WO2010109615A1 - Composition de résine durcissable pour disques optiques, et disque optique - Google Patents

Composition de résine durcissable pour disques optiques, et disque optique Download PDF

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WO2010109615A1
WO2010109615A1 PCT/JP2009/055994 JP2009055994W WO2010109615A1 WO 2010109615 A1 WO2010109615 A1 WO 2010109615A1 JP 2009055994 W JP2009055994 W JP 2009055994W WO 2010109615 A1 WO2010109615 A1 WO 2010109615A1
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meth
resin composition
curable resin
acrylate
mass
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PCT/JP2009/055994
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Japanese (ja)
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松田　安弘
川田　雄一
裕己 橘
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株式会社日本触媒
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Priority to PCT/JP2009/055994 priority Critical patent/WO2010109615A1/fr
Priority to PCT/JP2009/070126 priority patent/WO2010064610A1/fr
Publication of WO2010109615A1 publication Critical patent/WO2010109615A1/fr

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    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/254—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of protective topcoat layers
    • G11B7/2542—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of protective topcoat layers consisting essentially of organic resins

Definitions

  • the present invention relates to a curable resin composition for optical disks and an optical disk.
  • blue laser light having a wavelength of 405 nm is employed to increase the capacity of the optical recording medium.
  • NA numerical aperture
  • the laser beam spot diameter during recording / reproducing is reduced to about 0.44 times that of DVD, and the signal is reduced.
  • a protective layer is provided on the disk surface viewed from the laser incident side in order to protect the reflective film and the recording layer.
  • the thickness of this protective layer was about 600 ⁇ m for DVD, but is considerably thin, about 100 ⁇ m for Blu-ray Disc.
  • Blu-ray discs can reduce recording laser beam spot distortion (bokeh) caused by tilting the disc surface due to disc warp, etc., by reducing the thickness of the protective layer, and achieve highly reliable recording and playback. I am doing so.
  • Japanese Patent Application Laid-Open No. 2006-351102 describes that the thickness of the protective layer is required to be highly uniform because unevenness in the thickness of the protective layer (light transmission film) causes a serious problem in recording and reproducing information.
  • Japanese Patent Application Laid-Open No. 2007-115356 describes the necessity of controlling the thickness of the protective layer (transparent cover layer) to 100 ⁇ m ⁇ 2 ⁇ m.
  • Japanese Patent Application Laid-Open No. 2008-126518 discloses that a laser spot position may fluctuate due to scratches (permanent deformation) such as dents generated in an optical recording medium, which may cause problems in recording and reproducing information. Is described.
  • Japanese Patent Application Laid-Open No. 2000-322768 describes a technique for preventing the protective layer (light transmission layer) from being scratched or deformed so as not to hinder the recording and reproduction.
  • a method of measuring the amount of deformation a method of measuring the load and displacement during deformation while pushing a minute diamond indenter is adopted.
  • JP-A-2002-157782 and JP-A-2003-132596 when stored in a high-temperature / high-humidity environment or a low-temperature environment, if the optical recording medium is warped, the loading of the drive device is hindered. In addition, since a reading error occurs when a warp accompanied by a twist occurs, it is described that an optical recording medium with a small warp occurring in various environments is required.
  • the protective layer There are mainly two methods for forming the protective layer. There are a sheet bonding method in which a polycarbonate sheet is bonded with an ultraviolet curable adhesive, and a spin coating method in which an ultraviolet curable resin is applied by spin coating and the resin is cured by irradiating ultraviolet rays. At present, the spin coating method has become the mainstream in terms of cost. However, when the protective layer is formed using an ultraviolet curable resin, in addition to the above-mentioned film thickness uniformity being required, the optical recording medium is warped mainly due to the curing shrinkage of the ultraviolet curable resin. happenss.
  • Japanese Patent Application Laid-Open No. 2003-263780 discloses an optical disk having a protective layer (light transmissive layer) excellent in transparency, abrasion resistance, and mechanical properties, with a tensile elastic modulus of the protective layer in a specific range. It is described that it is desirable to do.
  • Japanese Patent Application Laid-Open No. 2007-217134 discloses an optical recording medium having excellent dimensional stability against changes in the environment of a cured coating film obtained by ultraviolet irradiation.
  • an optical disc having a protective layer (light transmissive layer) on the reflective film for example, a Blu-ray disc that reads information with blue laser light
  • a protective layer for example, a Blu-ray disc that reads information with blue laser light
  • long-term storage stability high temperature environment or low temperature environment
  • Japanese Patent Application Laid-Open Nos. 2006-4458 and 2003-263780 disclose that an optical disk having a protective layer (light transmissive layer) excellent in transparency and mechanical properties is used as a protective layer for an optical disk. It is described that it is desirable that the tensile modulus of the layer be in a specific range.
  • Japanese Patent Application Laid-Open No. 2007-102980 discloses that the thickness of the protective layer and the thickness of the protective layer at 30.degree. It is described that the product with the elastic modulus is not more than a specific value.
  • a hard hard coat layer is formed on a protective layer having a low elastic modulus, a crack may occur in the hard coat layer depending on use conditions, which has been a problem.
  • the protective layer has a low-viscosity resin composition that does not substantially contain an organic solvent.
  • the hard coat material needs to be further improved in order to prevent deformation of the optical disk and dents and cracks after being pushed in from the hard coat layer.
  • the problems to be solved by the present invention are a reflective film for reflecting laser light for reading information on a substrate, and a protective layer (transparent cover layer) having a thickness of 20 ⁇ m to 150 ⁇ m on the reflective film.
  • a protective layer transparent cover layer
  • a Blu-ray disc that reads information with blue light having a wavelength of around 400 nm
  • the present invention provides a curable resin composition for optical discs that is excellent in low warpage in a storage test under an environment and a residual film property under a high temperature environment) and has a small amount of permanent deformation such as dents.
  • An object of the present invention is to provide an optical disc using a cured product as a protective layer.
  • the inventors of the present invention have set the radical polymerizable unsaturated group equivalent and the content of specific (meth) acrylates in a specific range in the curable resin composition for optical discs.
  • High transparency, long-term storage stability (low warpage in storage tests in high and low temperature environments, residual film properties in high temperature environments), and permanent areas such as dents after pressing the protective layer The present invention was completed by finding that an optical disk with a small amount of deformation could be obtained.
  • the composition is adjusted so that the relationship between the amount of the radical polymerizable unsaturated group in the curable resin composition and the specific (meth) acrylic acid ester is within a certain range, the curable resin composition is cured. Whether the cured product obtained has a high or low elastic modulus, the amount of permanent deformation due to the dent generated after the protective film is pushed in becomes extremely small and can be suitably used for an optical disc.
  • the curable resin composition for an optical disk of the present invention is present on a base and a reflective film for reflecting information-reading laser light, and on the reflective film, in order to solve the above problems.
  • the radical polymerizable unsaturated group equivalent (A) capable of forming a crosslinked structure is adjusted according to the content (B) of the adduct-containing (meth) acrylic acid ester into which the soft component can be introduced, and A ⁇
  • B the content of the adduct-containing (meth) acrylic acid ester into which the soft component can be introduced
  • the alkylene oxide adduct-containing polyfunctional (meth) acrylic acid esters are preferably diacrylates of bisphenol A alkylene oxide adducts.
  • the viscosity of the curable resin composition of the present invention at 25 ° C is preferably 800 mPa ⁇ s or more and 3500 mPa ⁇ s or less.
  • the storage elastic modulus E ′ at 25 ° C. of the cured product obtained by curing the curable resin composition is preferably 10 MPa or more and 150 MPa or less. Moreover, it is also a preferable aspect that the storage elastic modulus E ′ at 25 ° C. of the cured product obtained by curing the curable resin composition is 1200 MPa or more and 2100 MPa or less. Further, the light transmittance of each wavelength at a thickness of 100 ⁇ m of the cured product obtained by curing the curable resin composition is 85.0% or more at (X) 400 nm, and (Y) 35.0 at 380 nm.
  • the curable resin composition preferably contains a polyfunctional (meth) acrylate and / or a multi-branched reactive compound.
  • the optical disk of the present invention is characterized by having a protective layer formed by curing the curable resin composition for optical disks.
  • the optical disc is obtained by curing a resin composition for hard coat, which is formed directly on the protective layer and contains a multibranched reactive compound and / or a polymer having a reactive group in a side chain, and a polymerization initiator. It is preferable to have a hard coat layer obtained.
  • the multibranched reactive compound is preferably a dendrimer and / or a hyperbranched polymer having two or more reactive groups at its terminals.
  • Addition-containing polyfunctional (meth) acrylic acid esters and / or caprolactone adducts obtained from caprolactone adducts with n 1 or 2 per monovalent addition to a polyhydric alcohol having a valence of 4 or more
  • Examples of the present invention are represented by ⁇ , comparative examples are represented by ⁇ , the radical polymerizable unsaturated group equivalent (g / eq) A in the curable resin composition is plotted on the horizontal axis, and the alkylene oxide adduct-containing polyfunctional is plotted on the vertical axis. It is the graph which plotted content (mass%) B of (meth) acrylic acid ester and caprolactone adduct containing polyfunctional (meth) acrylic acid ester. The line at the top of the graph indicates the boundary line (A / 6.6), and the line at the bottom of the graph indicates the boundary line (A / 35), that is, the upper and lower limits of the present invention.
  • Curable resin composition for optical disk is present on a substrate and reflects a laser beam for reading information, and is present on the reflective film and has a thickness of 20 ⁇ m or more and 150 ⁇ m or less.
  • an alkylene oxide adduct-containing polyfunctional (meth) acrylic acid ester or caprolactone adduct-containing polyfunctional (meth) acrylic acid ester, and a photopolymerization initiator, Radical polymerizable unsaturated group equivalent (g / eq) in the resin composition is A
  • the curable resin composition When the content (% by mass) of the polyfunctional (meth) acrylic acid ester containing an alkylene oxide adduct and the polyfunctional (meth) acrylic acid ester containing a caprolactone adduct is B, 6.6 ⁇ A ⁇ B ⁇ 35 is satisfied.
  • curable resin composition for optical disks of the present invention
  • the curable resin composition of the present invention comprises an alkylene oxide adduct-containing polyfunctional (meth) acrylic acid ester and / or a caprolactone adduct-containing polyfunctional (meth) acrylic acid ester (hereinafter simply referred to as “adduct-containing (meta) )) (Sometimes referred to as “acrylate esters”).
  • the adduct-containing (meth) acrylic acid esters are (meth) acrylic acid esters obtained by esterification with (meth) acrylic acid containing a ring-opened product of an oxyalkylene skeleton or caprolactone in the molecule. is there.
  • the liquid viscosity and the physical properties of the cured product can be adjusted.
  • alkylene oxide adduct-containing polyfunctional (meth) acrylic acid esters examples include di (meth) acrylate of bisphenol A ethylene oxide adduct, di (meth) acrylate of bisphenol A propylene oxide adduct, and cyclohexanedimethanol.
  • the number of repeating oxyalkylene skeletons in these alkylene oxide adduct-containing polyfunctional (meth) acrylic esters is preferably 4 or more and 16 or less, and more preferably 6 or more and 14 or less.
  • polyfunctional (meth) acrylic acid esters containing caprolactone adduct examples include diacrylate of ⁇ -caprolactone adduct such as neopentyl glycol hydroxypivalate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and the like.
  • adduct-containing polyfunctional (meth) acrylic acid esters include di (meth) acrylate of ethylene oxide adduct of bisphenol A, tri (meth) acrylate of ethylene oxide adduct of trimethylolpropane, and neodymium hydroxypivalate.
  • Diacrylate of ⁇ -caprolactone adduct of pentyl glycol is preferred.
  • di (meth) acrylate of ethylene oxide 10 mol adduct of bisphenol A is more preferable.
  • the compounding amount of the adduct-containing polyfunctional (meth) acrylic acid ester is preferably 8% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass, and 70% by mass in the curable resin composition. % Or less, more preferably 65% by mass or less, and still more preferably 60% by mass or less.
  • a dent may be formed when the protective layer is pushed in.
  • it exceeds 70% by mass the curing shrinkage rate and the internal distortion increase, for example, when the warp of the optical disk increases or the protection May crack or crack in the layer.
  • the curable resin composition of the present invention is not limited to the above-mentioned polyfunctional (meth) acrylic acid esters containing alkylene oxide adducts and / or polyfunctional (meth) acrylic acid esters containing caprolactone adducts. You may contain the material which has group.
  • Examples of the material having a radical polymerizable unsaturated group include an oligomer and / or polymer having at least one radical polymerizable group; a multi-branched reactive compound; and a polymerizable monomer.
  • the compound having a radically polymerizable unsaturated group can be cured by active energy rays such as heat, ultraviolet rays, electron beams and gamma rays.
  • Examples of the oligomer and / or polymer having a radical polymerizable unsaturated group include a saturated or unsaturated polybasic acid or an anhydride thereof (for example, maleic acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, Terephthalic acid, tetrahydrophthalic acid, etc.) and saturated or unsaturated polyhydric alcohols (eg, ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1 , 5-pentanediol, polyethylene glycol, polypropylene glycol, 1,4-dimethylolbenzene, trimethylolpropane, pentaerythritol, etc.) and (meth) acrylic acid to obtain polyester (meth) acrylate; Saturated polyhydric alcohols (eg For example, ethylene glycol, neopenty
  • oligomers and / or polymers having both radical polymerizable groups and ion polymerizable groups include epoxy resins (for example, phenol novolac epoxy resins, cresol novolac epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, trisphenol methane type).
  • epoxy resins for example, phenol novolac epoxy resins, cresol novolac epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, trisphenol methane type.
  • epoxy resin polybutanediene-modified epoxy resin, alicyclic epoxy resin, brominated phenol novolak epoxy resin, brominated bisphenol A type epoxy resin, amino group-containing epoxy resin, etc.
  • epoxy resin polybutanediene-modified epoxy resin, alicyclic epoxy resin, brominated phenol novolak epoxy resin, brominated bisphenol A type epoxy resin, amino group-containing epoxy resin, etc.
  • a polybasic acid anhydride eg, maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.
  • the curable resin composition of the present invention includes, as an oligomer and / or polymer having at least one radical polymerizable group, urethane (meth) acrylate, epoxy (meth) acrylate, and polyester (meth) acrylate. It is essential to include at least one selected from the group consisting of:
  • the isocyanate component constituting the urethane (meth) acrylate is preferably a polyvalent isocyanate having an alicyclic skeleton or an aromatic ring skeleton, particularly preferably 2 having an alicyclic skeleton.
  • Divalent isocyanate examples of the divalent isocyanate having an alicyclic skeleton include isophorone diisocyanate.
  • the polyhydric alcohol component constituting the urethane (meth) acrylate is preferably a polyhydric alcohol having an oxyalkylene skeleton, and more preferably a dihydric alcohol.
  • Examples of the dihydric alcohol having an oxyalkylene skeleton include oligoethylene glycol, oligopropylene glycol, oligobutylene glycol, and oligo (ethylene-propylene) glycol, and oligoethylene glycol and oligo (ethylene-propylene) glycol are particularly preferable.
  • the number of repeating oxyalkylene skeletons is preferably 4 or more and 12 or less, and more preferably 6 or more and 10 or less.
  • the hydroxyl group-containing (meth) acrylate component constituting the urethane (meth) acrylate is preferably a hydroxyl group-containing acrylate, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 1,4-butanediol monoacrylate, and the like. Of these, 2-hydroxyethyl acrylate is particularly preferred.
  • the urethane (meth) acrylate may contain urethane (meth) acrylate in which an isocyanate component and a hydroxyl group-containing (meth) acrylate component are directly urethane-bonded in the composition.
  • the preferred isocyanate component and hydroxyl group-containing (meth) acrylate component in the case where the isocyanate component and the hydroxyl group-containing (meth) acrylate component contain urethane (meth) acrylate directly bonded by urethane are the same as described above.
  • Urethane (meth) acrylate is a raw material isocyanate component of 15% by mass to 30% by mass, a raw material polyhydric alcohol component of 45% by mass to 65% by mass, and a raw material hydroxyl group-containing (meth) acrylate component in 100% by mass of the raw material composition. Is preferably 5% by mass to 40% by mass, the raw material isocyanate component is 18% by mass to 25% by mass, the raw material polyhydric alcohol component is 50% by mass to 60% by mass, and the raw material hydroxyl group-containing (meth) acrylate The component is more preferably 15% by mass or more and 32% by mass or less.
  • the isocyanate component and the hydroxyl group-containing (meth) acrylate component contain urethane (meth) acrylate in which the urethane bond is directly bonded
  • the content is 100 as the total of urethane (meth) acrylate having a polyhydric alcohol component.
  • mass% it is preferably 1 mass% or more and 20 mass% or less, and particularly preferably 5 mass% or more and 15 mass% or less.
  • the method for synthesizing urethane (meth) acrylate that can be used as a material having a radically polymerizable unsaturated group is not particularly limited.
  • a raw material isocyanate component and a raw material hydroxyl group-containing (meth) acrylate are reacted, and then a polyhydric alcohol component is used in this order.
  • Method of reacting Method of charging raw material isocyanate component, raw material hydroxyl group-containing (meth) acrylate, and polyhydric alcohol component in a batch; reacting raw material isocyanate component and polyhydric alcohol component, then hydroxyl group-containing (meth) acrylate The method of making it react is mentioned.
  • (Meth) acrylate can also be synthesized at the same time, which is particularly preferable because productivity is improved.
  • the raw material hydroxyl group-containing (meth) acrylate is divided into initial addition and subsequent addition. It is also preferable to add partly the raw material hydroxyl group-containing (meth) acrylate after the addition of the polyhydric alcohol component.
  • the content thereof is preferably 20% by mass or more, more preferably 30% by mass or more, and 80% by mass in the curable resin composition.
  • the following is preferable, and more preferably 70% by mass or less.
  • Each of these components can be contained alone or in combination of two or more. If the total content is less than 20% by mass, the long-term storage stability of the optical disk may be inferior, and if it is more than 80% by mass, the viscosity is high and workability may be reduced.
  • the oligomer / polymer having a radical polymerizable group contained in the curable resin composition for optical disks can be arbitrarily selected.
  • a cured product of a single oligomer / polymer having a radical polymerizable group (hereinafter referred to as “single cured product”).
  • the glass transition temperature is preferably ⁇ 10 ° C. or higher, more preferably ⁇ 5 ° C. or higher, preferably 45 ° C. or lower, more preferably 40 ° C. or lower.
  • the elastic modulus at 25 ° C. of the single cured product is preferably 50 MPa or more, more preferably 55 MPa or more, preferably 900 MPa or less, more preferably 850 MPa or less, and still more preferably 800 MPa or less.
  • the single cured product is produced under the same conditions as those for curing the curable resin composition for optical disks. That is, after adding and mixing the photopolymerization initiator used in the curable resin composition for optical discs to the oligomer / polymer so as to have the same addition rate, curing conditions (light irradiation time, Curing is performed with the same irradiation height, irradiation amount, and cured product thickness).
  • the glass point transition temperature is a value obtained by dynamic viscoelasticity measurement, and a temperature having a maximum tan ⁇ value is adopted.
  • a tensile mode As the measurement conditions, a tensile mode, a frequency of 1 Hz, a clamp distance of 25 mm, an amplitude of 0.1%, and a heating rate of 5 ° C./min are employed.
  • the glass point transition temperature of the single cured product exceeds 45 ° C., the warp of the optical disk may increase.
  • the glass point transition temperature of the single cured product is less than ⁇ 10 ° C., the optical disk may be dented or the long-term storage stability may be deteriorated.
  • the elastic modulus of the single cured product is a value obtained by dynamic viscoelasticity measurement using the single cured product obtained in the same manner, and is a value of the storage elastic modulus E ′ at 25 ° C.
  • the elastic modulus of the single cured product is less than 50 MPa, the long-term storage stability of the optical disk may be deteriorated. In particular, when the protective layer is pushed in, a dent may be formed. On the other hand, when the elastic modulus of the single cured product exceeds 900 MPa, the warp of the obtained optical disk may increase or the long-term storage stability may deteriorate.
  • the glass transition temperature of the single cured product is preferably 30 ° C. or higher, and 60 ° C. or lower. More preferably, it is 55 ° C. or less, more preferably 50 ° C. or less.
  • the elastic modulus at 25 ° C. of the single cured product is preferably 100 MPa or more, preferably 2000 MPa or less, more preferably 1500 MPa or less, and further preferably 1000 MPa or less.
  • the warp of the optical disk may increase.
  • the glass transition temperature of the single cured product is less than 30 ° C.
  • the optical disk may be dented, and when the elastic modulus is less than 100 MPa, the long-term storage stability of the optical disk may be deteriorated.
  • the protective layer is pushed in, a dent may be formed.
  • the glass transition temperature and elastic modulus employ the above-described measuring methods.
  • the elastic modulus of the single cured product is not particularly limited, and other than the above-described low elastic modulus and high elastic modulus can be adopted, but the above-described low elastic modulus is a particularly preferable embodiment.
  • R 1 is an alkylene group having 2 to 8 carbon atoms
  • R 2 is a hydrogen atom or a methyl group
  • m is a positive integer
  • examples of the alkylene group having 2 to 8 carbon atoms represented by R 1 include, for example, ethylene group, trimethylene group, propylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group.
  • m is a positive integer, preferably an integer of 1 to 20, more preferably an integer of 1 to 10, more preferably an integer of 1 to 5.
  • the vinyl polymer represented by the above formula (1) may be a copolymer having a structural unit derived from a cationically polymerizable monomer, and preferred embodiments of the copolymer and polymerization method described above can be employed.
  • the multi-branched reactive compound is a three-dimensionally branched product prepared from a compound having one reactive group X in one molecule and two or more reactive groups Y capable of reacting with the reactive group X.
  • Such multi-branched reactive compounds differ greatly from conventional linear polymers, for example: (I) soluble in organic solvents and low viscosity; (II) amorphous materials; (III ) As the inside of the molecule becomes sparse and the outside becomes denser, the shape will not change depending on the environment and the shape will remain spherical; (IV) the density will be low; (V) there will be many end groups; Therefore, the multi-branch type reactive compound has, for example, (I) a high curing rate; (II) a coating film after curing is not easily damaged; (III) a warp after being applied to a substrate is small due to a small shrinkage rate. ; (IV) It has excellent toughness and is difficult to cause cracking and peeling of the coating film.
  • the hyperbranched reactive compound is a highly branched compound having a highly branched molecular skeleton composed of a dendrimer represented by the following formula (2) and / or a hyperbranched polymer represented by the following formula (3).
  • Dendrimers and hyperbranched polymers with low regularity are preferred.
  • dendrimers are capable of intensively arranging reactive functional groups on the outermost surface as compared with linear polymers generally used.
  • hyperbranched polymers are not as good as dendrimers, they can introduce many reactive functional groups on the outermost surface and are excellent in curability.
  • a compound having a core part, having regular branch repeating units radially from the core part, and having two or more branch repeating units is referred to as a dendrimer.
  • a part or all of the terminal groups (usually the reactive group Y) may be replaced with other reactive groups.
  • a dendrimer that can be used as a multi-branched reactive compound requires that at least two or more terminal groups have reactivity.
  • the terminal group is preferably a radical polymerizable double bond group, and more preferably a (meth) acryloyl group. Further, a part of the end group may be replaced with a non-reactive substituent.
  • the hyperbranched polymer that can be used as the multi-branched reactive compound has a constitution of a branched repeating unit like the dendrimer, but the core portion is not essential.
  • the hyperbranched polymer that can be used as the multi-branched reactive compound may have partially missing portions, irregular or discontinuous portions in the branch repeating unit.
  • a part or all of the plurality of terminal groups (usually the reactive group Y) may be replaced with other reactive groups.
  • the hyperbranched polymer that can be used as the multi-branched reactive compound requires that at least two or more terminal groups have reactivity.
  • the terminal group is preferably a radical polymerizable double bond group, and more preferably a (meth) acryloyl group. Further, a part of the end group may be replaced with a non-reactive substituent.
  • the blending amount thereof is preferably 10% by mass or more and less than 90% by mass, more preferably 30% by mass or more and 70% by mass or less, in the curable resin composition. is there.
  • the blending amount of the multi-branched reactive compound is less than 10% by mass, the crosslinking density is lowered, so that the curing rate is lowered and the coating strength of the cured product may be insufficient.
  • the compounding quantity of a multi-branch type reactive compound is 90 mass or more, when the curvature of the laminated body obtained by apply
  • a monofunctional and / or polyfunctional polymerizable monomer can be used in addition to the oligomer / polymer having the radical polymerizable group as long as the physical properties of the protective layer are not lowered. .
  • Examples of the monofunctional and / or polyfunctional polymerizable monomer include styrene, vinyltoluene, 4-t-butylstyrene, ⁇ -methylstyrene, 4-chlorostyrene, 4-methylstyrene, 4-chloromethylstyrene, Styrene monomers such as divinylbenzene; allyl ester monomers such as diallyl phthalate, diallyl isophthalate, triallyl cyanurate, triallyl isocyanurate; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, tetrahydrofurfuryl (me
  • Vinyl ether monomers trimethylolpropane diallyl ether, pentaerythritol triallyl ether, allyl glycidyl ether, methylol melami Allyl ether monomers such as allyl ether of glycerol, adipic acid ester of glyceryl diallyl ether, allyl acetal, allyl ether of methylol glyoxalurein; maleic acid ester monomers such as diethyl maleate and dibutyl maleate; dibutyl fumarate, fumarate Fumaric acid ester monomers such as dioctyl acid; 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-isobutyl- 1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-cyclohexy
  • a heteropolymeric monomer can be preferably used.
  • 4- Vinyloxycyclohexyl and 4-vinyloxymethylcyclohexylmethyl (meth) acrylate can be preferably used.
  • bifunctional or higher-functional (meth) acrylic ester compounds, (meth) acrylic ester compounds having an alicyclic structure substituent, and (meth) acrylic derivatives having an ether structure have good curability.
  • the use of these materials is preferable because, for example, the protective layer has high transparency and hardness, and is excellent in long-term storage stability of the optical disk (change in warpage during heating acceleration test, remaining film property).
  • the blending amount thereof is preferably 0% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and preferably 70% by mass or less in the curable resin composition. More preferably, it is 60 mass% or less, More preferably, it is 50 mass% or less.
  • the blending amount of the polymerizable monomer exceeds 70% by mass, the curing shrinkage rate and the internal strain increase, and for example, the warp of the optical disk may increase or the protective layer may be cracked or cracked.
  • the curable resin composition of the present invention contains a photopolymerization initiator as an essential component. By including the photopolymerization initiator, there is an effect that it can be quickly cured by light irradiation.
  • radical photopolymerization initiator examples include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy- 2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) butanone, oligo ⁇ 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone ⁇ , 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-) Acetophenones such as methylpropionyl) benzyl] phenyl ⁇ -2-methylpropan-1-one Benzoins such as benzoin, benzoin methyl ether, benzoin ethyl
  • radical photopolymerization initiators may be used alone or in combination of two or more.
  • acetophenones are preferred, and specifically, 1-hydroxycyclohexyl phenyl ketone, oligo ⁇ 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] ] Propanone ⁇ , 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl ⁇ -2-methyl Propan-1-one is preferred.
  • oligo ⁇ 2-hydroxy-2-methyl-1- is selected for the purpose of improving the durability of an optical disk using a curable resin composition for an optical disk as a protective layer and suppressing an increase in warpage during a heat resistance test.
  • [4- (1-Methylvinyl) phenyl] propanone ⁇ is particularly preferred.
  • the blending amount of the photopolymerization initiator is preferably 0.1% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 8% by mass or less, and further preferably 1% by mass or more and 5% by mass in the curable resin composition. % Or less.
  • a composition may not fully harden
  • the blending amount of the photopolymerization initiator exceeds 10% by mass, the generation of odor and coloring of the cured product increase, the recyclability of the composition decreases, and the long-term storage stability of the optical disk deteriorates. There is a case.
  • the curable resin composition of the present invention may contain a thermal polymerization initiator as a polymerization initiator.
  • thermal polymerization initiator a thermal radical polymerization initiator that generates a polymerization initiation radical by heating is suitable.
  • the thermal polymerization initiator is included, the heat generated when the composition is cured with ultraviolet rays is utilized, and the effect of further curing can be achieved.
  • thermal radical polymerization initiator examples include methyl ethyl ketone peroxide, cyclohexanone peroxide, 1,1-bis (t-hexylperoxy) -cyclohexane, cumene hydroperoxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, cumylperoxy Neodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexanoate, t-butylperoxy-2- Organic peroxide initiators such as ethylhexanoate and t-butylperoxybenzoate; 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2 , 2'-azobis (2,4-dimethyl-4- Toxivaleronitrile), 2,
  • radicals can be efficiently generated by the catalytic action of metal soaps such as methyl ethyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide, t-butylperoxybenzoate, benzoyl peroxide and / or amine compounds.
  • metal soaps such as methyl ethyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide, t-butylperoxybenzoate, benzoyl peroxide and / or amine compounds.
  • Preferred compounds are 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile).
  • the blending amount of the polymerization initiator is preferably 0.05% by mass or more and 20% by mass or less, more preferably 0.1% by mass or more and 15% by mass or less, and further preferably 0.2% by mass in the curable resin composition. It is 10 mass% or less.
  • the blending amount of the polymerization initiator is less than 0.05% by mass, the curable resin composition may not be sufficiently cured.
  • the amount of the polymerization initiator exceeds 20% by mass, the generation of odor and coloring of the cured product increase, or the long-term storage stability of the laminate obtained by applying to a plastic substrate and curing, for example. (Changes in warp during heating acceleration test, residual film property) may deteriorate.
  • the curable resin composition of the present invention may contain an ultraviolet absorber, a thermal polymerization accelerator, a photosensitizer, and a photopolymerization accelerator.
  • UV absorber In the case of containing an ultraviolet absorber, there are effects that the recyclability of the composition can be improved, the curing speed can be adjusted, and the warp of the optical disk can be reduced.
  • UV absorber include benzotriazole UV absorbers, hydroxyphenyltriazine UV absorbers, benzophenone UV absorbers, salicylic acid UV absorbers, and inorganic oxide UV absorbers.
  • phenyl salicylate (2,2′-hydroxy-5-methylphenyl) benzotriazole, 2-hydroxybenzophenone, glycol salicylate, t-butylmethoxydibenzoylmethane, ethylhexyl methoxycinnamate, dimethyl PABA ( Para-aminobenzoic acid)) octyl, dimethyl PABA ethylhexyl, etc.
  • conventionally known ultraviolet absorbers can be mentioned.
  • the ultraviolet absorber is 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole (trade name “TINUVIN (registered trademark) PS”, Ciba Specialty Chemicals Co., Ltd.), 2- ⁇ 2-hydroxy-4- (1-octyloxycarbonylethoxy) phenyl ⁇ -4,6-bis (4-phenylphenyl) -1,3,5-triazine (trade name “TINUVIN”) 479 ”, manufactured by Ciba Specialty Chemicals), 2- ⁇ 2-hydroxy-5- (2-methacryloyloxyethyl) phenyl ⁇ benzotriazole (trade name“ RUVA93 ”, manufactured by Otsuka Chemical Co., Ltd.), octyl-3 - ⁇ 3-t-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazole-2-yl) Nenyl ⁇ propionic acid, 2-ethylhexyl-3- ⁇ 3
  • the addition amount of the ultraviolet absorber is preferably 0.03% by mass or more and 0.4% by mass or less, more preferably 0.03% by mass or more and 0.3% by mass or less, and more preferably in the curable resin composition. Is 0.05 mass% or more and 0.2 mass% or less, Most preferably, it is 0.05 mass% or more and 0.1 mass% or less.
  • thermal polymerization accelerator capable of effectively generating radicals by promoting the decomposition of the thermal polymerization initiator.
  • the thermal polymerization accelerator include metal soaps such as cobalt, copper, tin, zinc, manganese, iron, zirconium, chromium, vanadium, calcium, and potassium, primary, secondary, tertiary amine compounds, and quaternary ammonium. Examples thereof include salts, thiourea compounds, and ketone compounds. These thermal polymerization accelerators may be used alone or in combination of two or more.
  • cobalt octylate, cobalt naphthenate, copper octylate, copper naphthenate, manganese octylate, manganese naphthenate, dimethylaniline, trietalamine, triethylbenzylammonium chloride, di (2-hydroxy) Ethyl) p-toluidine, ethylenethiourea, acetylacetone, methyl acetoacetate are preferred.
  • the blending amount of the thermal polymerization accelerator is preferably 0.001% by mass to 20% by mass, more preferably 0.001% by mass to 10% by mass, and still more preferably 0.01% by mass in the curable resin composition. % To 5% by mass, most preferably 0.05% to 3% by mass. When the blending amount of the thermal polymerization accelerator is within such a range, it is preferable from the viewpoints of curability of the composition, physical properties of the cured product, and economical efficiency.
  • photosensitization is capable of effectively generating radicals by transferring excitation energy from an excited state generated by photoexcitation to a photopolymerization initiator and promoting decomposition of the photopolymerization initiator.
  • An agent can be used.
  • photosensitizer examples include 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and the like. These photosensitizers may be used alone or in combination of two or more.
  • the blending amount of the photosensitizer is preferably 0.05 parts by mass or more and 20% by mass or less, more preferably 0.1 parts by mass or more and 15% by mass or less, and further preferably 0.2% by mass in the curable resin composition. Part or more and 10% by mass or less. If the compounding quantity of a photosensitizer is in such a range, it is preferable at the point of sclerosis
  • a photopolymerization accelerator capable of promoting the decomposition of the photopolymerization initiator and generating radicals effectively can be used.
  • the photopolymerization accelerator include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoic acid.
  • Examples include -2-n-butoxyethyl, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, and the like.
  • These photopolymerization accelerators may be used alone or in combination of two or more. Of these photopolymerization accelerators, triethanolamine, methyldiethanolamine, and triisopropanolamine are preferable.
  • the blending amount of the photopolymerization accelerator is preferably 0.05% by mass to 20% by mass or less, more preferably 0.1% by mass to 15% by mass, and further preferably 0.2% by mass in the curable resin composition. It is within the range of 10% by mass or less. When the blending amount of the photopolymerization accelerator is within such a range, it is preferable from the viewpoint of curability of the composition, physical properties of the cured product, and economic efficiency.
  • the total amount of the blending amount is the total amount in the curable resin composition.
  • it is preferably in the range of 0.05 to 20% by mass, more preferably 0.1 to 15% by mass, and further preferably 0.2 to 10% by mass. If the total amount of the combination amount such as the polymerization initiator is within such a range, the curability of the curable resin composition, the physical properties of the cured product obtained by curing the curable resin composition, and the economical point Is preferable.
  • the curable resin composition of the present invention may contain a surface function modifier as necessary. By adding the surface conditioner, the fingerprint removal resistance is improved.
  • a fluorine compound or a silicone compound is generally used.
  • a polyether-modified fluorine compound, a polyether-modified fluorine compound having a reactive group (for example, (meth) acrylate), a non-reactive silicone, a reactive (for example (meth) acrylate) silicone, a high Either molecular silicone or macromonomer silicone can be used.
  • the curable resin composition of the present invention may contain fine particles made of a metal oxide.
  • fine particles made of a metal oxide the hardness of the coating film after curing is improved, and there is an effect that a coating having low reflectivity is obtained with less damage.
  • the metal oxide constituting the fine particles contains at least one metal element selected from the group consisting of Si, Ti, Zr, Zn, Sn, In, La, and Y.
  • the metal oxide constituting the fine particles may be a single oxide containing these elements or a complex oxide containing these elements.
  • Specific examples of the metal oxide constituting the fine particles include, for example, SiO, SiO 2 , TiO 2 , ZrO 2 , ZnO, SnO 2 , In 2 O 3 , La 2 O 3 , Y 2 O 3 , SiO 2 —Al.
  • Examples thereof include 2 O 3 , SiO 2 —Zr 2 O 3 , SiO 2 —Ti 2 O 3 , Al 2 O 3 —ZrO 2 , and TiO 2 —ZrO 2 .
  • the fine particles comprising these metal oxides may be used alone or in combination of two or more. Of these fine particles made of a metal oxide, SiO 2 , TiO 2 , ZrO 2 , and ZnO 2 are preferable.
  • the average particle size of the fine particles comprising metal oxide is preferably 1 nm to 300 nm, more preferably 1 nm to 50 nm. If the average particle diameter of the fine particles exceeds 300 nm, the transparency of the cured product may be impaired.
  • the average particle diameter of fine particles means the volume average particle diameter calculated
  • the compounding amount of the fine particles made of metal oxide is preferably 0% by mass to 80% by mass, more preferably 0% by mass to 50% by mass in the curable resin composition. If the amount of fine particles exceeds 80% by mass, the cured product may become brittle.
  • the curable resin composition of the present invention further includes, as necessary, a low shrinkage agent (reactive oligomer or polymer, non-reactive oligomer or polymer), color pigment, plasticizer, chain transfer agent, polymerization.
  • a low shrinkage agent reactive oligomer or polymer, non-reactive oligomer or polymer
  • color pigment plasticizer
  • chain transfer agent polymerization.
  • Inhibitor, near infrared absorber, light stabilizer, antioxidant, flame retardant, matting agent, dye, antifoaming agent, leveling agent, antistatic agent, dispersant, slip agent, surface modifier, shaking A change agent, a thixotropic agent, etc. can be added.
  • the presence of these additives does not particularly affect the effects of the present invention.
  • These additives may be used alone or in combination of two or more.
  • the compounding amount of the additive may be set as appropriate according to the type and purpose of use of the additive, the method of using the curable resin composition, and the like, and is not particularly limited.
  • the compounding amount of the low shrinkage agent, the color pigment, the plasticizer or the auxiliary change agent is preferably 1% by mass or more and 40% by mass or less, more preferably 5% by mass or more and 30% by mass or less in the curable resin composition. More preferably, it is in the range of 10 mass% or more and 25 mass% or less.
  • Polymerization inhibitors, antioxidants, matting agents, dyes, antifoaming agents, leveling agents, antistatic agents, dispersants, slip agents, surface modifiers or auxiliary agents are added to the curable resin composition. Among these, the range is preferably 0.0001% by mass to 10% by mass, more preferably 0.001% by mass to 5% by mass, and still more preferably 0.01% by mass to 3% by mass.
  • the curable resin composition for an optical disk of the present invention has a radical polymerizable unsaturated group equivalent (g / eq) in the curable resin composition of A and an alkylene oxide adduct-containing polyfunctional in the curable resin composition.
  • g / eq radical polymerizable unsaturated group equivalent
  • alkylene oxide adduct-containing polyfunctional (meth) acrylic acid esters When the content (mass%) of (meth) acrylic acid esters and caprolactone adduct-containing polyfunctional (meth) acrylic acid esters is B, it is necessary to satisfy 6.6 ⁇ A ⁇ B ⁇ 35. is there.
  • the curable resin composition of the present invention a crosslinked structure is formed by a radically polymerizable unsaturated group, and a soft component is formed by an alkylene oxide skeleton and / or a caprolactone component of an adduct-containing (meth) acrylic acid ester.
  • the curable resin composition of the present invention is prepared by blending adduct-containing (meth) acrylic acid esters and adjusting the ratio of A and B (A ⁇ B) within a predetermined range.
  • the shrinkage of the cured product is reduced, the resilience of the cured product obtained by curing the curable resin composition of the present invention is improved, and the elastic modulus, loss tangent, and glass transition temperature can be adjusted.
  • the reason why A ⁇ B is defined without defining the respective preferable ranges for A and B is that the curable resin composition of the present invention contains an adduct that can introduce a soft component. This is because the preferred range of the radical polymerizable unsaturated group equivalent (A) capable of forming a crosslinked structure varies depending on the content (B) of (meth) acrylic acid esters.
  • the range of A ⁇ B is defined.
  • the elastic modulus, loss tangent, and glass transition temperature have practical properties, and there is very little resilience and warpage of the laminate. It has an outstanding effect on the protective layer of the optical disk.
  • a ⁇ B is less than 6.6, the cross-linked structure is reduced, so that the balance between the elastic modulus and loss tangent is deteriorated, and the amount of permanent deformation is increased, that is, a depression is formed when the protective layer is pushed. It becomes easy.
  • a ⁇ B exceeds 35, the cross-linked structure is large, the warpage of the laminate due to curing shrinkage is increased, the resilience at the time of deformation is deteriorated, and a dent is easily formed.
  • the radical polymerizable unsaturated group equivalent (g / eq) will be described.
  • the radical polymerizable unsaturated group equivalent is the amount of the curable resin composition material per mole of the radical polymerizable unsaturated group.
  • the mass of the photopolymerization initiator is not considered.
  • the radically polymerizable unsaturated group is an ethylenically unsaturated group having radical polymerizability.
  • the radical polymerizable unsaturated group equivalent in the curable resin composition is calculated from the reaction calorific value using an optical DSC (photo DSC) apparatus.
  • the optical DSC apparatus is a thermal analysis apparatus having a structure in which the DSC apparatus includes a UV irradiation unit. A UV curable resin sample is placed in the optical DSC apparatus and irradiated with a UV lamp in the apparatus, thereby accompanying a curing reaction. The curing exotherm can be observed as a DSC curve.
  • the following method is preferred.
  • ⁇ Optical DSC measurement method About 5 mg of the curable resin composition is accurately weighed in an aluminum dish having a diameter of about 5 mm. Irradiation intensity of 5 mJ / cm using an ultraviolet irradiation device (Seiko Denshi Kogyo Co., Ltd., UV-1 (light source: 200 W mercury-xenon lamp, filter: 365 nm interference filter and 20% ND filter)) in a nitrogen gas atmosphere at 30 ° C.
  • an ultraviolet irradiation device Seiko Denshi Kogyo Co., Ltd., UV-1 (light source: 200 W mercury-xenon lamp, filter: 365 nm interference filter and 20% ND filter)
  • the amount of heat generated by the curable resin composition with a differential scanning calorimeter (DSC) (DSC6200, manufactured by Seiko Denshi Kogyo Co., Ltd.) while irradiating 2 seconds of ultraviolet rays for 5 minutes (mJ / mg: 1 mg of resin composition (photopolymerization started) Measure the calorific value per cure) excluding the agent.
  • the amount of heat generated by curing 2-ethylhexyl acrylate (molecular weight: 184) was measured and found to be 420 mJ / mg. Based on this, the amount of radical polymerizable unsaturated groups was calculated.
  • the calorific value of a curable resin composition measured was 250 mJ / mg.
  • the radical polymerizable unsaturated group equivalent in the curable resin composition of the present invention is preferably 250 g / eq or more, more preferably 300 g / eq or more, further preferably 350 g / eq or more, and preferably 600 g / eq or less, More preferably, it is 550 g / eq or less, More preferably, it is 500 g / eq or less. If the radically polymerizable unsaturated group equivalent is within the above range, the hardness of the resulting cured product can be adjusted to a more appropriate range, and a protective layer having a smaller permanent deformation can be formed.
  • the light transmittance of each wavelength at a thickness of 100 ⁇ m of the composition is (X) 85.0% or more at 400 nm and (Y) 35.0% or more 85 at 380 nm. It is preferably within a range of 0.0% or less and (Z) within a range of 0.1% or more and 50.0% or less at 360 nm.
  • the composition is excellent in recyclability, and the optical disc having a protective layer formed by curing the composition is excellent in transparency and corrosiveness of the reflective film.
  • an optical disk having a small surface and excellent surface lubricity and long-term storage stability (low warpage and residual film properties during a heating acceleration test) can be obtained.
  • the light transmittance at a wavelength of 400 nm is preferably 85.0% or more, more preferably 88% or more, and most preferably 90% or more. If the light transmittance at a wavelength of 400 nm is less than 85.0%, the transparency may be inferior and accurate data recording and reproduction on the optical disc may not be possible.
  • the light transmittance at a wavelength of 380 nm is preferably 35.0% or more and 85.0% or less, more preferably 45.0% or more and 85.0% or less, and most preferably 45.0% or more and 75.0%. % Or less.
  • the light transmittance at a wavelength of 380 nm is out of the above range, when the composition is inferior in recyclability, the long-term storage stability of the optical disk (change in warpage during heating acceleration test, residual film property) is deteriorated, reflection When the corrosiveness of the film is lowered, the lubricity of the surface may be lowered.
  • the light transmittance at a wavelength of 360 nm is preferably 0.1% to 50.0%, more preferably 0.5% to 50.0%, and most preferably 5% to 30.0%.
  • the light transmittance at a wavelength of 360 nm is outside the above range, when the composition is inferior in recyclability, the long-term storage stability of the optical disk (change in warpage during heating acceleration test, residual film property) is deteriorated, reflection When the corrosiveness of the film is lowered, the lubricity of the surface may be lowered.
  • the light transmittance is a value obtained by injecting the curable resin composition into a quartz glass cell through a 100 ⁇ m spacer and measuring the light transmittance at each wavelength using a spectrophotometer. In that case, air is adopted as a blank.
  • the viscosity of the curable resin composition of the present invention is preferably 800 mPa ⁇ s or more, more preferably 1000 mPa ⁇ s or more, preferably 3500 mPa ⁇ s or less, more preferably 2500 mPa ⁇ s or less at 25 ° C.
  • the viscosity is a value calculated using a B-type viscometer (model “RB80L”: manufactured by Toki Sangyo Co., Ltd.) under the condition of a temperature of 25 ° C. If the viscosity is out of the range of 800 mPa ⁇ s to 3500 mPa ⁇ s, the thickness of the protective layer may not be controlled to 100 ⁇ m ⁇ 2 ⁇ m. Specifically, when the thickness of the protective layer in the center becomes thinner, In some cases, the thickness of the protective layer of the portion increases.
  • the curable resin composition of the present invention includes the above-mentioned alkylene oxide adduct-containing polyfunctional (meth) acrylic acid esters and / or caprolactone adduct-containing polyfunctional (meth) acrylic acid esters, photopolymerization initiators, and the like. It can be obtained by mixing and stirring by the above method.
  • the curable resin composition of the present invention can be cured by irradiation with ultraviolet rays. Curing here refers to a state without fluidity.
  • the wavelength of the ultraviolet rays used may be in the range of 150 nm to 450 nm. Examples of the light source that emits such a wavelength include sunlight, low-pressure mercury lamp, high-pressure mercury lamp, ultra-high pressure mercury lamp, metal halide lamp, gallium lamp, xenon lamp, flash type xenon lamp, and carbon arc lamp.
  • Irradiation integrated light quantity is preferably 0.1 J / cm 2 or more 3J / cm 2 or less, more preferably 0.2 J / cm 2 or more 2.0 J / cm 2 or less, more preferably 0.3 J / cm 2 or more 1. Within the range of 0 J / cm 2 or less.
  • the heating temperature may be appropriately adjusted according to the type of the base material and the like, and is not particularly limited. It is in the range of not lower than 170 ° C and lower than 170 ° C.
  • the heating time may be appropriately adjusted according to the application area and the like, and is not particularly limited, but is preferably 1 minute to 24 hours, more preferably 10 minutes to 12 hours, and even more preferably 30 minutes or more. Within 6 hours or less.
  • an electron beam having an acceleration voltage of preferably 10 kV to 500 kV, more preferably 20 kV to 300 kV, and even more preferably 30 kV to 200 kV is used. That's fine.
  • the irradiation amount of the electron beam is preferably 2 kGy or more and 500 kGy or less, more preferably 3 kGy or more and 300 kGy or less, and further preferably 4 kGy or more and 200 kGy or less.
  • the cured product obtained by curing the curable resin composition of the present invention preferably has a light transmittance at 405 nm at a thickness of 100 ⁇ m of 85% or more, more preferably 88% or more, and still more preferably 89%. That's it.
  • the light transmittance is a value measured by a spectrophotometer using the obtained cured product.
  • a cured product obtained by curing the curable resin composition of the present invention is a (meth) acrylic acid ester, a photopolymerization initiator, an oligomer having at least one radical polymerizable group and / or an ion polymerizable group.
  • the said light transmittance can be achieved by containing a polymer and a polymerizable monomer suitably and performing sufficient hardening by predetermined hardening conditions and methods.
  • the light transmittance at 405 nm is less than 85%, the transparency is inferior, and thus when used as a protective layer of an optical disk, errors may increase when reading recorded information.
  • the cured product obtained by curing the curable resin composition of the present invention has a weight loss when it is kept in an oven at 70 ° C. for 100 hours (hereinafter sometimes simply referred to as “mass reduction”). It is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, preferably 2.0% by mass or less, more preferably 1.5% by mass or less, and most preferably 1.0% by mass or less. is there.
  • the thickness of the cured product to be measured is 100 ⁇ ⁇ 2 ⁇ m.
  • the cause of the mass decrease is considered to be an unreacted (meth) acrylic acid ester component, a residue of the initiator and its decomposition product, or a low molecular weight additive.
  • Mass reduction includes oligomers and / or polymers having radically polymerizable groups, (meth) acrylic acid esters, and photopolymerization initiators, and is sufficiently cured by predetermined curing conditions and methods to be within the above range. It becomes possible to do.
  • the storage elastic modulus E ′ at 25 ° C. is 10 MPa or more, preferably 20 MPa or more. 150 MPa or less, more preferably 120 MPa or less, still more preferably 100 MPa or less.
  • the storage elastic modulus E ′ is a value obtained by dynamic viscoelasticity measurement using the obtained cured product. Measurement conditions will be described later.
  • a cured product having a storage elastic modulus E ′ of 10 MPa or more and 150 MPa or less can be obtained by sufficiently curing the curable resin composition under a predetermined curing condition or curing method.
  • the storage elastic modulus E ′ is less than 10 MPa, the long-term storage stability of the optical disk may be deteriorated. In particular, the optical disk is sometimes recessed. Moreover, when the storage elastic modulus is larger than 150 MPa, the warp of the obtained optical disk may increase or the long-term storage stability may deteriorate.
  • the loss tangent tan ⁇ at 25 ° C. is preferably 0.10 or more, and 0.70 or less. More preferably, it is 0.60 or less, More preferably, it is 0.50 or less, Most preferably, it is 0.40 or less.
  • the loss tangent tan ⁇ is a value obtained by dynamic viscoelasticity measurement as with the storage elastic modulus E ′. Note that the same measurement conditions are used.
  • the loss tangent tan ⁇ exceeds 0.70, the long-term storage stability of the optical disk may be deteriorated. In particular, the optical disk is sometimes recessed. Further, when the loss tangent tan ⁇ is less than 0.10, the warp of the obtained optical disk may increase or the long-term storage stability may deteriorate.
  • the glass point transition temperature is preferably 0 ° C. or higher, more preferably 5 ° C. or higher. More preferably, it is 10 degreeC or more, and 30 degrees C or less is preferable.
  • the glass point transition temperature is a value obtained by dynamic viscoelasticity measurement in the same manner as the storage elastic modulus E ′, and the temperature of the maximum tan ⁇ value is adopted. The measurement conditions are the same as the storage elastic modulus E ′.
  • the glass point transition temperature exceeds 30 ° C., the warp of the optical disk may increase.
  • the glass point transfer temperature is less than 0 ° C., the optical disk may be recessed, and the long-term storage stability may be deteriorated.
  • the storage elastic modulus E ′ at 25 ° C. is preferably 1200 MPa or more, more preferably 1400 MPa. As described above, more preferably 1600 MPa or more, most preferably 1800 MPa or more, and preferably 2100 MPa or less.
  • the storage elastic modulus E ′ is a value obtained by dynamic viscoelasticity measurement using a cured product obtained in the same manner as described above.
  • the loss tangent tan ⁇ at 25 ° C. is preferably 0.03 or more, and 0.12 or less. Is preferable, more preferably 0.10 or less, and still more preferably 0.07 or less.
  • the loss tangent tan ⁇ is a value obtained by dynamic viscoelasticity measurement as with the storage elastic modulus E ′. Note that the same measurement conditions are used. If the loss tangent tan ⁇ exceeds 0.12, the long-term storage stability of the optical disk may deteriorate. In particular, the optical disk is sometimes recessed.
  • the glass point transfer temperature is preferably 60 ° C. or higher, more preferably 70 ° C. or higher. More preferably, it is 75 degreeC or more, Most preferably, it is 80 degreeC or more, 90 degreeC or less is preferable, More preferably, it is 85 degreeC or less.
  • the glass point transition temperature is a value obtained by dynamic viscoelasticity measurement in the same manner as the storage elastic modulus E ′, and the temperature of the maximum tan ⁇ value is adopted. The measurement conditions are the same as the storage elastic modulus E ′. If the glass point transition temperature is less than 60 ° C., the optical disk may be dented or the long-term storage stability may be deteriorated.
  • the curable resin composition of the present invention is suitably used for optical disks.
  • the cured product obtained by curing the curable resin composition of the present invention is particularly excellent in scratch resistance and hardness, and further, since the warpage of the substrate is small over a long period of time, it is a blue-violet laser as a laser beam for information reading and writing, in particular. It can be suitably used for an optical disc using light (Blu-ray Disc (registered trademark)).
  • optical disk of the present invention has a protective layer formed by curing the above-described curable resin composition for an optical disk of the present invention.
  • the optical disk of the present invention can be obtained by forming a protective layer formed by curing the curable resin composition for an optical disk of the present invention on a reflective film formed on a substrate.
  • a conventionally known optical disk manufacturing method is used except for the protective layer manufacturing method.
  • the protective layer obtained by curing the curable resin composition of the present invention preferably has a thickness of 20 ⁇ m or more, more preferably 30 ⁇ m or more, still more preferably 50 ⁇ m or more, particularly preferably 70 ⁇ m or more, and most preferably 80 ⁇ m or more.
  • the protective layer preferably has a thickness of 150 ⁇ m or less, more preferably 120 ⁇ m or less, and still more preferably 105 ⁇ m or less.
  • the thickness of the protective layer is less than 20 ⁇ m, the protection of the functional layer such as the recording layer and the reflective layer in the protective layer may be insufficient, and if the thickness exceeds 150 ⁇ m, the thickness and the like can be controlled. It can be difficult.
  • the substrate used for the optical disc examples include resin molded products such as polymethyl methacrylate (PMMA), polystyrene (PS), polyethylene terephthalate (PET), acrylonitrile-butadiene-styrene copolymer (ABS), and polycarbonate (PC). And film; Glass etc. are mentioned. Among these, polycarbonate (PC) is preferable.
  • PMMA polymethyl methacrylate
  • PS polystyrene
  • PET polyethylene terephthalate
  • ABS acrylonitrile-butadiene-styrene copolymer
  • PC polycarbonate
  • film; Glass etc. are mentioned.
  • PC polycarbonate
  • the term “on the reflective film” means not only a mode in which a protective layer is directly laminated on the reflective film, but also a functional layer such as a recording layer or a dielectric layer is laminated on the reflective film, and the protective layer is protected on the functional layer.
  • a layer is laminated
  • stacked is also meant.
  • an optical disc having a multilayer structure with two or more information recording layers is manufactured. Between these information recording layers, an intermediate layer is formed by curing a transparent ultraviolet curable resin with ultraviolet rays.
  • the composition of the present invention is suitable for forming a protective layer of an optical disk, but may be used as an ultraviolet curable resin for this intermediate layer.
  • optical disc of the present invention examples include a Blu-ray disc (registered trademark). Since the optical disk of the present invention is excellent in transparency, it can be suitably used for an optical disk for recording / reproduction using, for example, an oscillator of 380 nm to 430 nm.
  • Protective layer for Blu-ray Disc has low warpage (low shrinkage), transparency (light transmission), adhesion to polycarbonate substrate, low corrosivity, recyclability, fast curing (productivity) , Characteristics such as dimensional stability (change in warpage during accelerated test, residual film property, small amount of permanent deformation such as dents) are required, but the curable resin composition for optical disc of the present invention is cured. This protective layer satisfies all the above characteristics.
  • this invention is not limited to embodiment mentioned above, A various change is possible in the range shown to the claim.
  • the optical disc of the present invention has a hard coat layer directly formed on the protective layer.
  • the hard coat resin composition for forming the hard coat layer include (1) a hard coat containing a multi-branched reactive compound and / or a polymer having a reactive group in a side chain, and a polymerization initiator.
  • Resin composition for hard coat containing a caprolactone adduct-containing polyfunctional (meth) acrylic acid ester obtained from a caprolactone adduct and a photopolymerization initiator Sometimes referred to as Dokoto resin composition);. Is suitable.
  • the first hard coat resin composition will be described.
  • multi-branched reactive compound those exemplified as the compound having a radical polymerizable unsaturated group that can constitute the curable resin composition of the present invention can be used.
  • a dendrimer represented by the above formula (3) and / or a hyperbranched polymer represented by the above formula (4) is preferable.
  • the polymer having a reactive group in the side chain has a repeating unit represented by the above formula (1) exemplified as an oligomer / polymer having a radical polymerizable group that can constitute the curable resin composition of the present invention.
  • Vinyl polymers can be used.
  • Examples of the polymer having a reactive group in the side chain other than the vinyl polymer represented by the above formula (1) include, for example, a copolymer of methyl methacrylate and methacrylic acid described in JP-A No. 11-263893.
  • a (meth) acrylic polymer having a plurality of polymerizable double bonds in the molecule obtained by esterifying an unsaturated epoxy compound glycidyl methacrylate can be mentioned.
  • the blending amount of the multi-branched reactive compound and / or the polymer having a reactive group in the side chain is preferably 10% by mass or more and less than 90% by mass in the first hard coat resin composition, more preferably 30%. It is not less than 70% by mass. If the blending amount of the multi-branched reactive compound and / or the polymer having a reactive group in the side chain is less than 10% by mass, the crosslinking density is lowered, so the curing speed is lowered and the coating strength of the cured product is insufficient. May be. Further, when the blending amount is 90% by mass or more, there is a case where the warpage of the laminate obtained by applying to the substrate and curing is increased.
  • the first hard coat resin composition contains a polymerization initiator as an essential component, but is a thermal polymerization initiator that generates a polymerization initiating radical by heating; photopolymerization that generates a polymerization initiating radical by irradiation with ultraviolet rays. And a photocationic polymerization initiator that generates a polymerization initiating cation upon irradiation with ultraviolet rays.
  • a polymerization initiator may be used alone or in combination of two or more. It is also preferable to further add a thermal polymerization accelerator, a photosensitizer, a photopolymerization accelerator, and the like.
  • thermal polymerization accelerator thermal polymerization accelerator, photosensitizer, and photopolymerization accelerator, those exemplified as those that can constitute the curable resin composition of the present invention can be used.
  • the suitable range of these compounding quantities is the same as that of the curable resin composition of this invention.
  • the first hard coat resin composition contains an oligomer and / or polymer having a reactive group in addition to the multi-branched reactive compound, the polymer having a reactive group in the side chain, and the polymerization initiator. Also good.
  • the reactive group in the oligomer and / or polymer is preferably a (meth) acryloyl group.
  • As the oligomer or polymer having a (meth) acryloyl group urethane (meth) acrylate, (meth) acryloyl group pendant polymer, epoxy resin, vinyl ether group pendant polymer, epoxy (meth) acrylate, and polyester (meth) acrylate are preferable.
  • the amount of the oligomer and / or polymer having the (meth) acryloyl group in the hard coat resin composition is preferably 20% by mass to 80% by mass, and more preferably. Is 30 mass% or more and 70 mass% or less.
  • the blending amount of the oligomer and / or polymer having the (meth) acryloyl group exceeds 80% by mass, the content of the multi-branched reactive compound decreases, and thus warpage after application to the substrate increases. In some cases, the toughness is lowered and the coating film is cracked and peeled off, or the long-term storage stability is deteriorated.
  • the first hard coat resin composition may contain a polymerizable monomer such as a (meth) acrylic monofunctional monomer or a (meth) acrylic polyfunctional monomer.
  • the polymerizable monomer is not particularly limited as long as it can be co-cured with the multi-branched reactive compound. Specifically, for example, it may constitute the curable resin composition of the present invention. What was illustrated as a monofunctional and / or polyfunctional polymerizable monomer can be used.
  • the amount of the polymerizable monomer is preferably 0% by mass to 80% by mass, more preferably 10% by mass to 60% by mass in the hard coat resin composition. It is.
  • the compounding amount of the polymerizable monomer exceeds 80% by mass, the curing shrinkage rate and the internal strain increase, and for example, the warpage of the laminate obtained by applying to a plastic substrate and curing may increase.
  • alkylene oxide adduct-containing polyfunctional (meth) acrylic acid ester obtained from an alkylene oxide adduct in which the addition repeating unit per valence to the polyhydric alcohol of 4 or more is n 1 or 2
  • tetra (meth) acrylate of ethylene oxide 4 mol adduct of pentaerythritol tetra (meth) acrylate of ethylene oxide 8 mol adduct of pentaerythritol
  • Tetra (meth) acrylate of propylene oxide 8 mol adduct of pentaerythritol hexa (meth) acrylate of ethylene oxide 6 mol adduct of dipentaerythritol, ethylene oxide 12 mol of dipentaerythritol Adduct hexa
  • An alkylene oxide adduct-containing product obtained from an alkylene oxide adduct having n 1,2 per 1 valence addition unit to the polyhydric alcohol of 4 or more valence in the second hard coat resin composition
  • Caprolactone adduct-containing polyfunctional (meta) obtained from a caprolactone adduct having n 1,2 per unit valence to a functional (meth) acrylic acid ester and / or a polyhydric alcohol having a valence of 4 or more.
  • the total amount of acrylic acid esters is preferably 30% by mass or more, more preferably 40% by mass or more, preferably 80% by mass or less, and more preferably 70% by mass or less. If the total amount exceeds 80% by mass, warpage after application to the laminate of the substrate / protective layer may increase. On the other hand, if the total amount is less than 30% by mass, the scratch resistance and hardness decrease. Hard coat performance may not be exhibited.
  • the second hard coat resin composition contains a photopolymerization initiator as an essential component.
  • the photopolymerization initiator include a photopolymerization initiator that generates a polymerization initiation radical upon irradiation with ultraviolet rays, and a photocationic polymerization initiator that generates a polymerization initiation cation upon irradiation with ultraviolet rays. These polymerization initiators may be used alone or in combination of two or more. It is also preferable to further add a thermal polymerization accelerator, a photosensitizer, a photopolymerization accelerator, and the like.
  • thermal polymerization accelerator thermal polymerization accelerator, photosensitizer, and photopolymerization accelerator, those exemplified as those that can constitute the curable resin composition of the present invention can be used.
  • the blending amount of the photopolymerization initiator is preferably 0.5% by mass to 20% by mass, more preferably 1% by mass to 15% by mass, and still more preferably based on the total amount of the second hard coat resin composition. 2% by mass to 10% by mass.
  • the blending amount of the photopolymerization initiator is less than 0.5% by mass, the composition may not be cured sufficiently.
  • the blending amount of the photopolymerization initiator exceeds 20% by mass, the physical properties of the cured product will not be further improved, but rather adversely affected and the economy may be impaired.
  • the second hard coat resin composition preferably contains vinyl ether group-containing (meth) acrylic acid esters.
  • Vinyl ether group-containing (meth) acrylic acid esters have good adhesion to the polycarbonate usually used as a substrate and an effect of reducing the viscosity of the hard coat material with a high dilution effect.
  • vinyl ether group-containing (meth) acrylic acid esters examples include 2-vinyloxyethyl (meth) acrylate, 3-vinyloxyethyl (meth) acrylate, 2-vinyloxypropyl (meth) acrylate, and (meth) acrylic acid 1 -Methyl-2-vinyloxyethyl, 4-vinyloxybutyl (meth) acrylate, 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxycyclohexyl (meth) acrylate, 4-vinyloxymethylcyclohexyl methyl (meth) acrylate , 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, 2- (2-vinyloxyisopropoxy) propyl (meth) acrylate, 2- ⁇ 2- (2-vinyloxyethoxy) (meth) acrylate ) Ethoxy ⁇ ethyl.
  • the blending amount of the vinyl ether group-containing (meth) acrylic acid ester in the second hard coat resin composition is preferably 5% by mass to 35% by mass, more preferably 10% by mass to 30% by mass.
  • the second hard coat resin composition is preferably 20 mPa ⁇ s or more and 100 mPa ⁇ s or less at 25 ° C. More preferably, it is 30 mPa * s or more and 80 mPa * s, More preferably, it is 40 mPa * s or more and 70 mPa * s. If the viscosity of the resin composition for hard coat is within the above range, the hard coat layer can be formed with a uniform thickness. However, if the viscosity of the hard coat resin composition is out of the above range, the thickness of the center portion of the hard coat layer may be reduced or the thickness of the end portion may be increased.
  • the viscosity is a value calculated using a B-type viscometer (model “RB80L” manufactured by Toki Sangyo Co., Ltd.) under the condition of a temperature of 25 ° C.
  • the second hard coat resin composition may contain an oligomer and / or polymer having a reactive group.
  • the reactive group in the oligomer and / or polymer is preferably a (meth) acryloyl group.
  • As the oligomer or polymer having a (meth) acryloyl group urethane (meth) acrylate, (meth) acryloyl group pendant polymer, epoxy resin, vinyl ether group pendant polymer, epoxy (meth) acrylate, and polyester (meth) acrylate are preferable.
  • the amount of the oligomer and / or polymer having a (meth) acryloyl group is preferably 3% by mass or more and 20% by mass or less, more preferably 5% by mass or more and 15% by mass or less. is there. If the blending amount of the oligomer and / or polymer exceeds 20% by mass, the viscosity may increase and an appropriate hard coat layer thickness may not be formed. Moreover, if it is less than 3 mass%, the curvature after apply
  • the second hard coat resin composition may contain a polymerizable monomer such as a (meth) acrylic monofunctional monomer or a (meth) acrylic polyfunctional monomer.
  • a polymerizable monomer such as a (meth) acrylic monofunctional monomer or a (meth) acrylic polyfunctional monomer.
  • these polymerizable monomers for example, those exemplified as monofunctional and / or polyfunctional polymerizable monomers that can constitute the curable resin composition of the present invention can be used.
  • the compounding amount of the polymerizable monomer is preferably more than 0% by mass and less than 60% by mass, and more preferably 10% by mass to 50% by mass with respect to the total amount of the composition. It is. When the blending amount of the polymerizable monomer exceeds 60% by mass, the curing shrinkage rate and the internal strain increase, and for example, the warpage after coating and curing on the substrate / protective layer laminate may increase.
  • the cured product obtained by curing the second hard coat resin composition preferably has a storage elastic modulus E ′ at 25 ° C. of 600 MPa to 2000 MPa, more preferably 700 MPa to 1800 MPa, most preferably 700 MPa to 1600 MPa. It is as follows. When the storage elastic modulus E ′ exceeds 2000 MPa, the toughness is lowered and cracks may occur when the hard coat layer is deformed. Further, if the storage elastic modulus E ′ is less than 600 MPa, the intended hardness may not be obtained.
  • the storage elastic modulus E ′ is a value obtained by dynamic viscoelasticity measurement using the obtained cured product.
  • the glass transition temperature of the cured product of the second hard coat resin composition is not particularly limited, but the glass point transition temperature is preferably 40 ° C.
  • the temperature is 90 ° C. or lower, and most preferably 50 ° C. or higher and 80 ° C. or lower.
  • the glass point transition temperature is a value obtained by dynamic viscoelasticity measurement in the same manner as the storage elastic modulus E ′, and the temperature of the maximum tan ⁇ value is adopted.
  • the measurement conditions of the dynamic viscoelasticity measurement are as follows: sample size width 8 mm ⁇ length 50 mm ⁇ thickness 100 ⁇ m, tension mode, frequency 1 Hz, clamp distance 25 mm, amplitude 0.1%, temperature increase rate 5 ° C./min. It is preferable to adopt.
  • the first and second hard coat resin compositions may further contain, as necessary, non-reactive resins (for example, acrylic resins, urethane acrylate resins, polyester resins, polyurethane resins, polystyrene resins, Vinyl chloride resin, etc.), color pigments, plasticizers, chain transfer agents, polymerization inhibitors, ultraviolet absorbers, near infrared absorbers, light stabilizers, antioxidants, flame retardants, matting agents, dyes, antifoaming An agent, a leveling agent, an antistatic agent, a dispersant, a slip agent, a surface modifier, a thixotropic agent, a thixotropic agent, fine particles comprising a metal oxide, and the like can be added.
  • non-reactive resins for example, acrylic resins, urethane acrylate resins, polyester resins, polyurethane resins, polystyrene resins, Vinyl chloride resin, etc.
  • color pigments plasticizers
  • chain transfer agents polymerization
  • the first and second hard coat resin compositions are obtained by mixing and stirring the multi-branched reactive compound, a polymer having a reactive group in the side chain, a polymerization initiator, and the like by a known method. Can do.
  • the coating method and the curing method when forming the hard coat layer using the hard coat resin composition the same method as the coating method and curing method in the curable resin composition of the present invention should be adopted. That's fine.
  • the optical disk of the present invention has an antistatic layer, an adhesive layer, an adhesive layer, an easy-adhesion layer, a strain relaxation layer, an antiglare layer (non-glare) layer, a photocatalyst layer, etc.
  • Various functional layers such as a layer, an ultraviolet shielding layer, a heat ray shielding layer, an electromagnetic wave shielding layer, a gas barrier layer, a reflective layer, a recording layer, and a dielectric layer may be laminated and applied.
  • the lamination order of the protective layer obtained by curing the curable resin composition of the present invention and each functional layer is not particularly limited, and the lamination method is not particularly limited.
  • the present invention will be described more specifically with reference to examples and comparative examples.
  • the present invention is not limited by the following examples and comparative examples, and is suitable within a range that can meet the purpose described above and below. It is also possible to carry out with modification, and they are all included in the technical scope of the present invention.
  • Residual film properties Measure the thickness of the cured layer before and after the heating acceleration test (the total of the protective layer and hard coat layer if a hard coat layer is formed) using a laser focus displacement meter, and the remaining film rate (%) was calculated by the following general formula, and the remaining film property was evaluated according to the following criteria.
  • Residual film ratio (%) thickness of cured layer after heating acceleration test / thickness of cured layer before heating acceleration test ⁇ 100 ⁇ : Remaining film ratio is 97.0% to less than 103% ⁇ : Remaining film ratio is less than 97.0% or 103% or more.
  • ⁇ Initial warpage increase> The obtained substrate / cured layer laminate was placed on a horizontal glass plate so that the cured layer (cured film of the composition) was on the upper surface side, and then the warp of the laser displacement reading method manufactured by Nippon Shokubai Co., Ltd. Using an angle measuring device, the radial tilt value at a radius of 58 mm was measured in an environment of a temperature of 25 ° C. and a relative humidity of 50%. As the initial warpage increase amount, the warpage change amount before and after coating was adopted.
  • ⁇ War increase after heating acceleration test> The obtained substrate / cured layer laminate was kept in an oven at 70 ° C. for 100 hours, and the warpage value when the substrate was left in an environment of 25 ° C. and 50% relative humidity for 24 hours increased the initial warpage.
  • the radial tilt value was measured in the same manner as the amount. Thereby, the amount of warpage increase before and after the heating acceleration test was obtained.
  • ⁇ Glass point transfer temperature Tg> It is a value obtained by the same measurement method and conditions as the storage elastic modulus E ′ at 25 ° C., and the temperature of the maximum tan ⁇ value was adopted.
  • ⁇ Permanent deformation amount> Using the obtained substrate / cured layer laminate, using a micro-compression tester (manufactured by Shimadzu Corporation, model MCT-W500), the test conditions were as follows: flat indenter used 50 ⁇ m diameter, load speed 20 mN / second, maximum load 300 mN, A value obtained by measuring the amount of deformation remaining in the substrate / protective layer laminate when the holding time at the maximum load was 90 seconds, the unloading speed was 20 mN / sec, and the holding time after complete unloading was 90 seconds was adopted. In this test, when the amount of permanent deformation exceeds 1 ⁇ m, reading errors due to laser light are likely to occur due to dents or the like, and the long-term storage stability may be poor.
  • ⁇ Light transmittance of the composition The light transmittance of the obtained composition at 400 nm, 380 nm, and 360 nm was measured using a spectrophotometer (model UV-3100, manufactured by Shimadzu Corporation).
  • the light transmittance is a value obtained by injecting the composition into a quartz glass cell through a 100 ⁇ m spacer and measuring the transmittance at each wavelength using a spectrophotometer. Air was used as a blank.
  • Viscosity increase rate (%) (viscosity after recovery ⁇ initial viscosity) / initial viscosity ⁇ 100 ⁇ : Viscosity increase rate is less than 10% ⁇ : Viscosity increase rate is 10% or more.
  • ⁇ Scratch resistance> Using a wear resistance tester (model IMC-154A, manufactured by Imoto Seisakusho Co., Ltd.) on the surface of the cured layer (protective layer or hard coat layer) of the obtained substrate / cured layer laminate, a load of 200 g / Under the condition of cm 2 , steel wool # 0000 was reciprocated 10 times at a reciprocating speed of 30 mm / second and a reciprocating distance of 25 mm, and then the degree of damage was visually observed and evaluated according to the following criteria. A: No change (scratches are not recognized) ⁇ : Several or more very shallow scratches are observed. ⁇ : Innumerable deep scratches are observed.
  • ⁇ Pencil hardness> The surface of the cured product layer of the obtained substrate / cured layer laminate was measured according to JIS-K5400 using a pencil scratch hardness tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd.). The load was 1000 g.
  • a vinyl polymer P (VEEA) -1 was obtained.
  • the reaction rate of the monomer is 99.6% by analyzing the mixed solution after the reaction is stopped by gas chromatography (GC), and the content of ethyl acetate is 0.1%. There was found.
  • the number average molecular weight (Mn) of the obtained vinyl polymer is 2210
  • the molecular weight distribution (Mw / Mn) is 1.60
  • the radical polymerizable unsaturated group equivalent is 186.
  • VEEA vinyl polymer P
  • Mn number average molecular weight of the obtained vinyl polymer
  • Mw / Mn molecular weight distribution
  • Optical disc No. 1-44 A curable resin composition for an optical disk was applied on a polycarbonate substrate having a thickness of 1.1 mm and dimensions of 120 mm ⁇ 120 mm with a spin coater at a thickness of 100 ⁇ m.
  • the obtained polycarbonate substrate was cured by irradiation 15 times at a lamp height of 2 cm using a UV irradiator having a xenon flash UV lamp (model RC-742, manufactured by Xenon, USA).
  • the integrated irradiation light quantity at 320 to 390 nm was about 0.6 J / cm 2 .
  • the thickness of the protective layer was 100 ⁇ 2 ⁇ m.
  • Optical disc No. 45-88 Using a spin coater, a curable resin composition for an optical disc was applied at a thickness of 100 ⁇ m on a polycarbonate (PC) substrate having dimensions of 120 mm ⁇ 120 mm and a thickness of 1 mm.
  • the obtained PC substrate was UV-cured with an irradiation integrated light quantity of 500 mJ / cm 2 using a UV irradiation machine (manufactured by Eye Graphics Co., Ltd.) having an ultrahigh pressure mercury lamp.
  • the previously prepared curable resin composition for hard coat layer was applied at a thickness of 3 ⁇ m to the PC substrate on which the cured product layer was laminated.
  • the obtained PC substrate was UV-cured with an irradiation integrated light quantity of 500 mJ / cm 2 using a UV irradiation machine (manufactured by Eye Graphics Co., Ltd.) having an ultrahigh pressure mercury lamp. Table 5 shows the results of evaluation of the obtained optical disk.
  • UV-6640B Urethane acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) (radical polymerizable unsaturated group equivalent; 814)
  • UV-6100B urethane acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) (radically polymerizable unsaturated group equivalent; 828)
  • UV-7000B urethane acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) (radically polymerizable unsaturated group equivalent; 489)
  • UV-3000B urethane acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) (radical polymerizable unsaturated group equivalent; 3588)
  • CN-981 Urethane acrylate (Sartomer Co., Ltd.) (radically polymerizable unsaturated group equivalent; 709)
  • CN-2300 Hyperbranched polyester acrylate (8 acrylate functional groups, manufactured by Sartomer Japan, Inc.)
  • CN-2302 Hyperbranched polyester acrylate (16 acrylate functional groups, manufactured by Sartomer Japan, Inc.)
  • CN-2304 Hyperbranched polyester acrylate (18 acrylate functional groups, manufactured by Sartomer Japan, Inc.) -Biscoat # 1000: Dendrimer type acrylate (Osaka Organic Chemical Co., Ltd.)-Biscoat # 1020: Dendrimer type acrylate (Osaka Organic Chemical Co., Ltd.)-P- (VEEA) -2: Vinyl-based weight of Production Example 2 Combined VEEA: 2- (2-vinyloxyethoxy) ethyl acrylate (manufactured by Nippon Shokubai Co., Ltd.) NP-2PO-A: Diacrylate of propylene oxide 2-mol adduct of neopentyl glycol (trade name “SR-9003” "Sartomer Co
  • the curable resin composition for an optical disc of the present invention has transparency and suppresses warpage of the entire optical disc, and further has long-term storage stability (low warpage and high temperature environment in a storage test under a high temperature environment and a low temperature environment). It is possible to use for an optical disc, for example, a Blu-ray disc (registered trademark), which is excellent in the residual film property below and a small amount of permanent deformation such as a dent.
  • a Blu-ray disc registered trademark

Abstract

L'invention porte sur une composition de résine durcissable pour des disques optiques, et sur un disque optique qui utilise celle-ci en tant que couche protectrice, qui a une transparence élevée, qui permet un enregistrement et une reproduction hautement fiables, et qui a une excellente stabilité au stockage à long terme (autrement dit, présente un faible gauchissement dans un environnement haute température et un test de stockage basse température, et une faible quantité de changements permanents tels qu'une indentation ou une formation de film résiduel dans des environnements haute température). La composition de résine durcissable pour disques optiques forme un film réfléchissant sur un substrat de telle sorte qu'une lumière laser peut être réfléchie pour la lecture d'informations, et une couche protectrice sur le film réfléchissant mentionné ci-dessus qui a une épaisseur entre 20 µm et 150 µm. La composition de résine comprend un oligomère et/ou un polymère ayant un groupe polymérisable par radicaux, un ester d'acide (méth)acrylique polyfonctionnel contenant un additif, et un initiateur de photopolymérisation. Si l'équivalent de groupe insaturé polymérisable par radicaux (g/éq) dans la composition de résine durcissable mentionnée ci-dessus est représenté par A et la teneur (% en masse) de l'ester d'acide (méth)acrylique contenant un additif dans la composition de résine durcissable mentionnée ci-dessus est représentée par B, alors 6,6 ≤ A ÷ B ≤ 35.
PCT/JP2009/055994 2008-12-02 2009-03-25 Composition de résine durcissable pour disques optiques, et disque optique WO2010109615A1 (fr)

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JP2013199609A (ja) * 2012-03-26 2013-10-03 Jnc Corp 光硬化性組成物
JP2016000819A (ja) * 2015-07-27 2016-01-07 セイコーエプソン株式会社 紫外線硬化型インク組成物
CN106519149A (zh) * 2016-11-08 2017-03-22 苏州太湖电工新材料股份有限公司 一种环保型无溶剂浸渍树脂及其制备方法
JP2019064086A (ja) * 2017-09-29 2019-04-25 日東電工株式会社 ハードコートフィルム

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JP2003263780A (ja) * 2002-03-11 2003-09-19 Tdk Corp 光情報媒体
JP2005319459A (ja) * 2004-04-08 2005-11-17 Tdk Corp 光記録媒体の製造方法及び光記録媒体
WO2006018986A1 (fr) * 2004-08-18 2006-02-23 Konica Minolta Medical & Graphic, Inc. Support d’enregistrement holographique, procédé d’enregistrement holographique et support d’informations holographiques

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JP2003231725A (ja) * 2002-02-08 2003-08-19 Mitsubishi Rayon Co Ltd 活性エネルギー線硬化性組成物、及び光ディスク
JP2003263780A (ja) * 2002-03-11 2003-09-19 Tdk Corp 光情報媒体
JP2005319459A (ja) * 2004-04-08 2005-11-17 Tdk Corp 光記録媒体の製造方法及び光記録媒体
WO2006018986A1 (fr) * 2004-08-18 2006-02-23 Konica Minolta Medical & Graphic, Inc. Support d’enregistrement holographique, procédé d’enregistrement holographique et support d’informations holographiques

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013199609A (ja) * 2012-03-26 2013-10-03 Jnc Corp 光硬化性組成物
JP2016000819A (ja) * 2015-07-27 2016-01-07 セイコーエプソン株式会社 紫外線硬化型インク組成物
CN106519149A (zh) * 2016-11-08 2017-03-22 苏州太湖电工新材料股份有限公司 一种环保型无溶剂浸渍树脂及其制备方法
CN106519149B (zh) * 2016-11-08 2019-11-15 苏州太湖电工新材料股份有限公司 一种环保型无溶剂浸渍树脂及其制备方法
JP2019064086A (ja) * 2017-09-29 2019-04-25 日東電工株式会社 ハードコートフィルム
JP7152138B2 (ja) 2017-09-29 2022-10-12 日東電工株式会社 ハードコートフィルム

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