WO2011061953A1 - Uv-curable resin composition for use in optical disc, cured product, and article - Google Patents

Uv-curable resin composition for use in optical disc, cured product, and article Download PDF

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Publication number
WO2011061953A1
WO2011061953A1 PCT/JP2010/058505 JP2010058505W WO2011061953A1 WO 2011061953 A1 WO2011061953 A1 WO 2011061953A1 JP 2010058505 W JP2010058505 W JP 2010058505W WO 2011061953 A1 WO2011061953 A1 WO 2011061953A1
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Prior art keywords
meth
acrylate
curable resin
resin composition
ultraviolet curable
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PCT/JP2010/058505
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French (fr)
Japanese (ja)
Inventor
大祐 小林
正弘 内藤
潤 木戸場
隼 本橋
雄一朗 松尾
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日本化薬株式会社
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Application filed by 日本化薬株式会社 filed Critical 日本化薬株式会社
Priority to SG2012056289A priority Critical patent/SG182792A1/en
Priority to JP2011505712A priority patent/JP4824840B2/en
Priority to CN2010800627728A priority patent/CN102741927A/en
Publication of WO2011061953A1 publication Critical patent/WO2011061953A1/en

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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
    • G11B7/257—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers
    • G11B7/2572—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers consisting essentially of organic materials
    • G11B7/2575—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers consisting essentially of organic materials resins
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
    • G11B7/246—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes

Definitions

  • the present invention relates to an ultraviolet curable resin composition useful for an optical disc having an organic dye recording layer.
  • Optical disc recording media that are currently in practical use include CD-R, CD-RW, and the like, in which a recording layer, a reflective layer, and a protective layer made of an ultraviolet curable resin are laminated on a polycarbonate substrate having a thickness of 1.2 mm.
  • a DVD-R, DVD + R, DVD-RW, DVD + RW, DVD which is composed of a 0.6 mm thick polycarbonate substrate and a 0.6 mm thick polycarbonate substrate having a recording layer and a reflective layer bonded together with an ultraviolet curable resin.
  • -RAM is present.
  • a Blu-ray Disc having a recording capacity about five times that of a single-layer DVD has been released.
  • a reflective layer, a recording layer, and an interface layer are formed on a transparent or opaque plastic substrate having a thickness of 1.1 mm, and then a light transmission layer having a thickness of about 0.1 mm is laminated on the interface layer.
  • the recording layer an organic dye or an inorganic compound, a light-transmitting inorganic material as the interface layer, and a cured layer of an ultraviolet curable resin as the light-transmitting layer are used.
  • a Blu-ray disc having a recording layer made of an organic dye recording is performed by irradiating the recording layer with a laser beam and utilizing deformation due to a volume change of the organic dye.
  • a technique for forming a curable resin having an elastic modulus at 25 ° C. of 40 MPa or less on an interface layer for the purpose of assisting the volume change of the dye and obtaining excellent recording signal characteristics (for example, jitter characteristics) Patent Document 1
  • Patent Document 2 A technique for forming a curable resin having an elastic modulus of 34 to 96 MPa at 25 ° C. has been proposed.
  • an environmental test is performed in which the optical disk recording medium is left for 100 hours in an environment of temperature 80 ° C./relative humidity 80% RH.
  • both the elastic modulus at 5 ° C. and 55 ° C. on the interface layer is 100 MPa or less, and the elastic modulus at 5 ° C. and 55 ° C.
  • Patent Document 3 for forming a curable resin having an elastic modulus ratio of 10 or less has been proposed.
  • Patent Documents 1 to 3 do not show specific examples of the curable resin formed on the interface.
  • Japanese Unexamined Patent Publication No. 2008-123631 Japanese Unexamined Patent Publication No. 2008-269703 Japanese Unexamined Patent Publication No. 2009-026379
  • An object of the present invention is to provide an ultraviolet curable resin composition capable of imparting excellent recording signal characteristics and durability in an optical disc having an organic dye recording layer.
  • the inventors of the present invention are excellent in an optical disk having an organic dye recording layer according to an ultraviolet curable resin composition containing a (meth) acrylate having a specific structure.
  • the present inventors have found that recording signal characteristics and durability can be imparted, and have completed the present invention.
  • An ultraviolet curable resin composition for an optical disc having an organic dye recording layer containing (A) a (meth) acrylate having an alkylene group having 7 to 18 carbon atoms and (B) a photopolymerization initiator.
  • the (meth) acrylate (A) having an alkylene group having 7 to 18 carbon atoms is isooctyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate, stearyl (meth) acrylate, cetyl (meth) Acrylate, isomyristyl (meth) acrylate, tridecyl (meth) acrylate, 2-ethyl-2-butyl-propanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate and 1,10-decanediol di
  • the ultraviolet curable resin composition for optical disks according to (1) above which is at least one selected from the group consisting of (meth) acrylates.
  • (C) The ultraviolet curable resin composition for optical disks according to (1) or (2) above, which contains (meth) acrylates other than (A).
  • the (meth) acrylate (A) having an alkylene group having 7 to 18 carbon atoms is contained in an amount of 10 to 95% by weight based on the entire composition, according to any one of the above (1) to (3) UV curable resin composition for optical discs.
  • (Meth) acrylate (C) other than (A) is a reaction product of polyester polyol or polyether polyol, polyisocyanate and hydroxy (meth) acrylate, and / or ethylene oxide-modified bisphenol A type diacrylate. 6.
  • the ultraviolet curable resin composition containing (meth) acrylate having an alkylene group having 7 to 18 carbon atoms according to the present invention is used for the light transmission layer of an optical disc having an organic dye recording layer, it is possible to record at high temperature and high humidity. A highly reliable optical disk can be provided for long-time use.
  • the ultraviolet curable resin composition for optical disks having the organic dye recording layer of the present invention (hereinafter simply referred to as “ultraviolet curable resin composition”) is a (meth) acrylate having a C 7-18 alkylene group and photopolymerization. Contains an initiator.
  • (meth) acrylate means methacrylate or acrylate, and the kind thereof is not particularly limited.
  • the (meth) acrylate (A) having an alkylene group having 7 to 18 carbon atoms contained in the ultraviolet curable resin composition of the present invention is limited to a linear or branched structure within the range of 7 to 18 carbon atoms.
  • the carbon number is less than 7, the recording signal characteristics and durability are not excellent.
  • the carbon number exceeds 18, the liquid is separated and it is difficult to apply uniformly. This is undesirable in manufacturing.
  • Examples of the (meth) acrylate (A) having an alkylene group having 7 to 18 carbon atoms include lauryl (meth) acrylate (for example, Bremer LA manufactured by NOF Corporation), isooctyl (meth) acrylate (for example, Kyoeisha Chemical ( Light acrylate IO-A), isodecyl (meth) acrylate (for example, SR-395 manufactured by Sartomer Co.), stearyl (meth) acrylate (for example, light acrylate IS-A manufactured by Kyoeisha Chemical Co., Ltd.) ), Cetyl (meth) acrylate (for example, Bremer CA manufactured by NOF Corporation), isomyristyl (meth) acrylate (for example, light acrylate IM-A manufactured by Kyoeisha Chemical Co., Ltd.), tridecyl (meth) acrylate ( For example, Sartomer Co., Ltd.
  • lauryl (meth) acrylate for example,
  • the content of the component (A) in the ultraviolet curable resin composition is usually 10 to 95% by weight, preferably 20 to 80% by weight. If it is less than 10% by weight, the change in the volume of the dye cannot be assisted, and the jitter value (%), which is an indicator of the recording signal characteristics, becomes worse.
  • the photopolymerization initiator (B) contained in the ultraviolet curable resin composition of the present invention is not particularly limited.
  • 1-hydroxycyclohexyl phenyl ketone (Irgacure 184; manufactured by Ciba Specialty Chemicals)
  • 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer (ONE-Rifened)
  • 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl- 1-propan-1-one (Irgacure 2959; manufactured by Ciba Specialty Chemicals)
  • 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl ⁇ - 2-Methyl-propan-1-one (Irgacure 127; Ciba Specialty Chemicals 2,2-dimethoxy-2-phenylacetophenone (Irgacure 651; manufactured by Ciba
  • these components (B) can be used alone or in combination of two or more at any ratio.
  • the content of the component (B) in the ultraviolet curable resin composition is usually 0.5 to 20% by weight, preferably 1 to 10% by weight.
  • amines that can serve as photopolymerization initiation assistants can be used in combination with the above photopolymerization initiator.
  • examples of amines that can be used include benzoic acid 2-dimethylaminoethyl ester, dimethylaminoacetophenone, p-dimethylaminobenzoic acid ethyl ester, and p-dimethylaminobenzoic acid isoamyl ester.
  • the content in the ultraviolet curable resin composition of the present invention is usually 0.005 to 5% by weight, preferably 0.01 to 3% by weight.
  • the ultraviolet curable resin composition of the present invention may further contain (meth) acrylate (C) other than (A) in addition to the above components.
  • (meth) acrylates (C) other than (A) contained in the ultraviolet curable resin composition of the present invention include (meth) acrylates having at least one (meth) acryloyl group.
  • (meth) acrylate means methacrylate or acrylate, and the kind thereof is not particularly limited, but (meth) acrylate (C) other than (A) includes (C-1) epoxy (meth). Acrylate, (C-2) urethane (meth) acrylate, (C-3) (meth) acrylate monomer, and the like can be used.
  • (C-1) epoxy (meth) acrylate and / or (C-2) urethane (meth) acrylate and (C-3) (meth) acrylate monomer are used alone or in combination. It is preferable to use (C-2) urethane (meth) acrylate and (C-3) (meth) acrylate monomer in combination.
  • the epoxy (meth) acrylate (C-1) that can be used in the present invention has a function of improving curability and improving the hardness and curing speed of a cured product.
  • any epoxy (meth) acrylate may be used as long as it is obtained by reacting a glycidyl ether type epoxy compound with (meth) acrylic acid, but is preferably used in the present invention.
  • Examples of glycidyl ether type epoxy compounds for obtaining epoxy (meth) acrylates include diglycidyl ether of bisphenol A or its alkylene oxide adduct, diglycidyl ether of bisphenol F or its alkylene oxide adduct, hydrogenated bisphenol A or its Diglycidyl ether of alkylene oxide adduct, hydrogenated bisphenol F or diglycidyl ether of its alkylene oxide adduct, ethylene glycol diglycidyl ether, propylene glycol Le diglycidyl ether, neopentyl glycol diglycidyl ether, butanediol diglycidyl ether hexanediol diglycidyl ether to, cyclohexanedimethanol diglycidyl ether, and polypropylene glycol diglycidyl ether.
  • Epoxy (meth) acrylate is obtained by reacting these glycidyl ether type epoxy compounds with (meth) acrylic acid under the following conditions.
  • (Meth) acrylic acid is reacted at a ratio of 0.9 to 1.5 mol, more preferably 0.95 to 1.1 mol, per 1 equivalent of epoxy group of the glycidyl ether type epoxy compound.
  • the reaction temperature is preferably 80 to 120 ° C., and the reaction time is about 10 to 35 hours.
  • a catalyst such as triphenylphosphine, 2,4,6-tris (dimethylaminomethyl) phenol (TAP), triethanolamine, tetraethylammonium chloride and the like.
  • TAP 2,4,6-tris (dimethylaminomethyl) phenol
  • TAP 2,4,6-tris (dimethylaminomethyl) phenol
  • triethanolamine tetraethylammonium chloride and the like.
  • paramethoxyphenol, methylhydroquinone or the like can be used as a polymerization inhibitor.
  • the epoxy (meth) acrylate (C-1) is more preferably bisphenol A type epoxy (meth) acrylate obtained from a bisphenol A type epoxy compound.
  • the molecular weight of the epoxy (meth) acrylate (C-1) is preferably 500 to 10,000.
  • the urethane (meth) acrylate (C-2) that can be used in the present invention has a function of improving the mechanical properties (warpage, distortion, etc.) of an optical disk bonded using the ultraviolet curable resin composition of the present invention.
  • Urethane (meth) acrylate is obtained by reacting a polyhydric alcohol, polyisocyanate, and a hydroxy (meth) acrylate compound.
  • polyhydric alcohol examples include neopentyl glycol, 3-methyl-1,5-pentanediol, (poly) ethylene glycol, (poly) propylene glycol, 1,4-butanediol, 1,6-hexanediol, tri
  • polyhydric alcohols and polybasic acids for example, succinic acid, phthalic acid, hexahydrophthalic anhydride, terephthalic acid, adipic acid, methylolpropane, pentaerythritol, tricyclodecane dimethylol, bis- [hydroxymethyl] -cyclohexane, etc.
  • polyester polyol or polyether polyol is preferable.
  • polyisocyanate examples include isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, diphenylmethane-4,4'-diisocyanate, and dicyclopentanyl isocyanate.
  • hydroxy (meth) acrylate compound examples include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, dimethylol cyclohexyl mono (meth) acrylate, and hydroxycaprolactone (meth) acrylate. .
  • hydroxyethyl (meth) acrylate is preferable, and 2-hydroxyethyl (meth) acrylate is particularly preferable.
  • the reaction is performed, for example, as follows. That is, the polyhydric alcohol is mixed with an organic polyisocyanate per equivalent of the hydroxyl group so that the isocyanate group is preferably 1.1 to 2.0 equivalent, and reacted at a reaction temperature of preferably 70 to 90 ° C. Synthesize oligomers. Next, the hydroxy (meth) acrylate compound is mixed so that the hydroxyl group is preferably 1 to 1.5 equivalents per equivalent of the isocyanate group of the urethane oligomer, and reacted at 70 to 90 ° C. to react with the target urethane (meth). ) Acrylate can be obtained.
  • UX-0937 polyether urethane acrylate (manufactured by Nippon Kayaku Co., Ltd.).
  • the molecular weight of the urethane (meth) acrylate (C-2) is preferably about 400 to 10,000.
  • the (meth) acrylate monomer (C-3) that can be used as the (meth) acrylate (C) other than (A) is not particularly limited.
  • phenoxyethyl (meth) has one (meth) acryloyl group.
  • the (meth) acrylate monomer having one (meth) acryloyl group has a function of improving the mechanical properties (suppression of warpage, distortion, etc.) of an optical disk formed with the ultraviolet curable resin composition of the present invention as a light transmission layer.
  • (Meth) acrylate monomer (C-3) that can be used as (meth) acrylate (C) other than (A)
  • the (meth) acrylate monomer having two (meth) acryloyl groups is cyclohexane-1,4-dimethanoldi (Meth) acrylate, cyclohexane-1,3-dimethanol di (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate (for example, KAYARAD R-684, manufactured by Nippon Kayaku Co., Ltd., tricyclodecane dimethylol di Acrylate, etc.), dioxane glycol di (meth) acrylate (for example, KAYARAD R-604, dioxane glycol diacrylate, etc., manufactured by Nippon Kayaku Co., Ltd.), neopentyl glycol di (meth) acrylate, dicyclopentanyl di ( Meta) Acu 1,6-hex
  • (Meth) acrylate monomer (C-3) that can be used as (meth) acrylate (C) other than (A)
  • the (meth) acrylate monomer having three (meth) acryloyl groups is trimethylolpropane tri (meth).
  • (meth) acrylate monomer (C-3) that can be used as (meth) acrylate (C) other than (A), as (meth) acrylate monomer having four (meth) acryloyl groups, pentaerythritol polyethoxytetra (meth) ) Acrylate, pentaerythritol polypropoxytetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and the like.
  • pentaerythritol polyethoxytetra (meth) ) Acrylate pentaerythritol polypropoxytetra (meth) acrylate
  • pentaerythritol tetra (meth) acrylate ditrimethylolpropane tetra
  • (Meth) acrylate monomer (C-3) that can be used as (meth) acrylate (C) other than (A)
  • the (meth) acrylate monomer having five (meth) acryloyl groups is dipentaerythritol penta (meth). Examples thereof include acrylate and caprolactone-modified dipentaerythritol penta (meth) acrylate.
  • (Meth) acrylate monomer (C-3) that can be used as (meth) acrylate (C) other than (A) (meth) acrylate monomer having 6 (meth) acryloyl groups is dipentaerythritol hexa (meth) Examples thereof include acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate.
  • the (meth) acrylate monomer that can be used in the present invention may be a polyfunctional monomer having 7 or more (meth) acryloyl groups.
  • these components (C) can be used alone or in combination of two or more at any ratio.
  • the content of the component (C) in the ultraviolet curable resin composition is usually 30 to 80% by weight, preferably 40 to 70% by weight.
  • (C-1) and / or (C-2) and (C-3) are usually ultraviolet rays. It is 5 to 70 parts by weight, preferably about 10 to 60 parts by weight with respect to 100 parts by weight of the curable resin composition, and the component (C-3) is (
  • the total of component (C-3) and component (A) is used in a range of 20 to 80 parts by weight, preferably 25 to 75 parts by weight.
  • the ultraviolet curable resin composition of the present invention includes a rust inhibitor, antioxidant, organic solvent, silane coupling agent, polymerization inhibitor, leveling agent, antistatic agent, surface lubricant, fluorescent whitening as necessary.
  • Any known hindered amine compound can be used without particular limitation. Specific examples thereof include 1,2,2,6,6-pentamethyl-4-piperidyl alcohol, 2,2,6,6-tetra Examples thereof include methyl-4-piperidyl alcohol, 1,2,2,6,6-pentamethyl-4-piperidyl (meth) acrylate (manufactured by Adeka Co., Ltd., LA-82).
  • the ultraviolet curable resin composition of the present invention can be obtained by mixing and dissolving the aforementioned components at room temperature to 80 ° C., and if necessary, impurities may be removed by an operation such as filtration.
  • impurities may be removed by an operation such as filtration.
  • the ultraviolet curable resin composition of the present invention can be suitably used as a coating agent for a light transmission layer on the laser incident side of a Blu-ray disc or the like.
  • the composition is applied to the optical disk substrate by an arbitrary method such as a spin coating method, a 2P method, a roll coating method, or a screen printing method so that the thickness of the applied resin is 1 to 100 ⁇ m.
  • the film is cured by irradiating ultraviolet rays to near ultraviolet rays (wavelength of 200 to 400 nm) from one side or both sides.
  • Irradiation dose is preferably from about 50 ⁇ 1500mJ / cm 2, particularly preferably 100 ⁇ 1000mJ / cm 2 approximately.
  • any light source may be used as long as it is a lamp that emits ultraviolet to near ultraviolet rays.
  • a low-pressure, high-pressure or ultrahigh-pressure mercury lamp, metal halide lamp, (pulse) xenon lamp, or electrodeless lamp can be used.
  • the ultraviolet curable resin composition of this invention is applicable also when a light-transmitting layer consists of a some layer.
  • a first resin layer in which a light transmission layer is formed on a recording layer or an interface layer, and a second resin formed on a surface opposite to the recording layer or interface layer side when viewed from the first resin layer When comprised from a layer, it can be used conveniently for said 1st resin layer.
  • the thickness of the first resin layer is usually 1 ⁇ m to 50 ⁇ m, preferably 5 ⁇ m to 40 ⁇ m, more preferably 10 ⁇ m to 30 ⁇ m.
  • the thickness of the second resin layer is usually 50 ⁇ m to 100 ⁇ m, preferably 60 ⁇ m to 95 ⁇ m, more preferably 70 ⁇ m to 90 ⁇ m.
  • the light transmission layer is formed by any method such that the film thickness of the resin applied as the first resin layer is 1 ⁇ m to 50, specifically,
  • the composition is applied to the optical disk substrate by spin coating, 2P, roll coating, screen printing, or the like.
  • the film is cured by irradiating ultraviolet rays to near ultraviolet rays (wavelength of 200 to 400 nm) from one side or both sides.
  • the irradiation amount is preferably 50 to 1500 mJ / cm 2 , particularly preferably about 100 to 1000 cmJ / cm 2 .
  • the composition is applied to the optical disk substrate by any method such as spin coating, 2P method, roll coating method, screen printing method or the like so that the film thickness becomes 50 ⁇ m to 100 ⁇ m as the second resin layer. .
  • the film is cured by irradiating ultraviolet rays to near ultraviolet rays (wavelength of 200 to 400 nm) from one side or both sides. Irradiation dose is preferably from about 50 ⁇ 1500mJ / cm 2, particularly preferably 100 ⁇ 1000mJ / cm 2 approximately.
  • any light source may be used as long as it is a lamp that irradiates ultraviolet to near ultraviolet rays.
  • a low-pressure, high-pressure or ultrahigh-pressure mercury lamp, metal halide lamp, (pulse) xenon lamp, or electrodeless lamp can be used.
  • Examples 1 to 4 and Comparative Examples 1 to 2 were prepared with ultraviolet curable resin compositions having the compositions shown in Table 1.
  • each component shown with the abbreviation in Table 1 is as follows.
  • LA lauryl acrylate, manufactured by NOF Corporation, acrylate having an alkylene group having 12 carbon atoms ISA: isostearyl acrylate, manufactured by Kyoeisha Chemical Co., Ltd., acrylate having an alkylene group having 18 carbon atoms NDDA: 1,9 -Nonanediol diacrylate, manufactured by Hitachi Chemical Co., Ltd., diacrylate having an alkylene group of 9 carbon atoms HDDA: 1,6-hexanediol diacrylate, manufactured by Nippon Kayaku Co., Ltd., alkylene of 6 carbon atoms Group-containing diacrylate
  • VA Behenyl acrylate, manufactured by NOF Corporation, acrylate having 22 alkylene groups UA-1: polytetramethylene glycol (molecular weight 850), isophorone diisocyanate, 2-hydroxyethyl acrylate 3 Reacting the components in a
  • Urethane acrylate BPE-10 Ethylene oxide 10 mol modified bisphenol A type diacrylate, Dai-ichi Kogyo Seiyaku Co., Ltd.
  • FA-512A Dicyclopentenyloxyethyl acrylate, Hitachi Chemical Co., Ltd.
  • Irgacure 184 1-hydroxycyclohexyl phenyl ketone, manufactured by Ciba Specialty Chemicals, Inc.
  • LA-82 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, manufactured by Asahi Denka Co., Ltd.
  • PMP 4 -Mercaptophenol
  • a Blu-ray disc having an organic dye recording layer was prepared and evaluated for characteristics.
  • a reflective layer was formed by sputtering a silver alloy to a thickness of 100 nm on a polycarbonate substrate having a diameter of 12 cm and a thickness of 1.1 mm having guide grooves with a track pitch of 0.32 ⁇ m. Thereafter, a dye solution in which an azo dye was dissolved in a TFP (tetrafluoropropanol) solvent was applied by spin coating, and dried at 80 ° C. for 30 minutes to form an organic dye recording layer.
  • TFP tetrafluoropropanol
  • ZnS—SiO 2 (molar ratio 80:20) was sputtered to a thickness of about 15 nm to form an interface layer, and a Blu-ray Disc substrate was produced.
  • a Blu-ray disc substrate is placed on a spin table so that the interface layer is on top, and a circular cap treatment is performed so as to cover the inner diameter of 11.5 mm, and then the UV curable resin composition of the present invention is 2.0 g in the center cap. Supplied on top. 3.
  • spin coating was performed at a speed range of 1000 rpm to 1500 rpm for 4 seconds to 7 seconds, and each coating film thickness was 25 ⁇ m.
  • the xenon flash lamp was irradiated with two shots, and cured so that the fluidity of the surface disappeared. 4).
  • the ultraviolet curable resin composition of the present invention was completely cured by irradiation from the upper side at 400 mJ / cm 2 for 3 seconds. 5.
  • the cured UV-curable resin composition of the present invention is placed on a spin table so that a circular cap treatment is performed so as to cover the inner diameter of 11.5 mm, and then BRD-864 (Nippon Kayaku Co., Ltd. Blu-ray) is applied.
  • the resin for the light transmission layer for disk was supplied onto the cap at the center of 3.0 g. 6.
  • a reflective layer was formed by sputtering a silver alloy to a thickness of 100 nm on a polycarbonate substrate having a diameter of 12 cm and a thickness of 1.1 mm having guide grooves with a track pitch of 0.32 ⁇ m. Thereafter, a dye solution in which an azo dye was dissolved in a TFP (tetrafluoropropanol) solvent was applied by spin coating, and dried at 80 ° C. for 30 minutes to form an organic dye recording layer.
  • TFP tetrafluoropropanol
  • ZnS—SiO 2 (molar ratio 80:20) was sputtered to a thickness of about 15 nm to form an interface layer, and a Blu-ray Disc substrate was produced.
  • a Blu-ray disc substrate is placed on a spin table so that the interface layer is on top, and a circular cap treatment is performed so as to cover the inner diameter of 11.5 mm, and then the UV curable resin composition of the present invention is 2.0 g in the center cap. Supplied on top. 3.
  • spin coating was performed at a speed range of 800 rpm to 1300 rpm for 4 seconds to 7 seconds, and the coating film thickness was 100 ⁇ m.
  • the xenon flash lamp was irradiated with two shots, and cured so that the fluidity of the surface disappeared. 4).
  • the ultraviolet curable resin composition of the present invention was completely cured by irradiating at 400 mJ / cm 2 from the upper side for 3 seconds to produce the Blu-ray Disc of the present invention.
  • the Blu-ray disc of the present invention and the Blu-ray disc of Comparative Example 1 were allowed to stand for 250 hours in an environment of 80 ° C. and 85% RH.
  • the recording signal characteristics (jitter value) of the Blu-ray disc before and after the durability test were measured using a Blu-ray Disc data signal measuring device ODU-1000 manufactured by Pulse Tech Co., Ltd., and evaluated according to the following criteria.
  • the jitter value is one of the electrical signals of the optical disk. The higher these values are, the more the signal data of the Blu-ray disk is degraded. When the value is 10% or more, it becomes difficult to read and write data. Evaluation of jitter value ⁇ Jitter value is less than 10.0%.
  • X Jitter value of 10.0% or more.

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  • Optical Record Carriers And Manufacture Thereof (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Manufacturing Optical Record Carriers (AREA)
  • Polymerisation Methods In General (AREA)
  • Paints Or Removers (AREA)

Abstract

Disclosed is a UV-curable resin which can impart excellent recording signal characteristics and durability to optical discs having an organic dye recording layer. The disclosed UV-curable resin is suitable for use as an agent for forming a light-transmitting layer on optical discs having an organic dye recording layer, and comprises (1) (A) a (meth) acrylate having a C7-18 alkylene group, and (B) a photo-polymerisation initiator.

Description

光ディスク用紫外線硬化型樹脂組成物、硬化物及び物品Ultraviolet curable resin composition for optical disc, cured product and article
　本発明は、有機色素記録層を有する光ディスクに有用な紫外線硬化型樹脂組成物に関する。 The present invention relates to an ultraviolet curable resin composition useful for an optical disc having an organic dye recording layer.
　現在、実用化されている光ディスク記録媒体としては、厚さ１．２ｍｍのポリカーボネート基板上に記録層、反射層、紫外線硬化型樹脂からなる保護層を積層したＣＤ－Ｒ、ＣＤ－ＲＷや、厚さ０．６ｍｍのポリカーボネート基板と、記録層及び反射層を備えた厚さ０．６ｍｍのポリカーボネート基板を紫外線硬化型樹脂で貼り合わせて構成されるＤＶＤ－Ｒ、ＤＶＤ＋Ｒ、ＤＶＤ－ＲＷ、ＤＶＤ＋ＲＷ、ＤＶＤ－ＲＡＭが存在している。 Optical disc recording media that are currently in practical use include CD-R, CD-RW, and the like, in which a recording layer, a reflective layer, and a protective layer made of an ultraviolet curable resin are laminated on a polycarbonate substrate having a thickness of 1.2 mm. A DVD-R, DVD + R, DVD-RW, DVD + RW, DVD, which is composed of a 0.6 mm thick polycarbonate substrate and a 0.6 mm thick polycarbonate substrate having a recording layer and a reflective layer bonded together with an ultraviolet curable resin. -RAM is present.
　また、近年、単層タイプのＤＶＤの約５倍の記録容量を有するブルーレイディスク（ＢＤ－Ｒ）が発売されている。ブルーレイディスクは、厚さ１．１ｍｍの透明または不透明のプラスチック製の基板上に反射層、記録層及び界面層を形成し、ついで界面層上に厚さ約０．１ｍｍの光透過層を積層した構造で、光透過層を通して記録／再生するディスクである。記録層には有機色素や無機化合物、界面層としては光透過性の無機物、光透過層としては紫外線硬化型樹脂の硬化物層が使用されている。 In recent years, a Blu-ray Disc (BD-R) having a recording capacity about five times that of a single-layer DVD has been released. In the Blu-ray Disc, a reflective layer, a recording layer, and an interface layer are formed on a transparent or opaque plastic substrate having a thickness of 1.1 mm, and then a light transmission layer having a thickness of about 0.1 mm is laminated on the interface layer. A disc having a structure for recording / reproducing through a light transmission layer. As the recording layer, an organic dye or an inorganic compound, a light-transmitting inorganic material as the interface layer, and a cured layer of an ultraviolet curable resin as the light-transmitting layer are used.
　有機色素からなる記録層を有するブルーレイディスクでは、記録層にレーザー光を照射し、有機色素の体積変化による変形を利用して記録を行う。色素の体積変化を補助し、優れた記録信号特性（例えば、ジッタ特性）を得る目的で、界面層上に２５℃での弾性率が４０ＭＰａ以下の硬化性樹脂を形成させる技術（特許文献１）、２５℃での弾性率が３４～９６ＭＰａの硬化性樹脂を形成させる技術（特許文献２）が提案されている。 In a Blu-ray disc having a recording layer made of an organic dye, recording is performed by irradiating the recording layer with a laser beam and utilizing deformation due to a volume change of the organic dye. A technique for forming a curable resin having an elastic modulus at 25 ° C. of 40 MPa or less on an interface layer for the purpose of assisting the volume change of the dye and obtaining excellent recording signal characteristics (for example, jitter characteristics) (Patent Document 1) A technique (Patent Document 2) for forming a curable resin having an elastic modulus of 34 to 96 MPa at 25 ° C. has been proposed.
　また、前述の光ディスク記録媒体の信頼性の評価指標として、温度８０℃／相対湿度８０％ＲＨの環境下で１００時間放置する環境試験が行われている。この環境試験前後の記録信号の劣化度合いを所定の範囲以内にするために、界面層上に５℃と５５℃での弾性率が共に１００ＭＰａ以下であり、かつ５℃の弾性率と５５℃の弾性率の比が１０以下である硬化性樹脂を形成させる技術（特許文献３）が提案されている。 Also, as an evaluation index for the reliability of the optical disk recording medium described above, an environmental test is performed in which the optical disk recording medium is left for 100 hours in an environment of temperature 80 ° C./relative humidity 80% RH. In order to keep the degree of deterioration of the recording signal before and after this environmental test within a predetermined range, both the elastic modulus at 5 ° C. and 55 ° C. on the interface layer is 100 MPa or less, and the elastic modulus at 5 ° C. and 55 ° C. A technique (Patent Document 3) for forming a curable resin having an elastic modulus ratio of 10 or less has been proposed.
　しかしながら、特許文献１～３には界面上に形成する硬化性樹脂の具体例が示されていない。 However, Patent Documents 1 to 3 do not show specific examples of the curable resin formed on the interface.
日本国特開２００８－１２３６３１号公報Japanese Unexamined Patent Publication No. 2008-123631 日本国特開２００８－２６９７０３号公報Japanese Unexamined Patent Publication No. 2008-269703 日本国特開２００９－０２６３７９号公報Japanese Unexamined Patent Publication No. 2009-026379
　本発明は、有機色素記録層を有する光ディスクにおいて、優れた記録信号特性及び耐久性を付与できる紫外線硬化型樹脂組成物を提供することを目的とする。 An object of the present invention is to provide an ultraviolet curable resin composition capable of imparting excellent recording signal characteristics and durability in an optical disc having an organic dye recording layer.
　本発明者らは、前記課題を解決すべく鋭意研究を重ねた結果、特定の構造を有する（メタ）アクリレートを含有する紫外線硬化型樹脂組成物によれば、有機色素記録層を有する光ディスクに優れた記録信号特性及び耐久性を付与できることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention are excellent in an optical disk having an organic dye recording layer according to an ultraviolet curable resin composition containing a (meth) acrylate having a specific structure. The present inventors have found that recording signal characteristics and durability can be imparted, and have completed the present invention.
　即ち、本発明は、次の（１）～（７）に関するものである。
（１）　（Ａ）炭素数７～１８のアルキレン基を有する（メタ）アクリレート及び（Ｂ）光重合開始剤を含有する有機色素記録層を有する光ディスク用紫外線硬化型樹脂組成物。
（２）　炭素数７～１８のアルキレン基を有する（メタ）アクリレート（Ａ）が、イソオクチル（メタ）アクリレート、ラウリル（メタ）アクリレート、イソデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、セチル（メタ）アクリレート、イソミリスチル（メタ）アクリレート、トリデシル（メタ）アクリレート、２－エチル－２－ブチル－プロパンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート及び１，１０－デカンジオールジ（メタ）アクリレートからなる群から選ばれる１種以上である上記（１）に記載の光ディスク用紫外線硬化型樹脂組成物。
（３）　（Ｃ）（Ａ）以外の（メタ）アクリレートを含有する上記（１）又は上記（２）に記載の光ディスク用紫外線硬化型樹脂組成物。
（４）　炭素数７～１８のアルキレン基を有する（メタ）アクリレート（Ａ）が、組成物全体に対して１０～９５重量％含有する上記（１）～（３）のいずれか１項に記載の光ディスク用紫外線硬化型樹脂組成物。
（５）　（Ａ）以外の（メタ）アクリレート（Ｃ）が、ポリエステルポリオール又はポリエーテルポリオールとポリイソシアネートとヒドロキシ（メタ）アクリレートとの反応物、及び／又はエチレンオキサイド変性ビスフェノールＡ型ジアクリレートである上記（１）～（４）のいずれか１項に記載の光ディスク用紫外線硬化型樹脂組成物。
（６）　上記（１）～（５）のいずれか１項に記載の光ディスク用紫外線硬化型樹脂組成物に活性エネルギー線を照射して得られる硬化物。
（７）　光ディスク基板に、上記（１）～（５）のいずれか１項に記載の光ディスク用紫外線硬化型樹脂組成物を塗布し、活性エネルギー線を照射して得られる光ディスク。 That is, the present invention relates to the following (1) to (7).
(1) An ultraviolet curable resin composition for an optical disc having an organic dye recording layer containing (A) a (meth) acrylate having an alkylene group having 7 to 18 carbon atoms and (B) a photopolymerization initiator.
(2) The (meth) acrylate (A) having an alkylene group having 7 to 18 carbon atoms is isooctyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate, stearyl (meth) acrylate, cetyl (meth) Acrylate, isomyristyl (meth) acrylate, tridecyl (meth) acrylate, 2-ethyl-2-butyl-propanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate and 1,10-decanediol di The ultraviolet curable resin composition for optical disks according to (1) above, which is at least one selected from the group consisting of (meth) acrylates.
(3) (C) The ultraviolet curable resin composition for optical disks according to (1) or (2) above, which contains (meth) acrylates other than (A).
(4) The (meth) acrylate (A) having an alkylene group having 7 to 18 carbon atoms is contained in an amount of 10 to 95% by weight based on the entire composition, according to any one of the above (1) to (3) UV curable resin composition for optical discs.
(5) (Meth) acrylate (C) other than (A) is a reaction product of polyester polyol or polyether polyol, polyisocyanate and hydroxy (meth) acrylate, and / or ethylene oxide-modified bisphenol A type diacrylate. 6. The ultraviolet curable resin composition for optical disks according to any one of (1) to (4) above.
(6) A cured product obtained by irradiating the ultraviolet ray curable resin composition for optical disks according to any one of (1) to (5) with active energy rays.
(7) An optical disc obtained by applying the ultraviolet curable resin composition for optical disc according to any one of (1) to (5) above to an optical disc substrate and irradiating with active energy rays.
　有機色素記録層を有する光ディスクの光透過層に、本発明の炭素数７～１８のアルキレン基を有する（メタ）アクリレートを含有する紫外線硬化型樹脂組成物を使用した場合、記録時及び高温高湿下での長時間の使用において信頼性の高い光ディスクを提供できる。 When the ultraviolet curable resin composition containing (meth) acrylate having an alkylene group having 7 to 18 carbon atoms according to the present invention is used for the light transmission layer of an optical disc having an organic dye recording layer, it is possible to record at high temperature and high humidity. A highly reliable optical disk can be provided for long-time use.
　本発明の有機色素記録層を有する光ディスク用紫外線硬化型樹脂組成物（以下、単に「紫外線硬化型樹脂組成物」という）は、炭素数７～１８のアルキレン基を有する（メタ）アクリレート及び光重合開始剤を含有する。尚、本発明において（メタ）アクリレートとはメタクリレート又はアクリレートを意味し、その種類は特に限定されない。 The ultraviolet curable resin composition for optical disks having the organic dye recording layer of the present invention (hereinafter simply referred to as “ultraviolet curable resin composition”) is a (meth) acrylate having a C 7-18 alkylene group and photopolymerization. Contains an initiator. In the present invention, (meth) acrylate means methacrylate or acrylate, and the kind thereof is not particularly limited.
　本発明の紫外線硬化型樹脂組成物に含有される炭素数７～１８のアルキレン基を有する（メタ）アクリレート（Ａ）としては、炭素数７～１８の範囲では、直鎖または分岐構造に制限されることなく使用することができるが、炭素数が７未満であると記録信号特性及び耐久性に優れず、一方、炭素数が１８を超えると液が分離し、均一に塗布することが困難となり、製造上望ましくない。炭素数７～１８のアルキレン基を有する（メタ）アクリレート（Ａ）としては、ラウリル（メタ）アクリレート（例えば、日油（株）社製ブレンマー　ＬＡ）、イソオクチル（メタ）アクリレート（例えば、共栄社化学（株）社製ライトアクリレート　ＩＯ－Ａ）、イソデシル（メタ）アクリレート（例えば、サートマー（株）社製　ＳＲ－３９５）、ステアリル（メタ）アクリレート（例えば、共栄社化学（株）社製ライトアクリレート　ＩＳ－Ａ）、セチル（メタ）アクリレート（例えば、日油（株）社製ブレンマー　ＣＡ）、イソミリスチル（メタ）アクリレート（例えば、共栄社化学（株）社製ライトアクリレート　ＩＭ－Ａ）、トリデシル（メタ）アクリレート（例えば、サートマー（株）社製　ＳＲ－４８９）、２－エチル－２－ブチル－プロパンジオールジ（メタ）アクリレート（例えば、第一工業製薬（株）社製ニューフロンディア　Ｃ９Ａ）、１，９－ノナンジオールジ（メタ）アクリレート（例えば、日立化成工業（株）社製ファンクリル　ＦＡ－１２９ＡＳ）及び１，１０－デカンジオールジ（メタ）アクリレート（例えば、新中村化学（株）社製ＮＫエステル　Ａ－ＤＯＤ－Ｎ）が好ましい。中でも好ましくは炭素数７～１４アルキレン基を有する（メタ）アクリレートが好ましい。 The (meth) acrylate (A) having an alkylene group having 7 to 18 carbon atoms contained in the ultraviolet curable resin composition of the present invention is limited to a linear or branched structure within the range of 7 to 18 carbon atoms. However, when the carbon number is less than 7, the recording signal characteristics and durability are not excellent. On the other hand, when the carbon number exceeds 18, the liquid is separated and it is difficult to apply uniformly. This is undesirable in manufacturing. Examples of the (meth) acrylate (A) having an alkylene group having 7 to 18 carbon atoms include lauryl (meth) acrylate (for example, Bremer LA manufactured by NOF Corporation), isooctyl (meth) acrylate (for example, Kyoeisha Chemical ( Light acrylate IO-A), isodecyl (meth) acrylate (for example, SR-395 manufactured by Sartomer Co.), stearyl (meth) acrylate (for example, light acrylate IS-A manufactured by Kyoeisha Chemical Co., Ltd.) ), Cetyl (meth) acrylate (for example, Bremer CA manufactured by NOF Corporation), isomyristyl (meth) acrylate (for example, light acrylate IM-A manufactured by Kyoeisha Chemical Co., Ltd.), tridecyl (meth) acrylate ( For example, Sartomer Co., Ltd. SR-489), 2-ethyl-2 Butyl-propanediol di (meth) acrylate (for example, New Frontier C9A manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 1,9-nonanediol di (meth) acrylate (for example, fan manufactured by Hitachi Chemical Co., Ltd.) Kuryl FA-129AS) and 1,10-decanediol di (meth) acrylate (for example, NK ester A-DOD-N manufactured by Shin-Nakamura Chemical Co., Ltd.) are preferable. Of these, (meth) acrylates having a C7-14 alkylene group are preferred.
　（Ａ）成分の紫外線硬化型樹脂組成物中の含有量は通常１０～９５重量％、好ましくは２０～８０重量％である。１０重量％未満では色素の体積変化を補助できず、記録信号特性の指標であるジッタ値（％）が悪くなる。 The content of the component (A) in the ultraviolet curable resin composition is usually 10 to 95% by weight, preferably 20 to 80% by weight. If it is less than 10% by weight, the change in the volume of the dye cannot be assisted, and the jitter value (%), which is an indicator of the recording signal characteristics, becomes worse.
　本発明の紫外線硬化型樹脂組成物に含有される光重合開始剤（Ｂ）としては、特に限定はされないが、例えば、１－ヒドロキシシクロヘキシルフェニルケトン（イルガキュアー１８４；チバ・スペシャリティ・ケミカルズ製）、２－ヒドロキシ－２－メチル－［４－（１－メチルビニル）フェニル］プロパノールオリゴマー（ＯＮＥ-Ｒｉｆｉｎｅｄ）、１－[４－（２－ヒドロキシエトキシ）－フェニル]－２－ヒドロキシ－２－メチル－１－プロパン－１－オン（イルガキュアー２９５９；チバ・スペシャリティ・ケミカルズ製）、２－ヒドロキシ－１－｛４－［４－（２－ヒドロキシ－２－メチル－プロピオニル）－ベンジル]－フェニル｝－２－メチル－プロパン－１－オン（イルガキュアー１２７；チバ・スペシャリティ・ケミカルズ製）、２，２－ジメトキシ－２－フェニルアセトフェノン（イルガキュアー６５１；チバ・スペシャリティ・ケミカルズ製）、２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン（ダロキュア１１７３；チバ・スペシャリティ・ケミカルズ製）、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノプロパン－１－オン（イルガキュアー９０７；チバスペシャリティ・ケミカルズ製）、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）－ブタン－１－オン、２－クロロチオキサントン、２，４－ジメチルチオキサントン、２，４－ジイソプロピルチオキサントン、イソプロピルチオキサントン、２，４，６－トリメチルベンゾイルジフェニルフォスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド、ビス（２，６－ジメトキシベンゾイル）－２，４，４－トリメチルペンチルフォスフィンオキサイド等を挙げることができる。 The photopolymerization initiator (B) contained in the ultraviolet curable resin composition of the present invention is not particularly limited. For example, 1-hydroxycyclohexyl phenyl ketone (Irgacure 184; manufactured by Ciba Specialty Chemicals), 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer (ONE-Rifened), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl- 1-propan-1-one (Irgacure 2959; manufactured by Ciba Specialty Chemicals), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl}- 2-Methyl-propan-1-one (Irgacure 127; Ciba Specialty Chemicals 2,2-dimethoxy-2-phenylacetophenone (Irgacure 651; manufactured by Ciba Specialty Chemicals), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur 1173; Ciba Specialty) Chemicals), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907; manufactured by Ciba Specialty Chemicals), 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl) -butan-1-one, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2, 4, 6- Trimethyl benzoyl) - phenyl phosphine oxide, and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide and the like.
　本発明の紫外線硬化型樹脂組成物においては、これら（Ｂ）成分は、１種または２種以上を任意の割合で混合して使用することができる。（Ｂ）成分の紫外線硬化型樹脂組成物中の含有量は通常０．５～２０重量％、好ましくは１～１０重量％である。 In the ultraviolet curable resin composition of the present invention, these components (B) can be used alone or in combination of two or more at any ratio. The content of the component (B) in the ultraviolet curable resin composition is usually 0.5 to 20% by weight, preferably 1 to 10% by weight.
　更に、光重合開始助剤となりうるアミン類等を上記の光重合開始剤と併用することもできる。使用しうるアミン類等としては、安息香酸２－ジメチルアミノエチルエステル、ジメチルアミノアセトフェノン、ｐ－ジメチルアミノ安息香酸エチルエステルまたはｐ－ジメチルアミノ安息香酸イソアミルエステル等が挙げられる。該アミン類等の光重合開始助剤を使用する場合、本発明の紫外線硬化型樹脂組成物中の含有量は通常０．００５～５重量％、好ましくは０．０１～３重量％である。 Furthermore, amines that can serve as photopolymerization initiation assistants can be used in combination with the above photopolymerization initiator. Examples of amines that can be used include benzoic acid 2-dimethylaminoethyl ester, dimethylaminoacetophenone, p-dimethylaminobenzoic acid ethyl ester, and p-dimethylaminobenzoic acid isoamyl ester. When a photopolymerization initiation aid such as the amine is used, the content in the ultraviolet curable resin composition of the present invention is usually 0.005 to 5% by weight, preferably 0.01 to 3% by weight.
　本発明の紫外線硬化型樹脂組成物は、上記成分以外にさらに（Ａ）以外の（メタ）アクリレート（Ｃ）を含んでいても良い。
　本発明の紫外線硬化型樹脂組成物に含有される（Ａ）以外の（メタ）アクリレート（Ｃ）としては、例えば（メタ）アクリロイル基を１個以上有する（メタ）アクリレートを挙げることができる。尚、本発明において（メタ）アクリレートとはメタクリレート又はアクリレートを意味し、その種類は特に限定されないが、（Ａ）以外の（メタ）アクリレート（Ｃ）としては、（Ｃ－１）エポキシ（メタ）アクリレート、（Ｃ－２）ウレタン（メタ）アクリレート、（Ｃ－３）（メタ）アクリレートモノマー等を用いることができる。特に、本発明においては、（Ｃ－１）エポキシ（メタ）アクリレート及び／又は（Ｃ－２）ウレタン（メタ）アクリレートと（Ｃ－３）（メタ）アクリレートモノマーとをそれぞれ単独であるいは併用して用いることが好ましく、（Ｃ－２）ウレタン（メタ）アクリレートと（Ｃ－３）（メタ）アクリレートモノマーとを併用して用いることがより好ましい。 The ultraviolet curable resin composition of the present invention may further contain (meth) acrylate (C) other than (A) in addition to the above components.
Examples of (meth) acrylates (C) other than (A) contained in the ultraviolet curable resin composition of the present invention include (meth) acrylates having at least one (meth) acryloyl group. In the present invention, (meth) acrylate means methacrylate or acrylate, and the kind thereof is not particularly limited, but (meth) acrylate (C) other than (A) includes (C-1) epoxy (meth). Acrylate, (C-2) urethane (meth) acrylate, (C-3) (meth) acrylate monomer, and the like can be used. In particular, in the present invention, (C-1) epoxy (meth) acrylate and / or (C-2) urethane (meth) acrylate and (C-3) (meth) acrylate monomer are used alone or in combination. It is preferable to use (C-2) urethane (meth) acrylate and (C-3) (meth) acrylate monomer in combination.
　本発明において用いうるエポキシ（メタ）アクリレート（Ｃ－１）は、硬化性の向上や硬化物の硬度や硬化速度を向上させる機能がある。また、本発明において、エポキシ（メタ）アクリレートとしては、グリシジルエーテル型エポキシ化合物と、（メタ）アクリル酸を反応させることにより得られたものであればいずれも使用できるが、本発明で好ましく使用されるエポキシ（メタ）アクリレートを得るためのグリシジルエーテル型エポキシ化合物としては、ビスフェノールＡ或いはそのアルキレンオキサイド付加体のジグリシジルエーテル、ビスフェノールＦ或いはそのアルキレンオキサイド付加体のジグリシジルエーテル、水素添加ビスフェノールＡ或いはそのアルキレンオキサイド付加体のジグリシジルエーテル、水素添加ビスフェノールＦ或いはそのアルキレンオキサイド付加体のジグリシジルエーテル、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、ブタンジオールジグリシジルエーテル、へキサンジオールジグリシジルエーテル、シクロヘキサンジメタノールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル等を挙げることができる。 The epoxy (meth) acrylate (C-1) that can be used in the present invention has a function of improving curability and improving the hardness and curing speed of a cured product. In the present invention, any epoxy (meth) acrylate may be used as long as it is obtained by reacting a glycidyl ether type epoxy compound with (meth) acrylic acid, but is preferably used in the present invention. Examples of glycidyl ether type epoxy compounds for obtaining epoxy (meth) acrylates include diglycidyl ether of bisphenol A or its alkylene oxide adduct, diglycidyl ether of bisphenol F or its alkylene oxide adduct, hydrogenated bisphenol A or its Diglycidyl ether of alkylene oxide adduct, hydrogenated bisphenol F or diglycidyl ether of its alkylene oxide adduct, ethylene glycol diglycidyl ether, propylene glycol Le diglycidyl ether, neopentyl glycol diglycidyl ether, butanediol diglycidyl ether hexanediol diglycidyl ether to, cyclohexanedimethanol diglycidyl ether, and polypropylene glycol diglycidyl ether.
　エポキシ（メタ）アクリレートは、これらグリシジルエーテル型エポキシ化合物と、（メタ）アクリル酸を、下記のような条件で反応させることにより得られる。 Epoxy (meth) acrylate is obtained by reacting these glycidyl ether type epoxy compounds with (meth) acrylic acid under the following conditions.
　グリシジルエーテル型エポキシ化合物のエポキシ基１当量に対して、（メタ）アクリル酸を０．９～１．５モル、より好ましくは０．９５～１．１モルの比率で反応させる。反応温度は８０～１２０℃が好ましく、反応時間は１０～３５時間程度である。反応を促進させるために、例えばトリフェニルフォスフィン、２，４，６－トリス（ジメチルアミノメチル）フェノール（ＴＡＰ）、トリエタノールアミン、テトラエチルアンモニウムクロライド等の触媒を使用するのが好ましい。又、反応中、重合を防止するために重合禁止剤として、例えば、パラメトキシフェノール、メチルハイドロキノン等を使用することもできる。 (Meth) acrylic acid is reacted at a ratio of 0.9 to 1.5 mol, more preferably 0.95 to 1.1 mol, per 1 equivalent of epoxy group of the glycidyl ether type epoxy compound. The reaction temperature is preferably 80 to 120 ° C., and the reaction time is about 10 to 35 hours. In order to accelerate the reaction, it is preferable to use a catalyst such as triphenylphosphine, 2,4,6-tris (dimethylaminomethyl) phenol (TAP), triethanolamine, tetraethylammonium chloride and the like. Further, in order to prevent polymerization during the reaction, for example, paramethoxyphenol, methylhydroquinone or the like can be used as a polymerization inhibitor.
　本発明において、エポキシ（メタ）アクリレート（Ｃ－１）としては、ビスフェノールＡ型のエポキシ化合物より得られた、ビスフェノールＡ型エポキシ（メタ）アクリレートがより好ましい。本発明において、エポキシ（メタ）アクリレート（Ｃ－１）の分子量としては５００～１００００が好ましい。 In the present invention, the epoxy (meth) acrylate (C-1) is more preferably bisphenol A type epoxy (meth) acrylate obtained from a bisphenol A type epoxy compound. In the present invention, the molecular weight of the epoxy (meth) acrylate (C-1) is preferably 500 to 10,000.
　本発明において用いうるウレタン（メタ）アクリレート（Ｃ－２）は本発明の紫外線硬化型樹脂組成物を用いて貼り合せた光ディスクの機械的特性（反り、ゆがみ等）を向上させる機能がある。ウレタン（メタ）アクリレートは、多価アルコール、ポリイソシアネート及びヒドロキシ（メタ）アクリレート化合物を反応させることによって得られる。 The urethane (meth) acrylate (C-2) that can be used in the present invention has a function of improving the mechanical properties (warpage, distortion, etc.) of an optical disk bonded using the ultraviolet curable resin composition of the present invention. Urethane (meth) acrylate is obtained by reacting a polyhydric alcohol, polyisocyanate, and a hydroxy (meth) acrylate compound.
　多価アルコールとしては、例えば、ネオペンチルグリコール、３－メチル－１，５－ペンタンジオール、（ポリ）エチレングリコール、（ポリ）プロピレングリコール、１，４－ブタンジオール、１，６－ヘキサンジオール、トリメチロールプロパン、ペンタエリスリトール、トリシクロデカンジメチロール、ビス－〔ヒドロキシメチル〕－シクロヘキサン等、これら多価アルコールと多塩基酸（例えば、コハク酸、フタル酸、ヘキサヒドロ無水フタル酸、テレフタル酸、アジピン酸、アゼライン酸、テトラヒドロ無水フタル酸等）との反応によって得られるポリエステルポリオール、多価アルコールとε－カプロラクトンとの反応によって得られるカプロラクトンアルコール、ポリカーボネートポリオール（例えば１，６－ヘキサンジオールとジフェニルカーボネートとの反応によって得られるポリカーボネートジオール等）又はポリエーテルポリオール（例えばポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール、エチレンオキサイド変性ビスフェノールＡ等）等が挙げられる。中でも、ポリエステルポリオール又はポリエーテルポリオールが好ましい。 Examples of the polyhydric alcohol include neopentyl glycol, 3-methyl-1,5-pentanediol, (poly) ethylene glycol, (poly) propylene glycol, 1,4-butanediol, 1,6-hexanediol, tri These polyhydric alcohols and polybasic acids (for example, succinic acid, phthalic acid, hexahydrophthalic anhydride, terephthalic acid, adipic acid, methylolpropane, pentaerythritol, tricyclodecane dimethylol, bis- [hydroxymethyl] -cyclohexane, etc. Polyester polyol obtained by reaction with azelaic acid, tetrahydrophthalic anhydride, etc., caprolactone alcohol obtained by reaction of polyhydric alcohol and ε-caprolactone, polycarbonate polyol (for example, 1,6-hexanediol) Le polycarbonate diols obtained by reacting diphenyl carbonate) or polyether polyols (such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide-modified bisphenol A, etc.) and the like. Among these, polyester polyol or polyether polyol is preferable.
　ポリイソシアネートとしては、例えばイソホロンジイソシアネート、ヘキサメチレンジイソシアネート、トリレンジイソシアネート、キシレンジイソシアネート、ジフェニルメタン－４，４’－ジイソシアネート又はジシクロペンタニルイソシアネート等が挙げられる。 Examples of the polyisocyanate include isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, diphenylmethane-4,4'-diisocyanate, and dicyclopentanyl isocyanate.
　ヒドロキシ（メタ）アクリレート化合物としては、例えばヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート、ジメチロールシクロヘキシルモノ（メタ）アクリレート又はヒドロキシカプロラクトン（メタ）アクリレート等が挙げられる。中でも、ヒドロキシエチル（メタ）アクリレートが好ましく、２－ヒドロキシエチル（メタ）アクリレートが特に好ましい。 Examples of the hydroxy (meth) acrylate compound include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, dimethylol cyclohexyl mono (meth) acrylate, and hydroxycaprolactone (meth) acrylate. . Of these, hydroxyethyl (meth) acrylate is preferable, and 2-hydroxyethyl (meth) acrylate is particularly preferable.
　前記反応は、例えば、以下のようにして行う。即ち、多価アルコールにその水酸基１当量あたり有機ポリイソシアネートをそのイソシアネート基が好ましくは１．１～２．０当量になるように混合し、反応温度を好ましくは７０～９０℃で反応させ、ウレタンオリゴマーを合成する。次いで、ウレタンオリゴマーのイソシアネート基１当量あたり、ヒドロキシ（メタ）アクリレート化合物をその水酸基が好ましくは１～１．５当量となるように混合し、７０～９０℃で反応させて目的とするウレタン（メタ）アクリレートを得ることができる。また、ＵＸ－０９３７：ポリエーテル系ウレタンアクリレート（日本化薬（株）製）等として市場より入手することも可能である。ウレタン（メタ）アクリレート（Ｃ－２）の分子量としては４００～１００００程度が好ましい。 The reaction is performed, for example, as follows. That is, the polyhydric alcohol is mixed with an organic polyisocyanate per equivalent of the hydroxyl group so that the isocyanate group is preferably 1.1 to 2.0 equivalent, and reacted at a reaction temperature of preferably 70 to 90 ° C. Synthesize oligomers. Next, the hydroxy (meth) acrylate compound is mixed so that the hydroxyl group is preferably 1 to 1.5 equivalents per equivalent of the isocyanate group of the urethane oligomer, and reacted at 70 to 90 ° C. to react with the target urethane (meth). ) Acrylate can be obtained. It is also possible to obtain from the market as UX-0937: polyether urethane acrylate (manufactured by Nippon Kayaku Co., Ltd.). The molecular weight of the urethane (meth) acrylate (C-2) is preferably about 400 to 10,000.
　（Ａ）以外の（メタ）アクリレート（Ｃ）として用いうる（メタ）アクリレートモノマー（Ｃ－３）は特に限定されないが、例えば、（メタ）アクリロイル基を１つ有するものとして、フェノキシエチル（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、ベンジル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、モルホリン（メタ）アクリレート、フェニルグリシジル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、エトキシジエチレングリコール（メタ）アクリレート、メトキシジトリプロピレングリコール（メタ）アクリレート、トリシクロデカン（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタジエンオキシエチル（メタ）アクリレート、ジシクロペンテニルアクリレート（例えば、日立化成工業（株）社製ＦＡＮＣＲＹＬ　ＦＡ－５１１Ａ）、ジシクロペンテニルオキシエチルアクリレート（例えば、日立化成工業（株）社製ＦＡＮＣＲＹＬ　ＦＡ－５１２Ａ）、ジシクロペンテニルオキシメタクリレート（例えば、日立化成工業（株）社製ＦＡＮＣＲＹＬ　ＦＡ－５１２Ｍ）、ジシクロペンタニルアクリレート（例えば、日立化成工業（株）社製ＦＡＮＣＲＹＬ　ＦＡ－５１３Ａ）、ジシクロペンタニルメタクリレート（例えば、日立化成工業（株）社製ＦＡＮＣＲＹＬ　ＦＡ－５１３Ｍ）、１－アダマンチルアクリレート（例えば、出光興産（株）社製Ａｄａｍａｎｔａｔｅ　ＡＡ）、２－メチル－２－アダマンチルアクリレート（例えば、出光興産（株）社製Ａｄａｍａｎｔａｔｅ　ＭＡ）、２－エチル－２－アダマンチルアクリレート（例えば、出光興産（株）社製Ａｄａｍａｎｔａｔｅ　ＥＡ）、１－アダマンチルメタクリレート（例えば、出光興産（株）社製Ａｄａｍａｎｔａｔｅ　ＡＭ）、エチレンオキサイド変性フェノキシ化リン酸（メタ）アクリレート、エチレンオキサイド変性ブトキシ化リン酸（メタ）アクリレート及びエチレンオキサイド変性オクチルオキシ化リン酸（メタ）アクリレート等を挙げることができる。（メタ）アクリロイル基を１つ有する（メタ）アクリレートモノマーは本発明の紫外線硬化型樹脂組成物を光透過層として形成させた光ディスクの機械的特性（反り、ゆがみ等の抑制）を向上させる機能を有する。 The (meth) acrylate monomer (C-3) that can be used as the (meth) acrylate (C) other than (A) is not particularly limited. For example, phenoxyethyl (meth) has one (meth) acryloyl group. Acrylate, phenoxypolyethylene glycol (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, morpholine (meth) acrylate, phenylglycidyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, ethoxydiethylene glycol (meth) ) Acrylate, methoxyditripropylene glycol (meth) acrylate, tricyclodecane (meth) acrylate, isobornyl (meth) acrylate, dicyclopentadieneoxyethyl (meth) Acrylate, dicyclopentenyl acrylate (for example, FANCYL FA-511A manufactured by Hitachi Chemical Co., Ltd.), dicyclopentenyloxyethyl acrylate (for example, FANCRYL FA-512A manufactured by Hitachi Chemical Co., Ltd.), dicyclopentenyloxy Methacrylate (for example, FANCYL FA-512M manufactured by Hitachi Chemical Co., Ltd.), dicyclopentanyl acrylate (for example, FANCYL FA-513A manufactured by Hitachi Chemical Co., Ltd.), dicyclopentanyl methacrylate (for example, Hitachi Chemical) FANCRRYL FA-513M manufactured by Kogyo Co., Ltd., 1-adamantyl acrylate (for example, Adamantate AA manufactured by Idemitsu Kosan Co., Ltd.), 2-methyl-2-adamantyl acrylate (for example, Idemitsu Kosan Co., Ltd.) Adamantate MA), 2-ethyl-2-adamantyl acrylate (for example, Idamantate EA by Idemitsu Kosan Co., Ltd.), 1-adamantyl methacrylate (for example, Adamantate AM by Idemitsu Kosan Co., Ltd.), ethylene oxide modified phenoxy And phosphoric acid (meth) acrylate, ethylene oxide-modified butoxylated phosphoric acid (meth) acrylate, and ethylene oxide-modified octyloxyphosphoric acid (meth) acrylate. The (meth) acrylate monomer having one (meth) acryloyl group has a function of improving the mechanical properties (suppression of warpage, distortion, etc.) of an optical disk formed with the ultraviolet curable resin composition of the present invention as a light transmission layer. Have.
　（Ａ）以外の（メタ）アクリレート（Ｃ）として用いうる（メタ）アクリレートモノマー（Ｃ－３）について（メタ）アクリロイル基を２個有する（メタ）アクリレートモノマーとしては、シクロヘキサン－１，４－ジメタノールジ（メタ）アクリレート、シクロヘキサン－１，３－ジメタノールジ（メタ）アクリレート、トリシクロデカンジメチロールジ（メタ）アクリレート（例えば、日本化薬（株）社製、ＫＡＹＡＲＡＤ　Ｒ－６８４、トリシクロデカンジメチロールジアクリレート等）、ジオキサングリコールジ（メタ）アクリレート（例えば、日本化薬（株）社製、ＫＡＹＡＲＡＤ　Ｒ－６０４、ジオキサングリコールジアクリレート等）、ネオペンチルグリコールジ（メタ）アクリレート、ジシクロペンタニルジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、アルキレンオキサイド変性１，６－ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、アルキレンオキサイド変性ネオペンチルグリコールジ（メタ）アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、エチレンオキサイド変性ビスフェノールＡ型ジ（メタ）アクリレート及びエチレンオキサイド変性リン酸ジ（メタ）アクリレート等を挙げることができる。本発明においては、特にエチレンオキサイド変性ビスフェノールＡ型ジ（メタ）アクリレートを用いることが好ましい。 (Meth) acrylate monomer (C-3) that can be used as (meth) acrylate (C) other than (A) The (meth) acrylate monomer having two (meth) acryloyl groups is cyclohexane-1,4-dimethanoldi (Meth) acrylate, cyclohexane-1,3-dimethanol di (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate (for example, KAYARAD R-684, manufactured by Nippon Kayaku Co., Ltd., tricyclodecane dimethylol di Acrylate, etc.), dioxane glycol di (meth) acrylate (for example, KAYARAD R-604, dioxane glycol diacrylate, etc., manufactured by Nippon Kayaku Co., Ltd.), neopentyl glycol di (meth) acrylate, dicyclopentanyl di ( Meta) Acu 1,6-hexanediol di (meth) acrylate, alkylene oxide modified 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, alkylene oxide modified neopentyl glycol di (meth) acrylate, Hydroxypivalic acid neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ethylene oxide modified bisphenol A type di (meth) acrylate and ethylene oxide modified di (meth) acrylate phosphoric acid Etc. In the present invention, it is particularly preferable to use ethylene oxide-modified bisphenol A type di (meth) acrylate.
　（Ａ）以外の（メタ）アクリレート（Ｃ）として用いうる（メタ）アクリレートモノマー（Ｃ－３）について（メタ）アクリロイル基を３個有する（メタ）アクリレートモノマーとしては、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールオクタントリ（メタ）アクリレート、トリメチロールプロパンポリエトキシトリ（メタ）アクリレート、トリメチロールプロパンポリプロポキシトリ（メタ）アクリレート、トリメチロールプロパンポリエトキシポリプロポキシトリ（メタ）アクリレート、トリス［（メタ）アクロイルオキシエチル］イソシアヌレ－ト、カプロラクトン変性トリス［（メタ）アクリロイルオキシエチル］イソシアヌレ－ト、ペンタエリスリトールトリ（メタ）アクリレート、エチレンオキサイド変性トリメチロールプロパントリ（メタ）アクリレート、プロピレンオキサイド変性トリメチロールプロパントリ（メタ）アクリレート等を挙げることができる。 (Meth) acrylate monomer (C-3) that can be used as (meth) acrylate (C) other than (A) The (meth) acrylate monomer having three (meth) acryloyl groups is trimethylolpropane tri (meth). Acrylate, trimethylol octane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, trimethylolpropane polypropoxytri (meth) acrylate, trimethylolpropane polyethoxypolypropoxytri (meth) acrylate, tris [(meta ) Acroyloxyethyl] isocyanurate, caprolactone modified tris [(meth) acryloyloxyethyl] isocyanurate, pentaerythritol tri (meth) acrylate, ethylene oxide modification Trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate.
　（Ａ）以外の（メタ）アクリレート（Ｃ）として用いうる（メタ）アクリレートモノマー（Ｃ－３）について（メタ）アクリロイル基を４個有する（メタ）アクリレートモノマーとしては、ペンタエリスリトールポリエトキシテトラ（メタ）アクリレート、ペンタエリスリトールポリプロポキシテトラ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート等を挙げることができる。 Regarding (meth) acrylate monomer (C-3) that can be used as (meth) acrylate (C) other than (A), as (meth) acrylate monomer having four (meth) acryloyl groups, pentaerythritol polyethoxytetra (meth) ) Acrylate, pentaerythritol polypropoxytetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and the like.
　（Ａ）以外の（メタ）アクリレート（Ｃ）として用いうる（メタ）アクリレートモノマー（Ｃ－３）について（メタ）アクリロイル基を５個有する（メタ）アクリレートモノマーとしては、ジペンタエリスリトールペンタ（メタ）アクリレート、カプロラクトン変性ジペンタエリスリトールペンタ（メタ）アクリレート等を挙げることができる。 (Meth) acrylate monomer (C-3) that can be used as (meth) acrylate (C) other than (A) The (meth) acrylate monomer having five (meth) acryloyl groups is dipentaerythritol penta (meth). Examples thereof include acrylate and caprolactone-modified dipentaerythritol penta (meth) acrylate.
　（Ａ）以外の（メタ）アクリレート（Ｃ）として用いうる（メタ）アクリレートモノマー（Ｃ－３）について（メタ）アクリロイル基を６個有する（メタ）アクリレートモノマーとしては、ジペンタエリスリトールヘキサ（メタ）アクリレート、カプロラクトン変性ジペンタエリスリトールヘキサ（メタ）アクリレート等を挙げることができる。なお、本発明において用いうる（メタ）アクリレートモノマーは、（メタ）アクリロイル基を７個以上有する多官能のものであってもよい。 (Meth) acrylate monomer (C-3) that can be used as (meth) acrylate (C) other than (A) (meth) acrylate monomer having 6 (meth) acryloyl groups is dipentaerythritol hexa (meth) Examples thereof include acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate. The (meth) acrylate monomer that can be used in the present invention may be a polyfunctional monomer having 7 or more (meth) acryloyl groups.
　本発明の紫外線硬化型樹脂組成物においては、これら（Ｃ）成分は、１種または２種以上を任意の割合で混合して使用することができる。（Ｃ）成分の紫外線硬化型樹脂組成物中の含有量は通常３０～８０重量％、好ましくは４０～７０重量％である。また、（Ｃ）成分として（Ｃ－１）及び／又は（Ｃ－２）と（Ｃ－３）とを併せて用いる場合、通常（Ｃ－１）及び／又は（Ｃ－２）はそれぞれ紫外線硬化型樹脂組成物１００重量部に対して、５～７０重量部、好ましくは１０～６０重量部程度であり、（Ｃ－３）成分は紫外線硬化型樹脂組成物１００重量部に対して、（Ｃ－３）成分と（Ａ）成分の合計が２０～８０重量部、好ましくは２５～７５重量部の範囲を満たすように用いられる。 In the ultraviolet curable resin composition of the present invention, these components (C) can be used alone or in combination of two or more at any ratio. The content of the component (C) in the ultraviolet curable resin composition is usually 30 to 80% by weight, preferably 40 to 70% by weight. In addition, when (C-1) and / or (C-2) and (C-3) are used in combination as the component (C), (C-1) and / or (C-2) are usually ultraviolet rays. It is 5 to 70 parts by weight, preferably about 10 to 60 parts by weight with respect to 100 parts by weight of the curable resin composition, and the component (C-3) is ( The total of component (C-3) and component (A) is used in a range of 20 to 80 parts by weight, preferably 25 to 75 parts by weight.
　本発明の紫外線硬化型樹脂組成物には、必要に応じて防錆剤、酸化防止剤、有機溶剤、シランカップリング剤、重合禁止剤、レベリング剤、帯電防止剤、表面潤滑剤、蛍光増白剤、光安定剤（例えば、ヒンダードアミン化合物等）、充填剤等の添加剤を加えてもよい。ヒンダードアミン化合物は公知のものであれば特に限定なく使用することができるが、具体例として例えば、１，２，２，６，６－ペンタメチル－４－ピペリジルアルコール、２，２，６，６－テトラメチル－４－ピペリジルアルコール、１，２，２，６，６－ペンタメチル－４－ピペリジル（メタ）アクリレート（アデカ（株）製、ＬＡ－８２）などが挙げられる。 The ultraviolet curable resin composition of the present invention includes a rust inhibitor, antioxidant, organic solvent, silane coupling agent, polymerization inhibitor, leveling agent, antistatic agent, surface lubricant, fluorescent whitening as necessary. You may add additives, such as an agent, a light stabilizer (for example, hindered amine compound etc.), and a filler. Any known hindered amine compound can be used without particular limitation. Specific examples thereof include 1,2,2,6,6-pentamethyl-4-piperidyl alcohol, 2,2,6,6-tetra Examples thereof include methyl-4-piperidyl alcohol, 1,2,2,6,6-pentamethyl-4-piperidyl (meth) acrylate (manufactured by Adeka Co., Ltd., LA-82).
　本発明の紫外線硬化型樹脂組成物は、前記した各成分を常温～８０℃で混合溶解して得ることができ、必要により夾雑物をろ過等の操作により取り除いてもよい。本発明の紫外線硬化型樹脂組成物は、塗布性を考え、２５℃の粘度が３０～２０００ｍＰａ・ｓの範囲となるように、成分の配合比を適宜調節することが好ましい。 The ultraviolet curable resin composition of the present invention can be obtained by mixing and dissolving the aforementioned components at room temperature to 80 ° C., and if necessary, impurities may be removed by an operation such as filtration. In the ultraviolet curable resin composition of the present invention, it is preferable to appropriately adjust the blending ratio of the components so that the viscosity at 25 ° C. is in the range of 30 to 2000 mPa · s in view of applicability.
　本発明の紫外線硬化型樹脂組成物は、ブルーレイディスク等のレーザー入射側の光透過層用コート剤として好適に使用できる。具体的には塗布した樹脂の膜厚が１～１００μｍとなるように任意の方法、例えば、スピンコート法、２Ｐ法、ロールコート法、スクリーン印刷法等で組成物を光ディスク基板に塗工する。塗工後、片側もしくは両面から紫外～近紫外（波長２００～４００ｎｍ付近）の光線を照射して硬化させる。照射量は約５０～１５００ｍＪ／ｃｍ2が好ましく、特に好ましくは、１００～１０００ｍＪ／ｃｍ2程度である。紫外～近紫外の光線照射による硬化には、紫外～近紫外の光線を照射するランプであれば光源を問わない。例えば、低圧、高圧若しくは超高圧水銀灯、メタルハライドランプ、（パルス）キセノンランプ、または無電極ランプ等が挙げられる。 The ultraviolet curable resin composition of the present invention can be suitably used as a coating agent for a light transmission layer on the laser incident side of a Blu-ray disc or the like. Specifically, the composition is applied to the optical disk substrate by an arbitrary method such as a spin coating method, a 2P method, a roll coating method, or a screen printing method so that the thickness of the applied resin is 1 to 100 μm. After coating, the film is cured by irradiating ultraviolet rays to near ultraviolet rays (wavelength of 200 to 400 nm) from one side or both sides. Irradiation dose is preferably from about 50 ~ 1500mJ / cm 2, particularly preferably 100 ~ 1000mJ / cm 2 approximately. For curing by irradiation with ultraviolet to near ultraviolet rays, any light source may be used as long as it is a lamp that emits ultraviolet to near ultraviolet rays. For example, a low-pressure, high-pressure or ultrahigh-pressure mercury lamp, metal halide lamp, (pulse) xenon lamp, or electrodeless lamp can be used.
　また本発明の紫外線硬化型樹脂組成物は、光透過層が複数の層からなる場合にも適用することができる。例えば、光透過層が記録層又は界面層上に形成される第一の樹脂層と、第一の樹脂層からみて記録層又は界面層側とは反対の面上に形成される第二の樹脂層から構成される場合において、前記第一の樹脂層に好適に使用することができる。
　この場合において、前記第一の樹脂層の厚さは通常１μｍ～５０μｍであり、好ましくは５μｍ～４０μｍ、より好ましくは１０μｍ～３０μｍである。
　また、前記第二の樹脂層の厚さは通常５０μｍ～１００μｍであり、好ましくは６０μｍ～９５μｍ、より好ましくは７０μｍ～９０μｍである。 Moreover, the ultraviolet curable resin composition of this invention is applicable also when a light-transmitting layer consists of a some layer. For example, a first resin layer in which a light transmission layer is formed on a recording layer or an interface layer, and a second resin formed on a surface opposite to the recording layer or interface layer side when viewed from the first resin layer When comprised from a layer, it can be used conveniently for said 1st resin layer.
In this case, the thickness of the first resin layer is usually 1 μm to 50 μm, preferably 5 μm to 40 μm, more preferably 10 μm to 30 μm.
The thickness of the second resin layer is usually 50 μm to 100 μm, preferably 60 μm to 95 μm, more preferably 70 μm to 90 μm.
　光透過層が二層から構成される場合において、光透過層の形成方法としては、具体的には第一の樹脂層として塗布した樹脂の膜厚が１μｍ～５０となるように任意の方法、例えば、スピンコート法、２Ｐ法、ロールコート法、スクリーン印刷法等で組成物を光ディスク基板に塗工する。塗工後、片側もしくは両面から紫外～近紫外（波長２００～４００ｎｍ付近）の光線を照射して硬化させる。照射量は５０～１５００ｍＪ／ｃｍ2が好ましく、特に好ましくは、１００～１０００ｃｍＪ／ｃｍ2程度である。硬化後、第二の樹脂層として膜厚が５０μｍ～１００μｍとなるように任意の方法、例えば、スピンコート法、２Ｐ法、ロールコート法、スクリーン印刷法等で組成物を光ディスク基板に塗工する。塗工後、片側もしくは両面から紫外～近紫外（波長２００～４００ｎｍ付近）の光線を照射して硬化させる。照射量は約５０～１５００ｍＪ／ｃｍ2が好ましく、特に好ましくは、１００～１０００ｍＪ／ｃｍ2程度である。さらに紫外～近紫外の光線照射による硬化には、紫外～近紫外の光線を照射するランプであれば光源を問わない。例えば、低圧、高圧若しくは超高圧水銀灯、メタルハライドランプ、（パルス）キセノンランプ、または無電極ランプ等が挙げられる。 In the case where the light transmission layer is composed of two layers, the light transmission layer is formed by any method such that the film thickness of the resin applied as the first resin layer is 1 μm to 50, specifically, For example, the composition is applied to the optical disk substrate by spin coating, 2P, roll coating, screen printing, or the like. After coating, the film is cured by irradiating ultraviolet rays to near ultraviolet rays (wavelength of 200 to 400 nm) from one side or both sides. The irradiation amount is preferably 50 to 1500 mJ / cm 2 , particularly preferably about 100 to 1000 cmJ / cm 2 . After curing, the composition is applied to the optical disk substrate by any method such as spin coating, 2P method, roll coating method, screen printing method or the like so that the film thickness becomes 50 μm to 100 μm as the second resin layer. . After coating, the film is cured by irradiating ultraviolet rays to near ultraviolet rays (wavelength of 200 to 400 nm) from one side or both sides. Irradiation dose is preferably from about 50 ~ 1500mJ / cm 2, particularly preferably 100 ~ 1000mJ / cm 2 approximately. Further, for curing by irradiation with ultraviolet to near ultraviolet rays, any light source may be used as long as it is a lamp that irradiates ultraviolet to near ultraviolet rays. For example, a low-pressure, high-pressure or ultrahigh-pressure mercury lamp, metal halide lamp, (pulse) xenon lamp, or electrodeless lamp can be used.
　以下、本発明を実施例により更に具体的に説明するが、本発明はこれら実施例により何ら制限されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
　実施例１～４、比較例１～２を表１に示した組成からなる紫外線硬化型樹脂組成物を調整した。 Examples 1 to 4 and Comparative Examples 1 to 2 were prepared with ultraviolet curable resin compositions having the compositions shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
  
Figure JPOXMLDOC01-appb-T000001
  
　なお、表１中に略称で示した各成分は下記の通りである。
　ＬＡ：ラウリルアクリレート、日油（株）社製、炭素数１２のアルキレン基を有するアクリレート
　ＩＳＡ：イソステアリルアクリレート、共栄社化学（株）社製、炭素数１８のアルキレン基を有するアクリレート
　ＮＤＤＡ：１，９－ノナンジオールジアクリレート、日立化成工業（株）社製、炭素数９のアルキレン基を有するジアクリレート
　ＨＤＤＡ：１，６－ヘキサンジオールジアクリレート、日本化薬（株）社製、炭素数６のアルキレン基を有するジアクリレート
　ＶＡ：ベヘニルアクリレート、日油（株）社製、炭素数２２のアルキレン基を有するアクリレート
　ＵＡ－１：ポリテトラメチレングリコール（分子量８５０）、イソホロンジイソシアネート、２－ヒドロキシエチルアクリレートの３成分をモル比１：２：２で反応させて得られたウレタンアクリレート
　ＢＰＥ－１０：エチレンオキサイド１０モル変性ビスフェノールＡ型ジアクリレート、第一工業製薬（株）社製
　ＦＡ－５１２Ａ：ジシクロペンテニルオキシエチルアクリレート、日立化成工業（株）社製
　イルガキュアー１８４：１－ヒドロキシシクロヘキシルフェニルケトン、チバ・スペシャルティ・ケミカルズ（株）社製
　ＬＡ－８２：１，２，２，６，６－ペンタメチル－４－ピペリジルメタアクリレート、旭電化（株）社製
　ＰＭＰ：４－メルカプトフェノール In addition, each component shown with the abbreviation in Table 1 is as follows.
LA: lauryl acrylate, manufactured by NOF Corporation, acrylate having an alkylene group having 12 carbon atoms ISA: isostearyl acrylate, manufactured by Kyoeisha Chemical Co., Ltd., acrylate having an alkylene group having 18 carbon atoms NDDA: 1,9 -Nonanediol diacrylate, manufactured by Hitachi Chemical Co., Ltd., diacrylate having an alkylene group of 9 carbon atoms HDDA: 1,6-hexanediol diacrylate, manufactured by Nippon Kayaku Co., Ltd., alkylene of 6 carbon atoms Group-containing diacrylate VA: Behenyl acrylate, manufactured by NOF Corporation, acrylate having 22 alkylene groups UA-1: polytetramethylene glycol (molecular weight 850), isophorone diisocyanate, 2-hydroxyethyl acrylate 3 Reacting the components in a molar ratio of 1: 2: 2. Urethane acrylate BPE-10: Ethylene oxide 10 mol modified bisphenol A type diacrylate, Dai-ichi Kogyo Seiyaku Co., Ltd. FA-512A: Dicyclopentenyloxyethyl acrylate, Hitachi Chemical Co., Ltd. Irgacure 184 : 1-hydroxycyclohexyl phenyl ketone, manufactured by Ciba Specialty Chemicals, Inc. LA-82: 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, manufactured by Asahi Denka Co., Ltd. PMP: 4 -Mercaptophenol
　得られた本発明の紫外線硬化型樹脂組成物を用いて有機色素記録層を有するブルーレイディスクを作製し、特性評価を行った。 Using the resulting ultraviolet curable resin composition of the present invention, a Blu-ray disc having an organic dye recording layer was prepared and evaluated for characteristics.
　有機色素記録層を有するブルーレイディスクの作製（実施例１～３、比較例１～２）
１．トラックピッチ０．３２μｍの案内溝を有する直径１２ｃｍ、厚み１．１ｍｍのポリカーボネート基板に銀合金を１００ｎｍの膜厚になるようスパッタし、反射層を形成した。その後、アゾ色素をＴＦＰ（テトラフルオロプロパノール）溶剤に溶かした色素溶液をスピンコート法により塗布し、８０℃で３０分間乾燥して有機色素記録層を形成した。さらに、ＺｎＳ－ＳｉＯ２（モル比８０：２０）を約１５ｎｍの厚みになるようスパッタし、界面層を形成し、ブルーレイディスク基板を作製した。
２．ブルーレイディスク基板を界面層が上になるようスピンテーブルに乗せ、内径１１．５ｍｍまで覆う様に円状のキャップ処理を行い、ついで本発明の紫外線硬化型樹脂組成物を２．０ｇ中心部のキャップ上に供給した。
３．本発明の紫外線硬化型樹脂組成物の粘度に合わせ、１０００ｒｐｍから１５００ｒｐｍの速度範囲で４秒から７秒間スピンコートし、各塗布膜厚が２５μｍとなるよう塗布した。スピンコート終了間際にキセノンフラッシュランプを２ショット照射し、表面の流動性が無くなる程度に硬化させた。
４．高圧水銀ランプを使用し、上側から４００ｍＪ／ｃｍ2で３秒間照射して本発明の紫外線硬化型樹脂組成物を完全硬化させた。
５．硬化した本発明の紫外線硬化型樹脂組成物が上になるようスピンテーブルに乗せ、内径１１．５ｍｍまで覆う様に円状のキャップ処理を行い、ついでＢＲＤ－８６４（日本化薬（株）製ブルーレイディスク用光透過層用樹脂）を３．０ｇ中心部のキャップ上に供給した。
６．１５００ｒｐｍの速度範囲で４秒から７秒間スピンコートし、塗布膜厚が７５μｍとなるよう塗布した。スピンコート終了間際にキセノンフラッシュランプを２ショット照射し、表面の流動性が無くなる程度に硬化させた。
７．高圧水銀ランプを使用し、上側から４００ｍＪ／ｃｍ2で３秒間照射してＢＲＤ－８６４を完全硬化させ、本発明のブルーレイディスクを作製した。 Production of Blu-ray Disc with Organic Dye Recording Layer (Examples 1-3, Comparative Examples 1-2)
1. A reflective layer was formed by sputtering a silver alloy to a thickness of 100 nm on a polycarbonate substrate having a diameter of 12 cm and a thickness of 1.1 mm having guide grooves with a track pitch of 0.32 μm. Thereafter, a dye solution in which an azo dye was dissolved in a TFP (tetrafluoropropanol) solvent was applied by spin coating, and dried at 80 ° C. for 30 minutes to form an organic dye recording layer. Further, ZnS—SiO 2 (molar ratio 80:20) was sputtered to a thickness of about 15 nm to form an interface layer, and a Blu-ray Disc substrate was produced.
2. A Blu-ray disc substrate is placed on a spin table so that the interface layer is on top, and a circular cap treatment is performed so as to cover the inner diameter of 11.5 mm, and then the UV curable resin composition of the present invention is 2.0 g in the center cap. Supplied on top.
3. In accordance with the viscosity of the ultraviolet curable resin composition of the present invention, spin coating was performed at a speed range of 1000 rpm to 1500 rpm for 4 seconds to 7 seconds, and each coating film thickness was 25 μm. Immediately after the end of spin coating, the xenon flash lamp was irradiated with two shots, and cured so that the fluidity of the surface disappeared.
4). Using a high pressure mercury lamp, the ultraviolet curable resin composition of the present invention was completely cured by irradiation from the upper side at 400 mJ / cm 2 for 3 seconds.
5. The cured UV-curable resin composition of the present invention is placed on a spin table so that a circular cap treatment is performed so as to cover the inner diameter of 11.5 mm, and then BRD-864 (Nippon Kayaku Co., Ltd. Blu-ray) is applied. The resin for the light transmission layer for disk) was supplied onto the cap at the center of 3.0 g.
6. Spin coating was performed for 4 to 7 seconds at a speed range of 1500 rpm, and the coating film thickness was 75 μm. Immediately after the end of spin coating, the xenon flash lamp was irradiated with two shots, and cured so that the fluidity of the surface disappeared.
7). Using a high-pressure mercury lamp, BRD-864 was completely cured by irradiating from the upper side at 400 mJ / cm 2 for 3 seconds to produce a Blu-ray Disc of the present invention.
　有機色素記録層を有するブルーレイディスクの作製（実施例４）
１．トラックピッチ０．３２μｍの案内溝を有する直径１２ｃｍ、厚み１．１ｍｍのポリカーボネート基板に銀合金を１００ｎｍの膜厚になるようスパッタし、反射層を形成した。その後、アゾ色素をＴＦＰ（テトラフルオロプロパノール）溶剤に溶かした色素溶液をスピンコート法により塗布し、８０℃で３０分間乾燥して有機色素記録層を形成した。さらに、ＺｎＳ－ＳｉＯ２（モル比８０：２０）を約１５ｎｍの厚みになるようスパッタし、界面層を形成し、ブルーレイディスク基板を作製した。
２．ブルーレイディスク基板を界面層が上になるようスピンテーブルに乗せ、内径１１．５ｍｍまで覆う様に円状のキャップ処理を行い、ついで本発明の紫外線硬化型樹脂組成物を２．０ｇ中心部のキャップ上に供給した。
３．本発明の紫外線硬化型樹脂組成物の粘度に合わせ、８００ｒｐｍから１３００ｒｐｍの速度範囲で４秒から７秒間スピンコートし、塗布膜厚が１００μｍとなるよう塗布した。スピンコート終了間際にキセノンフラッシュランプを２ショット照射し、表面の流動性が無くなる程度に硬化させた。
４．高圧水銀ランプを使用し、上側から４００ｍＪ／ｃｍ2で３秒間照射して本発明の紫外線硬化型樹脂組成物を完全硬化させ、本発明のブルーレイディスクを作製した。 Production of Blu-ray Disc with Organic Dye Recording Layer (Example 4)
1. A reflective layer was formed by sputtering a silver alloy to a thickness of 100 nm on a polycarbonate substrate having a diameter of 12 cm and a thickness of 1.1 mm having guide grooves with a track pitch of 0.32 μm. Thereafter, a dye solution in which an azo dye was dissolved in a TFP (tetrafluoropropanol) solvent was applied by spin coating, and dried at 80 ° C. for 30 minutes to form an organic dye recording layer. Further, ZnS—SiO 2 (molar ratio 80:20) was sputtered to a thickness of about 15 nm to form an interface layer, and a Blu-ray Disc substrate was produced.
2. A Blu-ray disc substrate is placed on a spin table so that the interface layer is on top, and a circular cap treatment is performed so as to cover the inner diameter of 11.5 mm, and then the UV curable resin composition of the present invention is 2.0 g in the center cap. Supplied on top.
3. In accordance with the viscosity of the ultraviolet curable resin composition of the present invention, spin coating was performed at a speed range of 800 rpm to 1300 rpm for 4 seconds to 7 seconds, and the coating film thickness was 100 μm. Immediately after the end of spin coating, the xenon flash lamp was irradiated with two shots, and cured so that the fluidity of the surface disappeared.
4). Using a high pressure mercury lamp, the ultraviolet curable resin composition of the present invention was completely cured by irradiating at 400 mJ / cm 2 from the upper side for 3 seconds to produce the Blu-ray Disc of the present invention.
ブルーレイディスクの耐久性試験前後の記録信号特性
　本発明のブルーレイディスク及び比較例１のブルーレイディスクを、８０℃、８５％ＲＨ環境下、２５０時間放置した。ブルーレイディスクデータ信号測定装置パルステック社製ＯＤＵ－１０００を用いて、耐久性試験前後のブルーレイディスクの記録信号特性（ジッタ値）を測定し、下記基準で評価した。ジッタ値は光ディスクの電気信号のひとつであり、これらの数値が高いほど、ブルーレイディスクの信号データが劣化していることを示し、１０％以上となるとデータの読み書きが困難となる。
ジッタ値の評価
　　○・・・ジッタ値１０．０％未満。
　　×・・・ジッタ値１０．０％以上。 Recording signal characteristics before and after the durability test of the Blu-ray Disc The Blu-ray disc of the present invention and the Blu-ray disc of Comparative Example 1 were allowed to stand for 250 hours in an environment of 80 ° C. and 85% RH. The recording signal characteristics (jitter value) of the Blu-ray disc before and after the durability test were measured using a Blu-ray Disc data signal measuring device ODU-1000 manufactured by Pulse Tech Co., Ltd., and evaluated according to the following criteria. The jitter value is one of the electrical signals of the optical disk. The higher these values are, the more the signal data of the Blu-ray disk is degraded. When the value is 10% or more, it becomes difficult to read and write data.
Evaluation of jitter value ○ Jitter value is less than 10.0%.
X: Jitter value of 10.0% or more.
　紫外線硬化型樹脂組成物の保存時の外観評価
　本発明および比較例の紫外線硬化型樹脂組成物を調整後、室温（２５℃、４５％ＲＨ）で２４時間保存して液の外観を観察した。保存時に液が分離した場合、均一に紫外線硬化型樹脂組成物を塗布し、硬化させることが困難になることから好ましくない。
液の外観の評価
　　○・・・紫外線硬化型樹脂組成物が分離していない。
　　×・・・紫外線硬化型樹脂組成物が分離。 Appearance evaluation during storage of ultraviolet curable resin composition After preparing the ultraviolet curable resin compositions of the present invention and comparative examples, they were stored at room temperature (25 ° C., 45% RH) for 24 hours, and the appearance of the liquid was observed. When the liquid is separated during storage, it is not preferable because it is difficult to uniformly apply and cure the ultraviolet curable resin composition.
Evaluation of the appearance of the liquid ○ The ultraviolet curable resin composition is not separated.
X: UV curable resin composition separated.
　表１の結果より、炭素数７～１８のアルキレン基を有する（メタ）アクリレートを含有する実施例１～４の本発明の樹脂組成物は、良好な塗布性を有しつつ、耐久性試験前後において良好な記録信号特性が得られた。一方、炭素数７～１８のアルキレン基を有する（メタ）アクリレートを含有しない比較例１は耐久性試験前後に良好な記録信号特性が得られなかった。また同様に炭素数７～１８のアルキレン基を有する（メタ）アクリレートを含有しない比較例２は、室温で２４時間保存した際、液の分離による外観不良が生じた。 From the results shown in Table 1, the resin compositions of the present invention of Examples 1 to 4 containing (meth) acrylates having an alkylene group having 7 to 18 carbon atoms have good coatability and before and after the durability test. Good recording signal characteristics were obtained. On the other hand, Comparative Example 1 which does not contain (meth) acrylate having an alkylene group having 7 to 18 carbon atoms did not obtain good recording signal characteristics before and after the durability test. Similarly, Comparative Example 2 which does not contain (meth) acrylate having an alkylene group having 7 to 18 carbon atoms exhibited poor appearance due to liquid separation when stored at room temperature for 24 hours.
　本発明を特定の態様を参照して詳細に説明したが、本発明の精神と範囲を離れることなく様々な変更および修正が可能であることは、当業者にとって明らかである。
　なお、本出願は、２０１０年１月２９日付で出願された日本特許出願（特願２０１０－０１７５７５）に基づいており、その全体が引用により援用される。また、ここに引用されるすべての参照は全体として取り込まれる。 Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on Jan. 29, 2010 (Japanese Patent Application No. 2010-017575), which is incorporated by reference in its entirety. Also, all references cited herein are incorporated as a whole.

Claims (7)

  1. 　（Ａ）炭素数７～１８のアルキレン基を有する（メタ）アクリレート及び（Ｂ）光重合開始剤を含有する有機色素記録層を有する光ディスク用紫外線硬化型樹脂組成物。 (A) An ultraviolet curable resin composition for an optical disc having an organic dye recording layer containing a (meth) acrylate having an alkylene group having 7 to 18 carbon atoms and (B) a photopolymerization initiator.
  2. 　炭素数７～１８のアルキレン基を有する（メタ）アクリレート（Ａ）が、イソオクチル（メタ）アクリレート、ラウリル（メタ）アクリレート、イソデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、セチル（メタ）アクリレート、イソミリスチル（メタ）アクリレート、トリデシル（メタ）アクリレート、２－エチル－２－ブチル－プロパンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート及び１，１０－デカンジオールジ（メタ）アクリレートからなる群から選ばれる１種以上である請求項１に記載の光ディスク用紫外線硬化型樹脂組成物。 (Meth) acrylate (A) having an alkylene group having 7 to 18 carbon atoms is selected from isooctyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate, stearyl (meth) acrylate, cetyl (meth) acrylate, Myristyl (meth) acrylate, tridecyl (meth) acrylate, 2-ethyl-2-butyl-propanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate and 1,10-decanediol di (meth) The ultraviolet curable resin composition for optical disks according to claim 1, which is at least one selected from the group consisting of acrylates.
  3. 　（Ｃ）（Ａ）以外の（メタ）アクリレートを含有する請求項１又は請求項２に記載の光ディスク用紫外線硬化型樹脂組成物。 The ultraviolet curable resin composition for optical discs according to claim 1 or 2, which contains (meth) acrylates other than (C) (A).
  4. 　炭素数７～１８のアルキレン基を有する（メタ）アクリレート（Ａ）が、組成物全体に対して１０～９５重量％含有する請求項１～３のいずれか１項に記載の光ディスク用紫外線硬化型樹脂組成物。 The ultraviolet curable type for optical disks according to any one of claims 1 to 3, wherein the (meth) acrylate (A) having an alkylene group having 7 to 18 carbon atoms is contained in an amount of 10 to 95% by weight based on the whole composition. Resin composition.
  5. 　（Ａ）以外の（メタ）アクリレート（Ｃ）が、ポリエステルポリオール又はポリエーテルポリオールとポリイソシアネートとヒドロキシ（メタ）アクリレートとの反応物、及び／又はエチレンオキサイド変性ビスフェノールＡ型ジアクリレートである請求項１～４のいずれか１項に記載の光ディスク用紫外線硬化型樹脂組成物。 The (meth) acrylate (C) other than (A) is a reaction product of polyester polyol or polyether polyol, polyisocyanate and hydroxy (meth) acrylate, and / or ethylene oxide-modified bisphenol A type diacrylate. 5. The ultraviolet curable resin composition for optical disks according to any one of 1 to 4.
  6. 　請求項１～５のいずれか１項に記載の光ディスク用紫外線硬化型樹脂組成物に活性エネルギー線を照射して得られる硬化物。 A cured product obtained by irradiating the ultraviolet curable resin composition for optical disks according to any one of claims 1 to 5 with active energy rays.
  7. 　光ディスク基板に、請求項１～５のいずれか１項に記載の光ディスク用紫外線硬化型樹脂組成物を塗布し、活性エネルギー線を照射して得られる光ディスク。 An optical disc obtained by applying an ultraviolet curable resin composition for optical discs according to any one of claims 1 to 5 to an optical disc substrate and irradiating with active energy rays.
PCT/JP2010/058505 2010-01-29 2010-05-20 Uv-curable resin composition for use in optical disc, cured product, and article WO2011061953A1 (en)

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