cured film of the ultraviolet curable composition on which the second light reflecting layer is laminated may be directly laminated with the first light reflecting layer. An intermediate layer composed of a cured film of an ultraviolet curable composition on which a light reflecting layer is laminated, and a second intermediate layer composed of a cured film of an ultraviolet curable composition between the first light reflecting layer and a first intermediate layer. It may be provided so as to be directly laminated with one light reflecting layer. In addition to the intermediate layer on which the second light reflecting layer is laminated, it has a second intermediate layer laminated on the first light reflecting layer, so that suitable pit formation and light reflecting layer and field adhesion can be achieved. Or, it becomes easy to suitably adjust a plurality of required characteristics such as suppression of warpage of the optical disk.
 本発明においては、前記第一の光反射層と積層される第二の中間層として、紫外線硬化型組成物の硬化膜から形成される中間層を使用することが好ましい。第一の中間層に使用する紫外線硬化型組成物の硬化膜としては、25℃における弾性率が500~3000MPaであることが好ましく、1000~2000MPaであることがより好ましい。当該第二の中間層に使用する硬化膜の弾性率は、当該範囲とすることにより、第一の光反射層との接着力が良好であり、また硬化時の反りが小さいディスクとなる。また、当該第二の中間層は、上記第二の光反射層が積層される中間層より300MPa以上、好ましくは500MPa以上低いことが好ましい。 In the present invention, it is preferable to use an intermediate layer formed from a cured film of an ultraviolet curable composition as the second intermediate layer laminated with the first light reflecting layer. The cured film of the ultraviolet curable composition used for the first intermediate layer preferably has an elastic modulus at 25 ° C. of 500 to 3000 MPa, more preferably 1000 to 2000 MPa. By setting the elastic modulus of the cured film used for the second intermediate layer within the above range, the adhesive force with the first light reflecting layer is good, and the disc has a small warp during curing. The second intermediate layer is preferably 300 MPa or more, preferably 500 MPa or more lower than the intermediate layer on which the second light reflecting layer is laminated.
 また、光ディスク中の反射膜間の中間層の厚さは、5~30μm程度の厚さで形成されるが、当該中間層が複数層からなる場合には、当該第二の中間層は、上記第二の光反射層が積層される中間層よりも厚く形成することで好適に反りを低減しやすくなる。このため、上記第二の光反射層が積層される中間層の厚さを10μm以下、好ましくは2~5μmとし、当該第二の中間層の厚さをこれよりも厚く3~25μm程度とすることが好ましい。 In addition, the thickness of the intermediate layer between the reflective films in the optical disk is formed with a thickness of about 5 to 30 μm. When the intermediate layer is composed of a plurality of layers, the second intermediate layer is By forming the second light reflection layer to be thicker than the intermediate layer on which the second light reflection layer is laminated, it becomes easy to reduce the warp suitably. Therefore, the thickness of the intermediate layer on which the second light reflecting layer is laminated is set to 10 μm or less, preferably 2 to 5 μm, and the thickness of the second intermediate layer is set to about 3 to 25 μm thicker than this. It is preferable.
 第二の中間層に使用する紫外線硬化型組成物は、25℃におけるB型粘度が1000mPa以下であることが好ましく、50~600mPaであることが特に好ましい。粘度を上記範囲とすることで、当該第二の中間層上に、第二の光反射層が積層される中間層を好適に積層できる。 The ultraviolet curable composition used for the second intermediate layer preferably has a B-type viscosity at 25 ° C. of 1000 mPa or less, particularly preferably 50 to 600 mPa. By setting the viscosity within the above range, an intermediate layer on which the second light reflecting layer is laminated can be suitably laminated on the second intermediate layer.
 また、第二の中間層が、第二の光反射層が積層される中間層に比して表面張力が高いことが好ましい。これにより、第一の中間層が形成された上に第二の光反射層が積層される中間層を好適に塗布することができる。 Further, it is preferable that the second intermediate layer has a higher surface tension than the intermediate layer on which the second light reflecting layer is laminated. Thereby, the intermediate layer in which the second light reflection layer is laminated on the first intermediate layer can be suitably applied.
 前記第二の中間層に使用する紫外線硬化型組成物としては、上記第二の光反射層が積層される中間層に使用する紫外線硬化性化合物として列記した紫外線硬化性化合物から適宜使用できる。 The UV curable composition used for the second intermediate layer can be suitably used from the UV curable compounds listed as the UV curable compounds used for the intermediate layer on which the second light reflecting layer is laminated.
 なかでも、前記紫外線硬化性化合物として一分子中に三以上の(メタ)アクリロイル基を有する(メタ)アクリレートモノマーを40~80質量%含有し、ウレタン(メタ)アクリレートを使用する場合には、40質量%以下であることが好ましい。 In particular, when the ultraviolet curable compound contains 40 to 80% by mass of a (meth) acrylate monomer having three or more (meth) acryloyl groups in one molecule and urethane (meth) acrylate is used, It is preferable that it is below mass%.
 また、使用する重合開始剤としては、特に制限されず、上記第二の光反射層が積層される中間層に使用する重合開始剤として列記した各種の重合開始剤を使用できる。重合開始剤の含有量は、2~10質量%であることが好ましい。 Further, the polymerization initiator to be used is not particularly limited, and various polymerization initiators listed as polymerization initiators used for the intermediate layer on which the second light reflecting layer is laminated can be used. The content of the polymerization initiator is preferably 2 to 10% by mass.
 添加剤においても第二の光反射層が積層される中間層に使用する添加剤として列記したものを好適に使用できる。 Also in the additives, those listed as additives used for the intermediate layer on which the second light reflecting layer is laminated can be suitably used.
[光透過層]
 本発明の光ディスクにおいては、前記第二の光反射層が積層される中間層上の第二の光反射層上に直接、あるいは、他の層を介して光透過層が形成される。当該光透過層としては、レーザー光の発振波長が370~430nmであるブルーレーザーを効率良く透過することが好ましく、100μmの厚さにおいて405nmの光の透過率が85%以上であることが好ましく、90%以上であることが特に好ましい。
[Light transmission layer]
In the optical disk of the present invention, a light transmission layer is formed directly on the second light reflection layer on the intermediate layer on which the second light reflection layer is laminated or via another layer. As the light transmission layer, it is preferable to efficiently transmit a blue laser having an oscillation wavelength of laser light of 370 to 430 nm, and a transmittance of 405 nm light is preferably 85% or more at a thickness of 100 μm. 90% or more is particularly preferable.
 本発明の光ディスクにおける光透過層の厚みは、光ディスクの構成により適宜調整すればよく、光ディスク中に形成される中間層と光透過層との総厚さが70~110μmであることが好ましい。光透過層の厚みは、通常、約100μmに設定されるが、厚みは光透過率や信号の読み取り及び記録に大きく影響を及ぼすため、十分な管理が必要である。光透過層は、当該厚さの硬化層単層で形成されていても、複数層が積層されていてもよい。 The thickness of the light transmission layer in the optical disk of the present invention may be appropriately adjusted according to the structure of the optical disk, and the total thickness of the intermediate layer and the light transmission layer formed in the optical disk is preferably 70 to 110 μm. The thickness of the light transmission layer is usually set to about 100 μm, but the thickness greatly affects the light transmittance and signal reading and recording, and therefore needs to be sufficiently managed. The light transmission layer may be formed of a single cured layer having the thickness or a plurality of layers may be laminated.
 本発明の光ディスクにおける光透過層は、硬化時に反りが生じ難く、長時間にわたり荷重が加わった際にも再生信号のエラーが増加し難く、経時でエラーが回復することにより好適に信号再生が可能な光ディスクを提供することが好ましい。 The light-transmitting layer in the optical disk of the present invention is less likely to warp during curing, and the error of the reproduction signal does not increase easily even when a load is applied for a long time, and the signal can be suitably reproduced by recovering the error over time. It is preferable to provide a simple optical disc.
 このような光透過層としては、例えば、稜間角136°のビッカース圧子を用いて荷重100mNで押し込むことによって得られる弾性率(25℃)が1500MPa以下、好ましくは50~1300MPa、より好ましくは400~900MPa、最も好ましくは400~600MPaである光透過層を好ましく使用できる。当該光透過層により、紫外線硬化時に反りが生じにくく、かつ、長時間の荷重に対しても変形が回復しやすくなるため良好に情報の記録・再生を行うことができる。 As such a light transmission layer, for example, an elastic modulus (25 ° C.) obtained by pressing with a load of 100 mN using a Vickers indenter with a ridge angle of 136 ° is 1500 MPa or less, preferably 50 to 1300 MPa, more preferably 400. A light-transmitting layer having a pressure of ˜900 MPa, most preferably 400-600 MPa can be preferably used. The light transmission layer is less likely to warp during UV curing, and deformation is easily recovered even with a long-time load, so that information can be recorded / reproduced satisfactorily.
 ビッカース圧子を用いた弾性率は、ISO標準規格ISO14577に従って測定することができる。
 ISO14577において、稜間角136°のビッカース圧子を押し込むことによって得られる弾性率は、押し込み弾性率EITとして表される。塑性変形率は、押し込みクリープCITと表され、次の式から求められる。
Figure JPOXMLDOC01-appb-I000002
 ここで、h1:荷重が100mNに達した時の押し込み深さ、h2:荷重が100mNに達した後に60秒間保持した時の押し込み深さ、である。
The elastic modulus using a Vickers indenter can be measured according to ISO standard ISO14577.
In ISO14577, the elastic modulus obtained by pressing a Vickers indenter with a ridge-to-ridge angle of 136 ° is expressed as indentation elastic modulus EIT . The plastic deformation rate is expressed as indentation creep CIT and is obtained from the following equation.
Figure JPOXMLDOC01-appb-I000002
Here, h1: indentation depth when the load reaches 100 mN, h2: indentation depth when the load is held for 60 seconds after reaching the load of 100 mN.
 ISO14577に従った測定器として、フィッシャー・インスツルメンツ製のフィッシャースコープHM2000を用いて測定することができる。 As a measuring instrument according to ISO14577, measurement can be performed using a Fisherscope HM2000 manufactured by Fischer Instruments.
 また、本発明に使用する光透過層は、稜間角136°のビッカース圧子を用いて荷重100mNで押し込み60秒間保持した時の塑性変形率が、30~90%であることが好ましく、40~90%であることがより好ましく、40~60%であることが特に好ましい。塑性変形率を当該範囲とすることで、長時間の荷重によって生じる変形が経時で回復しやすくなる。 The light transmission layer used in the present invention preferably has a plastic deformation rate of 30 to 90% when pressed with a load of 100 mN and held for 60 seconds using a Vickers indenter with a ridge angle of 136 °, and 40 to It is more preferably 90%, particularly preferably 40 to 60%. By setting the plastic deformation rate within the above range, deformation caused by a long-time load is easily recovered with time.
 また、光透過層の周波数3.5Hzにて測定される動的粘弾性スペクトルにおける60℃の損失弾性率(E’’)が10MPa以下であることが好ましく、0.1~7MPaであることがより好ましく、1~7MPaとすることが更に好ましい。。60℃の損失弾性率が当該範囲であると、長時間にわたり荷重が加わった際にも再生信号のエラーが増加し難く、経時でエラーが回復することにより好適に信号再生がしやすくなる。 The loss elastic modulus (E ″) at 60 ° C. in the dynamic viscoelastic spectrum measured at a frequency of 3.5 Hz of the light transmission layer is preferably 10 MPa or less, and preferably 0.1 to 7 MPa. More preferred is 1-7 MPa. . When the loss elastic modulus at 60 ° C. is in this range, the error of the reproduction signal hardly increases even when a load is applied for a long time, and the signal is preferably easily reproduced by recovering the error with time.
 動的粘弾性スペクトルの測定に際しては、光透過層をダンベルカッターでJIS K 7127の試験片タイプ5の形状に打ち抜き試験片とし、この試験片を用いて、レオメトリックス社製の動的粘弾性測定装置RSA-II(周波数3.5Hz、昇温速度3℃/分)により測定できる。 When measuring the dynamic viscoelastic spectrum, the light transmission layer was punched into a JIS K 7127 test piece type 5 shape with a dumbbell cutter, and this test piece was used to measure dynamic viscoelasticity manufactured by Rheometrics. It can be measured with an apparatus RSA-II (frequency 3.5 Hz, temperature rising rate 3 ° C./min).
 また、上記にて測定される動的粘弾性スペクトルにおける60℃の損失正接(tanδ)が、0.25以下の光透過層であることが好ましく、0.01~0.20以下であることが特に好ましい。60℃の損失正接が当該範囲であると長時間にわたり荷重が加わった際にも再生信号のエラーが増加し難く、経時でエラーが回復することにより好適に信号再生がしやすくなる。 Further, the loss tangent (tan δ) at 60 ° C. in the dynamic viscoelasticity spectrum measured above is preferably a light transmission layer of 0.25 or less, and preferably 0.01 to 0.20 or less. Particularly preferred. When the loss tangent at 60 ° C. is within this range, even when a load is applied for a long time, the error of the reproduction signal hardly increases, and the error is recovered over time, so that the signal reproduction is easily facilitated.
 また、本発明の光ディスクの中間層及び光透過層は、レーザー光の発振波長が370~430nmであるブルーレーザーを効率良く透過することが好ましく、100μmの厚さにおいて405nmの光の透過率が85%以上であることが好ましく、90%以上であることが特に好ましい。 In addition, the intermediate layer and the light transmission layer of the optical disk of the present invention preferably efficiently transmit a blue laser having a laser light oscillation wavelength of 370 to 430 nm, and have a light transmittance of 405 nm at a thickness of 100 μm of 85. % Or more is preferable, and 90% or more is particularly preferable.
[光ディスクの構成]
 本発明の光ディスクは、基板上に、少なくとも第一の光反射層、紫外線硬化型組成物の硬化膜からなる中間層、第二の光反射層及び光透過層を順に有し、前記紫外線硬化型組成物の硬化膜からなる中間層が前記第二の光反射層と直接積層され、前記光透過層側からブルーレーザーを入射して情報の再生を行う光ディスクである。
[Configuration of optical disc]
The optical disk of the present invention comprises, on the substrate, at least a first light reflecting layer, an intermediate layer composed of a cured film of an ultraviolet curable composition, a second light reflecting layer and a light transmitting layer in this order, and the ultraviolet curable type An optical disc in which an intermediate layer made of a cured film of the composition is directly laminated with the second light reflection layer, and information is reproduced by making a blue laser incident from the light transmission layer side.
 本発明の光ディスクは、再生専用のディスクと、記録・再生可能なディスクのいずれであっても良い。再生専用光ディスクの場合には、前記基板上、及び第二の光反射層を積層する中間層上に情報記録用のピットが設けられた構成である。詳細には、1枚の円形樹脂基板を射出成形する際に、情報記録部位である記録トラック(グルーブ)と呼ばれるレーザー光をトラッキングするための案内溝を設け、次に記録トラックを有する基板上に、、第一の光反射層、紫外線硬化型組成物の硬化膜からなる中間層、及び第二の光反射層が順に積層され、前記第二の光反射層上に少なくとも光透過層を有する。この場合には第二の中間層上にピットが形成される。また、前記第一の光反射層と、紫外線硬化型組成物の硬化膜からなる中間層との間に、さらに紫外線硬化型組成物の硬化膜からなる第二の中間層を設けた構成も好ましく使用できる。 The optical disc of the present invention may be either a reproduction-only disc or a recordable / reproducible disc. In the case of a read-only optical disc, information recording pits are provided on the substrate and an intermediate layer on which the second light reflecting layer is laminated. Specifically, a guide groove for tracking a laser beam called a recording track (groove), which is an information recording portion, is provided when a single circular resin substrate is injection-molded, and then on the substrate having the recording track. The first light reflecting layer, the intermediate layer composed of the cured film of the ultraviolet curable composition, and the second light reflecting layer are sequentially laminated, and at least the light transmitting layer is provided on the second light reflecting layer. In this case, pits are formed on the second intermediate layer. A configuration in which a second intermediate layer made of a cured film of an ultraviolet curable composition is further provided between the first light reflecting layer and the intermediate layer made of a cured film of the ultraviolet curable composition is also preferable. Can be used.
 また、記録・再生可能なディスクは、前記基板と第一の光反射層との間及び第二の中間層と第二の光反射層との間に情報記録層が設けられた構成である。詳細には、1枚の円形樹脂基板上に第一の光反射層を形成し、次いで相変化膜又は光磁気記録膜等の第一の情報記録層を設け、更に、該第一の光反射層上に、紫外線硬化型組成物の硬化膜からなる中間層、及び第二の光反射層、第二の情報記録層を形成して、当該層上に更に光透過層を形成することで、二層の情報記録層を有する構成とすることができる。当該構成においても上記と同様に、第一の光反射層と、紫外線硬化型組成物の硬化膜からなる中間層との間に、さらに紫外線硬化型組成物の硬化膜からなる第二の中間層を設けてもよい。あるいは、再生専用のディスク及び記録・再生可能なディスク共に、更に層を積層して三層以上の情報記録部位や情報記録層を有する構成としてもよい。 Further, the recordable / reproducible disc has a configuration in which an information recording layer is provided between the substrate and the first light reflecting layer and between the second intermediate layer and the second light reflecting layer. Specifically, a first light reflecting layer is formed on one circular resin substrate, then a first information recording layer such as a phase change film or a magneto-optical recording film is provided, and the first light reflecting layer is further provided. By forming an intermediate layer composed of a cured film of an ultraviolet curable composition on the layer, a second light reflecting layer, and a second information recording layer, and further forming a light transmitting layer on the layer, It can be set as the structure which has two layers of information recording layers. In this configuration as well, as described above, a second intermediate layer made of a cured film of an ultraviolet curable composition is further interposed between the first light reflecting layer and the intermediate layer made of a cured film of the ultraviolet curable composition. May be provided. Alternatively, both the read-only disc and the recordable / reproducible disc may have a structure in which three or more layers of information recording portions and information recording layers are further laminated.
 中間層や光透過層を形成するに際し塗布した紫外線硬化型組成物を紫外線照射することにより硬化させる場合、例えばメタルハライドランプ、高圧水銀灯などを用いた連続光照射方式で行うこともできるし、USP5904795記載の閃光照射方式で行うこともできる。効率よく硬化出来る点で閃光照射方式がより好ましい。 In the case of curing the ultraviolet curable composition applied in forming the intermediate layer or the light transmitting layer by irradiating with ultraviolet rays, for example, it can be performed by a continuous light irradiation method using a metal halide lamp, a high pressure mercury lamp, or the like, and described in US Pat. No. 5,904,795. It can also be performed by the flash irradiation method. The flash irradiation method is more preferable in that it can be cured efficiently.
 紫外線を照射する場合、積算光量は0.05~1J/cmとなるようにコントロールするのが好ましい。積算光量は0.05~0.8J/cmであることがより好ましく、0.05~0.6J/cmであることが特に好ましい。本発明の光ディスクに使用する紫外線硬化型組成物は、積算光量が少量であっても、十分に硬化し、光ディスク端面や表面のタックが発生せず、更に光ディスクの反りや歪みが発生しない。 When irradiating with ultraviolet rays, it is preferable to control the accumulated light amount to be 0.05 to 1 J / cm 2 . More preferably accumulated light amount is 0.05 ~ 0.8J / cm 2, particularly preferably 0.05 ~ 0.6J / cm 2. The ultraviolet curable composition used for the optical disk of the present invention is sufficiently cured even when the integrated light quantity is small, and does not cause tacking of the end face or surface of the optical disk, and further does not cause warping or distortion of the optical disk.
 また、書込可能な光ディスクの場合には、光反射層上に情報記録層が設けられる。情報記録層としては、情報の記録・再生が可能であればよく、相変化型記録層、光磁気記録層、あるいは有機色素型記録層のいずれであってもよい。 In the case of a writable optical disc, an information recording layer is provided on the light reflecting layer. The information recording layer only needs to be capable of recording / reproducing information, and may be any of a phase change recording layer, a magneto-optical recording layer, and an organic dye recording layer.
 情報記録層が相変化型記録層である場合には、当該情報記録層は通常、誘電体層と相変化膜から構成される。誘電体層は、相変化層に発生する熱を緩衝する機能、ディスクの反射率を調整する機能を求められ、ZnSとSiOの混合組成が用いられる。相変化膜は、膜の相変化により非晶状態と結晶状態で反射率差を生じるものであり、Ge-Sb-Te系、Sb-Te系、Ag-In-Sb-Te系合金を用いることができる。 When the information recording layer is a phase change recording layer, the information recording layer is usually composed of a dielectric layer and a phase change film. The dielectric layer is required to have a function of buffering heat generated in the phase change layer and a function of adjusting the reflectivity of the disk, and a mixed composition of ZnS and SiO 2 is used. The phase change film causes a difference in reflectance between the amorphous state and the crystalline state due to the phase change of the film, and uses a Ge—Sb—Te, Sb—Te, or Ag—In—Sb—Te alloy. Can do.
 また、本発明の光ディスクにおいては、光透過層が最表面の層であってもよいが、更にその表層にハードコート層を設けてもよい。ハードコート層は、光ディスクの反りの観点から、膜厚が薄いことが好ましく、5μm以下が好ましい。 In the optical disc of the present invention, the light transmission layer may be the outermost layer, but a hard coat layer may be further provided on the surface layer. The hard coat layer is preferably thin from the viewpoint of warping of the optical disc, and is preferably 5 μm or less.
 本発明の光ディスクは、光透過層の面に荷重をかけたのちの信号エラーSERが10-2以下であることが、信号の再生不良が少ないので、好ましい。 In the optical disc of the present invention, it is preferable that the signal error SER after applying a load to the surface of the light transmission layer is 10 −2 or less because there are few signal reproduction failures.
[実施態様]
 以下、本発明の光ディスクの具体例として、二層型光ディスクの具体的構成の一例を以下に示す。
[Embodiment]
Hereinafter, as a specific example of the optical disc of the present invention, an example of a specific configuration of a two-layer optical disc is shown below.
 二層型光ディスクの好ましい実施態様としては、例えば、図1に示したように、基板1上に、第一の光反射層2と、紫外線硬化型組成物の硬化膜からなる中間層3とが積層され、さらにその上に、第二の光反射層4と、光透過層5とが積層され、光透過層5側からブルーレーザーを入射して情報の記録又は再生を行う二層型光ディスクの構成が例示できる。層の厚さとしては、光透過層5の厚さと中間層3の厚さの和が100±10μmの範囲である。基板1の厚さは1.1mm程度、光反射膜は銀等の薄膜である。 As a preferred embodiment of the two-layer type optical disc, for example, as shown in FIG. 1, a first light reflecting layer 2 and an intermediate layer 3 made of a cured film of an ultraviolet curable composition are formed on a substrate 1. A two-layer type optical disc in which a second light reflecting layer 4 and a light transmitting layer 5 are stacked thereon, and a blue laser is incident from the light transmitting layer 5 side to record or reproduce information. The configuration can be exemplified. As the thickness of the layer, the sum of the thickness of the light transmission layer 5 and the thickness of the intermediate layer 3 is in the range of 100 ± 10 μm. The thickness of the substrate 1 is about 1.1 mm, and the light reflecting film is a thin film such as silver.
 当該構成においては図2のように、最表層にハードコート層6が設けられていてもよい。ハードコート層6は、高硬度で、耐摩耗性に優れる層であることが好ましい。ハードコート層の厚さは、1~5μmであることが好ましく、3~5μmであることがより好ましい。また、図3のように、第一の光反射層2と第二の光反射層4との間に、第二の光反射層4と積層される紫外線硬化型組成物の硬化膜からなる中間層3と、第一の光反射層2と積層される第二の中間層7とが設けられた構成も好ましい。 In this configuration, as shown in FIG. 2, a hard coat layer 6 may be provided as the outermost layer. The hard coat layer 6 is preferably a layer having high hardness and excellent wear resistance. The thickness of the hard coat layer is preferably 1 to 5 μm, and more preferably 3 to 5 μm. Further, as shown in FIG. 3, an intermediate made of a cured film of an ultraviolet curable composition laminated with the second light reflecting layer 4 between the first light reflecting layer 2 and the second light reflecting layer 4. A configuration in which the layer 3 and the second intermediate layer 7 laminated with the first light reflection layer 2 are also preferable.
 図1に示す光ディスクの製造方法を以下に説明する。
 まず、ポリカーボネート樹脂を射出成形することによって、記録トラック(グルーブ)と呼ばれるレーザー光をトラッキングするための案内溝を有する基板1を作製する。次に基板1の記録トラック側の表面に、銀合金などをスパッタまたは蒸着することにより第一の光反射層2を成膜する。この上に記録トラックを有する中間層3を形成する紫外線硬化型組成物を塗布し、その上に記録トラック(グルーブ)を形成するための型を貼り合わせ、この貼り合わせたディスクの片面または両面から紫外線を照射して、紫外線硬化型組成物を硬化させる。その後、型を剥離して、中間層3の記録トラック(グルーブ)を有する側の表面に、銀合金などをスパッタまたは蒸着することにより第二の光反射層4を成膜し、この上に、紫外線硬化型組成物を塗付した後、紫外線照射により硬化させ、光透過層5を形成することで、図1の光ディスクを作製する。図2の光ディスクの場合には、この上に更にスピンコート等によりハードコート層6を形成する。
A method for manufacturing the optical disk shown in FIG. 1 will be described below.
First, a substrate 1 having a guide groove for tracking a laser beam called a recording track (groove) is manufactured by injection molding a polycarbonate resin. Next, the first light reflecting layer 2 is formed on the surface of the substrate 1 on the recording track side by sputtering or vapor-depositing a silver alloy or the like. An ultraviolet curable composition for forming the intermediate layer 3 having a recording track is applied thereon, and a mold for forming a recording track (groove) is bonded thereon, from one or both sides of the bonded disk. The ultraviolet curable composition is cured by irradiating with ultraviolet rays. Thereafter, the mold is peeled off, and the second light reflecting layer 4 is formed on the surface of the intermediate layer 3 on the side having the recording track (groove) by sputtering or vapor deposition of silver alloy or the like. After applying the ultraviolet curable composition, it is cured by ultraviolet irradiation to form the light transmission layer 5, thereby producing the optical disk of FIG. In the case of the optical disk of FIG. 2, a hard coat layer 6 is further formed thereon by spin coating or the like.
 図3に示す光ディスクの製造方法を以下に説明する。
 まず、ポリカーボネート樹脂を射出成形にすることによって、記録トラック(グルーブ)と呼ばれるレーザー光をトラッキングするための案内溝を有する基板1を作製する。次に、基板1の記録トラック側の表面に、銀合金などをスパッタまたは蒸着することにより第一の光反射層2を成膜する。
A method for manufacturing the optical disk shown in FIG. 3 will be described below.
First, a substrate 1 having a guide groove for tracking laser light called a recording track (groove) is manufactured by injection molding polycarbonate resin. Next, the first light reflecting layer 2 is formed on the surface of the substrate 1 on the recording track side by sputtering or vapor-depositing a silver alloy or the like.
 この上に、中間層を形成するが、まず、基板1に形成された第一の光反射層2上に、記録トラックを有する中間層3を積層するための第二の中間層7を形成する。当該第二の中間層7は、紫外線硬化型組成物を塗布し、ディスクの片面または両面から紫外線を照射して、紫外線硬化型組成物を硬化又は半硬化させ、その上に記録トラックを有する中間層3を形成するための紫外線硬化型組成物を塗布し、その上に記録トラック(グルーブ)を形成するための型を貼り合わせ、この貼り合わせたディスクの片面または両面から紫外線を照射して、紫外線硬化型組成物を硬化させる。その後、型を剥離して、中間層3の記録トラック(グルーブ)を有する側の表面に、銀合金などをスパッタまたは蒸着することにより第二の光反射層4を成膜し、この上に、紫外線硬化型組成物を塗付した後、紫外線照射により硬化させ、光透過層5を形成することで、図3の光ディスクを作製できる。また、光反射層に相変化型記録層を用いる場合でも上記と同様の方法により光ディスクを作成することができる。 An intermediate layer is formed thereon. First, a second intermediate layer 7 for laminating an intermediate layer 3 having a recording track is formed on the first light reflecting layer 2 formed on the substrate 1. . The second intermediate layer 7 is formed by applying an ultraviolet curable composition, irradiating ultraviolet rays from one or both sides of the disk, curing or semi-curing the ultraviolet curable composition, and having a recording track thereon. An ultraviolet curable composition for forming the layer 3 is applied, a mold for forming a recording track (groove) is bonded thereon, and ultraviolet light is irradiated from one or both surfaces of the bonded disk, The ultraviolet curable composition is cured. Thereafter, the mold is peeled off, and the second light reflecting layer 4 is formed on the surface of the intermediate layer 3 on the side having the recording track (groove) by sputtering or vapor deposition of silver alloy or the like. The optical disk shown in FIG. 3 can be produced by applying the ultraviolet curable composition and then curing it by ultraviolet irradiation to form the light transmission layer 5. Even when a phase change recording layer is used for the light reflection layer, an optical disc can be produced by the same method as described above.
 次に、合成例及び実施例を挙げて本発明を詳細に説明するが、本発明はこれら実施例に限定されるものではない。以下実施例中の「部」は「質量部」を表す。 Next, the present invention will be described in detail with reference to synthesis examples and examples, but the present invention is not limited to these examples. Hereinafter, “parts” in the examples represent “parts by mass”.
 下記表1に示した組成(表中の組成の数値は質量部を表す)により配合した各組成物を60℃で3時間加熱、溶解して、実施例1~3及び比較例1~3の各実施例及び比較例の紫外線硬化型組成物を調製した。得られた組成物について、下記の評価を行い、得られた結果を表1に示す。 Each composition formulated according to the composition shown in Table 1 below (the numerical values in the table represent parts by mass) were heated and dissolved at 60 ° C. for 3 hours to obtain Examples 1 to 3 and Comparative Examples 1 to 3. The ultraviolet curable composition of each Example and the comparative example was prepared. The obtained composition was evaluated as follows, and the obtained results are shown in Table 1.
<試験方法:粘度の測定方法>
 紫外線硬化型組成物について、25℃における粘度をB型粘度計((株)東京計器製、BM型)を用いて測定した。
<Test method: Method for measuring viscosity>
About the ultraviolet curable composition, the viscosity in 25 degreeC was measured using the B-type viscosity meter (the Tokyo Keiki make, BM type | mold).
<試験方法:弾性率の測定方法>
 紫外線硬化型組成物を、ガラス板上に硬化塗膜が100±10μmになるように塗布した後、メタルハライドランプ(コールドミラー付き、ランプ出力120W/cm)を用いて窒素雰囲気中で500mJ/cmで硬化させた。この硬化塗膜の弾性率をティー・エイ・インストルメント(株)社の自動動的粘弾性測定装置で測定し、25℃における動的弾性率E’を弾性率とした。
<Test method: Measurement method of elastic modulus>
The UV curable composition was applied on a glass plate so that the cured coating film was 100 ± 10 μm, and then 500 mJ / cm 2 in a nitrogen atmosphere using a metal halide lamp (with a cold mirror, lamp output 120 W / cm). And cured. The elastic modulus of this cured coating film was measured with an automatic dynamic viscoelasticity measuring apparatus manufactured by TA Instruments Inc., and the dynamic elastic modulus E ′ at 25 ° C. was defined as the elastic modulus.
<試験方法:Potential Volatiles>
 紫外線硬化後に110℃環境下1時間静置した際の重量減少率を、ASTM規格のDesignation:D5403に従って測定した。
 ASTMのD5403において、紫外線硬化後に110℃環境下に1時間静置した際の重量減少率は、Potential Volatilesとして表され、次の式から求めた。
 Potential Volatiles=100[(C-D)/(B-A)]
 ここで、A:ガラス基板の重さ、B:ガラス基板+硬化前の中間層、C:ガラス基板+硬化後の中間層、D:ガラス基板+110℃環境下に1時間静置後の中間層、である。
<Test method: Potential Volatiles>
The weight reduction rate when allowed to stand in an environment of 110 ° C. for 1 hour after UV curing was measured according to ASTM specification Design: D5403.
In ASTM D5403, the weight reduction rate after standing for 1 hour in a 110 ° C. environment after UV curing was expressed as Potential Volatiles, and was determined from the following equation.
Potential Volatiles = 100 [(CD) / (BA)]
Here, A: weight of glass substrate, B: glass substrate + intermediate layer before curing, C: glass substrate + intermediate layer after curing, D: glass substrate + intermediate layer after standing for 1 hour in 110 ° C. environment .
<試験方法:光ディスクの耐久性試験>
 記録トラック(グルーブ)が形成され、銀を主成分とする合金からなる反射膜が積層されたポリカーボネート円盤に各実施例および各比較例の紫外線硬化型組成物ディスペンサで塗布し、透明ポリカーボネート円盤を重ね合わせた。次いでスピンコーターで硬化塗膜の膜厚が10~20μmになるよう回転させた。次いで、XENON社製「フラッシュ照射装置RC-800」を用い、透明基板側から空気中で15ショット紫外線を照射して、各組成物を使用した光ディスクサンプルを作製した。
<Test method: optical disk durability test>
The recording disk (groove) is formed and applied to the polycarbonate disk on which the reflective film made of an alloy containing silver as a main component is laminated with the ultraviolet curable composition dispenser of each example and each comparative example, and the transparent polycarbonate disk is stacked. Combined. Subsequently, it was rotated with a spin coater so that the film thickness of the cured coating film became 10 to 20 μm. Next, using a “flash irradiation device RC-800” manufactured by XENON, 15-shot ultraviolet rays were irradiated in air from the transparent substrate side to prepare optical disk samples using the respective compositions.
 得られた各サンプルのPIエラー数を測定し、その後エスペック社製「エタック恒温高湿器SD01」を使用して、80℃85%RH96時間の環境試験を行った。試験後各サンプルのPIエラー数を測定した。 The number of PI errors of each obtained sample was measured, and then an environmental test was performed at 80 ° C. and 85% RH 96 hours using “Etac constant temperature and high humidity device SD01” manufactured by Espec. After the test, the number of PI errors in each sample was measured.
 PIエラー比はAudio Dev株式会社製「SA300」により測定した。環境試験前後でのPIエラー数よりPIエラー比(環境試験後のPIエラー数/環境試験前のPIエラー数)を求めた。 PI error ratio was measured by “SA300” manufactured by Audio Dev Co., Ltd. The PI error ratio (number of PI errors after the environmental test / number of PI errors before the environmental test) was determined from the number of PI errors before and after the environmental test.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
 表中のオリゴマー等は、下記のとおりである。
 FAU-742TP:ウレタンアクリレート(分子量850のポリテトラメチレングリコールの両端にトリレンジイソシアネート/ヒドロキシエチルアクリレートを反応させたウレタンアクリレート) DIC株式会社製 分子量Mw:3700
 V5530:ビスフェノールA型エポキシアクリレート(分子量850のビスフェノールA型エポキシ樹脂の両端にアクリル酸を反応させたエポキシアクリレート) DIC株式会社製
 TMP(3EO)TA:トリメチロールプロパン1モルに3モルのエチレンオキサイドを付加して得たトリオールのトリアクリレート
 DPGDA:ジプロピレングリコールジアクリレート
 Photomer4094:Glyceryl[4PO]triacrylate コグニスジャパン(株)製
 Photomer4017:Hexanediol diacrylate コグニスジャパン(株)製
 THFA:テトラヒドロフルフリルアクリレート
 開始剤A:1-ヒドロキシ-シクロヘキシル-フェニル-ケトン(分子量:204.3) チバ・スペシャルティ・ケミカルズ(株)製
 開始剤B:2-メチル-1-[4-(メチルチオ)フェニル]-2-モルフォリノプロパン-1-オン(分子量:279.4)チバ・スペシャルティ・ケミカルズ(株)製
 開始剤C:KIP150:下式(i)で表されるオリゴ[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(m=2及び3の混合物、分子量:469)
The oligomers in the table are as follows.
FAU-742TP: urethane acrylate (urethane acrylate obtained by reacting tolylene diisocyanate / hydroxyethyl acrylate on both ends of polytetramethylene glycol having a molecular weight of 850) Molecular weight Mw: 3700, manufactured by DIC Corporation
V5530: Bisphenol A type epoxy acrylate (epoxy acrylate in which acrylic acid is reacted on both ends of bisphenol A type epoxy resin having a molecular weight of 850) DIC Corporation TMP (3EO) TA: 3 mol of ethylene oxide per 1 mol of trimethylolpropane Triol of triol obtained by addition DPGDA: Dipropylene glycol diacrylate Photor 4094: Glyceryl [4PO] triacrylate Cognis Japan Co., Ltd. Photomer 4017: Hexadidiol diacrylate Cognis Japan Co., Ltd. THFA: Tetrahydrofurfuryl acrylate -Hydroxy-cyclohexyl-phenyl-ketone (molecular weight: 204.3) Ciba Specialte Initiator B: 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (molecular weight: 279.4) Ciba Specialty Chemicals Co., Ltd. Manufactured initiator C: KIP150: oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone represented by the following formula (i) (mixture of m = 2 and 3, molecular weight) : 469)
Figure JPOXMLDOC01-appb-C000006
(式(i)中、Rは水素原子又はメチル基を表し、mは2~3である。)
 開始剤D: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(分子量:348)
 開始剤E:2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン(分子量:164.2) チバ・スペシャルティ・ケミカルズ(株)製
 没食子酸:(大日本住友製薬(株)製)
Figure JPOXMLDOC01-appb-C000006
(In formula (i), R represents a hydrogen atom or a methyl group, and m is 2 to 3.)
Initiator D: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (molecular weight: 348)
Initiator E: 2-hydroxy-2-methyl-1-phenyl-propan-1-one (molecular weight: 164.2) Ciba Specialty Chemicals Co., gallic acid: (Dainippon Sumitomo Pharma Co., Ltd.)
 表1に示すように、中間層の重量減少率が低い実施例1~10の光ディスクは、PIエラー比が小さく、高温高湿環境下での耐久性は良好であった。一方、比較例1~4は、PIエラー比が大きく、高温高湿環境下での耐久性がなかった。 As shown in Table 1, the optical discs of Examples 1 to 10 having a low weight loss rate of the intermediate layer had a small PI error ratio and good durability under a high temperature and high humidity environment. On the other hand, Comparative Examples 1 to 4 had a large PI error ratio and were not durable in a high temperature and high humidity environment.
本発明の光ディスクの一例を示す図である。It is a figure which shows an example of the optical disk of this invention. ハードコート層を有する本発明の光ディスクの一例を示す図である。It is a figure which shows an example of the optical disk of this invention which has a hard-coat layer. 二層の中間層を有する本発明の光ディスクの一例を示す図である。It is a figure which shows an example of the optical disk of this invention which has a 2 layer intermediate | middle layer.
 1 基板
 2 第一光反射層
 3 中間層
 4 第二光反射層
 5 光透過層
 6 ハードコート層
 7 第二中間層
DESCRIPTION OF SYMBOLS 1 Substrate 2 First light reflection layer 3 Intermediate layer 4 Second light reflection layer 5 Light transmission layer 6 Hard coat layer 7 Second intermediate layer

Claims (13)

  1. 基板上に、少なくとも第一の光反射層、紫外線硬化型組成物の硬化膜からなる中間層、第二の光反射層及び光透過層を順に有し、前記紫外線硬化型組成物の硬化膜からなる中間層が前記第二の光反射層と直接積層され、前記光透過層側からブルーレーザーを入射して情報の再生を行う光ディスクであって、
     前記第二の光反射層が積層される中間層を形成する紫外線硬化型組成物の硬化膜が、紫外線硬化後に110℃環境下に1時間静置した際の重量減少率が3.5質量%以下であることを特徴とする光ディスク。
    On the substrate, at least a first light reflection layer, an intermediate layer composed of a cured film of an ultraviolet curable composition, a second light reflective layer, and a light transmission layer in that order, from the cured film of the ultraviolet curable composition An intermediate layer is directly laminated with the second light reflecting layer, and reproduces information by injecting a blue laser from the light transmitting layer side,
    The cured film of the ultraviolet curable composition forming the intermediate layer on which the second light reflecting layer is laminated has a weight reduction rate of 3.5% by mass when left in an environment of 110 ° C. for 1 hour after ultraviolet curing. An optical disc characterized by:
  2. 前記第二の光反射層が積層される中間層を形成する紫外線硬化型組成物の硬化膜の25℃における弾性率が、800~3000MPaである請求項1に記載の光ディスク。 2. The optical disk according to claim 1, wherein the cured film of the ultraviolet curable composition forming the intermediate layer on which the second light reflecting layer is laminated has an elastic modulus at 25 ° C. of 800 to 3000 MPa.
  3. 前記第二の光反射層が積層される中間層に使用する紫外線硬化型組成物が、紫外線硬化性化合物と重合開始剤とを含有し、
     前記紫外線硬化性化合物として一分子中に二以上の(メタ)アクリロイル基を有する(メタ)アクリレートモノマーを50質量%以上含有し、一分子中に一の(メタ)アクリロイル基を有する(メタ)アクリレートモノマーの含有量が10質量%以下である請求項1又は2に記載の光ディスク。
    The ultraviolet curable composition used for the intermediate layer on which the second light reflecting layer is laminated contains an ultraviolet curable compound and a polymerization initiator,
    (UV) curable compound containing 50% by mass or more of (meth) acrylate monomer having two or more (meth) acryloyl groups in one molecule, and (meth) acrylate having one (meth) acryloyl group in one molecule The optical disk according to claim 1, wherein the monomer content is 10% by mass or less.
  4. 前記第二の光反射層が積層される中間層に使用する紫外線硬化型組成物が、前記紫外線硬化性化合物100質量部に対する重合開始剤の含有量が2~10質量部であり、分子量が215以下の重合開始剤の含有量が、5質量部以下である請求項1~3のいずれかに記載の光ディスク。 The ultraviolet curable composition used for the intermediate layer on which the second light reflecting layer is laminated has a polymerization initiator content of 2 to 10 parts by mass and a molecular weight of 215 with respect to 100 parts by mass of the ultraviolet curable compound. The optical disk according to any one of claims 1 to 3, wherein the content of the following polymerization initiator is 5 parts by mass or less.
  5. 前記紫外線硬化型組成物100質量部に対する分子量が215を越える重合開始剤の含有量が1質量部以上である請求項4に記載の光ディスク。 The optical disk according to claim 4, wherein the content of the polymerization initiator having a molecular weight exceeding 215 with respect to 100 parts by mass of the ultraviolet curable composition is 1 part by mass or more.
  6. 前記紫外線硬化型組成物の25℃におけるB型粘度が1000mPa・s以下である請求項1~5のいずれかに記載の光ディスク。 6. The optical disc according to claim 1, wherein the ultraviolet curable composition has a B-type viscosity at 25 ° C. of 1000 mPa · s or less.
  7. 前記第一の光反射層と、前記第二の光反射層が積層される紫外線硬化型組成物の硬化膜からなる中間層との間に、紫外線硬化型組成物の硬化膜からなる第二の中間層が、前記第一の光反射層と直接積層されるよう設けられた請求項1~6のいずれかに記載の光ディスク。 A second layer made of a cured film of an ultraviolet curable composition is interposed between the first light reflective layer and an intermediate layer made of a cured film of an ultraviolet curable composition on which the second light reflective layer is laminated. The optical disc according to any one of claims 1 to 6, wherein an intermediate layer is provided so as to be directly laminated on the first light reflecting layer.
  8. 前記第二の中間層を形成する紫外線硬化型組成物の硬化膜の25℃における弾性率が、500~3000MPaであり、25℃におけるB型粘度が1000mPa・s以下である請求項7に記載の光ディスク。 8. The cured film of the ultraviolet curable composition forming the second intermediate layer has an elastic modulus at 25 ° C. of 500 to 3000 MPa, and a B-type viscosity at 25 ° C. of 1000 mPa · s or less. optical disk.
  9. 基板上に、少なくとも第一の光反射層、紫外線硬化型組成物の硬化膜からなる中間層、第二の光反射層及び光透過層を順に有し、前記紫外線硬化型組成物の硬化膜からなる中間層が前記第二の光反射層と直接積層され、前記光透過層側からブルーレーザーを入射して情報の再生を行う光ディスクの前記第二の硬化膜を形成する紫外線硬化型組成物であって、
     紫外線硬化性化合物と重合開始剤とを含有し、
     前記紫外線硬化性化合物100質量部に対する重合開始剤の含有量が2~10質量部であり、分子量が215以下の重合開始剤の含有量が、5質量部以下であることを特徴とする光ディスク中間層用紫外線硬化型組成物。
    On the substrate, at least a first light reflection layer, an intermediate layer composed of a cured film of an ultraviolet curable composition, a second light reflective layer, and a light transmission layer in that order, from the cured film of the ultraviolet curable composition An intermediate layer is directly laminated with the second light reflecting layer, and an ultraviolet curable composition for forming the second cured film of the optical disc that reproduces information by entering a blue laser from the light transmitting layer side. There,
    Containing an ultraviolet curable compound and a polymerization initiator,
    The content of the polymerization initiator with respect to 100 parts by mass of the ultraviolet curable compound is 2 to 10 parts by mass, and the content of the polymerization initiator with a molecular weight of 215 or less is 5 parts by mass or less. UV curable composition for layers.
  10. 前記紫外線硬化性化合物が、一分子中に二以上の(メタ)アクリロイル基を有する(メタ)アクリレートモノマーを50質量%含有し、一分子中に一の(メタ)アクリロイル基を有する(メタ)アクリレートモノマーの含有量が10質量%以下である請求項9に記載の光ディスク中間層用紫外線硬化型組成物。 The ultraviolet curable compound contains 50% by mass of (meth) acrylate monomer having two or more (meth) acryloyl groups in one molecule, and (meth) acrylate having one (meth) acryloyl group in one molecule. The ultraviolet curable composition for an optical disc intermediate layer according to claim 9, wherein the monomer content is 10% by mass or less.
  11. 分子量が215を越える重合開始剤の含有量が1質量%以上である請求項9又は10に記載の光ディスク中間層用紫外線硬化型組成物。 The ultraviolet curable composition for an optical disc intermediate layer according to claim 9 or 10, wherein the content of the polymerization initiator having a molecular weight exceeding 215 is 1% by mass or more.
  12. 前記分子量が215を越える重合開始剤が、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルフォリノプロパン-1-オン、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、および、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から選ばれる少なくとも一種である請求項11に記載の光ディスク中間層用紫外線硬化型組成物。 The polymerization initiator having a molecular weight exceeding 215 is 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, oligo [2-hydroxy-2-methyl-1- [4 12. The ultraviolet curable composition for an optical disc intermediate layer according to claim 11, which is at least one selected from-(1-methylvinyl) phenyl] propanone and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
  13. 前記紫外線硬化型組成物が、没食子酸を含有する請求項9~12のいずれかに記載の光ディスク中間層用紫外線硬化型組成物。 The ultraviolet curable composition for optical disc intermediate layer according to any one of claims 9 to 12, wherein the ultraviolet curable composition contains gallic acid.
PCT/JP2010/059329 2009-06-08 2010-06-02 Optical disc and ultraviolet-curable composition for intermediate layer of optical disc WO2010143568A1 (en)

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