WO2015056660A1 - 樹脂シート、及びその用途 - Google Patents
樹脂シート、及びその用途 Download PDFInfo
- Publication number
- WO2015056660A1 WO2015056660A1 PCT/JP2014/077280 JP2014077280W WO2015056660A1 WO 2015056660 A1 WO2015056660 A1 WO 2015056660A1 JP 2014077280 W JP2014077280 W JP 2014077280W WO 2015056660 A1 WO2015056660 A1 WO 2015056660A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin sheet
- meth
- acrylate
- light irradiation
- sheet according
- Prior art date
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- 229920005989 resin Polymers 0.000 title claims abstract description 169
- 239000011347 resin Substances 0.000 title claims abstract description 169
- 239000000203 mixture Substances 0.000 claims abstract description 52
- 230000001681 protective effect Effects 0.000 claims abstract description 14
- -1 acrylate compound Chemical class 0.000 claims description 49
- 238000001723 curing Methods 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 239000000758 substrate Substances 0.000 claims description 24
- 238000000016 photochemical curing Methods 0.000 claims description 22
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 17
- 229920001187 thermosetting polymer Polymers 0.000 claims description 17
- 239000003999 initiator Substances 0.000 claims description 12
- 230000009477 glass transition Effects 0.000 claims description 7
- 230000001678 irradiating effect Effects 0.000 claims description 7
- 238000005266 casting Methods 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 109
- 238000000034 method Methods 0.000 description 29
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- 238000004519 manufacturing process Methods 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 10
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- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 7
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 7
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- 238000012545 processing Methods 0.000 description 7
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- 239000005056 polyisocyanate Substances 0.000 description 6
- 229920001228 polyisocyanate Polymers 0.000 description 6
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 5
- 238000003426 chemical strengthening reaction Methods 0.000 description 5
- 238000013007 heat curing Methods 0.000 description 5
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
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- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
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- 125000000524 functional group Chemical group 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- YCOZIPAWZNQLMR-UHFFFAOYSA-N pentadecane Chemical compound CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 4
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- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 3
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- 239000012965 benzophenone Substances 0.000 description 3
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 3
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- 238000013461 design Methods 0.000 description 3
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
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- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 2
- PFEFOYRSMXVNEL-UHFFFAOYSA-N 2,4,6-tritert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 PFEFOYRSMXVNEL-UHFFFAOYSA-N 0.000 description 2
- HNURKXXMYARGAY-UHFFFAOYSA-N 2,6-Di-tert-butyl-4-hydroxymethylphenol Chemical compound CC(C)(C)C1=CC(CO)=CC(C(C)(C)C)=C1O HNURKXXMYARGAY-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- BYPFICORERPGJY-UHFFFAOYSA-N 3,4-diisocyanatobicyclo[2.2.1]hept-2-ene Chemical compound C1CC2(N=C=O)C(N=C=O)=CC1C2 BYPFICORERPGJY-UHFFFAOYSA-N 0.000 description 2
- SKKHNUKNMQLBTJ-UHFFFAOYSA-N 3-bicyclo[2.2.1]heptanyl 2-methylprop-2-enoate Chemical compound C1CC2C(OC(=O)C(=C)C)CC1C2 SKKHNUKNMQLBTJ-UHFFFAOYSA-N 0.000 description 2
- ZVVFVKJZNVSANF-UHFFFAOYSA-N 6-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]hexyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCCCCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 ZVVFVKJZNVSANF-UHFFFAOYSA-N 0.000 description 2
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- FGUUNXDRMVKHCF-UHFFFAOYSA-N bis(hydroxymethyl)tricyclo[5.2.1.0(2,6)]decane Chemical compound C12CCCC2(CO)C2(CO)CC1CC2 FGUUNXDRMVKHCF-UHFFFAOYSA-N 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
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- VBJHDYCFGAXWDN-UHFFFAOYSA-N decane prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.CCCCCCCCCC VBJHDYCFGAXWDN-UHFFFAOYSA-N 0.000 description 2
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
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- LYDHLGJJJAWBDY-UHFFFAOYSA-N 1-isocyanato-4-[2-(4-isocyanatocyclohexyl)propan-2-yl]cyclohexane Chemical compound C1CC(N=C=O)CCC1C(C)(C)C1CCC(N=C=O)CC1 LYDHLGJJJAWBDY-UHFFFAOYSA-N 0.000 description 1
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- NEUPRVAMTYHIQV-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(3,5-ditert-butyl-4-hydroxyphenyl)disulfanyl]phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(SSC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 NEUPRVAMTYHIQV-UHFFFAOYSA-N 0.000 description 1
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- MIRQGKQPLPBZQM-UHFFFAOYSA-N 2-hydroperoxy-2,4,4-trimethylpentane Chemical compound CC(C)(C)CC(C)(C)OO MIRQGKQPLPBZQM-UHFFFAOYSA-N 0.000 description 1
- DWXWICVXNZIDJM-UHFFFAOYSA-N 2-isocyanatoethyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=CC(CCC(=O)OCCN=C=O)=CC(C(C)(C)C)=C1O DWXWICVXNZIDJM-UHFFFAOYSA-N 0.000 description 1
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- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
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- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
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- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
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- RGBXDEHYFWDBKD-UHFFFAOYSA-N propan-2-yl propan-2-yloxy carbonate Chemical compound CC(C)OOC(=O)OC(C)C RGBXDEHYFWDBKD-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical class CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
- B29C39/02—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/52—Amides or imides
- C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F20/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
- B29K2033/04—Polymers of esters
- B29K2033/08—Polymers of acrylic acid esters, e.g. PMA, i.e. polymethylacrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/06—Crosslinking by radiation
Definitions
- the present invention is a resin sheet obtained by photocuring a photocurable composition and having a curved shape, which is excellent in optical characteristics and thermomechanical characteristics, and useful as a base material for display, and a display It is related with uses, such as a protection board for screens, a screen, a touch-panel board, and a face body for protection surfaces.
- a flat glass plate has been often used as a base material for a display.
- a flat glass substrate is used for a protective plate (cover) which is the forefront of the display, a liquid crystal display, an organic EL display, a touch panel, and the like.
- curved displays are a hot topic in television and in-vehicle applications from the viewpoint of design and visibility.
- the use of a glass plate is more difficult in a curved display.
- the ease of breaking when thin glass is bent is a big problem from the viewpoint of safety both in the manufacturing process and in the end product.
- a glass plate is manufactured by a casting method or a float method, but it is difficult to manufacture a glass plate having a curvature in the first place. For example, even if a flat glass plate is bent by heating, the susceptibility to cracking increases due to the stress strain remaining inside.
- in-mold molding is expensive, it is not suitable for mass production, and polishing a flat glass plate requires a lot of time. Furthermore, both in-mold molding and polishing become more difficult as the area increases.
- Patent Document 1 Although a high-performance and flat resin sheet can be obtained, a resin sheet having a curvature cannot be obtained. In particular, when cured sufficiently, since it is a crosslinked resin, it is difficult to bend it by a technique such as heating.
- Patent Document 2 can improve the fragility by chemical strengthening, small-sized parts are manufactured by hand, which is inferior in productivity and is not practical.
- chemical strengthening is performed by exchanging metal ions in glass at a high temperature.
- thin glass there is a problem that it is deformed by a high temperature chemical strengthening process, and a thin film having a certain curvature. Chemical strengthening of glass is even more difficult.
- the present invention is a resin sheet having a curved shape under such a background, and is excellent in optical performance and thermomechanical characteristics, and is required for lighter and thinner, improved safety, curved surface display, protective surface, and the like. Provide a substrate that can be used.
- the present inventors have made a resin sheet photocured using the photocurable composition (A) having a curvature radius of 0.1 to at least in one direction within the plane. It has been found that a resin sheet having a predetermined shape can be obtained by curving and curing within a range of 5 m.
- the curvature radius (m) is the reciprocal of the curvature.
- the gist of the present invention is a transparent resin sheet having a thickness of 0.1 to 10 mm obtained by curing the photocurable composition (A), and has a radius of curvature of 0.1 in at least one direction in the plane.
- the present invention relates to a resin sheet that is curved in a range of 1 to 5 m.
- the photocurable composition (A) is photocured, it is fixed with a fixing jig so that the radius of curvature is in the range of 0.1 to 5 m in at least one direction within the surface. It is preferable to obtain a resin sheet by curing. This is to obtain a resin sheet having a curved shape while completing the curing by curving the resin sheet photocured in a semi-cured state to a desired curvature radius and thermally curing. This utilizes the fact that the shape of the crosslinked resin by curing is determined at the final stage of curing (polymerization). By this method, it is not necessary to prepare a curved mold and it is not necessary to cut the resin sheet, and a resin sheet having a desired curved shape can be manufactured.
- the photocurable composition (A) having a thickness of 0.1 to 10 mm obtained by casting light in a mold comprising two transparent flat plates facing each other. It is a transparent resin sheet, and it is preferable to obtain a resin sheet under the following light irradiation condition 1.
- Light irradiation condition 1 The step (1) of irradiating light from either the upper surface side or the lower surface side of the mold and the step (2) of irradiating light from the other side are sequentially performed, and in the step (2) light irradiation amount (Xb) (J / cm 2 ) is the amount of light irradiation in the step (1) (Xa) (J / cm 2) greater than that.
- the amount of light irradiation in the above steps (1) and (2) is shown as an average value of the entire surface.
- the resin sheet having a curved shape obtained under the light irradiation condition 1 is obtained by utilizing the curing shrinkage of the photocurable composition.
- a photocurable composition particularly a photocurable composition containing a (meth) acryloyl group, is a liquid, and causes volume shrinkage of several to several tens of percent when it is cured (called cure shrinkage).
- cure shrinkage volume shrinkage
- a resin sheet curved in a shape is obtained.
- the light irradiation from the upper surface side is sufficiently strong, the light reaches the lower surface at once, and the upper surface and the lower surface are cured in the same manner, resulting in a substantially flat resin sheet, but the light irradiation from the upper surface side is weak In this case, the light does not reach the lower surface sufficiently, and the lower surface cures with a delay, so that the lower surface side of the resin sheet is finally contracted to obtain a convexly curved resin sheet.
- the curving direction tends to be curved in the direction that coincides with the transport direction. This is because curing starts from the front end in the transport direction and cure shrinkage occurs in the transport direction as the curing proceeds toward the rear end.
- the degree of curvature is greater for a composition with greater cure shrinkage, and a resin sheet having a curved shape with a small curvature radius is obtained.
- the end portions at both ends in the transport direction refer to a portion 1 cm inside from the end portion where the amount of light can be measured.
- the present invention also provides a touch panel substrate in which a transparent conductive film is formed on at least one surface of the resin sheet.
- a resin sheet having a curved shape excellent in optical characteristics and thermomechanical characteristics can be produced with high productivity.
- the resin sheet having a desired curved shape of the present invention is suitable as a protective plate for a display, a screen, a touch panel substrate, and a protective surface.
- thermosetting of this invention It is a figure of the specific example of the fixing jig used by the thermosetting of this invention. It is a figure of the specific example of the fixing jig used by the thermosetting of this invention. It is a figure of the specific example of the fixing jig used by the thermosetting of this invention.
- (meth) acrylate is a generic term for acrylate and methacrylate
- (meth) acryloyl is a generic term for acryloyl and methacryloyl.
- polyfunctional here means having two or more (meth) acryloyl groups in a molecule
- the photocurable composition (A) used in the present invention may be any composition as long as it can be cured by light irradiation, and in particular, it is a composition containing a (meth) acryloyl group in terms of the productivity of the resin sheet. Is preferred.
- the photocurable composition (A) preferably contains the following components (A1) and (A2) from the viewpoint of the heat resistance of the resin sheet.
- Examples of the polyfunctional (meth) acrylate compound (A1) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, Propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate 1,6-hexanediol di (meth) acrylate, nonanediol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) ) Acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene
- pentadecane di (meth) acrylate, 2,2-bis [4- ( ⁇ - (meth) acryloyloxyethoxy) cyclohexyl] propane, 1,3-bis ((meth) acryloyloxymethyl) cyclohexane, 1,3-bis ((meth) acryloyloxyethyloxymethyl) cyclohexane, 1,4-bis ((meth) acryloyloxymethyl) cyclohexane, 1,4-bis ((meth) acryloyloxyethyloxymethyl) cyclohexane, etc.
- Bifunctional (meth) acrylates such as aromatic compounds such as carbonate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate , Dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether
- polyfunctional (meth) acrylate compound (A1) those containing an alicyclic structure are preferable in terms of rigidity and little heat discoloration. Moreover, it is preferable to contain polyfunctional (meth) acrylate and urethane (meth) acrylate in terms of surface hardness, and in particular, in terms of heat resistance, bis (hydroxy) tricyclo [5.2.1.0].
- the urethane (meth) acrylate suitably used in the present invention is obtained, for example, by reacting polyisocyanate and a hydroxyl group-containing (meth) acrylate using a catalyst such as dibutyltin dilaurate as necessary. It is preferable.
- polyisocyanate examples include aliphatic polyisocyanates such as ethylene diisocyanate and hexamethylene diisocyanate, isophorone diisocyanate, bis (isocyanatomethyl) tricyclo [5.2.1.0 2,6 ] decane, and norbornene diisocyanate.
- Polyisocyanates having an alicyclic structure such as a trimer compound of added xylylene diisocyanate and isophorone diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate,
- polyisocyanates having an aromatic ring such as lid diisocyanate.
- isophorone diisocyanate and norbornene diisocyanate are preferable in terms of low curing shrinkage.
- hydroxyl group-containing (meth) acrylate examples include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3- (meth) Examples include acryloyloxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol tri (meth) acrylate. Of these, pentaerythritol tri (meth) acrylate and dipentaerythritol tri (meth) acrylate are preferable in terms of the pencil hardness of the resin sheet.
- urethane (meth) acrylate obtained by reaction of polyisocyanate and hydroxyl group-containing (meth) acrylate may be used.
- reactants acrylate compounds are preferable from the viewpoint of curing speed, and 2-9 functions, particularly 2-6 functions, are particularly preferable from the viewpoint of surface hardness and flexural modulus.
- the content ratio (weight ratio) is multifunctional in terms of thermomechanical properties of the resin sheet.
- (Meth) acrylate / urethane (meth) acrylate is preferably 95/5 to 50/50, more preferably 92/8 to 60/40, and particularly preferably 90/10 to 70/30. If the urethane (meth) acrylate content is too small, the pencil hardness tends to decrease, and if it is too large, the water absorption tends to increase.
- the photocurable composition (A) used in the present invention may contain a monofunctional (meth) acrylate.
- the monofunctional (meth) acrylate include methyl (meth) acrylate and ethyl.
- alicyclic skeletons such as cyclohexyl (meth) acrylate, tricyclodecyl (meth) acrylate, tricyclodecyloxymethyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, and adamantyl (meth) acrylate (Meth) acrylate is preferred in terms of low cure shrinkage.
- the monofunctional (meth) acrylate When the monofunctional (meth) acrylate is contained as the photocurable composition (A), its content is 50 in terms of heat resistance with respect to 100 parts by weight of the polyfunctional (meth) acrylate compound.
- the amount is preferably not more than parts by weight, more preferably not more than 30 parts by weight, particularly preferably not more than 10 parts by weight. If the content is too large, the heat resistance tends to decrease.
- the minimum of content in the case of containing monofunctional (meth) acrylate is 0.001 weight part normally.
- the photopolymerization initiator (A2) used in the present invention is not particularly limited as long as it can generate radicals by irradiation with active energy rays, and various photopolymerization initiators can be used.
- examples include benzophenone, benzoin methyl ether, benzoin propyl ether, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2,6-dimethylbenzoyl diphenylphosphine oxide, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, and the like.
- photopolymerization initiators such as 1-hydroxycyclohexyl phenyl ketone and 2,4,6-trimethylbenzoyldiphenylphosphine oxide are particularly preferable. These photopolymerization initiators may be used alone or in combination of two or more.
- photopolymerization initiators (A2) are polyfunctional (meth) acrylate compounds (A1) (when monofunctional (meth) acrylates are contained, polyfunctional (meth) acrylate compounds (A1) and monofunctional ( It is preferably used in a proportion of usually 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, particularly 0.2 to 3 parts by weight, based on 100 parts by weight of the total of (meth) acrylate. Is preferred. If the amount used is too small, the polymerization rate tends to decrease and polymerization does not proceed sufficiently. If the amount is too large, the light transmittance of the resulting resin sheet tends to decrease (yellowing).
- thermal polymerization initiator may be used in combination with the photopolymerization initiator.
- known compounds can be used, such as hydroperoxide, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and the like.
- Hydroperoxides dialkyl peroxides such as di-t-butyl peroxide and dicumyl peroxide, t-butyl peroxybenzoates, peroxyesters such as t-butylperoxy (2-ethylhexanoate), benzoyl
- peroxides such as diacyl peroxides such as peroxides, peroxycarbonates such as diisopropylperoxycarbonate, peroxyketals, and ketone peroxides.
- the photocurable composition (A) used in the present invention includes a chain transfer agent, an oxidation agent, as appropriate. You may contain auxiliary components, such as an inhibitor, a ultraviolet absorber, a thickener, an antistatic agent, a flame retardant, an antifoamer, a coloring agent, and various fillers.
- chain transfer agent examples include polyfunctional mercaptan compounds such as pentaerythritol tetrakisthioglycolate and pentaerythritol tetrakisthiopropionate.
- polyfunctional mercaptan-based compounds are preferably used at a ratio of usually 10 parts by weight or less, more preferably 5 parts by weight or less, particularly 100 parts by weight of the polyfunctional (meth) acrylate-based compound (A1). Is preferably 3 parts by weight or less. When there is too much this usage-amount, there exists a tendency for the heat resistance and rigidity of the resin sheet obtained to fall.
- the lower limit of the polyfunctional mercaptan compound is usually 0.0001 parts by weight.
- antioxidants examples include 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, 2,4,6-tri-t-butylphenol, and 2,6-di- t-butyl-4-s-butylphenol, 2,6-di-t-butyl-4-hydroxymethylphenol, n-octadecyl- ⁇ - (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) ) Propionate, 2,6-di-t-butyl-4- (N, N-dimethylaminomethyl) phenol, 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 2,4 -Bis (n-octylthio) -6- (4-hydroxy-3 ', 5'-di-t-butylanilino) -1,3,5-triazine, 4,4-methylene-bis (2,6-di-)
- the ultraviolet absorber is not particularly limited as long as it is soluble in the photocurable composition (A), and various ultraviolet absorbers can be used. Specific examples include salicylic acid ester, benzophenone, triazole, hydroxybenzoate, and cyanoacrylate. These ultraviolet absorbers may be used in combination. Among these, from the viewpoint of compatibility with the photocurable composition (A), benzophenone or triazole, specifically (2-hydroxy-4-octyloxy-phenyl) -phenyl-methanone, 2-benzo UV absorbers such as triazol-2-yl-4-tert-octyl-phenol are preferred.
- the content of the ultraviolet absorber is usually preferably 0.001 to 1% by weight, particularly preferably 0.01 to 0.1% by weight, based on the photocurable composition (A). If the amount of the ultraviolet absorber is too small, the light resistance of the resin sheet tends to decrease, and if it is too large, the light transmittance of the resin sheet tends to decrease.
- the curing shrinkage of the photocurable composition (A) is that the radius of curvature of the resin sheet having a curved shape can be reduced. 6% or more is preferable. More preferably, it is 8 to 20% in terms of optical characteristics, and particularly preferably 10 to 15% in terms of moldability. In general, the upper limit of the curing shrinkage is 30%.
- adjusting the (meth) acrylate component and the blending amount can be mentioned.
- bis (hydroxymethyl) tricyclo [5.2.1.0 2,6 ] decane di (meth) acrylate (curing shrinkage 6%) having a relatively low curing shrinkage and relatively high curing shrinkage
- pentaerythritol tetra (meth) acrylate curing shrinkage 13%), it is possible to adjust the curing shrinkage in the range of 7 to 13%.
- polyethylene glycol di (meth) acrylates having different oxyethylene chain lengths, and it is easy to prepare photocurable compositions having different cure shrinkage rates.
- the photocurable composition (A) obtained above is cured to obtain a transparent resin sheet.
- the photocurable composition (A) is preferably photocured and then thermally cured.
- photocuring will be described.
- the curing degree in this specification means the reaction rate of the (meth) acryloyl group.
- the photocurable composition (A) is filled into a space of a mold composed of two flat plates at least one of which is transparent and a spacer for controlling the thickness.
- a glass plate is particularly preferable.
- the glass plate preferably has a thickness of 1 to 10 mm from the viewpoint of the strength of the mold, and more preferably, from the viewpoint of the surface smoothness of the resin sheet, at least one glass surface in contact with the photocurable composition (A) is optical. It is preferably polished. In particular, the surface smoothness Ra is preferably 50 nm or less.
- the glass plate may be chemically strengthened from the viewpoint of such strength. If the glass plate is too thick, the weight of the glass increases and the load on the equipment increases. In order to improve the demoldability of the resin sheet, the surface of the glass plate may be treated with a release agent.
- fine irregularities may be formed on the surface of the flat plate in contact with the photocurable composition (A).
- a resin sheet having a lens function, an antiglare function, or an anti-Newton ring function, or a resin sheet having a curved shape in the present invention can be obtained.
- the spacer controls the thickness of the resin sheet, but the material is not particularly limited, and a known material such as a resin is used. Among the resins, rubbery materials such as silicon resin are preferable.
- a light source to be used a general ultraviolet lamp can be used, but a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, an LED lamp, etc. are used because of the availability and price of the irradiation device. .
- the amount of irradiation light is preferably 0.1 to 100 J / cm 2 , more preferably 1 to 50 J / cm 2 , still more preferably 2 to 30 J / cm 2 , and particularly preferably 3 to 20 J / cm 2 . If the amount of irradiation light is too small, undulation tends to occur in the subsequent thermosetting, and if too much, it tends to be difficult to form a curved shape in the subsequent thermosetting.
- the illuminance is preferably 10 to 100,000 mW / cm 2 , more preferably 50 to 10,000 mW / cm 2 in terms of rapid light curing, and even more preferably 100 to 1000 mW / cm 2 in terms of curing to the inside of the resin sheet. 2 .
- Light irradiation can be performed from one side or both sides. It is also possible to divide it into multiple times.
- Examples of the method for producing a curved resin sheet of the present invention include: (i) after photocuring the fluorescent curable composition (A), the radius of curvature is in the range of 0.1 to 5 m in at least one direction in the plane. (Ii) a method in which the photocurable composition (A) is cast into a mold composed of two opposing transparent flat plates, and then specified. And the like, depending on the light irradiation conditions. This will be described in order below.
- the reaction rate of the (meth) acryloyl group by photocuring is preferably controlled to 50 to 90%. More preferably, it is 60 to 85%, particularly preferably 70 to 80%. If the reaction rate is too small, undulation is likely to occur in the subsequent thermosetting, and if it is too large, it tends to be difficult to form a curved shape in the subsequent thermosetting.
- the reaction rate of the (meth) acryloyl group can be measured by an analytical method such as solid-state NMR or IR.
- Examples of a method for controlling the reaction rate within the above range include adjusting the type and amount of the polyfunctional (meth) acrylate compound (A1) and the photopolymerization initiator (A2), controlling the illuminance and the light amount, and adjusting the curing temperature. It is done.
- the obtained resin sheet is removed from the mold and peeled off.
- the resin sheet obtained here is called a photocured sheet. Since the photocuring sheet at this stage is flat, various processes such as printing, coating, cutting, cutting, drilling, and C surface processing can be easily performed.
- the photocured sheet after photocuring is fixed in a curved shape, and thermosetting is performed.
- the light-curing sheet is thermally cured while being fixed to a fixing jig so that the radius of curvature is 0.1 to 5 m in at least one direction in the plane, and the (meth) acryloyl group after heat-curing is cured.
- the reaction rate is 1 to 40%, particularly 5 to 30%, more preferably 10 to 20% higher than the reaction rate after photocuring. If the difference between the reaction rate after heat curing and the reaction rate after photocuring is too small, the curing tends to be insufficient, and if too large, the resin sheet tends to be easily deformed.
- An ordinary oven can be used as a heating device used for thermosetting.
- an infrared heater can be used.
- the atmosphere in the oven may be any of air, inert gas, and vacuum, but vacuum is preferred in order to complete the curing reaction.
- the heating temperature is usually 50 to 300 ° C, more preferably 100 to 250 ° C, particularly preferably 150 to 200 ° C. If the temperature is too low, thermosetting does not complete and the physical properties of the resin sheet tend to become unstable. Conversely, if the temperature is too high, the hue of the resin sheet tends to decrease.
- the heating time is usually 10 minutes to 20 hours, more preferably 30 minutes to 10 hours, particularly preferably 1 to 7 hours. If the heating time is too short, thermosetting is not completed and the physical properties of the resin sheet become unstable. On the contrary, if the length is too long, the hue of the resin sheet tends to decrease.
- the fixing jig is not particularly limited, and examples thereof include a vertical holder as shown in FIG. 1 and a horizontal holder as shown in FIG. 2 and FIG.
- the reaction rate of the (meth) acryloyl group after thermosetting is preferably 70% or more from the viewpoint of stabilization of physical properties. More preferably, it is 70 to 99%, particularly preferably 75 to 95%, still more preferably 80 to 90%. When the reaction rate is too low, thermomechanical properties such as heat resistance and surface hardness tend to be lowered. In general, the upper limit of the reaction rate is 99.9%.
- the resin sheet is removed from the fixing jig to obtain the resin sheet having the desired curved shape of the present invention.
- Light irradiation condition 1 The step (1) of irradiating light from either the upper surface side or the lower surface side of the mold and the step (2) of irradiating light from the other side are sequentially performed, and in the step (2) light irradiation amount (Xb) (J / cm 2 ) is the amount of light irradiation in the step (1) (Xa) (J / cm 2) greater than that.
- the light irradiation amount from both surfaces is a two-step light irradiation process in which the process (2) is performed after the process (1) is performed, and the light irradiation in the process (2) is performed.
- the amount (Xb) (J / cm 2 ) is more than the light irradiation amount (Xa) (J / cm 2 ) in the step (1), and a resin sheet having a curved shape can be efficiently obtained based on the principle described above. It is preferable at the point which can do.
- the light irradiation amounts (Xa) (J / cm 2 ) and (Xb) (J / cm 2 ) are preferably 2Xa ⁇ Xb, more preferably 3Xa ⁇ Xb, and particularly preferably 4Xa ⁇ Xb.
- Xa ⁇ Xb the curvature radius of the resin sheet tends not to be sufficiently small.
- the light irradiation in the above steps (1) and (2) refers to light irradiation almost uniformly over the predetermined width direction, and the light irradiation amount is shown as an average value. is there.
- the illuminance is preferably 10 to 100000 mW / cm 2 , more preferably 50 to 10,000 mW / cm 2 in terms of rapid curing, and more preferably in terms of curing to the inside of the resin sheet. 100 to 1000 mW / cm 2 .
- further light irradiation may be performed for the purpose of improving the degree of curing.
- a total light irradiation amount it is usually preferable to irradiate 1 J / cm 2 or more.
- it is 5 to 50 J / cm 2 in terms of stabilizing the curvature of the resin sheet , and particularly preferably 10 to 30 J / cm 2 in terms of hue of the resin sheet.
- a resin sheet that is curved in a range of curvature radius of 0.1 to 5 m can be obtained in any in-plane direction under the following light irradiation condition 2.
- Light Irradiation Condition 2 After the photocurable composition (A) is cast, the light irradiation amount (Xc) (J / cm to the central portion in the conveyance direction is applied to the light irradiation while the mold is conveyed in the horizontal direction. 2 ) is larger than the amount of light irradiation [(Xd) (J / cm 2 ) and (Xe) (J / cm 2 )] to both ends in the transport direction.
- the light irradiation amount (Xc) (J / cm 2 ), (Xd) (J / cm 2 ), (Xe) (J / cm 2 ) is more preferably Xc ⁇ 2Xd in that the radius of curvature is made sufficiently small.
- the light irradiation amount of the center part here is the total light irradiation amount from both the upper surface side and the lower surface side.
- the light irradiation amount of both ends is also the total light irradiation amount from both the upper surface side and the lower surface side.
- the degree of curing after photocuring is important.
- the degree of cure in the present invention can be obtained by measuring the reaction rate of the (meth) acryloyl group in the resin sheet by an analytical method such as solid NMR or IR.
- the reaction rate of the (meth) acryloyl group after photocuring is preferably 70% or more from the viewpoint of stabilization of physical properties. More preferably, it is 80% or more, and particularly preferably 85% or more. If the reaction rate is too small, thermomechanical properties such as heat resistance and surface hardness tend to be lowered. The upper limit of the reaction rate is usually 99%.
- Examples of the method for controlling the reaction rate after photocuring include (meth) acrylate components, types and amounts of photopolymerization initiators, control of illuminance and light amount, and curing temperature.
- measurement of the reaction rate during photocuring is difficult because the resin sheet is in a semi-cured state (gel state).
- the difference in reaction rate between the upper and lower surfaces after photocuring is also important.
- the difference in reaction rate is preferably 10% or less, more preferably 5% or less, and particularly preferably 3% or less. If the difference is too large, the curvature of the resin sheet tends to be unstable.
- each reaction rate of the upper surface and the lower surface is obtained by scraping the resin from the upper surface layer portion and the lower surface layer portion of the resin sheet and taking the reaction rate measured using solid NMR for the resin as its value. It is.
- the difference in reaction rate is preferably 10% or less, more preferably 5% or less, and particularly preferably 3% or less. If the difference is too large, the curvature of the resin sheet tends to be unstable.
- each reaction rate of a center part and both ends is extract
- the resin sheet having the curved shape of the present invention can be obtained by demolding and peeling the resin sheet from the mold. It is also possible to heat-treat the resin sheet in order to improve the degree of cure and remove stress strain.
- the heat treatment may be performed under atmospheric pressure, inert gas, or vacuum, and the temperature is 50 ° C. or higher, more preferably 100 ° C. or higher, and particularly preferably 150 ° C. or higher.
- the upper limit is usually 300 ° C.
- the production method of the resin sheet of the present invention is not particularly limited as long as it can be bent within a target curvature radius of 0.1 to 5 m, but the production methods (i) and (ii) are preferable.
- the thickness of the resin sheet of the present invention is 0.1 to 10 mm, preferably 0.2 to 5 mm, particularly preferably 0.2 to 2 mm, although it varies depending on the application. If the thickness is too thin, the rigidity of the display substrate tends to decrease, and if it is too thick, it tends to be difficult to reduce the weight and thickness of the display.
- the resin sheet of the present invention preferably has a total light transmittance of 85% or more, more preferably 88% or more, and particularly preferably 90% or more. If the total light transmittance is too small, the brightness of the display tends to decrease.
- the resin sheet of the present invention preferably has a phase difference of 10 nm or less, more preferably 5 nm or less, and particularly preferably 2 nm or less. If the phase difference is too large, the fineness of the image tends to decrease when used for a display.
- the lower limit value of the phase difference is usually 0.01 nm.
- the resin sheet of the present invention preferably has a glass transition temperature of 150 ° C. or higher from the viewpoint of heat resistance.
- a preferable range of the glass transition temperature is 170 to 400 ° C, more preferably 190 to 300 ° C, and still more preferably 200 to 250 ° C.
- the method of controlling suitably the kind of photocurable composition (A) mentioned above and content of a component is mentioned.
- the technique of raising the functional group number of a polyfunctional (meth) acrylate type compound (A1) is mentioned.
- the resin sheet of the present invention preferably has a pencil hardness of 3H or more, more preferably 5H or more, and particularly preferably 7H or more. If the pencil hardness is too low, the surface hardness as the protective plate tends to decrease. In adjusting such a pencil within the above range, a method of appropriately controlling the type of the photocurable composition (A) and the content of the components described above can be used. For example, a polyfunctional (meth) acrylate compound (A1), particularly a urethane (meth) acrylate having 3 to 6 functional groups may be used.
- the resin sheet of the present invention can be cut into a desired size by a known technique such as NC processing, punching processing, or laser processing.
- a curved resin sheet to a flat support or press the resin sheet to make it flat once before processing.
- the flexural modulus of the resin sheet is preferably 3 to 5 GPa. More preferably, it is 3.5 to 4 GPa. If the flexural modulus is too low, the curved shape is not stabilized, and the rigidity as a display substrate tends to be reduced. Conversely, if the flexural modulus is too high, cracks tend to occur during processing.
- a method of appropriately controlling the type of the photocurable composition (A) and the content of the components can be used.
- a polyfunctional (meth) acrylate compound (A1) particularly a urethane (meth) acrylate having 2 to 6 functional groups may be used.
- the resin sheet having a curved shape can be obtained by the method described in detail above, but the radius of curvature of the resin sheet of the present invention is 0.1 to 5 m in at least one direction in the plane, and the preferable lower limit is 0.
- the upper limit is preferably 3 m, more preferably 2 m, especially 1 m, especially 0.9 m, more preferably 0.8 m. If the radius of curvature is too small, it tends to be difficult to design as a display. Conversely, if it is too large, the impression as a curved display tends to be lacking.
- the radius of curvature of the resin sheet of the present invention preferably has an in-plane tolerance of 10% or less. More preferably, it is 7% or less, and particularly preferably 5% or less. If the in-plane tolerance is too large, it is difficult to design a display. The lower limit of the in-plane tolerance is usually 0.1%.
- the radius of curvature is obtained by equally cutting out nine test pieces from the resin sheet, measuring the radius of curvature in the bending direction with a caliper, and setting the average value thereof.
- an adhesive layer In the resin sheet having a curved shape of the present invention, an adhesive layer, a hard coat layer, a printing layer, a gas barrier film, and a transparent conductive film can be formed according to various uses.
- the transparent conductive film examples include inorganic films such as indium and tin oxide (ITO) and organic films such as poly (3,4-ethylenedioxythiophene) (PEDOT).
- ITO indium and tin oxide
- PEDOT poly (3,4-ethylenedioxythiophene)
- an ITO film is preferable in terms of conductivity and transparency.
- the film thickness of such a transparent conductive film is usually 100 to 5000 mm, preferably 200 to 3000 mm, more preferably 300 to 2000 mm. If the film thickness is too thick, the substrate tends to swell, and if it is too thin, the conductivity tends to be insufficient.
- the film forming temperature is preferably 50 ° C. to 300 ° C., more preferably 100 to 250 ° C., and further preferably 130 to 200 ° C. If the film forming temperature is too low, the conductivity tends to be insufficient. Conversely, if the film forming temperature is too high, the light transmittance of the resin sheet tends to decrease.
- the conductivity of the obtained resin sheet having a curved shape with a transparent conductive film is preferably 500 ⁇ / ⁇ or less, more preferably 200 ⁇ / ⁇ or less, and further preferably 100 ⁇ / ⁇ or less. Tend to decrease.
- the resin sheet having the curved shape of the present invention can be produced with high productivity, and the obtained resin sheet has an excellent effect on optical characteristics and thermomechanical characteristics, and a protective plate for display and a touch panel substrate. Furthermore, it is suitable as a face body for a protective surface.
- Solvents include alcohols such as methanol and isopropyl alcohol, aliphatic hydrocarbons such as hexane and octane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene and xylene, methyl acetate, ethyl acetate Esters such as acetone, ketones such as methyl ethyl ketone and ⁇ -butyl lactone, chlorinated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as ethyl ether and tetrahydrofuran, ethylene glycols, N, N-dimethylformamide N-methylpyrrolidone, gasoline, oil and the like.
- Examples of the chemical include alkaline water and hydrochloric acid
- Reaction rate of (meth) acryloyl group (%) A 50 mm ⁇ 50 mm test piece was cut out from a 150 mm ⁇ 150 mm resin sheet, freeze-pulverized, and then “AVANCE DPX-400” manufactured by BRUKER BIOSPIN, using a solid NMR probe, the observation nucleus was 13 C, and the rotation speed was 5000 Hz. , Measured at room temperature (25 ° C.). The carbonyl carbon in the unpolymerized (meth) acryloyl group is detected on the high magnetic field side (166 ppm), and the polymerized carbonyl carbon is detected on the low magnetic field side (176 ppm). The reaction rate (%) was calculated from the ratio of these peak areas.
- Pencil hardness A test piece of 50 mm ⁇ 50 mm was cut out from a resin sheet of 150 mm ⁇ 150 mm, and the pencil hardness was measured according to JIS K-5600.
- Phase difference (nm) A test piece having a length of 50 mm and a width of 50 mm was cut out from a resin sheet of 150 mm ⁇ 150 mm, and a retardation (nm) at a wavelength of 550 nm was measured at 25 ° C. using RETS100A manufactured by Otsuka Electronics.
- Solvent resistance A test piece of 50 mm ⁇ 50 mm was cut out from a 150 mm ⁇ 150 mm resin sheet, immersed in N-methylpyrrolidone at 40 ° C. for 10 minutes, and then the appearance was visually observed.
- the evaluation criteria are as follows. ⁇ ⁇ ⁇ ⁇ There was no abnormality in the appearance.
- X An abnormality such as cloudiness occurred in the appearance.
- a photocurable composition (A) consisting of 1 part of phenylketone (“Irgacure 184” manufactured by Ciba Specialty Chemicals) was injected at 23 ° C.
- the mold was placed horizontally and conveyed with a conveyor, and irradiated with ultraviolet rays at a light intensity of 10 J / cm 2 using a metal halide lamp.
- the obtained light-cured sheet was removed from the mold, and a 150 mm ⁇ 150 mm ⁇ 0.7 mm resin sheet (A-1) was obtained by laser cutting.
- the obtained resin sheet (A-1) was attached to a fixing jig (see FIG. 2) so as to have a radius of curvature of 0.4 m in one direction within the surface, and was mounted in a vacuum oven at 1000 Pa, Heat curing was carried out by heating at 200 ° C. for 5 hours to obtain a resin sheet (B-1) having a curved shape.
- the average curvature radius of the obtained resin sheet having a curved shape was 0.4 m, and various properties were as shown in Tables 2 and 3.
- a transparent conductive film made of ITO having a thickness of 300 mm was formed at 180 ° C. by sputtering, and a substrate with a transparent conductive film was obtained. It was 100 ⁇ / ⁇ and good.
- Examples 2 to 7 A photocurable sheet, a resin sheet (A-1), and a resin having a curved shape in the same manner as in Example 1 except that the photocurable composition shown in Table 1 and the photocurable conditions and thermosetting conditions shown in Table 2 were used. A sheet (B-1) and a substrate with a transparent conductive film were obtained. Various characteristics were as shown in Tables 2 and 3.
- Example 1 A photocurable sheet and a resin sheet having a curved shape were obtained in the same manner as in Example 1 except that the photocurable composition of Table 1 and the photocuring conditions and thermosetting conditions of Table 2 were used. However, the obtained resin sheet having a curved shape was wavy and the radius of curvature was not constant. Various characteristics were as shown in Tables 2 and 3.
- a resin sheet having a curved shape with a desired radius of curvature can be easily obtained, and the optical characteristics and mechanical characteristics of the obtained resin sheet are good, but compared.
- a resin sheet having a desired curved shape could not be obtained and could not be put to practical use.
- UV light is irradiated from the upper surface side with a light irradiation amount of 5 J / cm 2 , and then UV light is irradiated from the lower surface side with a light irradiation amount of 20 J / cm 2 .
- a resin sheet having a curved shape (convex shape) only in the conveyance direction of 150 mm ⁇ 150 mm ⁇ 0.7 mm was obtained.
- the reaction rate of the obtained resin sheet was constant, and the radius of curvature in the conveyance direction was 0.8 m.
- Tables 5 and 6 Various characteristics were as shown in Tables 5 and 6.
- a transparent conductive film made of ITO having a thickness of 300 mm was formed at 180 ° C. on the concave surface of the obtained resin sheet by sputtering, and a substrate with a transparent conductive film was obtained.
- the surface resistance was 100 ⁇ / ⁇ . It was good.
- Examples 9 to 11> Except using the photocurable composition of Table 4, it carried out similarly to Example 8, and obtained the resin sheet and the board
- Example 12 In the light irradiation from the upper surface side and the lower surface side, the light irradiation amount at the central portion in the transport direction and the both ends in the transport direction was controlled as shown in Table 5 using a light shielding filter so that the light irradiation condition 2 was satisfied. Otherwise, a resin sheet was obtained in the same manner as in Example 8. The obtained resin sheet was bowl-shaped with curvature in any direction, the radius of curvature in the conveyance direction was 0.8 m, and the radius of curvature in the transverse direction to the conveyance direction was also 0.8 m. A substrate with a transparent conductive film was obtained in the same manner as in Example 8. Various characteristics were as shown in Tables 5 and 6.
- Example 4 a resin sheet having a desired curved shape cannot be obtained, and Comparative Example 5 is inferior in terms of optical characteristics and mechanical characteristics, and any of the comparative examples can be put to practical use. There wasn't.
- the resin sheet having a curved shape obtained by the present invention can be advantageously used for various optical materials and electronic materials.
- It can be used for memory / recording applications, energy applications such as thin film battery substrates and solar cell substrates, optical communication applications such as optical waveguides, functional films / sheets, and various optical films / sheets.
- it can also be used for a mask for a protective surface, protective glasses, a lighting material, an automobile material, a building material, a medical material, a stationery, and the like.
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Abstract
Description
これは、半硬化状態に光硬化した樹脂シートを、所望の曲率半径に湾曲させて熱硬化することにより、硬化を完了すると共に湾曲形状を有する樹脂シートを得るものである。硬化による架橋樹脂の形状が、硬化(重合)の最終段階で決まることを利用したものである。かかる手法により、湾曲した成形型を用意する必要も無く、また樹脂シートを切削加工する必要も無く、所望の湾曲形状を有する樹脂シートを製造することができるのである。
光照射条件1:成形型の上面側及び下面側のいずれか一方から光照射する工程(1)、及び、残りの他方から光照射する工程(2)を順に行い、かつ、工程(2)での光照射量(Xb)(J/cm2)が、工程(1)での光照射量(Xa)(J/cm2)より多いこと。
湾曲の程度は、硬化収縮の大きな組成物ほど大きく、曲率半径の小さな湾曲形状を有する樹脂シートが得られる。
なお、本発明において、搬送方向両端部の端部とは、光量の測定可能な端部から1cm内側の部分をいうものである。
なお、本発明において、「(メタ)アクリレート」は、アクリレートとメタクリレートの、「(メタ)アクリロイル」は、アクリロイルとメタクリロイルの総称である。また、ここでいう多官能とは、分子内に2個以上の(メタ)アクリロイル基を有することを意味する。
具体的には、例えば、光硬化性組成物(A)が、下記成分(A1)及び(A2)を含有してなるものであることが樹脂シートの耐熱性の点で好ましい。
(A1)多官能(メタ)アクリレート系化合物
(A2)光重合開始剤
硬化に際しては、光硬化性組成物(A)を光硬化した後、熱硬化することが好ましく、まずは、光硬化について説明する。
なお、本明細書中の硬化度とは、(メタ)アクリロイル基の反応率を意味する。
光照射は、片面もしくは両面から行うことができる。また複数回に分けて行うことも可能である。
上記(i)の製造方法においては、光硬化による(メタ)アクリロイル基の反応率を50~90%に制御することが好ましい。より好ましくは60~85%、特に好ましくは70~80%である。反応率が小さすぎると、後段の熱硬化においてうねりが生じやすく、大きすぎると後段の熱硬化において湾曲形状を形成しづらくなる傾向にある。なお、(メタ)アクリロイル基の反応率は、固体NMRやIRなどの分析手法で測定できる。
反応率を上記範囲に制御する手法としては、多官能(メタ)アクリレート系化合物(A1)、光重合開始剤(A2)の種類や量、照度や光量の制御、硬化温度を調整することが挙げられる。
前記(ii)の製造方法において、最大の特徴は、下記の光照射条件1を行うことである。
光照射条件1:成形型の上面側及び下面側のいずれか一方から光照射する工程(1)、及び、残りの他方から光照射する工程(2)を順に行い、かつ、工程(2)での光照射量(Xb)(J/cm2)が、工程(1)での光照射量(Xa)(J/cm2)より多いこと。
光照射条件2:光硬化性組成物(A)が注型された後、成形型を水平方向に搬送しながら光照射するにあたり、搬送方向中央部への光照射量(Xc)(J/cm2)が、搬送方向両端部への光照射量〔(Xd)(J/cm2)及び(Xe)(J/cm2)〕よりも多いこと。
なお、光硬化中の反応率の測定は、樹脂シートが半硬化状態(ゲル状態)であるため困難である。
熱処理は、大気圧下、不活性ガス下、真空下のいずれでもよく、温度は50℃以上、より好ましくは100℃以上、特に好ましくは150℃以上である。なお、上限としては、通常300℃である。
面内公差(%)=100×(曲率半径の最大値-曲率半径の最小値)/(曲率半径の平均値)
なお、例中「部」、「%」とあるのは、重量基準を意味する。
150mm×150mmの樹脂シートから50mm×50mmの試験片を切り出し、凍結粉砕した後、BRUKER・BIOSPIN社製「AVANCE DPX-400」で、固体NMRプローブを用いて、観測核は13C、回転数は5000Hz、室温(25℃)で測定した。重合していない(メタ)アクリロイル基中のカルボニル炭素は高磁場側(166ppm)に、重合したカルボニル炭素は低磁場側(176ppm)に検出される。これらのピーク面積比より反応率(%)を算出した。
150mm×150mmの樹脂シートから50mm×50mmの試験片を均等に9個切り出し、湾曲方向の曲率半径をノギスによる測定から求めた。9個の平均値を樹脂シートの曲率半径とし、9個の中の最大値と最小値から、下記式に従って面内公差(%)を算出した。
面内公差(%)=100×(曲率半径の最大値-曲率半径の最小値)/(曲率半径の平均値)
150mm×150mmの樹脂シートから50mm×50mmの試験片を切り出し、平坦となるよう金枠に取り付けた後、日本電色社製ヘイズメーター「NDH-2000」で、全光線透過率(%)を測定した。
150mm×150mmの樹脂シートから長さ25mm×幅10mmの試験片を切り出し、島津製作所社製オートグラフ「AG-5kNE」(支点間距離20mm、0.5mm/分)で、凸方向から押圧して曲げ弾性率を測定した。
150mm×150mmの樹脂シートから50mm×50mmの試験片を切り出し、JIS K-5600に準じて、鉛筆硬度を測定した。
150mm×150mmの樹脂シートから長さ20mm×幅5mmの試験片を切り出し、レオロジー社製動的粘弾性装置「DVE-V4型 FTレオスペクトラー」の引っ張りモードを用いて、周波数10Hz、昇温速度3℃/分、歪0.025%で測定を行った。
得られた複素弾性率の実数部(貯蔵弾性率)に対する虚数部(損失弾性率)の比(tanδ)を求め、このtanδの最大ピーク温度をガラス転移温度(℃)とした。
150mm×150mmの樹脂シートから長さ50mm×幅50mmの試験片を切り出し、大塚電子社製RETS100Aを用いて、25℃で波長550nmの位相差(nm)を測定した。
150mm×150mmの樹脂シートから50mm×50mmの試験片を切り出し、N-メチルピロリドンに40℃で10分間浸漬した後、目視により外観の状態を観察した。評価基準は下記のとおりである。
○・・・外観に異常はなかった。
×・・・外観に白濁などの異常が発生した。
三菱化学社製の4端子法抵抗測定器(ロレスターMP)を用いて測定した。
<実施例1>
170mm×170mm×8mmサイズの2枚の光学研磨ガラス板を対向させ、厚さ0.7mm、幅1mmのシリコン板をスペーサーとした成形型の空間に、ビス(ヒドロキシメチル)トリシクロ[5.2.1.02,6]デカン=ジアクリレート(新中村化学社製「A-DCP」)90部、脂環構造含有の6官能ウレタンアクリレート(日本合成化学工業社製)10部、1-ヒドロキシシクロヘキシルフェニルケトン(チバスペシャリティケミカルズ社製「Irgacure184」)1部よりなる光硬化性組成物(A)を23℃で注液した。かかる成形型を水平に設置し、コンベアで搬送しながら、メタルハライドランプを用いて、光量10J/cm2で紫外線を照射した。得られた光硬化シートを脱型し、レーザーカットにより150mm×150mm×0.7mmの樹脂シート(A-1)を得た。次いで、得られた樹脂シート(A-1)を面内の一方向において曲率半径0.4mになるように固定治具(図2参照)に湾曲させて装着し、真空オーブン中で、1000Pa、200℃、5時間加熱して熱硬化を行い、湾曲形状を有する樹脂シート(B-1)を得た。得られた湾曲形状を有する樹脂シートの曲率半径の平均は0.4mであり、諸特性は表2及び表3に示される通りであった。
得られた樹脂シート(B-1)の凹面に、スパッタ法にて180℃で厚さ300ÅのITOよりなる透明導電膜を成膜し、透明導電膜付き基板を得たところ、表面抵抗値は100Ω/□であり良好であった。
表1の光硬化性組成物、表2の光硬化条件及び熱硬化条件であること以外は、実施例1と同様にして、光硬化シート、樹脂シート(A-1)、湾曲形状を有する樹脂シート(B-1)、及び透明導電膜付き基板を得た。諸特性は表2及び表3に示される通りであった。
表1の光硬化性組成物、表2の光硬化条件及び熱硬化条件であること以外は、実施例1と同様にして、光硬化シート、及び、湾曲形状を有する樹脂シートを得た。しかし、得られた湾曲形状を有する樹脂シートはうねっており曲率半径が一定では無かった。諸特性は表2及び表3に示される通りであった。
表1に示されるとおり、市販の厚さ0.7mmのポリカーボネート製シートを150mm×150mmに裁断し、実施例1と同様にして真空オーブン中で1000Pa、200℃で5時間熱処理を行ったが、変形が著しく所望の湾曲形状を有する樹脂シートは得られなかった。なお、元板の耐溶剤性試験を行ったところ、白濁した。諸特性は表2及び表3に示される通りであった。
表1の光硬化性組成物を用いて、表2の光硬化条件で得られた光硬化シートを、曲率半径0.4mになるよう固定治具(図1参照)に装着し、加熱せず室温で5時間放置した以外は実施例1と同様に行った。しかし、湾曲形状を有する樹脂シートは得られなかった。かかる平坦な樹脂シートの諸特性は表2及び表3に示される通りであった。
得られた樹脂シートの片面に、スパッタ法にて180℃で厚さ300ÅのITOよりなる透明導電膜を成膜し、透明導電膜付き基板を得たところ、表面抵抗値は100Ω/□であった。
<実施例8>
170×170×8mmサイズの2枚の光学研磨ガラス板を対向させ、厚さ0.7mm、幅1mmのシリコン板をスペーサーとした成形型の空間に、ビス(ヒドロキシメチル)トリシクロ[5.2.1.02,6]デカン=ジアクリレート(新中村化学社製「A-DCP」)100部、1-ヒドロキシシクロヘキシルフェニルケトン(チバスペシャリティケミカルズ社製「Irgacure184」)2部よりなる光硬化性組成物(A)を23℃で注液した。かかる成形型を水平に設置し、コンベアで搬送しながら、メタルハライドランプを用いて、上面側から光照射量5J/cm2で紫外線を照射した後、下面側から光照射量20J/cm2で紫外線を照射し、硬化させた。脱型して、150mm×150mm×0.7mmの搬送方向のみに湾曲形状(凸状)を有する樹脂シートを得た。得られた樹脂シートの反応率は一定であり、搬送方向の曲率半径は0.8mであった。また、諸特性は表5及び表6に示される通りであった。
表4の光硬化性組成物を用いる以外は実施例8と同様にして、樹脂シート、及び透明導電膜付き基板を得た。諸特性は表5及び6に示される通りであった。
上面側及び下面側からの光照射において、光照射条件2となるように、遮光フィルターを用いて、表5に示される通り搬送方向中央部と搬送方向両端部の光照射量を制御した。その他は、実施例8と同様にして、樹脂シートを得た。得られた樹脂シートは、いずれの方向にも曲率を有したお椀型であり、搬送方向の曲率半径は0.8m、搬送方向に対して横方向の曲率半径も0.8mであった。実施例8と同様にして透明導電膜付き基板を得た。諸特性は表5及び表6に示される通りであった。
表5に示される通り、上面側及び下面側から均等に光照射を行った以外は実施例8と同様に行った。得られた樹脂シートは平坦であった。諸特性は表5及び6に示される通りであった。
市販の厚さ0.7mmのポリカーボネート製シートを150mm×150mmに裁断し、200℃で加熱しながら一方向に湾曲させて、曲率半径0.6mの湾曲シートを得た。得られた湾曲シートに実施例8と同様にしてITO膜を成膜したが、ITO膜にクラックが入ったため抵抗値は測定不能となり、目的とする透明導電膜付き基板は得られなかった。なお、元板の耐溶剤性試験を行ったところ、白濁した。諸特性は表5及び6に示される通りであった。
Claims (15)
- 光硬化性組成物(A)を硬化して得られる厚さ0.1~10mmの透明な樹脂シートであって、面内の少なくとも一方向に曲率半径が0.1~5mの範囲で湾曲していることを特徴とする樹脂シート。
- 光硬化性組成物(A)を光硬化した後、面内の少なくとも一方向に曲率半径が0.1~5mの範囲となるように固定治具にて固定しながら熱硬化してなることを特徴とする請求項1記載の樹脂シート。
- 曲率半径の面内公差が10%以内であることを特徴とする請求項1または2記載の樹脂シート。
- 光硬化性組成物(A)が(メタ)アクリロイル基を含有する組成物であり、光硬化後の(メタ)アクリロイル基の反応率が50~90%であり、熱硬化後の(メタ)アクリロイル基の反応率が光硬化後の反応率より1~40%高いことを特徴とする請求項1~3いずれか一項に記載の樹脂シート。
- 光硬化性組成物(A)を、対向する2枚の透明な平板からなる成形型に注型した後、光照射を行って得られる厚さ0.1~10mmの透明な樹脂シートであって、下記の光照射条件1により、面内の少なくとも一方向に、曲率半径0.1~5mの範囲で湾曲していることを特徴とする請求項1記載の樹脂シート。
光照射条件1:成形型の上面側及び下面側のいずれか一方から光照射する工程(1)、及び、残りの他方から光照射する工程(2)を順に行い、かつ、工程(2)での光照射量(Xb)(J/cm2)が、工程(1)での光照射量(Xa)(J/cm2)より多いこと。 - 更に、下記の光照射条件2により、面内のいずれの方向にも、曲率半径0.1~5mの範囲で湾曲していることを特徴とする請求項5記載の樹脂シート。
光照射条件2:光硬化性組成物(A)が注型された後、成形型を水平方向に搬送しながら光照射するにあたり、搬送方向中央部への光照射量(Xc)(J/cm2)が、搬送方向両端部への光照射量((Xd)(J/cm2)及び(Xe)(J/cm2))よりも多いこと。 - 光硬化性組成物(A)の硬化収縮率が6%以上であることを特徴とする請求項5または6記載の樹脂シート。
- 光硬化性組成物(A)が、下記成分(A1)及び(A2)を含有してなることを特徴とする請求項1~7いずれか一項に記載の樹脂シート。
(A1)多官能(メタ)アクリレート系化合物
(A2)光重合開始剤 - ガラス転移温度が150℃以上であることを特徴とする請求項1~8いずれか一項に記載の樹脂シート。
- 曲げ弾性率が3~5GPaであることを特徴とする請求項1~9いずれか一項に記載の樹脂シート。
- 鉛筆硬度が3H以上であることを特徴とする請求項1~10いずれか一項に記載の樹脂シート。
- ディスプレイ用の保護板に用いられることを特徴とする請求項1~11いずれか一項に記載の樹脂シート。
- ディスプレイのスクリーンに用いられることを特徴とする請求項1~11いずれか一項に記載の樹脂シート。
- 保護面用の面体に用いられることを特徴とする請求項1~11いずれか一項に記載の樹脂シート。
- 請求項1~11いずれか一項に記載の樹脂シートの少なくとも一面に、透明導電膜が成膜されてなることを特徴とするタッチパネル基板。
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CN201480039001.5A CN105392827A (zh) | 2013-10-15 | 2014-10-14 | 树脂片及其用途 |
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JP7038477B2 (ja) * | 2017-02-27 | 2022-03-18 | デクセリアルズ株式会社 | 画像表示装置及びその製造方法 |
CN110027147B (zh) * | 2018-01-08 | 2021-10-29 | 阳程科技股份有限公司 | 异形光学胶脂的成型方法 |
KR102336513B1 (ko) * | 2020-12-30 | 2021-12-07 | 에스케이씨하이테크앤마케팅(주) | 향상된 곡면 보호 기능을 갖는 보호 필름 |
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JPH10268790A (ja) * | 1997-03-24 | 1998-10-09 | Seiko Epson Corp | 液晶表示パネル用ホルダ、それを用いた液晶表示装置、その液晶表示装置を用いた電子機器及び曲面液晶表示パネル製造冶具並びにそれを用いた曲面液晶表示パネル製造方法 |
JP2006193596A (ja) * | 2005-01-13 | 2006-07-27 | Nippon Synthetic Chem Ind Co Ltd:The | 樹脂成形体、その製造方法、及びその用途 |
JP2008221720A (ja) * | 2007-03-14 | 2008-09-25 | Ito Kogaku Kogyo Kk | 眼鏡レンズ用硝子製モールドとその製造方法及び眼鏡レンズの製造方法 |
JP2013068770A (ja) * | 2011-09-22 | 2013-04-18 | Dainippon Printing Co Ltd | 背面透過型ディスプレイ用曲面スクリーンの製造方法 |
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WO2009008111A1 (ja) * | 2007-07-10 | 2009-01-15 | Sharp Kabushiki Kaisha | 表示パネルの製造装置及び製造方法 |
CN102026795B (zh) * | 2008-05-13 | 2013-08-07 | 三菱瓦斯化学株式会社 | 可弯曲加工的聚碳酸酯树脂层压体和透光型电磁波屏蔽层压体以及它们的制造方法 |
JP5712912B2 (ja) | 2011-12-14 | 2015-05-07 | コニカミノルタ株式会社 | ディスプレイ用カバーガラス |
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JPH10268790A (ja) * | 1997-03-24 | 1998-10-09 | Seiko Epson Corp | 液晶表示パネル用ホルダ、それを用いた液晶表示装置、その液晶表示装置を用いた電子機器及び曲面液晶表示パネル製造冶具並びにそれを用いた曲面液晶表示パネル製造方法 |
JP2006193596A (ja) * | 2005-01-13 | 2006-07-27 | Nippon Synthetic Chem Ind Co Ltd:The | 樹脂成形体、その製造方法、及びその用途 |
JP2008221720A (ja) * | 2007-03-14 | 2008-09-25 | Ito Kogaku Kogyo Kk | 眼鏡レンズ用硝子製モールドとその製造方法及び眼鏡レンズの製造方法 |
JP2013068770A (ja) * | 2011-09-22 | 2013-04-18 | Dainippon Printing Co Ltd | 背面透過型ディスプレイ用曲面スクリーンの製造方法 |
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