WO2018168960A1 - 延伸フィルムおよび延伸フィルムの製造方法 - Google Patents
延伸フィルムおよび延伸フィルムの製造方法 Download PDFInfo
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- WO2018168960A1 WO2018168960A1 PCT/JP2018/010067 JP2018010067W WO2018168960A1 WO 2018168960 A1 WO2018168960 A1 WO 2018168960A1 JP 2018010067 W JP2018010067 W JP 2018010067W WO 2018168960 A1 WO2018168960 A1 WO 2018168960A1
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- Prior art keywords
- stretched film
- acrylic resin
- weight
- glass transition
- film
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 43
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 113
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- 230000009477 glass transition Effects 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims description 57
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 26
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- KNCYXPMJDCCGSJ-UHFFFAOYSA-N piperidine-2,6-dione Chemical group O=C1CCCC(=O)N1 KNCYXPMJDCCGSJ-UHFFFAOYSA-N 0.000 claims description 23
- 239000011258 core-shell material Substances 0.000 claims description 21
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- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 9
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
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- 239000003795 chemical substances by application Substances 0.000 description 34
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 27
- 239000011347 resin Substances 0.000 description 26
- 229920005989 resin Polymers 0.000 description 26
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 21
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- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 17
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- 230000000052 comparative effect Effects 0.000 description 10
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
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- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229920006397 acrylic thermoplastic Polymers 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
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- 238000003851 corona treatment Methods 0.000 description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
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- 125000003700 epoxy group Chemical group 0.000 description 4
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- 108700004121 sarkosyl Proteins 0.000 description 4
- KSAVQLQVUXSOCR-UHFFFAOYSA-M sodium lauroyl sarcosinate Chemical compound [Na+].CCCCCCCCCCCC(=O)N(C)CC([O-])=O KSAVQLQVUXSOCR-UHFFFAOYSA-M 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229920006037 cross link polymer Polymers 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
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- 230000001771 impaired effect Effects 0.000 description 3
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- 239000000113 methacrylic resin Substances 0.000 description 3
- RFUCOAQWQVDBEU-UHFFFAOYSA-N methyl 2-(hydroxymethyl)prop-2-enoate Chemical compound COC(=O)C(=C)CO RFUCOAQWQVDBEU-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
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- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
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- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 3
- HDPNBNXLBDFELL-UHFFFAOYSA-N 1,1,1-trimethoxyethane Chemical compound COC(C)(OC)OC HDPNBNXLBDFELL-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- FCYVWWWTHPPJII-UHFFFAOYSA-N 2-methylidenepropanedinitrile Chemical compound N#CC(=C)C#N FCYVWWWTHPPJII-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
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- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
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- SYGAXBISYRORDR-UHFFFAOYSA-N ethyl 2-(hydroxymethyl)prop-2-enoate Chemical compound CCOC(=O)C(=C)CO SYGAXBISYRORDR-UHFFFAOYSA-N 0.000 description 2
- MHCLJIVVJQQNKQ-UHFFFAOYSA-N ethyl carbamate;2-methylprop-2-enoic acid Chemical compound CCOC(N)=O.CC(=C)C(O)=O MHCLJIVVJQQNKQ-UHFFFAOYSA-N 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
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- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 2
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- MIYFFZILCMZNRY-UHFFFAOYSA-N 1-hydroxypentyl prop-2-enoate Chemical compound CCCCC(O)OC(=O)C=C MIYFFZILCMZNRY-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- HEWZVZIVELJPQZ-UHFFFAOYSA-N 2,2-dimethoxypropane Chemical compound COC(C)(C)OC HEWZVZIVELJPQZ-UHFFFAOYSA-N 0.000 description 1
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
- QNYBOILAKBSWFG-UHFFFAOYSA-N 2-(phenylmethoxymethyl)oxirane Chemical compound C1OC1COCC1=CC=CC=C1 QNYBOILAKBSWFG-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
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- 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
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
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- 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
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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- 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
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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
- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
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- 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
- B29K2021/00—Use of unspecified rubbers as moulding material
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- 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
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- 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
- B29K2035/00—Use of polymers of unsaturated polycarboxylic acids or derivatives thereof as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
- B29L2007/002—Panels; Plates; Sheets
-
- 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
- C08J2333/00—Characterised by the use 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; Derivatives of such polymers
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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
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
Definitions
- the present invention relates to a stretched film that can be used for an optical film or the like and a method for producing the stretched film.
- a large number of optical films are used for liquid crystal display devices.
- a liquid crystal display device usually two polarizing plates are arranged on both sides of a liquid crystal cell.
- a polarizing plate in which a polarizer protective film for protecting the polarizer is bonded to both sides of the polarizer with an adhesive is generally used.
- an optical film having high transparency is used.
- An optical film made of a cellulosic material is frequently used.
- an optical film made of an acrylic resin for example, Patent Documents 1 and 2).
- these acrylic resin-based films may lack mechanical properties, particularly flexibility, depending on the application.
- a stretched film may be used.
- use of acrylic rubber particles in the acrylic stretched film has been studied in order to further improve mechanical properties (Patent Document 3).
- JP 2009-205135 A Japanese Patent Laying-Open No. 2015-143842 JP 2009-84574 A
- the present invention has been made to solve the above problems.
- the object of the present invention is suitable for use as an optical film having excellent mechanical properties, particularly flexibility (MIT flex resistance), adhesive strength, and low dimensional change rate under high temperature and high humidity environment. It is providing the manufacturing method of the stretched film which is these, and a stretched film.
- the present invention ⁇ 1> (A) A method for producing a stretched film containing 1% to 50% by weight of an acrylic resin having a glass transition temperature of 120 ° C. or higher and (B) an acrylic rubber particle, wherein the stretching temperature in the stretching step is Tg + 20 ° C. It is related with the manufacturing method of a stretched film characterized by being -Tg + 55 degreeC.
- the stretched film has a shrinkage rate of 1.5% or less when left in an atmosphere of 85 ° C. and 85% RH for 120 hours, and has a MIT reciprocal folding number of 350 or more. It relates to the manufacturing method.
- the present invention relates to the production method according to ⁇ 1> or ⁇ 2>.
- ring structure is at least one selected from the group consisting of a glutarimide ring, a lactone ring, maleic anhydride, maleimide and glutaric anhydride.
- R 1 and R 2 each independently represents hydrogen or an alkyl group having 1 to 8 carbon atoms
- R 3 represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or a carbon atom
- the stretched film has a shrinkage ratio of 0.1% or more and 1.5% or less when left in an atmosphere of 85 ° C. and 85% RH for 120 hours. It relates to the manufacturing method described.
- the present invention relates to the production method according to any one of ⁇ 1> to ⁇ 9>, wherein an easy adhesion layer is provided on one side or both sides of the stretched film.
- the present invention relates to a stretched film having a shrinkage ratio of 1.5% or less when left standing and having a MIT reciprocal folding number of 350 or more.
- the stretched film is attached to a polycarbonate film with an adhesive and has a 90 ° peel strength value of 1.0 N / cm or more in an atmosphere of 23 ° C. and 50% RH. It relates to the described stretched film.
- ring structure is at least one selected from the group consisting of a glutarimide ring, a lactone ring, maleic anhydride, maleimide and glutaric anhydride.
- R 1 and R 2 each independently represents hydrogen or an alkyl group having 1 to 8 carbon atoms
- R 3 represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or a carbon atom
- the stretched film has any one of ⁇ 11> to ⁇ 17>, which has a shrinkage ratio of 0.1% to 1.5% when left in an atmosphere of 85 ° C. and 85% RH for 120 hours. It relates to the described stretched film.
- an optical film having excellent mechanical properties, excellent adhesive strength, and a small dimensional change rate under high temperature and high humidity particularly a stretched film and a stretched film that can be used as a polarizer protective film.
- a manufacturing method can be provided.
- the present invention relates to (A) an acrylic resin having a glass transition temperature of 120 ° C. or higher and (B) a stretched film containing 1% by weight to 50% by weight of acrylic rubber particles, at 85 ° C. and 85% RH atmosphere
- the stretched film has a shrinkage ratio of 1.5% or less when left to stand for 120 hours and a MIT reciprocal folding number of 350 or more.
- the stretched film of the present invention comprises (A) an acrylic resin having a glass transition temperature of 120 ° C. or higher (hereinafter also referred to as (A) an acrylic resin) and (B) acrylic rubber particles in an amount of 1% by weight to 50%.
- a stretched film comprising% by weight.
- (A) an acrylic resin having a glass transition temperature of 120 ° C. or higher and (B) an acrylic resin containing 1 wt% to 50 wt% of acrylic rubber particles are defined as an acrylic resin composition.
- the stretched film of the present invention has an improved shrinkage ratio when left in an atmosphere of 85 ° C. and 85% RH for 120 hours, has excellent MIT flex resistance, and is stretched when used as a polarizer protective film.
- 90 degree peel strength was tested by applying an easy-adhesive to one side of the film and then sticking it to a polycarbonate film using an instantaneous adhesive and peeling the polycarbonate film from the stretched film in an atmosphere of 23 ° C. and 50% RH. It has been improved.
- both the longitudinal direction (MD direction) and the width direction (TD direction) of the stretched film are 1.5% or less, preferably 1 .3% or less. When it is 1.5% or less, it is possible to suppress a decrease in contrast and unevenness of the periphery of the liquid crystal display device when bonded to a polarizer.
- the lower limit of the shrinkage rate is not particularly limited, and the shrinkage rate may be, for example, 0.1% or more in both the longitudinal direction (MD direction) and the width direction (TD direction) of the stretched film. .
- the shrinkage ratio is 0.1% or more, even when the polarizer itself shrinks when bonded to the polarizer, the stretched film easily follows the shrinkage.
- the shrinkage rate when left to stand in an atmosphere of 85 ° C. and 85% RH for 120 hours is the dimensional change before and after the stretched film was left to stand for 120 hours in an environmental test machine set to 85 ° C. and 85% RH. It can be measured using a three-dimensional measuring instrument.
- both the longitudinal direction (MD direction) and the width direction (TD direction) of the stretched film are 1.0 N / cm or more, preferably 1.2 N / cm or more.
- a peel strength of 1.0 N / cm or more is good in terms of reworkability and durability after bonding to a polarizer.
- the peel strength can be determined by measuring using an autograph and averaging data obtained between 10 mm and 60 mm.
- instant adhesive a commercially available instant adhesive can be used.
- instant adhesives include Toagosei Co., Ltd. product name “Aron Alpha Series” (Aron Alpha (registered trademark) No. 1 for professional use, Aron Alpha (registered trademark) Immediate multipurpose Extra, Aron Alpha (registered trademark) for plastics, etc. ) And the like.
- polycarbonate film a commercially available polycarbonate film can be used as it is.
- specific examples of commercially available polycarbonate films include “Pure Ace Series (registered trademark)” manufactured by Teijin Chemicals Ltd., and “Elmec Series (registered trademark)” manufactured by Kaneka Corporation (R140, R435). Etc.).
- (B) acrylic thermoplastic elastomers are being studied together with acrylic rubber particles.
- the acrylic thermoplastic elastomer in the film-forming film often has a dispersed shape extending long from a disk shape to a rod shape, (A) The interface between the acrylic resin having a glass transition temperature of 120 ° C. or higher increases and (A) the interface failure between the acrylic resin having a glass transition temperature of 120 ° C. or higher and the acrylic thermoplastic elastomer is likely to occur.
- the peel strength may be reduced, or cracks may be generated or the edge portion may be broken off when cutting after bonding to a polarizer.
- the acrylic rubber particles (B) of the present invention are used, the dispersion shape is close to a sphere compared to the case of using a thermoplastic elastomer, and (A) an acrylic resin having a glass transition temperature of 120 ° C. or higher. It is possible to suppress the interfacial area to be smaller and solve the above problem. In particular, when the stretching temperature is set high, the orientation is suppressed, and the dispersed shape of the (B) acrylic rubber particles can be made closer to a sphere, which is preferable.
- the stretched film of the present invention can be provided with an easy adhesion layer on one side or both sides of the film.
- an easy-adhesion layer for example, when used as a polarizer protective film, the adhesive between the polarizer protective film and the polarizer can be reinforced when bonded to the polarizer via an adhesive. it can.
- it is also possible to obtain the stretched film which has an easily bonding layer by providing an easily bonding layer in an unstretched film, and extending
- the easy-adhesion layer used in the present invention can be formed using a known technique described in JP-A-2009-193061, JP-A-2010-55062, or the like. That is, for example, it can be formed of an easy-adhesive composition containing a urethane resin having a carboxyl group and a crosslinking agent. By using the urethane resin, an easy-adhesion layer having excellent adhesion between the polarizer protective film and the polarizer can be obtained.
- the easy-adhesive composition is preferably an aqueous system from the viewpoint of workability and the viewpoint of environmental protection.
- the inner height of the stretched film of the present invention is preferably 1.0% or less. More preferably, it is 0.5% or less, More preferably, 0.3% or less is good. When the internal haze is lower than 1.0%, the quality when mounted on the liquid crystal panel is improved.
- the number of MIT reciprocating folds (hereinafter also referred to as the number of folds) until cutting in the MIT bending resistance test is improved.
- the number of times of bending is 350 times or more in both the longitudinal direction (MD direction) and the width direction (TD direction) of the stretched film, preferably 500 times or more. When it is 350 times or more, it is good in terms of risk of breakage due to the long film-forming process and reworkability after bonding to the liquid crystal panel.
- Uniaxial stretching or biaxial stretching in the stretched film according to the present invention can be carried out arbitrarily. However, biaxial stretching can increase the number of MIT reciprocal bendings until cutting in the MIT bending resistance test.
- the number of MIT reciprocal bendings can be 350 or more in the MIT bending resistance test depending on the processing method such as stretching conditions.
- the stretching conditions at that time are the direction of lowering the stretching temperature or the direction of increasing the stretching ratio, the risk of breakage in the stretching process increases.
- the effect of (B) acrylic rubber particles can realize a folding number of 350 or more in the MIT bending resistance test, and the risk of breakage during stretching is low.
- the dimensional change is small, it is possible to suppress a decrease in peel strength when bonded to a polarizer, and a polarizer protective film made of an acrylic resin composition having good transparency can be obtained.
- a strip-shaped test piece having a width of 15 mm is used using an MIT soft fatigue tester, the bending radius R of the bending clamp is 0.38 mm, the left and right bending angles are 135 degrees, and the bending speed. It is defined as the number of reciprocating bendings until cutting measured under the conditions of 175 times / min and load 1.96N.
- the glass transition temperature of the stretched film of the present invention is 110 ° C. or higher, preferably 115 ° C. or higher, more preferably 120 ° C. or higher.
- the glass transition temperature here is determined by a midpoint method using 10 mg of acrylic resin and 10 mg of acrylic resin composition, using a differential scanning calorimeter, in a nitrogen atmosphere at a heating rate of 20 ° C./min. It is a thing.
- the average refractive index of the acrylic resin (A) having a glass transition temperature of 120 ° C. or higher of the present invention is preferably 1.48 or higher.
- the refractive index difference between (A) an acrylic resin having a glass transition temperature of 120 ° C. or higher and (B) acrylic rubber particles is also preferably 0.02 or less, and more preferably 0.01 or less. .
- the refractive index difference between the acrylic resin and the (B) acrylic rubber particles is small. As the value gets smaller, the noise tends to decrease inside the stretched film.
- the average refractive index of the stretched film here can be measured using, for example, an Abbe refractometer.
- the internal haze here is the haze value measured using a haze meter (turbidimeter) for a glass cell in which the film obtained in a glass cell for liquid measurement is put and filled with pure water around it. Define.
- (A) an acrylic resin having a glass transition temperature of 120 ° C. or higher is used.
- the glass transition temperature of the acrylic resin is 120 ° C. or higher
- the glass transition temperature of the stretched film made of the acrylic resin composition mixed with the (B) acrylic rubber particles becomes high, for example, stretching in a high temperature environment
- the rate of dimensional change of the film is reduced.
- the stretched film of the present invention is often used by being laminated with another film. When the rate of dimensional change is small, distortion and warpage caused by the difference in dimensional change rate generated between the laminated film and other films. Occurrence can be suppressed.
- the acrylic resin (A) having a glass transition temperature of 120 ° C. or higher an acrylic resin having a ring structure in the main chain can be suitably used.
- the ring structure can include at least one ring structure selected from the group consisting of a glutarimide ring, a lactone ring, maleic anhydride, maleimide and glutaric anhydride. According to these, heat resistance can be imparted.
- the ring structure is glutarimide from the viewpoint of production simplicity, cost, and quality stability against moisture.
- an acrylic resin having a glass transition temperature of 120 ° C. or higher a method of introducing a carboxyl group such as methacrylic acid can be mentioned, but if the carboxyl group exceeds a certain amount, there is a risk of forming a crosslinked product. In order to increase the risk of foaming when forming a film, it is preferable to keep it below a certain amount.
- the amount of the carboxyl group in the acrylic resin is 0.6 mmol / g or less, preferably 0.4 mmol / g or less.
- the content of the ring structure in the acrylic resin having a glass transition temperature of 120 ° C. or higher is preferably in the range of 2% by weight to 80% by weight. A ring structure content within this range is preferred because both the glass transition temperature and the thickness direction retardation Rth are good.
- the content of the ring structure in the acrylic resin was calculated by measuring the molar ratio between the target ring structure portion and the other portion using 1 H-NMR, and performing weight conversion.
- the acrylic resin having a glutarimide ring as a ring structure is a resin containing a glutarimide unit represented by the following general formula (1) and a methyl methacrylate unit, and the acrylic acid ester unit is less than 1% by weight. It is obtained by heating and melting an acrylic resin and treating with an imidizing agent.
- R 1 and R 2 each independently represents hydrogen or an alkyl group having 1 to 8 carbon atoms
- R 3 represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or a carbon atom
- the content of the glutarimide ring according to the present invention is a value that can be measured, for example, by the following method. Performed using 1 H-NMR. Obtained from the peak area derived from the O—CH 3 proton of methyl methacrylate in the vicinity of 3.5 ppm to 3.8 ppm and the peak area derived from the N—R 3 proton of the glutarimide group in the vicinity of 3.0 ppm to 3.3 ppm. Weight conversion is performed using the obtained molar ratio.
- methyl methacrylate for example, methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) acrylic acid t- Butyl, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like may be used in combination, but when these are used in combination, the acrylate unit is preferably less than 1% by weight. Further, the acrylate unit is more preferably less than 0.5% by weight, and further preferably less than 0.3% by weight.
- nitrile monomers such as acrylonitrile and methacrylonitrile
- maleimide monomers such as maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide
- aromatic vinyl monomer such as styrene
- the structure of the methyl methacrylate resin is not particularly limited, and may be any of linear (chain) polymer, block polymer, core-shell polymer, branched polymer, ladder polymer, and crosslinked polymer.
- a block polymer it may be any of AB type, ABC type, ABA type, and other types of block polymers.
- the core-shell polymer it may be composed of only one core and only one shell, or each may be composed of multiple layers.
- the production method of polymethyl methacrylate is not particularly limited, and a known emulsion polymerization method, emulsion-suspension polymerization method, suspension polymerization method, bulk polymerization method, solution polymerization method and the like can be applied.
- the bulk polymerization method and the solution polymerization method are particularly preferable from the viewpoint of few impurities.
- it can be produced according to the method described in JP-A-56-8404, JP-B-6-86492, JP-B-7-37482, or JP-B-52-32665.
- the present invention includes a step (imidation step) in which a methyl methacrylate resin or an acrylic resin copolymerized with a monomer other than the methyl methacrylate monomer is heated and melted and treated with an imidizing agent. Thereby, an acrylic resin having glutarimide can be produced.
- the imidizing agent is not particularly limited as long as it can generate a glutarimide ring represented by the general formula (1), and examples thereof include those described in WO2005 / 054311.
- aliphatic hydrocarbon group-containing amines such as ammonia, methylamine, n-propylamine, i-propylamine, n-butylamine, i-butylamine, tert-butylamine, n-hexylamine, aniline
- aromatic hydrocarbon group-containing amines such as benzylamine, toluidine, and trichloroaniline
- alicyclic hydrocarbon-containing amines such as cyclohexylamine.
- urea-based compounds that generate the exemplified amine by heating such as urea, 1,3-dimethylurea, 1,3-diethylurea, and 1,3-dipropylurea, can also be used.
- imidizing agents methylamine, ammonia, and cyclohexylamine are preferably used from the viewpoints of cost and physical properties, and methylamine is particularly preferably used.
- the gaseous methylamine etc. at normal temperature may be used in a state dissolved in alcohols such as methanol.
- the ratio of glutarimide units and (meth) acrylic acid ester units in the obtained acrylic resin can be adjusted.
- the degree of imidization by adjusting the degree of imidization, the physical properties of the obtained acrylic resin, the optical characteristics of the stretched film formed by molding the acrylic resin according to the present invention, and the like can be adjusted.
- the imidizing agent is preferably 0.5 to 20 parts by weight with respect to 100 parts by weight of the acrylic resin containing methyl methacrylate units.
- the amount of the imidizing agent is within this range, the imidizing agent hardly remains in the resin, and the possibility of inducing appearance defects and foaming after molding is extremely low.
- the content of the glutarimide ring in the finally obtained resin composition is also appropriate, its heat resistance is unlikely to decrease and it is difficult to induce appearance defects after molding, which is preferable.
- a ring closure accelerator (catalyst) may be added as necessary in addition to the imidizing agent.
- the method of heating and melting and treating with an imidizing agent is not particularly limited, and any conventionally known method can be used.
- the acrylic resin containing the methyl methacrylate unit can be imidized by a method using an extruder, a batch type reaction vessel (pressure vessel), or the like.
- Extruder is not particularly limited.
- a single screw extruder, a twin screw extruder, or a multi-screw extruder can be used.
- An extruder may be used independently and may be used by connecting two or more in series.
- twin-screw extruder examples thereof include a non-meshing type same direction rotating type, a meshing type same direction rotating type, a non-meshing type different direction rotating type, a meshing type different direction rotating type, and the like.
- the meshing type co-rotating twin screw extruder can rotate at high speed, mixing of an imidizing agent (in the case of using a ring closure accelerator, an imidizing agent and a ring closure accelerator) with respect to the raw material polymer, This can be further promoted and is preferable.
- a methyl methacrylate resin is charged from the raw material charging portion of the extruder, the resin is melted, the inside of the cylinder is filled, and an imidizing agent is then added using an addition pump. By injecting into the extruder, the imidization reaction can proceed in the extruder.
- the processing temperature (resin temperature), time (reaction time), and resin pressure in the extruder are not particularly limited as long as glutarimidization is possible.
- a vent hole that can be depressurized below atmospheric pressure in order to remove unreacted imidizing agent and by-products. According to such a configuration, unreacted imidizing agent or by-products such as methanol and monomers can be removed.
- the structure of the batch reaction vessel is not particularly limited.
- An acrylic resin containing methyl methacrylate units can be melted and heated by heating, and has a structure to which an imidizing agent (an imidizing agent and a ring closing accelerator when a ring closing accelerator is used) can be added.
- an imidizing agent an imidizing agent and a ring closing accelerator when a ring closing accelerator is used
- imidization method examples include known methods such as those described in JP-A-2008-273140 and JP-A-2008-274187.
- the production method of the present invention can include a step of treating with an esterifying agent in addition to the imidization step.
- an esterifying agent in addition to the imidization step.
- the esterifying agent is not particularly limited as long as the carboxyl group remaining in the molecular chain can be esterified.
- the esterifying agent is preferably 0 to 30 parts by weight, more preferably 0 to 15 parts by weight, based on 100 parts by weight of the acrylic resin containing methyl methacrylate units. preferable. If the esterifying agent is within these ranges, the acid value can be adjusted to an appropriate range. On the other hand, when the amount is larger than this range, an unreacted esterifying agent may remain in the resin, which may cause foaming and odor generation when molding is performed using the obtained resin.
- a catalyst can be used in combination.
- the catalyst is not particularly limited as long as it can promote esterification. Examples thereof include aliphatic tertiary amines such as trimethylamine, triethylamine, and tributylamine. Among these, triethylamine is preferable from the viewpoint of cost and reactivity.
- esterification step only heat treatment or the like can be performed without treatment with an esterifying agent.
- heat treatment such as kneading or dispersion of the molten resin in the extruder
- dehydration reaction between carboxyl groups in the acrylic resin having a glutarimide ring by-produced in the imidization step carboxylic acid and alkyl
- a part or all of the carboxyl group can be converted into an acid anhydride group by a dealcoholization reaction of an ester group or the like.
- a ring closure accelerator catalyst
- the imide resin that has undergone the imidization step and the esterification step contains an unreacted imidizing agent, an unreacted esterifying agent, a volatile component by-produced by the reaction, and a resin decomposition product. It is possible to attach a vent hole that can be depressurized below.
- the acrylic resin having a lactone ring as a ring structure is not limited as long as it is a thermoplastic polymer having a lactone ring structure in the molecule (a thermoplastic polymer having a lactone ring structure introduced in the molecular chain).
- the production method is not limited, but preferably, the polymer (a) having a hydroxyl group and an ester group in the molecular chain is obtained by polymerization (polymerization step), and then the obtained polymer (a) is obtained. It is obtained by introducing a lactone ring structure into the polymer by heat treatment (lactone cyclization condensation step).
- a polymer having a hydroxyl group and an ester group in the molecular chain is obtained by performing a polymerization reaction of a monomer component containing an unsaturated monomer represented by the following general formula (2).
- R 4 and R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
- Examples of the unsaturated monomer represented by the general formula (2) include methyl 2- (hydroxymethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate, isopropyl 2- (hydroxymethyl) acrylate, 2 Examples include normal butyl-(hydroxymethyl) acrylate and tertiary butyl 2- (hydroxymethyl) acrylate. Of these, methyl 2- (hydroxymethyl) acrylate and ethyl 2- (hydroxymethyl) acrylate are preferred, and methyl 2- (hydroxymethyl) acrylate is particularly preferred from the viewpoint of high heat resistance improvement effect. These unsaturated monomers may be used alone or in combination of two or more.
- the content of the unsaturated monomer represented by the general formula (2) in the monomer component is preferably 5% by weight to 50% by weight, more preferably 10% by weight to 40% by weight, and still more preferably 10%. % By weight to 30% by weight.
- the content is less than 5% by weight, the heat resistance, solvent resistance and surface hardness of the resulting lactone ring-containing polymer may be lowered.
- the content is more than 50% by weight, a lactone ring structure is formed. In some cases, a cross-linking reaction occurs and the gelation easily occurs, and the fluidity is lowered and it is difficult to melt-mold. In addition, the unreacted hydroxyl group is likely to remain. There is a possibility that a silvery streak is likely to occur due to the generation of a chemical substance, or the thickness direction retardation Rth increases.
- the monomer component preferably contains another monomer other than the unsaturated monomer represented by the general formula (2).
- the other monomer is not limited as long as the effect of the present invention is not impaired.
- the unsaturated monomer represented by (3) is preferably mentioned.
- One of the other monomers may be used, or two or more may be used in combination.
- R 6 represents a hydrogen atom or a methyl group
- X represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an —OAc group, a —CN group, a —CO—R 7 group, or —C—
- O—R 8 group represents an O—R 8 group
- Ac group represents an acetyl group
- R 7 and R 8 represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms).
- the (meth) acrylic acid ester is not limited as long as it is a (meth) acrylic acid ester other than the unsaturated monomer represented by the general formula (2).
- methyl acrylate, ethyl acrylate Acrylates such as n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, cyclohexyl acrylate, benzyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, methacrylic acid
- methacrylic acid esters such as isobutyl, t-butyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate.
- methyl methacrylate is particularly preferred from the viewpoint of heat resistance and transparency.
- the content ratio in the monomer component is preferably 10% by weight to 95% by weight, more preferably 10% by weight in order to sufficiently exert the effects of the present invention. It is ⁇ 90 wt%, more preferably 40 wt% to 90 wt%, particularly preferably 50 wt% to 90 wt%.
- an acrylic resin having maleic anhydride, maleimide and glutaric anhydride structures In the present invention, it is also preferable to use an acrylic resin having a maleimide or glutaric anhydride structure as a ring structure.
- the maleic anhydride structure include styrene-N-phenylmaleimide-maleic anhydride copolymer.
- the maleimide structure include an olefin / maleimide copolymer as described in JP-A-2004-45893.
- Examples of the glutaric anhydride structure include a copolymer having a glutaric anhydride unit as described in JP-A-2003-137937.
- a core-shell type elastic body having a core layer made of a rubber-like polymer and a shell layer made of a glass-like polymer (also called a hard polymer) is preferable.
- the rubbery polymer constituting the core layer preferably has a Tg of 20 ° C. or less, more preferably ⁇ 60 ° C. to 20 ° C., and further preferably ⁇ 60 ° C. to 10 ° C. If the Tg of the rubbery polymer constituting the core layer exceeds 20 ° C., the mechanical strength of the acrylic resin composition may not be sufficiently improved.
- the Tg of the glassy polymer (hard polymer) constituting the shell layer is preferably 50 ° C.
- Tg of the glassy polymer constituting the shell layer is lower than 50 ° C, the heat resistance of the acrylic resin composition may be lowered.
- the content of the core layer in the core-shell type elastic body is preferably 30% to 95% by weight, more preferably 50% to 90% by weight.
- the content ratio of the shell layer in the core-shell type elastic body is preferably 5% by weight to 70% by weight, more preferably 10% by weight to 50% by weight.
- the core-shell type elastic body may contain any appropriate other component as long as the effects of the present invention are not impaired.
- the polymerizable monomer forming the rubber-like polymer preferably contains a (meth) acrylic acid ester.
- the (meth) acrylic acid ester is preferably contained in an amount of 50% by weight or more, more preferably 50% by weight to 99.9% by weight, More preferably, it is contained in an amount of 9% to 99.9% by weight.
- Examples of the (meth) acrylic acid ester include ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ( Examples include (meth) acrylic acid esters having an alkyl group with 2 to 20 carbon atoms, such as isononyl (meth) acrylate, lauroyl (meth) acrylate, and stearyl (meth) acrylate.
- (meth) acrylic acid esters having 2 to 10 carbon atoms in the alkyl group such as butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and isononyl (meth) acrylate, are preferable.
- Butyl, 2-ethylhexyl acrylate, and isononyl acrylate are more preferable. These may be used alone or in combination of two or more.
- the polymerizable monomer forming the rubbery polymer preferably contains a polyfunctional monomer having two or more vinyl groups in the molecule.
- the polyfunctional monomer having two or more vinyl groups in the molecule is preferably contained in an amount of 0.01 wt% to 20 wt%, preferably 0.1 wt% to More preferably, it is contained in an amount of 20% by weight, more preferably 0.1% by weight to 10% by weight, and particularly preferably 0.2% by weight to 5% by weight.
- polyfunctional monomer having two or more vinyl groups in the molecule examples include aromatic divinyl monomers such as divinylbenzene, ethylene di (meth) acrylate, butylene glycol di (meth) acrylate butylene, di ( Poly (meth) acrylic acid alkane polyols such as hexylene methacrylate, oligoethylene di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and di (meta) ) Urethane acrylate, di (meth) acrylic acid epoxy and the like.
- aromatic divinyl monomers such as divinylbenzene, ethylene di (meth) acrylate, butylene glycol di (meth) acrylate butylene, di
- Poly (meth) acrylic acid alkane polyols such as hexylene methacrylate, oligoethylene di (meth) acrylate, trimethylolpropane
- polyfunctional monomer having different reactive vinyl groups examples include allyl (meth) acrylate, diallyl maleate, diallyl fumarate, diallyl itaconate, and the like.
- allyl (meth) acrylate examples include ethylene dimethacrylate, butylene diacrylate, and allyl methacrylate. These may be used alone or in combination of two or more.
- the polymerizable monomer forming the rubbery polymer may include the above (meth) acrylic acid ester and another polymerizable monomer copolymerizable with a polyfunctional monomer having two or more vinyl groups in the molecule. good.
- the other polymerizable monomer is preferably contained in an amount of 0% by weight to 49.9% by weight, and more preferably 0% by weight to 39.9% by weight.
- Examples of the other polymerizable monomer include aromatic vinyl such as styrene, vinyl toluene and ⁇ -methylstyrene, vinyl cyanide such as aromatic vinylidene, acrylonitrile and methacrylonitrile, vinylidene cyanide, methyl methacrylate and urethane. Examples thereof include acrylate and urethane methacrylate.
- a monomer having a functional group such as an epoxy group, a carboxyl group, a hydroxyl group, and an amino group may be used.
- examples of the monomer having an epoxy group include glycidyl methacrylate, and examples of the monomer having a carboxyl group include methacrylic acid, acrylic acid, maleic acid, and itaconic acid.
- examples of the monomer having a hydroxyl group include 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate.
- examples of the monomer having an amino group include diethylaminoethyl (meth) acrylate. These may be used alone or in combination of two or more.
- any appropriate polymerizable monomer may be used as the polymerizable monomer for forming the glassy polymer constituting the shell layer.
- the polymerizable monomer forming the glassy polymer preferably contains at least one monomer selected from (meth) acrylic acid esters and aromatic vinyl monomers. In 100% by weight of the polymerizable monomer forming the glassy polymer, it is preferable that at least one selected from (meth) acrylic acid ester and aromatic vinyl monomer is contained in an amount of 50% by weight to 100% by weight, and 60% by weight. More preferably, it is contained in an amount of ⁇ 100% by weight.
- (meth) acrylic acid ester for example, those having 1 to 4 carbon atoms in the alkyl group such as methyl (meth) acrylate and ethyl (meth) acrylate are preferable, and methyl methacrylate is more preferable. These may be used alone or in combination of two or more.
- aromatic vinyl monomer examples include styrene, vinyl toluene, ⁇ -methyl styrene and the like, and among these, styrene is preferable. These may be used alone or in combination of two or more.
- the polymerizable monomer forming the glassy polymer may contain a polyfunctional monomer having two or more vinyl groups in the molecule.
- the polyfunctional monomer having two or more vinyl groups in the molecule is preferably contained in an amount of 0% by weight to 10% by weight, and 0% by weight to 8%. More preferably, it is contained in an amount of 0% by weight to 5% by weight.
- polyfunctional monomer having two or more vinyl groups in the molecule include the same ones as described above.
- the polymerizable monomer forming the glassy polymer includes the above (meth) acrylic acid ester and another polymerizable monomer copolymerizable with a polyfunctional monomer having two or more vinyl groups in the molecule. Also good.
- the other polymerizable monomer is preferably contained in an amount of 0% by weight to 50% by weight, and more preferably 0% by weight to 40% by weight.
- Examples of the other polymerizable monomer include vinyl cyanide such as acrylonitrile and methacrylonitrile, vinylidene cyanide, (meth) acrylic acid esters other than those described above, urethane acrylate, urethane methacrylate, and the like.
- Examples of the monomer having an epoxy group include glycidyl methacrylate, and examples of the monomer having a carboxyl group include methacrylic acid, acrylic acid, maleic acid, itaconic acid, and the like, and have a hydroxyl group.
- Examples of the monomer include 2-hydroxy methacrylate and 2-hydroxy acrylate, and examples of the monomer having an amino group include diethylaminoethyl methacrylate and diethylaminoethyl acrylate. These may be used alone or in combination of two or more.
- any suitable method capable of producing core-shell type particles can be adopted.
- a polymerizable monomer forming a rubbery polymer constituting the core layer is suspended or emulsion-polymerized to produce a suspension or emulsion dispersion containing rubbery polymer particles, and then the suspension
- a core-shell type having a multilayer structure in which a polymerizable monomer that forms a glassy polymer constituting a shell layer is added to an emulsified dispersion and radically polymerized, and the surface of rubbery polymer particles is coated with the glassy polymer.
- the method of obtaining an elastic body is mentioned.
- the polymerizable monomer that forms the rubber-like polymer and the polymerizable monomer that forms the glassy polymer may be polymerized in one stage, or may be polymerized in two or more stages by changing the composition ratio. Also good.
- the dispersion shape of the (B) acrylic rubber particles in the acrylic resin composition constituting the stretched film of the present invention is not particularly limited, but may be spherical, flat, or disc-shaped depending on a molding method or a stretching method.
- the dispersion particle diameter is not particularly limited, but in any dispersion shape, the average dispersion length in the major axis direction and the minor axis direction is preferably 10 nm to 500 nm, more preferably 100 nm to 400 nm, More preferably, it is 150 nm to 300 nm.
- the average dispersion length is 10 nm or less, the glass transition temperature of the acrylic resin composition tends to decrease.
- the average dispersion length exceeds 500 nm the dispersion state becomes non-uniform, haze increases, and the peel strength and the number of MIT reciprocal bending tend to decrease.
- the average dispersion length of the (B) acrylic rubber particles is generally measured visually using a transmission electron microscope (TEM).
- the core-shell type elastic body for example, (a) a soft inner layer and a hard outer layer, the inner layer having a (meth) acrylic crosslinked polymer layer, (b) a hard inner layer, Examples include a soft intermediate layer and a hard outer layer, the inner layer comprising at least one hard polymer layer, and the intermediate layer comprising a soft polymer comprising a (meth) acrylic crosslinked polymer layer. .
- Various properties (mechanical characteristics, optical characteristics, orientation birefringence, and photoelastic coefficient) of the acrylic resin composition can be arbitrarily controlled by appropriately selecting the monomer type of each layer.
- “Soft” preferably has a glass transition temperature of the polymer of less than 20 ° C.
- “hard” preferably has a glass transition temperature of the polymer of 20 ° C. or higher.
- a more preferable structure of the core-shell type elastic body include, for example, (i) a non-crosslinked methacrylic resin in which the shell layer of the multilayer structure particle contains 0.1 wt% or more, more preferably 1 wt% or more of an acrylate ester. (Ii) The shell layer of the multilayer structured particle is composed of two or more layers having different acrylate ester contents, and is a non-crosslinked methacrylic resin containing 1 wt% or more of the acrylate ester in total.
- a peracid (persulfuric acid, persulfate) in the presence of a latex of innermost layer particles made of a crosslinked methacrylic resin in which the core layer of the multilayer structure particle is polymerized using an organic peroxide as a redox initiator.
- the intermediate layer formed by copolymerizing acrylic acid ester, polyfunctional monomer, and other monomers as appropriate using phosphate as a pyrolytic initiator Those having a structure, etc. are exemplified.
- the core-shell elastic body is easily dispersed well in the acrylic resin composition of the present invention, and there are few defects due to non-dispersion and aggregation when a film is formed, strength, toughness, Excellent in heat resistance, transparency and appearance, and further whitening due to temperature change and stress is suppressed, and a film with excellent quality can be obtained.
- the content of the acrylic rubber particles in the acrylic resin composition constituting the stretched film of the present invention preferably includes 1% by weight to 50% by weight of the acrylic rubber particles with respect to the acrylic resin composition. More preferably, it is 2 to 35% by weight, and further preferably 3 to 25% by weight.
- the content of the acrylic rubber particles is less than 1% by weight, the mechanical properties of the acrylic resin composition are not sufficiently improved.
- the content exceeds 50% by weight, the heat resistance of the acrylic resin composition decreases. Or haze may deteriorate.
- the glass transition temperature of the acrylic resin composition constituting the stretched film of the present invention is preferably 115 ° C. or higher, and more preferably 120 ° C. or higher.
- the glass transition temperature here is a value measured using a differential scanning calorimeter (DSC, manufactured by SII, DSC7020) under a nitrogen atmosphere at a heating rate of 20 ° C./min and analyzed by the midpoint method. .
- DSC differential scanning calorimeter
- Acrylic resin compositions include antioxidants, heat stabilizers, light stabilizers, UV absorbers, specific wavelength absorbers or specific wavelength absorbing dyes for the purpose of cutting blue light, radical scavenging, if necessary. 1 or 2 of light-resistant stabilizers such as agents, retardation adjusting agents, catalysts, plasticizers, lubricants, antistatic agents, coloring agents, antishrinking agents, antibacterial / deodorizing agents, fluorescent whitening agents, compatibilizing agents, etc. A combination of two or more species may be added as long as the object of the present invention is not impaired.
- ultraviolet absorbers examples include triazine compounds, benzotriazole compounds, benzophenone compounds, cyanoacrylate compounds, benzoxazine compounds, and oxadiazole compounds.
- triazine compounds are preferable from the viewpoint of volatility when ultraviolet absorption performance with respect to the added amount or melt extrusion is performed.
- phase difference adjusting agent when a negative phase difference is imparted, for example, a compound having a styrene skeleton may be used, and an acrylonitrile-styrene copolymer is exemplified.
- the mixing method of (A) acrylic resin and (B) acrylic rubber particles is not particularly limited, and any conventionally known method can be used. For example, a method of supplying to an extruder using a gravimetric feeder and melt-kneading, (A) acrylic resin and (B) acrylic rubber particles are mixed in a solution state with a solvent having excellent compatibility, etc. Can be mentioned.
- the extruder to be used is not particularly limited, and various types of extruders can be used. Specifically, a single screw extruder, a twin screw extruder, a multi-screw extruder, or the like can be used. Among these, it is preferable to use a twin screw extruder. According to the twin-screw extruder, the degree of freedom of the conditions for uniformly mixing (A) acrylic resin and (B) acrylic rubber particles is wide. Further, (A) acrylic resin and (B) acrylic rubber particles may be introduced and mixed from the upstream side of the extruder using a raw material charging hopper or the like, or (B) only acrylic rubber particles may be extruded. You may throw in and mix from the middle of a machine using a side feeder, a weight type feeder, etc.
- a filter at the end of the extruder. It is preferable to install a gear pump in front of the filter in order to pressurize the (A) acrylic resin / acrylic resin composition.
- the type of filter it is preferable to use a stainless steel leaf disc filter capable of removing foreign substances from the molten polymer, and it is preferable to use a fiber type, a powder type, or a composite type thereof as the filter element.
- the film according to the present invention can be produced by a solution casting method or a spin coating method in which the acrylic resin composition according to the present invention is dissolved in a soluble solvent and then molded.
- melt extrusion method that does not use a solvent. According to the melt extrusion method, it is possible to reduce the burden on the global environment and the working environment due to manufacturing costs and solvents.
- the acrylic resin composition of the present invention is formed into a film by a melt extrusion method
- the acrylic resin composition of the present invention is preliminarily dried and then supplied to an extruder, and the acrylic resin composition is heated. Melt. Furthermore, it is supplied to a die such as a T die through a gear pump or a filter.
- the acrylic resin composition supplied to the T-die is extruded as a sheet-like molten resin, and cooled and solidified using a cooling roll or the like to obtain an unstretched film (also referred to as a raw film).
- an unstretched film also referred to as a raw film.
- the acrylic resin composition of the present invention is formed into an unstretched film by a solution casting method
- the acrylic resin composition of the present invention is made into a solution together with an organic solvent
- the solution is cast on a support and heated.
- This is a method for producing an unstretched film by drying.
- the solvent that can be used in the solvent casting method can be selected from known solvents.
- Halogenated hydrocarbon solvents such as methylene chloride and trichloroethane are preferred because they easily dissolve the acrylic resin of the present invention and have a low boiling point.
- non-halogen solvents having high polarity such as dimethylformamide and dimethylacetamide can also be used.
- aromatic solvents such as toluene, xylene and anisole, cyclic ether solvents such as dioxane, dioxolane, tetrahydrofuran and pyran, and ketone solvents such as methyl ethyl ketone can also be used. These solvents may be used alone. Moreover, you may mix and use multiple types.
- the amount of the solvent used may be any amount as long as the thermoplastic resin can be dissolved to such an extent that casting can be sufficiently performed. In the present specification, “dissolved” means that the resin is present in the solvent in a uniform state sufficient to perform casting. It is not necessary for the solute to be completely dissolved in the solvent.
- the resin concentration in the solution is preferably 1% by weight to 90% by weight, more preferably 5% by weight to 70% by weight, and still more preferably 10% by weight to 50% by weight.
- a stainless steel endless belt may be used.
- a film such as a polyimide film or a polyethylene terephthalate film can be used.
- the stretched film of the present invention is obtained by stretching an unstretched film (also referred to as a raw film). By stretching the unstretched film, a stretched film having a desired thickness can be produced, or the mechanical properties of the stretched film can be improved.
- a conventionally known method can be used as the stretching method.
- an unstretched original film formed by melt extrusion can be uniaxially or biaxially stretched to produce a film having a predetermined thickness.
- biaxial stretching is preferable.
- the stretching method may be simultaneous biaxial stretching or sequential biaxial stretching.
- the stretching ratio in the case of biaxial stretching, in both the MD direction and the TD direction of the film
- the stretching speed is preferably 1.1 times / minute or more, more preferably 5 times / minute or more. Moreover, it is preferable that it is 100 times / min or less, and it is more preferable that it is 50 times / min or less.
- the first-stage stretching speed and the second-stage stretching speed may be the same or different.
- the first-stage stretching is generally stretching in the longitudinal direction (MD direction)
- the second-stage stretching is stretching in the width direction (TD direction).
- the stretching temperature is not particularly limited, and the lower limit of the stretching temperature is the glass transition temperature (Tg) of the acrylic resin composition + 20 ° C., Tg + 21 ° C., Tg + 22 ° C., Tg + 25 ° C., Tg + 26 ° C., Tg + 29 ° C., Tg + 30 ° C., Tg + 31 ° C. , Tg + 36 ° C., Tg + 41 ° C., Tg + 45 ° C., or Tg + 55 ° C.
- the upper limit of the stretching temperature may be Tg + 55 ° C., Tg + 45 ° C., Tg + 41 ° C., or Tg + 36 ° C.
- the combination of the lower limit of the stretching temperature and the upper limit of the stretching temperature is not particularly limited as long as the lower limit of the stretching temperature is equal to or lower than the upper limit of the stretching temperature, and any combination may be used.
- the stretching temperature is preferably Tg + 20 ° C. to Tg + 55 ° C., more preferably Tg + 25 ° C. to Tg + 55 ° C., further preferably Tg + 30 ° C. to Tg + 45 ° C., and particularly preferably Tg + 35 ° C. to Tg + 45 ° C. .
- the stretching temperature may be Tg + 31 ° C. to Tg + 55 ° C., Tg + 31 ° C. to Tg + 45 ° C., Tg + 31 ° C.
- the stretching temperature is within this range, the dimensional change rate tends to be small when left in an atmosphere of 85 ° C. and 85% RH for 120 hours, and the peel strength when bonded to another film such as a polarizer is low. There is less concern about the decline. Furthermore, it is possible to suppress the decrease in the number of MIT reciprocating bendings that normally occur by stretching at a high temperature by adding acrylic rubber particles. That is, by setting the stretching temperature within the above range, it is possible to produce a well-balanced stretched film having a small dimensional change rate and excellent peel strength and MIT flex resistance.
- the stretching temperature in stretching in the width direction (TD direction) is preferably equal to or higher than the stretching temperature in stretching in the longitudinal direction (MD direction).
- the stretching temperature in stretching in the width direction (TD direction) performed as the first-stage stretching is preferably equal to or higher than the stretching temperature in stretching in the longitudinal direction (MD direction) performed as the first-stage stretching.
- the stretched film of this invention When using the stretched film of this invention as a polarizer protective film, it is bonded with a polarizer and becomes a polarizing plate.
- the polarizer is not particularly limited, and any conventionally known polarizer can be used.
- a polarizer obtained by adding iodine to stretched polyvinyl alcohol can be used.
- This polarizing plate can be used for various products by further bonding with various films. Although the use is not specifically limited, For example, it can use suitably for display fields, such as a liquid crystal display and an organic electroluminescent display.
- Glass-transition temperature (A) Using 10 mg of an acrylic resin and an acrylic resin composition, a differential scanning calorimeter (DSC, manufactured by SII, DSC7020) was used and measured at a heating rate of 20 ° C./min in a nitrogen atmosphere. Determined by the midpoint method.
- DSC differential scanning calorimeter
- MIT bending resistance test The film was cut into strips having a width of 15 mm and used as test pieces. Using this test piece, MIT soft fatigue tester model D manufactured by Toyo Seiki Co., Ltd., the test load was 1.96 N, the speed was 175 times / minute, the radius of curvature R of the folding clamp was 0.38 mm, and the bending angle was Measurements were made at 135 ° to the left and right. It performed about MD direction and TD direction, respectively, and the arithmetic average value was made into the frequency
- the obtained (A) acrylic resin was measured using 1 H-NMR BRUKER Avance III (400 MHz). Calculation was performed by weight conversion from the molar ratio of the target ring structure portion and other portions. Specifically, in the case of glutarimide, the peak area A derived from the O—CH 3 proton of methyl methacrylate in the vicinity of 3.5 to 3.8 ppm, and the N—CH of glutarimide in the vicinity of 3.0 to 3.3 ppm. From the area B of the peak derived from 3 protons, it can be calculated by weight conversion using the determined molar ratio.
- Resin (I) was obtained by cooling the resin which came out as a strand from the die
- the set temperature of each temperature control zone of the extruder was 240 to 260 ° C. and the screw rotation speed was 102 rpm.
- the resin (I) obtained from the hopper was supplied at 41 kg / hr, and the resin was melted and filled with a kneading block, and then 0.56 parts by weight of carbonic acid from 100 parts by weight of the methyl methacrylate resin from the nozzle. Dimethyl was injected to reduce carboxyl groups in the resin. A reverse flight was placed at the end of the reaction zone to fill the resin. By-products after reaction and excess dimethyl carbonate were removed by reducing the pressure of the vent hole to -0.092 MPa. The resin that emerged as a strand from the die provided at the exit of the extruder was cooled in a water tank and then pelletized with a pelletizer to obtain an acrylic resin (A1) having a glutarimide ring.
- the acrylic resin (A1) had a glutarimide content of 6% by weight, a glass transition temperature of 125 ° C., and an average refractive index of 1.50.
- Example 1 (Acrylic resin (A2) production example) Example 1 except that methyl methacrylate-styrene copolymer (styrene content 11 mol%) was used in place of the polymethyl methacrylate resin (Mw: 105,000) and the amount of monomethylamine was 14 parts by weight.
- an acrylic resin (A2) having a glutarimide ring was obtained.
- the acrylic resin (A2) had a glutarimide content of 79% by weight, a glass transition temperature of 134 ° C., and an average refractive index of 1.53.
- the obtained innermost layer polymer latex was kept at 80 ° C. in a nitrogen stream, 0.1 parts of potassium persulfate was added, and then a single unit consisting of 41 parts of n-butyl acrylate, 9 parts of styrene, and 1 part of allyl methacrylate.
- the monomer mixture was added continuously over 5 hours. During this time, 0.1 part of potassium oleate was added in three portions. After completing the addition of the monomer mixture, 0.05 part of potassium persulfate was further added and held for 2 hours in order to complete the polymerization.
- the resulting rubber particles had a polymerization conversion rate of 99% and a particle size of 240 nm.
- the obtained rubber particle latex was kept at 80 ° C., 0.05 parts of potassium persulfate was added, and then a monomer mixture of 21.5 parts of methyl methacrylate and 1.5 parts of n-butyl acrylate was continuously added for 1 hour. Added. After completion of the addition of the monomer mixture, the mixture was held for 1 hour to obtain a graft copolymer latex. The polymerization conversion rate was 99%.
- the obtained rubber-containing graft copolymer latex was salted out and coagulated with calcium chloride, heat-treated and dried to obtain white powdery acrylic rubber particles (B1).
- the obtained innermost layer polymer latex was kept at 80 ° C. in a nitrogen stream, and after adding 0.1 part of potassium persulfate, 32 parts of n-butyl acrylate, 7 parts of styrene, and 0.8 part of allyl methacrylate were used.
- the resulting monomer mixture was added continuously over 5 hours. During this time, 0.1 part of potassium oleate was added in three portions. After completing the addition of the monomer mixture, 0.05 part of potassium persulfate was further added and held for 2 hours in order to complete the polymerization.
- the resulting rubber particles had a polymerization conversion rate of 99% and a particle size of 240 nm.
- the obtained rubber particle latex was kept at 80 ° C., 0.05 part of potassium persulfate was added, and then a monomer mixture of 34 parts of methyl methacrylate, 3 parts of n-butyl acrylate and 3 parts of acrylonitrile was continuously added for 1 hour. Added. After completion of the addition of the monomer mixture, the mixture was held for 1 hour to obtain a graft copolymer latex. The polymerization conversion rate was 99%.
- the obtained rubber-containing graft copolymer latex was subjected to salting out coagulation, heat treatment and drying with calcium chloride to obtain white powdery acrylic rubber particles (B2).
- the resin mixture was supplied from the hopper at 2 kg / hr, the set temperature of each temperature control zone of the extruder was 260 ° C., and the screw rotation speed was 100 rpm.
- the resin that emerged as a strand from a die provided at the exit of the extruder was cooled in a water tank and then pelletized with a pelletizer to obtain an acrylic resin composition (C1).
- the acrylic resin composition (C1) was supplied from the hopper at 2 kg / hr, and the set temperature of each temperature control zone of the extruder was 270 ° C. and the screw rotation speed was 100 rpm.
- the sheet-like molten resin extruded from the T die provided at the exit of the extruder was cooled with a cooling roll to obtain a raw film (D1) having a width of 160 mm and a thickness of 160 ⁇ m.
- the resulting raw film (D1) was stretched twice (longitudinal and lateral) at a temperature 21 ° C. higher than the glass transition temperature. Simultaneous biaxial stretching was performed to produce a stretched film (E1).
- the stretched film (E1) obtained above is cut into a size of 90 mm ⁇ 90 mm using a cutter, and a hole is opened with a punch of ⁇ 1 mm at a location 20 mm inward from the four corners of the film.
- the hole spacing was measured using an original measuring instrument.
- the stretched film, whose pore spacing was measured was again measured for 120 hours in a Nagano Science LH-20 environmental tester set at 85 ° C. and 85% RH, and the pore spacing was measured again.
- the shrinkage rate was calculated from the difference in the hole spacing before and after standing in an atmosphere of 85 ° C. and 85% RH.
- corona discharge treatment One side of the raw film D1 obtained above was subjected to corona discharge treatment (corona discharge electron dose 100 W / m2 / min) to obtain a corona discharge treatment film (F1).
- Cross-linking agent manufactured by Nippon Shokubai, trade name: Epocross WS700, solid content: 25%
- 100 g of water-based urethane resin having a carboxyl group (Daiichi Kogyo Seiyaku, trade name: Superflex 210, solid content: 33%) 20 g was added and stirred for 3 minutes to obtain an easy-adhesive composition.
- the obtained easy-adhesive composition was applied to the corona discharge treated surface of the original fabric D1 subjected to the corona discharge treatment with a bar coater (number # 6).
- the raw fabric D1 coated with the easy-adhesive was put into a hot air dryer (80 ° C.), and the urethane composition was dried for about 1 minute to obtain an easy-adhesion-treated film (G1) on which an easy-adhesive layer was formed.
- the easy adhesion treatment film (G1) obtained above was 21 ° C. from the glass transition temperature at a stretch ratio of 2 times (vertical / horizontal). Biaxial stretching was performed at a high temperature to prepare a biaxially stretched film. The thickness of the easy-adhesion layer after biaxial stretching was 0.38 ⁇ m.
- the obtained biaxially stretched film was cut into a strip shape having a width of 15 mm and a length of 10 cm, and “Aron Alpha Series” manufactured by Toagosei Co., Ltd.
- the strength when peeling the polycarbonate film 90 degrees from the stretched film was defined as the peel strength.
- the peel strength here was measured using a small tabletop tester (Autograph) EZ-S manufactured by Shimadzu Corporation under an environment of 23 ° C./50% RH, and obtained under the condition of a peel rate of 30 mm / min.
- the obtained measurement data was obtained by averaging data having a peel length of 10 mm to 60 mm in the peel strength test, and the arithmetic average value measured three times was defined as the peel strength.
- the results are shown in Table 1.
- Example 2 A biaxially stretched film was produced in the same manner as in Example 1 except that the original film (D1) was simultaneously biaxially stretched at a temperature 26 ° C. higher than the glass transition temperature.
- the shrinkage rate, peel strength, and number of MIT reciprocal bendings were measured. The results are shown in Table 1. Moreover, it was 0.18 when the inside noise was measured.
- Example 3 A biaxially stretched film was produced in the same manner as in Example 1 except that the original film (D1) was simultaneously biaxially stretched at a temperature 31 ° C. higher than the glass transition temperature.
- the shrinkage rate, peel strength, and number of MIT reciprocal bendings were measured. The results are shown in Table 1. Moreover, it was 0.19 when the inside was measured.
- Example 4 A biaxially stretched film was prepared in the same manner as in Example 1 except that the original film (D1) was simultaneously biaxially stretched at a temperature 36 ° C. higher than the glass transition temperature.
- the shrinkage rate, peel strength, and number of MIT reciprocal bendings were measured. The results are shown in Table 1. Moreover, it was 0.18 when the inside noise was measured.
- Example 5 A biaxially stretched film was prepared in the same manner as in Example 1 except that the original film (D1) was simultaneously biaxially stretched at a temperature 41 ° C. higher than the glass transition temperature.
- the shrinkage rate, peel strength, and number of MIT reciprocal bendings were measured. The results are shown in Table 1. Moreover, it was 0.17 when the inside noise was measured.
- Example 6 A biaxially stretched film was prepared by performing the same operation as in Example 1 except that 15% by weight of the acrylic rubber particles (B1) and simultaneous stretching of the stretching temperature at a temperature 26 ° C. higher than the glass transition temperature were performed. Produced. In accordance with the above method, the shrinkage rate, peel strength, and number of MIT reciprocal bendings were measured. The results are shown in Table 1. Moreover, it was 0.19 when the inside was measured.
- Example 7 A biaxially stretched film was prepared in the same manner as in Example 1 except that 15% by weight of the acrylic rubber particles (B1) and simultaneous stretching was performed at a stretching temperature of 31 ° C. higher than the glass transition temperature. Was made. In accordance with the above method, the shrinkage rate, peel strength, and number of MIT reciprocal bendings were measured. The results are shown in Table 1. Moreover, it was 0.20 when the inside was measured.
- Example 8 The acrylic resin (A2) instead of the acrylic resin (A1), the acrylic rubber particles (B2) instead of the acrylic rubber particles (B1) are 23% by weight, and the stretching temperature is 22 ° C. higher than the glass transition temperature.
- a biaxially stretched film was produced in the same manner as in Example 1 except that simultaneous biaxial stretching was performed at the temperature. In accordance with the above method, the shrinkage rate, peel strength, and number of MIT reciprocal bendings were measured. The results are shown in Table 1.
- Example 9 Example 1 except that the acrylic rubber particles (B2) were replaced by 23% by weight instead of the acrylic rubber particles (B1) and the stretching temperature was 29 ° C. higher than the glass transition temperature. The same operation was performed to produce a biaxially stretched film. In accordance with the above method, the shrinkage rate, peel strength, and number of MIT reciprocal bendings were measured. The results are shown in Table 1. Moreover, it was 0.17 when the inside noise was measured.
- Example 10 Using 10% by weight of acrylic resin (A1) and acrylic rubber particles (B1), it was dissolved in methylene chloride to obtain a solution having a solid content concentration of 15% by weight. This solution was cast on a biaxially stretched polyethylene terephthalate film laid on a glass plate. The obtained sample was left at room temperature for 60 minutes. Thereafter, the sample was peeled off from the polyethylene terephthalate film, the four sides of the sample were fixed, dried at 100 ° C. for 10 minutes, and further dried at 140 ° C. for 10 minutes to obtain a 160 ⁇ m-thick original film (D1 ′). .
- a biaxially stretched film was produced in the same manner as in Example 1 except that the simultaneous biaxial stretching was performed at a stretching temperature 36 ° C. higher than the glass transition temperature.
- the shrinkage rate, peel strength, and number of MIT reciprocal bendings were measured. The results are shown in Table 1. Moreover, it was 0.16 when the inside noise was measured.
- Example 1 A biaxially stretched film was prepared in the same manner as in Example 1 except that simultaneous biaxial stretching was performed at 5% by weight of the acrylic rubber particles (B1) and a stretching temperature of 11 ° C. higher than the glass transition temperature. Was made. The shrinkage rate, peel strength, and number of MIT reciprocal bendings were measured according to the above methods. The results are shown in Table 1. Moreover, it was 0.23 when the inside was measured.
- Example 2 A biaxially stretched film was produced in the same manner as in Example 1 except that the simultaneous biaxial stretching was performed at a temperature higher by 11 ° C. than the glass transition temperature.
- the shrinkage rate, peel strength, and number of MIT reciprocal bendings were measured. The results are shown in Table 1. Moreover, it was 0.25 when the inside noise was measured.
- Example 3 A biaxially stretched film was prepared in the same manner as in Example 1 except that 15% by weight of the acrylic rubber particles (B1) and simultaneous biaxial stretching were performed at a stretching temperature of 16 ° C. higher than the glass transition temperature. Was made. In accordance with the above method, the shrinkage rate, peel strength, and number of MIT reciprocal bendings were measured. The results are shown in Table 1. Moreover, it was 0.27 when the inside was measured.
- Example 4 Example 1 except that the acrylic rubber particles (B2) were replaced by 23% by weight and the stretching temperature was 12 ° C. higher than the glass transition temperature instead of the acrylic rubber particles (B1). The same operation was performed to produce a biaxially stretched film.
- the shrinkage rate, peel strength, and number of MIT reciprocal bendings were measured. The results are shown in Table 1. Moreover, it was 0.13 when the inside was measured.
- Example 5 Comparative Example 5
- Example 1 Example 1 except that the acrylic rubber particles (B2) were replaced by 23% by weight and the stretching temperature was 19 ° C. higher than the glass transition temperature instead of the acrylic rubber particles (B1).
- the same operation was performed to produce a biaxially stretched film.
- the shrinkage rate, peel strength, and number of MIT reciprocal bendings were measured. The results are shown in Table 1. Moreover, it was 0.14 when the inside noise was measured.
- Example 7 The same operation as in Example 1 was performed except that the above-mentioned acrylic rubber particles (B1) were not added and the stretching temperature was 20 ° C. higher than the glass transition temperature. Was made.
- the shrinkage rate, peel strength, and number of MIT reciprocal bendings were measured. The results are shown in Table 1. Moreover, it was 0.15 when the inside was measured.
- Example 9 A biaxially stretched film was produced in the same manner as in Example 1 except that the simultaneous biaxial stretching was performed at a stretching temperature 61 ° C. higher than the glass transition temperature.
- the MIT bending resistance test was performed according to the above method, the number of MIT reciprocal bendings was 130.
- the stretching temperature within this range, the increase (deterioration) in dimensional change caused by adding acrylic rubber particles can be suppressed and cohesive failure caused by acrylic rubber particles can be suppressed, It turns out that it can be set as the stretched film containing the acrylic-type rubber particle excellent in the balance of mechanical characteristics, dimensional stability, and peeling strength.
- the stretching temperature is 155 to 165 ° C.
- the dimensional stability and the peel strength are particularly excellent, and the balance between mechanical properties, dimensional stability, and peel strength is further improved. It can be seen that a stretched film containing acrylic rubber particles can be obtained.
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Abstract
Description
<1>
(A)ガラス転移温度が120℃以上であるアクリル系樹脂及び(B)アクリル系ゴム粒子を1重量%~50重量%含有する延伸フィルムの製造方法であって、延伸工程における延伸温度がTg+20℃~Tg+55℃であることを特徴とする、延伸フィルムの製造方法に関する。
前記延伸フィルムは、85℃、85%RH雰囲気下に120時間静置した際の収縮率が1.5%以下であり、且つ、MIT往復折り曲げ回数が350回以上である、<1>に記載の製造方法に関する。
前記(B)アクリル系ゴム粒子がゴム状重合体からなるコア層とガラス状重合体からなるシェル層とを有するコアシェル型弾性体であって、コアシェル型弾性体の平均分散長が150nm~300nmであることを特徴とする、<1>又は<2>に記載の製造方法に関する。
前記延伸フィルムを接着剤でポリカーボネートフィルムに貼り付け、23℃、50%RH雰囲気において90度剥離強度の値が1.0N/cm以上であることを特徴とする、<1>~<3>のいずれか1つに記載の製造方法に関する。
(A)ガラス転移温度が120℃以上であるアクリル系樹脂が主鎖に環構造を持つことを特徴とする、<1>~<4>のいずれか1つに記載の製造方法に関する。
前記環構造がグルタルイミド環、ラクトン環、無水マレイン酸、マレイミド及び無水グルタル酸からなる群から選ばれる少なくとも1種であることを特徴とする、<5>に記載の製造方法に関する。
(A)ガラス転移温度が120℃以上であるアクリル系樹脂中の環構造の含有量が2重量%~80重量%であることを特徴とする、<5>または<6>に記載の製造方法に関する。
環構造が下記一般式(1)を含むことを特徴とする、<5>~<7>のいずれか1つに記載の製造方法に関する。
前記延伸フィルムは、85℃、85%RH雰囲気下に120時間静置した際の収縮率が0.1%以上1.5%以下である、<1>~<8>のいずれか1つに記載の製造方法に関する。
前記延伸フィルムの片面若しくは両面に易接着層が設けられている、<1>~<9>のいずれか1つに記載の製造方法に関する。
(A)ガラス転移温度が120℃以上であるアクリル系樹脂及び(B)アクリル系ゴム粒子を1重量%~50重量%含有する延伸フィルムであって、85℃、85%RH雰囲気下に120時間静置した際の収縮率が1.5%以下であり、且つ、MIT往復折り曲げ回数が350回以上である延伸フィルムに関する。
前記(B)アクリル系ゴム粒子がゴム状重合体からなるコア層とガラス状重合体からなるシェル層とを有するコアシェル型弾性体であって、コアシェル型弾性体の平均分散長が150nm~300nmであることを特徴とする、<11>に記載の延伸フィルムに関する。
前記延伸フィルムを接着剤でポリカーボネートフィルムに貼り付け、23℃、50%RH雰囲気において90度剥離強度の値が1.0N/cm以上であることを特徴とする、<11>または<12>に記載の延伸フィルムに関する。
(A)ガラス転移温度が120℃以上であるアクリル系樹脂が主鎖に環構造を持つことを特徴とする、<11>~<13>のいずれか1つに記載の延伸フィルムに関する。
前記環構造がグルタルイミド環、ラクトン環、無水マレイン酸、マレイミド及び無水グルタル酸からなる群から選ばれる少なくとも1種であることを特徴とする、<14>に記載の延伸フィルムに関する。
(A)ガラス転移温度が120℃以上であるアクリル系樹脂中の環構造の含有量が2重量%~80重量%であることを特徴とする、<14>または<15>に記載の延伸フィルムに関する。
環構造が下記一般式(1)を含むことを特徴とする、<14>~<16>のいずれか1つに記載の延伸フィルムに関する。
前記延伸フィルムは、85℃、85%RH雰囲気下に120時間静置した際の収縮率が0.1%以上1.5%以下である、<11>~<17>のいずれか1つに記載の延伸フィルムに関する。
前記延伸フィルムの片面若しくは両面に易接着層が設けられている、<11>~<18>のいずれか1つに記載の延伸フィルムに関する。
本発明の延伸フィルムは、(A)ガラス転移温度が120℃以上であるアクリル系樹脂(以下、(A)アクリル系樹脂ということもある)及び(B)アクリル系ゴム粒子を1重量%~50重量%含んでなる延伸フィルムである。ここで、(A)ガラス転移温度が120℃以上であるアクリル系樹脂及び(B)アクリル系ゴム粒子を1重量%~50重量%を含むアクリル系樹脂をアクリル系樹脂組成物と定義する。
本発明では、(A)ガラス転移温度が120℃以上であるアクリル系樹脂を使用する。アクリル系樹脂のガラス転移温度が120℃以上であると、(B)アクリル系ゴム粒子と混合したアクリル系樹脂組成物からなる延伸フィルムのガラス転移温度が高くなり、例えば、高温環境下での延伸フィルムの寸法変化率が小さくなる。実使用上、本発明の延伸フィルムは他のフィルムと積層されて用いることが多く、寸法変化率が小さいと、積層された他フィルムとの間に生じる寸法変化率の差から生じる歪や反りの発生を抑制することができる。
環構造としてグルタルイミド環を有するアクリル系樹脂は、下記一般式(1)で表されるグルタルイミド単位とメタクリル酸メチル単位とを含有する樹脂であり、アクリル酸エステル単位が1重量%未満であるアクリル系樹脂を加熱溶融し、イミド化剤で処理することによって得られる。
環構造としてラクトン環を有するアクリル系樹脂は、分子内にラクトン環構造を持つ熱可塑性の重合体(分子鎖中にラクトン環構造が導入された熱可塑性の重合体)であれば、限定はされず、その製造方法についても限定されないが、好ましくは、分子鎖中に水酸基とエステル基とを有する重合体(a)を重合によって得た(重合工程)後に、得られた重合体(a)を加熱処理することによりラクトン環構造を重合体に導入する(ラクトン環化縮合工程)ことによって得られる。
本発明においては、環構造としてマレイミドや無水グルタル酸構造を有するアクリル系樹脂を用いることも好ましい。無水マレイン酸構造としては、例えば、スチレン-N-フェニルマレイミド-無水マレイン酸共重合体などが挙げられる。マレイミド構造としては、例えば、特開2004-45893に記載されているようなオレフィン・マレイミド共重合体などが挙げられる。無水グルタル酸構造としては、例えば特開2003-137937に記載されているような無水グルタル酸単位を有する共重合体が挙げられる。
アクリル系ゴム粒子としては、ゴム状重合体からなるコア層とガラス状重合体(硬質重合体ともいう)からなるシェル層とを有するコアシェル型弾性体が好ましい。コア層を構成するゴム状重合体のTgは20℃以下が好ましく、-60℃~20℃がより好ましく、-60℃~10℃がさらに好ましい。コア層を構成するゴム状重合体のTgが20℃を超えると、アクリル系樹脂組成物の機械的強度の向上が十分ではないおそれがある。シェル層を構成するガラス状重合体(硬質重合体)のTgは、50℃以上が好ましく、50℃~140℃がより好ましく、60℃~130℃がさらに好ましい。シェル層を構成するガラス状重合体のTgが50℃より低いと、アクリル系樹脂組成物の耐熱性が低下するおそれがある。
本発明の延伸フィルムを構成するアクリル系樹脂組成物中の、アクリル系ゴム粒子の含有量は、アクリル系樹脂組成物に対してアクリル系ゴム粒子を1重量%~50重量%含むことが好ましく、より好ましくは2重量%~35重量%、さらに好ましくは3重量%~25重量%である。アクリル系ゴム粒子の含有量が1重量%未満であると、アクリル系樹脂組成物の機械的特性の向上が十分ではなく、50重量%を超えると、アクリル系樹脂組成物の耐熱性が低下したり、ヘイズが悪化するおそれがある。
本発明の延伸フィルムの製造方法の一実施形態について説明するが、本発明はこれに限定されない。つまり、本発明のアクリル系樹脂組成物を成形してフィルムを製造できる方法であれば、従来公知のあらゆる方法を用いることができる。
本発明の延伸フィルムを偏光子保護フィルムとして使用する場合は偏光子と貼合されて偏光板となる。偏光子は特に限定されるものではなく、従来公知の任意の偏光子を用いることができる。例えば、延伸されたポリビニルアルコールにヨウ素を含有させて得た偏光子等を挙げることができる。
(A)アクリル系樹脂およびアクリル系樹脂組成物10mgを用いて、示差走査熱量計(DSC、(株)SII製、DSC7020)を用いて、窒素雰囲気下、昇温速度20℃/minで測定し、中点法により決定した。
フィルムを幅15mmの短冊状にカットしこれを試験片とした。この試験片を、東洋精機(株)製のMIT耐柔疲労試験機型式Dを用いて、試験荷重1.96N、速度175回/分、折り曲げクランプの曲率半径Rは0.38mm、折り曲げ角度は左右へ135°で測定した。MD方向、TD方向についてそれぞれ行い、算術平均値をMIT往復折り曲げ回数とした。
フィルムを日本電色工業(株)製ヘイズメーターNDH2000を用いて測定した。内部ヘイズは、液体測定用ガラスセルに得られたフィルムをいれ、フィルムの両面に蒸留水が接触するようにして測定した。
(株)アタゴ社製アッベ屈折計3Tを用いて測定した。
得られた(A)アクリル系樹脂を1H-NMR BRUKER AvanceIII(400MHz)を用いて測定を行った。対象となる環構造部分とそれ以外の部分のモル比から重量換算を行い算出した。具体的にグルタルイミドのケースでは、3.5から3.8ppm付近のメタクリル酸メチルのO-CH3プロトン由来のピークの面積Aと、3.0から3.3ppm付近のグルタルイミドのN-CH3プロトン由来のピークの面積Bより、求められたモル比を用いて重量換算を行い算出できる。
(アクリル系樹脂(A1)製造例)
使用した押出機は口径40mmの噛合い型同方向回転式二軸押出機(L/D=90)である。押出機の各温調ゾーンの設定温度を250~280℃、スクリュー回転数は85rpmとした。メタクリル酸メチル樹脂(Mw:10.5万)を42.4kg/hrで供給し、ニーディングブロックによって上記メタクリル酸メチル樹脂を溶融、充満させた後、ノズルから上記メタクリル酸メチル樹脂100重量部に対して1.8重量部のモノメチルアミン(三菱ガス化学(株)製)を注入した。反応ゾーンの末端にはリバースフライトを入れて樹脂を充満させた。反応後の副生成物および過剰のメチルアミンをベント孔の圧力を-0.092MPaに減圧して除去した。押出機出口に設けられたダイスからストランドとして出てきた樹脂を、水槽で冷却した後、ペレタイザでペレット化することにより、樹脂(I)を得た。次いで、口径40mmの噛合い型同方向回転式二軸押出機にて、押出機各温調ゾーンの設定温度を240~260℃、スクリュー回転数102rpmとした。ホッパーから得られた樹脂(I)を41kg/hrで供給し、ニーディングブロックによって樹脂を溶融、充満させた後、ノズルから上記メタクリル酸メチル樹脂100重量部に対して0.56重量部の炭酸ジメチルを注入し樹脂中のカルボキシル基の低減を行った。反応ゾーンの末端にはリバースフライトを入れて樹脂を充満させた。反応後の副生成物および過剰の炭酸ジメチルをベント孔の圧力を-0.092MPaに減圧して除去した。押出機出口に設けられたダイスからストランドとして出てきた樹脂を、水槽で冷却した後、ペレタイザでペレット化し、グルタルイミド環を有するアクリル系樹脂(A1)を得た。当該アクリル系樹脂(A1)のグルタルイミド含有量は6重量%、ガラス転移温度は125℃、平均屈折率は1.50であった。
ポリメタクリル酸メチル樹脂(Mw:10.5万)の代わりにメタクリル酸メチル-スチレン共重合体(スチレン量11モル%)を用い、モノメチルアミン供給量を14重量部とした以外は、実施例1と同様にしてグルタルイミド環を有するアクリル系樹脂(A2)を得た。当該アクリル系樹脂(A2)のグルタルイミド含有量は79重量%、ガラス転移温度134℃、平均屈折率は1.53であった。
(アクリル系ゴム粒子(B1)の製造例)
以下の組成の混合物をガラス製反応器に仕込み、窒素気流中で攪拌しながら80℃に昇温したのり、メタクリル酸メチル27部、メタクリル酸アリル0.5部、t-ドデシルメルカプタン0.1部からなる単量体混合物とt-ブチルハイドロパーオキサイド0.1との混合液のうち25%を一括して仕込み、45分間の重合を行った。
脱イオン水 220部
ホウ酸 0.3部
炭酸ナトリウム 0.03部
N-ラウロイルサルコシン酸ナトリウム 0.09部
ソディウムホルムアルデヒドスルフォキシレート 0.09部
エチレンジアミン四酢酸-2-ナトリウム 0.006部
硫酸第一鉄 0.002部
続いてこの混合液の残り75%を1時間にわたって連続添加した。添加終了後、同温度で2時間保持し重合を完結させた。また、この間に0.2部のN-ラウロイルサルコシン酸ナトリウムを追加した。得られた最内層架橋メタクリル系重合体ラテックスの重合転化率(重合生成量/モノマー仕込量)は98%であった。
以下の組成の混合物をガラス製反応器に仕込み、窒素気流中で撹拌しながら80℃に昇温したのち、メタクリル酸メチル21部、メタクリル酸アリル0.4部、t-ドデシルメルカプタン0.08部からなる単量体混合物とt-ブチルハイドロパーオキサイド0.1部との混合液のうち25%を一括して仕込み、45分間の重合を行なった。
脱イオン水 220部
ホウ酸 0.3部
炭酸ナトリウム 0.03部
N-ラウロイルサルコシン酸ナトリウム 0.09部
ソディウムホルムアルデヒドスルフォキシレート 0.09部
エチレンジアミン四酢酸-2-ナトリウム 0.006部
硫酸第一鉄 0.002部
続いてこの混合液の残り75%を1時間にわたって連続添加した。添加終了後、同温度で2時間保持し重合を完結させた。また、この間に0.2部のN-ラウロイルサルコシン酸ナトリウムを追加した。得られた最内層架橋メタクリル系重合体ラテックスの重合転化率(重合生成量/モノマー仕込量)は98%であった。
上記、アクリル系樹脂製造例で製造したアクリル系樹脂(A1)と、アクリル系ゴム粒子(B1)を10重量%を含む混合物を、口径15mmの噛合い型同方向回転式二軸押出機(L/D=30)にて混練した。ホッパーから樹脂混合物を2kg/hrで供給し、押出機各温調ゾーンの設定温度を260℃、スクリュー回転数100rpmとした。押出機出口に設けられたダイスからストランドとして出てきた樹脂を水槽で冷却した後、ペレタイザでペレット化し、アクリル系樹脂組成物(C1)を得た。
上記で得られた延伸フィルム(E1)を90mm×90mmの大きさにカッターを用いて切り出し、フィルムの四隅から対角線の内側方向へ20mmの場所にΦ1mmのポンチで孔を開け、ミツトヨ製MF201型三次元測定器を用いて孔間隔を測定した。続いて孔間隔を測定した延伸フィルムを、85℃、85%RHに設定したナガノサイエンス製LH-20型環境試験機中で120時間静置した後の孔間隔を再度測定した。85℃、85%RH雰囲気下での静置前後の孔間隔差から、収縮率を算出した。
上記で得られた原反フィルムD1の片側に、コロナ放電処理(コロナ放電電子照射量100W/m2/min)を施し、コロナ放電処理フィルム(F1)を得た。
カルボキシル基を有する水系ウレタン樹脂(第一工業製薬、商品名:スーパーフレックス210、固形分:33%)100gに対して、架橋剤(日本触媒製、商品名:エポクロスWS700、固形分:25%)20gを添加し、3分間撹拌し、易接着剤組成物を得た。得られた易接着剤組成物を、コロナ放電処理を施した原反D1のコロナ放電処理面に、バーコーター(番線#6)で塗布した。易接着剤を塗布した原反D1を熱風乾燥機(80℃)に投入し、ウレタン組成物を約1分間乾燥させて、易接着層を形成した易接着処理フィルム(G1)を得た。
上記で得られた易接着処理フィルム(G1)を、(株)井元製作所製、二軸延伸装置(IMC-1905)を用いて、延伸倍率2倍(縦・横)、ガラス転移温度より21℃高い温度で同時二軸延伸を行い、二軸延伸フィルムを作成した。二軸延伸後の易接着層の厚みは0.38μmであった。得られた二軸延伸フィルムを幅15mm、長さ10cmの短冊状に切り出し、易接着層が施された側の一面に、東亞合成(株)製「アロンアルファシリーズ」(アロンアルファ プロ用No.1)を6滴滴下し、幅15mm、長さ10cmの短冊状に切り出した(株)カネカ製「エルメックシリーズ」(Rフィルム、厚み64μm)を、2kgのゴムローラー(JIS Z 0237準拠)を用いて均一に接着した。得られたポリカーボネートフィルムが接着された延伸フィルムを幅1cmの短冊状にカッターを用いてカットし、剥離強度試験サンプルとした。得られた剥離強度試験サンプルを、積水化学工業(株)製「ポリエチレンクロス両面テープ(50mm×15m)」を用いて、ステンレス製の台に延伸フィルム側が下側に、ポリカーボネートフィルムが上側になるように貼付し、延伸フィルムからポリカーボネートフィルムを90度剥離する際の強度を剥離強度とした。ここでの剥離強度は、23℃/50%RHの環境下で、(株)島津製作所製小型卓上試験機(オートグラフ)EZ-Sを用いて測定し、剥離速度30mm/minの条件で得られた測定データにおいて剥離強度試験における剥離長さが10mm~60mmの間のデータを平均化することにより求め、3回測定した算術平均値を剥離強度とした。結果を表1に示す。
上記、原反フィルム(D1)をガラス転移温度より26℃高い温度で同時二軸延伸を行った以外は、実施例1と同様の操作を行い、二軸延伸フィルムを作製した。上記の方法に従って、収縮率、剥離強度、MIT往復折り曲げ回数を測定した。結果を表1に示す。また、内部へイズを測定したところ、0.18であった。
上記、原反フィルム(D1)をガラス転移温度より31℃高い温度で同時二軸延伸を行った以外は、実施例1と同様の操作を行い、二軸延伸フィルムを作製した。上記の方法に従って、収縮率、剥離強度、MIT往復折り曲げ回数を測定した。結果を表1に示す。また、内部へイズを測定したところ、0.19であった。
上記、原反フィルム(D1)をガラス転移温度より36℃高い温度で同時二軸延伸を行った以外は、実施例1と同様の操作を行い、二軸延伸フィルムを作製した。上記の方法に従って、収縮率、剥離強度、MIT往復折り曲げ回数を測定した。結果を表1に示す。また、内部へイズを測定したところ、0.18であった。
上記、原反フィルム(D1)をガラス転移温度より41℃高い温度で同時二軸延伸を行った以外は、実施例1と同様の操作を行い、二軸延伸フィルムを作製した。上記の方法に従って、収縮率、剥離強度、MIT往復折り曲げ回数を測定した。結果を表1に示す。また、内部へイズを測定したところ、0.17であった。
上記、アクリル系ゴム粒子(B1)を15重量%、延伸温度をガラス転移温度より26℃高い温度で同時二軸延伸を行った以外は、実施例1と同様の操作を行い二軸延伸フィルムを作製した。上記の方法に従って、収縮率、剥離強度、MIT往復折り曲げ回数を測定した。結果を表1に示す。また、内部へイズを測定したところ、0.19であった。
上記、アクリル系ゴム粒子(B1)を15重量%、延伸温度をガラス転移温度より31℃高い温度で同時二軸延伸を行った以外は、実施例1と同様の操作を行い、二軸延伸フィルムを作製した。上記の方法に従って、収縮率、剥離強度、MIT往復折り曲げ回数を測定した。結果を表1に示す。また、内部へイズを測定したところ、0.20であった。
上記、アクリル系樹脂(A1)の代わりにアクリル系樹脂(A2)、アクリル系ゴム粒子(B1)の代わりにアクリル系ゴム粒子(B2)を23重量%、延伸温度をガラス転移温度より22℃高い温度で同時二軸延伸を行った以外は、実施例1と同様の操作を行い、二軸延伸フィルムを作製した。上記の方法に従って、収縮率、剥離強度、MIT往復折り曲げ回数を測定した。結果を表1に示す。
上記、アクリル系ゴム粒子(B1)の代わりにアクリル系ゴム粒子(B2)を23重量%、延伸温度をガラス転移温度より29℃高い温度で同時二軸延伸を行った以外は、実施例1と同様の操作を行い、二軸延伸フィルムを作製した。上記の方法に従って、収縮率、剥離強度、MIT往復折り曲げ回数を測定した。結果を表1に示す。また、内部へイズを測定したところ、0.17であった。
アクリル系樹脂(A1)とアクリル系ゴム粒子(B1)10重量%を用いて、塩化メチレンに溶解して固形分濃度15重量%の溶液を得た。この溶液を、ガラス板上に敷いた二軸延伸ポリエチレンテレフタレートフィルム上に流延した。得られたサンプルを、室温で60分間放置した。その後ポリエチレンテレフタレートフィルムからサンプルを剥し、サンプルの4辺を固定して100℃で10分間乾燥し、さらに140℃で10分間乾燥を行って、厚さ160μmの原反フィルム(D1’)を得た。延伸温度をガラス転移温度より36℃高い温度で同時二軸延伸を行った以外は、実施例1と同様の操作を行い、二軸延伸フィルムを作製した。上記の方法に従って、収縮率、剥離強度、MIT往復折り曲げ回数を測定した。結果を表1に示す。また、内部へイズを測定したところ、0.16であった。
上記、アクリル系ゴム粒子(B1)を5重量%、延伸温度をガラス転移温度より11℃高い温度で同時二軸延伸を行った以外は、実施例1と同様の操作を行い、二軸延伸フィルムを作製した。上記の方法に従って、収縮率、剥離強度、MIT往復折り曲げ回数を測定した。結果を表1に示す。また、内部へイズを測定したところ、0.23であった。
上記、延伸温度をガラス転移温度より11℃高い温度で同時二軸延伸を行った以外は、実施例1と同様の操作を行い、二軸延伸フィルムを作製した。上記の方法に従って、収縮率、剥離強度、MIT往復折り曲げ回数を測定した。結果を表1に示す。また、内部へイズを測定したところ、0.25であった。
上記、アクリル系ゴム粒子(B1)を15重量%、延伸温度をガラス転移温度より16℃高い温度で同時二軸延伸を行った以外は、実施例1と同様の操作を行い、二軸延伸フィルムを作製した。上記の方法に従って、収縮率、剥離強度、MIT往復折り曲げ回数を測定した。結果を表1に示す。また、内部へイズを測定したところ、0.27であった。
上記、アクリル系ゴム粒子(B1)の代わりにアクリル系ゴム粒子(B2)を23重量%、延伸温度をガラス転移温度より12℃高い温度で同時二軸延伸を行った以外は、実施例1と同様の操作を行い、二軸延伸フィルムを作製した。上記の方法に従って、収縮率、剥離強度、MIT往復折り曲げ回数を測定した。結果を表1に示す。また、内部へイズを測定したところ、0.13であった。
上記、アクリル系ゴム粒子(B1)の代わりにアクリル系ゴム粒子(B2)を23重量%、延伸温度をガラス転移温度より19℃高い温度で同時二軸延伸を行った以外は、実施例1と同様の操作を行い、二軸延伸フィルムを作製した。上記の方法に従って、収縮率、剥離強度、MIT往復折り曲げ回数を測定した。結果を表1に示す。また、内部へイズを測定したところ、0.14であった。
上記、アクリル系樹脂(A1)の代わりにアクリル系樹脂(A2)、アクリル系ゴム粒子(B1)の代わりにアクリル系ゴム粒子(B2)を23重量%、延伸温度をガラス転移温度より19℃高い温度で同時二軸延伸を行った以外は、実施例1と同様の操作を行い、二軸延伸フィルムを作製した。上記の方法に従って、収縮率、剥離強度、MIT往復折り曲げ回数を測定した。結果を表1に示す。
上記、アクリル系ゴム粒子(B1)を添加せず、延伸温度をガラス転移温度より20℃高い温度で同時二軸延伸を行った以外は、実施例1と同様の操作を行い、二軸延伸フィルムを作製した。上記の方法に従って、収縮率、剥離強度、MIT往復折り曲げ回数を測定した。結果を表1に示す。また、内部へイズを測定したところ、0.15であった。
上記、アクリル系樹脂(A1)の代わりにアクリル系樹脂(A2)、アクリル系ゴム粒子(B1)を添加せず、延伸温度をガラス転移温度より11℃高い温度で同時二軸延伸を行った以外は、実施例1と同様の操作を行い、二軸延伸フィルムを作製した。上記の方法に従って、収縮率、剥離強度、MIT往復折り曲げ回数を測定した。結果を表1に示す。また、内部へイズを測定したところ、0.15であった。
上記、延伸温度をガラス転移温度より61℃高い温度で同時二軸延伸を行った以外は、実施例1と同様の操作を行い、二軸延伸フィルムを作製した。上記の方法に従って、MIT耐屈曲試験を行ったところ、MIT往復折り曲げ回数が130回であった。
Claims (19)
- (A)ガラス転移温度が120℃以上であるアクリル系樹脂及び(B)アクリル系ゴム粒子を1重量%~50重量%含有する延伸フィルムの製造方法であって、延伸工程における延伸温度がTg+20℃~Tg+55℃であることを特徴とする、延伸フィルムの製造方法。
- 前記延伸フィルムは、85℃、85%RH雰囲気下に120時間静置した際の収縮率が1.5%以下であり、且つ、MIT往復折り曲げ回数が350回以上である、請求項1に記載の製造方法。
- 前記(B)アクリル系ゴム粒子がゴム状重合体からなるコア層とガラス状重合体からなるシェル層とを有するコアシェル型弾性体であって、コアシェル型弾性体の平均分散長が150nm~300nmであることを特徴とする、請求項1又は2に記載の製造方法。
- 前記延伸フィルムを接着剤でポリカーボネートフィルムに貼り付け、23℃、50%RH雰囲気において90度剥離強度の値が1.0N/cm以上であることを特徴とする、請求項1~3のいずれか1項に記載の製造方法。
- (A)ガラス転移温度が120℃以上であるアクリル系樹脂が主鎖に環構造を持つことを特徴とする、請求項1~4のいずれか1項に記載の製造方法。
- 前記環構造がグルタルイミド環、ラクトン環、無水マレイン酸、マレイミド及び無水グルタル酸からなる群から選ばれる少なくとも1種であることを特徴とする、請求項5に記載の製造方法。
- (A)ガラス転移温度が120℃以上であるアクリル系樹脂中の環構造の含有量が2重量%~80重量%であることを特徴とする、請求項5または6に記載の製造方法。
- 前記延伸フィルムは、85℃、85%RH雰囲気下に120時間静置した際の収縮率が0.1%以上1.5%以下である、請求項1~8のいずれか1項に記載の製造方法。
- 前記延伸フィルムの片面若しくは両面に易接着層が設けられている、請求項1~9のいずれか1項に記載の製造方法。
- (A)ガラス転移温度が120℃以上であるアクリル系樹脂及び(B)アクリル系ゴム粒子を1重量%~50重量%含有する延伸フィルムであって、85℃、85%RH雰囲気下に120時間静置した際の収縮率が1.5%以下であり、且つ、MIT往復折り曲げ回数が350回以上である延伸フィルム。
- 前記(B)アクリル系ゴム粒子がゴム状重合体からなるコア層とガラス状重合体からなるシェル層とを有するコアシェル型弾性体であって、コアシェル型弾性体の平均分散長が150nm~300nmであることを特徴とする、請求項11に記載の延伸フィルム。
- 前記延伸フィルムを接着剤でポリカーボネートフィルムに貼り付け、23℃、50%RH雰囲気において90度剥離強度の値が1.0N/cm以上であることを特徴とする、請求項11または12に記載の延伸フィルム。
- (A)ガラス転移温度が120℃以上であるアクリル系樹脂が主鎖に環構造を持つことを特徴とする、請求項11~13のいずれか1項に記載の延伸フィルム。
- 前記環構造がグルタルイミド環、ラクトン環、無水マレイン酸、マレイミド及び無水グルタル酸からなる群から選ばれる少なくとも1種であることを特徴とする、請求項14に記載の延伸フィルム。
- (A)ガラス転移温度が120℃以上であるアクリル系樹脂中の環構造の含有量が2重量%~80重量%であることを特徴とする、請求項14または15に記載の延伸フィルム。
- 前記延伸フィルムは、85℃、85%RH雰囲気下に120時間静置した際の収縮率が0.1%以上1.5%以下である、請求項11~17のいずれか1項に記載の延伸フィルム。
- 前記延伸フィルムの片面若しくは両面に易接着層が設けられている、請求項11~18のいずれか1項に記載の延伸フィルム。
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CN114986863A (zh) | 2022-09-02 |
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JP2023009094A (ja) | 2023-01-19 |
JP2021192106A (ja) | 2021-12-16 |
JP6933706B2 (ja) | 2021-09-08 |
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