WO2022114194A1 - グルタルイミド樹脂 - Google Patents
グルタルイミド樹脂 Download PDFInfo
- Publication number
- WO2022114194A1 WO2022114194A1 PCT/JP2021/043687 JP2021043687W WO2022114194A1 WO 2022114194 A1 WO2022114194 A1 WO 2022114194A1 JP 2021043687 W JP2021043687 W JP 2021043687W WO 2022114194 A1 WO2022114194 A1 WO 2022114194A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin
- glutarimide resin
- formula
- film
- glutarimide
- Prior art date
Links
- 239000011347 resin Substances 0.000 title claims abstract description 239
- 229920005989 resin Polymers 0.000 title claims abstract description 239
- KNCYXPMJDCCGSJ-UHFFFAOYSA-N piperidine-2,6-dione Chemical compound O=C1CCCC(=O)N1 KNCYXPMJDCCGSJ-UHFFFAOYSA-N 0.000 title claims abstract description 175
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000003118 aryl group Chemical group 0.000 claims abstract description 14
- 125000001424 substituent group Chemical group 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims description 49
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 45
- 125000000217 alkyl group Chemical group 0.000 claims description 34
- 239000011342 resin composition Substances 0.000 claims description 34
- 125000004432 carbon atom Chemical group C* 0.000 claims description 33
- 230000003287 optical effect Effects 0.000 claims description 28
- 238000004519 manufacturing process Methods 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 26
- 229910021529 ammonia Inorganic materials 0.000 claims description 19
- 230000009477 glass transition Effects 0.000 claims description 16
- 230000004580 weight loss Effects 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 238000002411 thermogravimetry Methods 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 5
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 abstract 4
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 abstract 1
- 125000006652 (C3-C12) cycloalkyl group Chemical group 0.000 abstract 1
- 125000000041 C6-C10 aryl group Chemical group 0.000 abstract 1
- 239000010408 film Substances 0.000 description 143
- 239000000178 monomer Substances 0.000 description 82
- 239000010410 layer Substances 0.000 description 51
- 229920000642 polymer Polymers 0.000 description 48
- 238000000034 method Methods 0.000 description 43
- 239000003795 chemical substances by application Substances 0.000 description 42
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 39
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 31
- -1 methacrylate ester Chemical class 0.000 description 28
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- 238000006243 chemical reaction Methods 0.000 description 21
- 239000012792 core layer Substances 0.000 description 19
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 17
- 239000002253 acid Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 16
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- 238000012360 testing method Methods 0.000 description 14
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- 238000001816 cooling Methods 0.000 description 13
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- 125000000524 functional group Chemical group 0.000 description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
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- 239000000126 substance Substances 0.000 description 11
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- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 10
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 5
- 230000032050 esterification Effects 0.000 description 5
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- 230000035484 reaction time Effects 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 125000005250 alkyl acrylate group Chemical group 0.000 description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000012986 chain transfer agent Substances 0.000 description 4
- 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 4
- 229920001971 elastomer Polymers 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
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- 239000012535 impurity Substances 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 229910003437 indium oxide Inorganic materials 0.000 description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 3
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- 229910052718 tin Inorganic materials 0.000 description 3
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- 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
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-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
- 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 2
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-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
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- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
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- 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
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- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 125000005342 perphosphate group Chemical group 0.000 description 2
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- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
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- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
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- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical compound CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
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- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-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
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- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
- C08F222/40—Imides, e.g. cyclic imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
- C08F222/40—Imides, e.g. cyclic imides
- C08F222/402—Alkyl substituted imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/48—Isomerisation; Cyclisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/19—Quaternary ammonium compounds
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/133305—Flexible substrates, e.g. plastics, organic film
-
- 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
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Definitions
- the present invention relates to a glutarimide resin and a method for producing the same, and a film and a substrate using the resin.
- a material having low dielectric constant and low dielectric loss tangent characteristics is required as an insulating substrate material for a printed circuit for a high frequency band or a substrate for an antenna.
- a glass material is used as a substrate for an antenna, but as the usage is expanded, further weight reduction is required, so that the glass material is being replaced with a resin.
- a resin that can form a substrate for an antenna for example, a cycloolefin polymer and the like are known (see Patent Document 1).
- the liquid crystal display device is equipped with various films such as a polarizing film in order to maintain its display quality.
- a plastic liquid crystal display device using a resin film instead of a glass substrate has also been put into practical use.
- a resin constituting an optical film that can be used in such a liquid crystal display device a (meth) acrylic resin containing a glutarimide unit is known (see, for example, Patent Document 2).
- the cycloolefin polymer described in Patent Document 1 is used for substrate applications because of its heat resistance, but its bending resistance (Folding property) is insufficient.
- the glutarimide resin described in Patent Document 2 has a small phase difference, there is room for improvement in heat resistance. In view of the above situation, it is an object of the present invention to provide a glutarimide resin having good heat resistance and small orientation birefringence.
- the present inventor has sufficient heat resistance while maintaining the orientation birefringence at a practically small level by using ammonia as a denaturing agent (imidizing agent). It has been found that a glutarimide resin can be obtained.
- the present invention is a repeating unit represented by the following general formula (1).
- R 1 and R 2 each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms.
- R 3 and R 4 independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms.
- R 5 and R 6 independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms
- R 7 is an alkyl group having 1 to 18 carbon atoms and a cycloalkyl group having 3 to 12 carbon atoms. , Or a substituent containing an aromatic ring having 5 to 15 carbon atoms.
- R 8 indicates hydrogen or an alkyl group having 1 to 8 carbon atoms
- R 9 indicates an aryl group having 6 to 10 carbon atoms.
- Containing glutarimide resin Containing glutarimide resin.
- the orientation birefringence of the glutarimide resin is ⁇ 3.0 ⁇ 10 -3 to 3.0 ⁇ 10 -3 , and more preferably ⁇ 1.5 ⁇ 10 -3 to 1.5 ⁇ 10. It is -3 .
- the glutarimide resin satisfies the following formulas (a) and (b).
- M1 is the content (mol%) of the repeating unit represented by the formula (1) in the glutarimide resin
- M2 is represented by the formula (2) in the glutarimide resin
- M4 is the content (mol%) of the repeating unit represented by the formula (4) in the glutarimide resin.
- the glass transition temperature of the glutarimide resin is 124 ° C. or higher.
- the 5% weight loss temperature in the TGA measurement of the glutarimide resin is 350 ° C. or higher.
- the glutarimide resin composition containing the glutarimide resin; the film or substrate containing the glutarimide resin composition; the substrate, the optical adjustment layer, and the transparent conductive layer are laminated in this order. Also related to transparent conductive films. Further, the present invention comprises a step of reacting a raw material resin containing the repeating unit represented by the general formula (3) and the repeating unit represented by the general formula (4) with ammonia. The content of the repeating unit represented by the general formula (4) in the raw material resin is the repeating unit represented by the general formula (3) and the general formula in the raw material resin.
- the present invention also relates to a method for producing a glutarimide resin, which is 3 mol% or more and 23 mol% or less with respect to the total content of the repeating unit represented by (4). Furthermore, the present invention also relates to a method for producing a glutarimide resin, which comprises a step of further reacting the glutarimide resin obtained by the above production method with ammonia.
- the present invention it is possible to provide a glutarimide resin having good heat resistance and small orientation birefringence. Further, it is possible to provide a simple production method capable of introducing two types of glutarimide ring structures at the same time. According to a preferred embodiment of the present invention, it is possible to provide a glutarimide resin having good bending resistance. Further, the glutarimide resin according to the present invention has good heat resistance even if the amount of the imidizing agent used in the production is reduced, so that the reaction time in the imidization step can be shortened, and thus the productivity is improved. It has the advantage that it can be achieved and the amount of gas emitted in the imidization step can be reduced.
- 6 is an NMR chart of the glutarimide resin of Example 2.
- 6 is an NMR chart of the glutarimide resin of Example 5 measured using heavy DMF.
- 6 is an NMR chart of the glutarimide resin of Example 5 measured using methylene dichloride.
- the glutarimide resin according to the present disclosure is a repeating unit represented by the following general formula (1).
- R 1 and R 2 each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms.
- R 1 a methyl group is preferable, and as R 2 , a hydrogen atom is preferable.
- R 3 and R 4 independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms.
- R 3 a methyl group is preferable, and as R 4 , a hydrogen atom is preferable.
- R 5 and R 6 independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms
- R 7 has an alkyl group having 1 to 18 carbon atoms and 3 to 12 carbon atoms.
- a cycloalkyl group or a substituent containing an aromatic ring having 5 to 15 carbon atoms is shown.
- Hydrogen is preferable as R5 .
- a methyl group is preferable as R6 .
- a methyl group is preferable as R7 .
- the (meth) acrylate ester unit can be used as the repeating unit represented by the formula (3).
- Methyl methacrylate units are preferable because they have an excellent balance between heat resistance and orientation birefringence.
- the proportion of the methyl methacrylate unit is preferably 50 to 100 mol%, more preferably 70 to 100 mol%, still more preferably 80 to 100 mol%, and 90. ⁇ 100 mol% is particularly preferable.
- R 8 represents hydrogen or an alkyl group having 1 to 8 carbon atoms
- R 9 represents an aryl group having 6 to 10 carbon atoms.
- Each of R 8 and R 9 may include a plurality of types.
- a hydrogen atom is preferable as R8 .
- a phenyl group is preferable as R 9 .
- Examples of the monomer constituting the repeating unit represented by the formula (4) include styrene, ⁇ -methylstyrene, vinyltoluene, vinylnaphthalene and the like. Of these, styrene is particularly preferable.
- the glutarimide resin according to the present disclosure preferably has an orientation birefringence of ⁇ 3.0 ⁇ 10 -3 or more and 3.0 ⁇ 10 -3 or less. More preferably, it is ⁇ 2.0 ⁇ 10 -3 or more and 2.0 ⁇ 10 -3 or less, and more preferably ⁇ 1.5 ⁇ 10 -3 or more and 1.5 ⁇ 10 -3 or less. Even more preferably, it is ⁇ 1.0 ⁇ 10 -3 or more and 1.0 ⁇ 10 -3 or less, and particularly preferably ⁇ 0.8 ⁇ 10 -3 or more and 0.8 ⁇ 10 -3 or less. .. If the orientation birefringence is outside the above range, the application may be limited.
- orientation birefringence refers to filming a glutarimide resin and stretching the film 100% at a temperature 5 to 8 ° C. higher than the glass transition temperature of the resin. Birefringence measured for the resulting stretched film is intended.
- the temperature at the time of stretching may be a temperature 5 ° C. higher than the glass transition temperature of the resin, or may be a temperature 8 ° C. higher than the glass transition temperature of the resin.
- the glutarimide resin according to the present disclosure preferably satisfies the following formula (a). 10 ⁇ M1 + M2 ⁇ 70 (a)
- M1 is the content (mol%) of the repeating unit represented by the formula (1) in the glutarimide resin
- M2 is the repeating unit represented by the formula (2) in the glutarimide resin.
- the lower limit is 10 mol% or more, preferably 15 mol% or more, and more preferably 20 mol. % Or more, more preferably 25 mol% or more, still more preferably 30 mol% or more, and particularly preferably 35 mol% or more.
- the upper limit is 70 mol% or less, preferably 65 mol% or less, more preferably 60 mol% or less, still more preferable. Is 55 mol% or less.
- the glutarimide resin in which M1 + M2 is in this range can increase the heat resistance while keeping the orientation birefringence at a practically sufficiently small level.
- the glutarimide resin according to the present disclosure has good heat resistance even if M1 + M2 has a relatively small value.
- M1 + M2 becomes a large value, it may become brittle when the glutarimide resin is formed into a film, but when the glutarimide resin has M1 + M2 in the above range, the brittleness of the film can be avoided.
- Both the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) contribute to heat resistance and orientation birefringence, but the repeating unit represented by the formula (1) is. Not only does it contribute more to heat resistance than the repeating unit represented by the formula (2), but it also contributes more to orientation birefringence. That is, by including the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2), it is possible to efficiently achieve both heat resistance and substantially small orientation birefringence. Further, since the repeating unit represented by the formula (2) can suppress the increase in the viscosity of the glutarimide resin as compared with the repeating unit represented by the formula (1), it is easy to handle in the subsequent manufacturing process. become.
- the glutarimide resin according to the present disclosure preferably satisfies the following formula (b). 5 ⁇ M4 ⁇ 25 (b)
- M4 is the content (mol%) of the repeating unit represented by the formula (4) in the glutarimide resin.
- the lower limit is 5 mol% or more, preferably 8 mol% or more, and more preferably 10 mol% or more. From the viewpoint of orientation birefringence and suppression of viscosity increase, the smaller the value of M4, the better.
- the upper limit is 25 mol% or less, more preferably 20 mol% or less, still more preferably 15. It is less than mol%.
- the glutarimide resin according to the present disclosure preferably satisfies the following formula (c). M1> M2 (c) When M1 is larger than M2, both high heat resistance and small orientation birefringence can be achieved at a higher level. More preferably, M1> M2 + 0.2.
- the value of M1 is preferably 7 mol% or more, more preferably 10 mol% or more, still more preferably 13 mol% or more, still more preferably 17 from the viewpoint of achieving both heat resistance and orientation birefringence. It is mol% or more, more preferably 20 mol% or more, and particularly preferably 23 mol% or more.
- the value of M2 is preferably 3 mol% or more, more preferably 5 mol% or more, still more preferably 7 mol% or more, still more preferably 8 from the viewpoint of achieving both heat resistance and orientation birefringence. It is mol% or more, more preferably 10 mol% or more, and particularly preferably 12 mol% or more.
- the value of (M1 + M2) / M4 is preferably 1.5 or more, and particularly preferably 2.0 or more, from the viewpoint of heat resistance. Further, from the viewpoint of orientation birefringence, it is preferably 4.0 or less, and particularly preferably 3.5 or less.
- M1, M2, and M4 can be determined based on the ratio of the peak areas derived from each structure calculated in the chart obtained by 1 H-NMR measurement.
- the above formulas (1) to (4) in which R 1 , R 3 , R 6 and R 7 are methyl groups, R 2 , R 4 , R 5 and R 8 are hydrogen atoms, and R 9 are phenyl groups are used.
- the method for identifying the contained glutarimide resin is shown below. 1 H-NMR Using Avance III (400 MHz) manufactured by BRUKER, 30 mg of the resin is dissolved in heavy DMSO, heavy DMF, or heavy methylene chloride, and 1 H-NMR measurement of the resin is performed.
- the area of the proton-derived peaks contained in CH 2 and CH 3 of methyl methacrylate (the formula (3)) and styrene (the formula (4)) around 0.5 to 2.3 ppm is from A and 2.7.
- the area of the peak derived from the N—CH 3 proton of the above formula (2) near 3.2 ppm is B, and the area of the peak derived from the N—H proton of the above formula (1) near 10.2 to 10.8 ppm is C.
- the area of the peak derived from the aromatic ring of styrene in the vicinity of 6.8 to 7.3 ppm is defined as D.
- the area of the proton-derived peak contained in CH 2 and CH 3 of methyl methacrylate (the above formula (3)) is represented by A- (10C + 10B / 3 + 2D / 5). That is, the molar ratio M1: M2: M3: M4 of the monomer units represented by the above formulas (1) to (4) in the glutarimide resin is C: B / 3: ⁇ A- (10C + 10B / 3 + 2D / / 5) ⁇ / 5: Represented by D / 5.
- monomer units and impurities other than the above formulas (1) to (4) are not taken into consideration.
- the glutarimide resin according to the present disclosure preferably has an imidization ratio of 20% or more and 85% or more based on the IR spectrum.
- the imidization ratio based on the IR spectrum is the absorption (1700 cm -1 ) derived from the imidecarbonyl group of NH in the above formula (1) in the IR spectrum measured for the glutarimide resin.
- Imidization rate (%) 100 ⁇ (S1 + S2) / (S1 + S2 + S3)
- the lower limit is preferably 20% or more, and more preferably 30% or more. , 40% or more is more preferable, and 50% or more is particularly preferable. From the viewpoint of orientation birefringence, the smaller the value of the imidization ratio based on the IR spectrum, the better.
- the upper limit is preferably 85% or less, more preferably 80% or less, still more preferably 75% or less. , 70% or less is particularly preferable.
- the glass transition temperature of the glutarimide resin is preferably 124 ° C. or higher, preferably 125 ° C. or higher, more preferably 127 ° C. or higher, more preferably 130 ° C. or higher, and 135 ° C. or higher. It is more preferably 140 ° C. or higher, further preferably 145 ° C. or higher, and particularly preferably 145 ° C. or higher.
- the glass transition temperature was measured at a heating rate of 20 ° C./min under a nitrogen atmosphere using a differential scanning calorimeter (DSC, differential scanning calorimeter DSC7000X manufactured by Hitachi High-Tech Science Co., Ltd.) using 10 mg of resin. It can be determined by law.
- the 5% weight loss temperature in the TGA measurement of the glutarimide resin is preferably 350 ° C. or higher, more preferably 370 ° C. or higher, further preferably 375 ° C. or higher, and more preferably 380 ° C. or higher. Especially preferable.
- a thermogravimetric measuring device (TGA: Hitachi High-Tech Science Co., Ltd .: STA7200) was used to raise the temperature of 15 mg of the resin from room temperature to 10 ° C./min under a nitrogen atmosphere. It can be measured as the temperature when the thermogravimetric weight loss (% by weight) becomes 5%.
- the photoelastic coefficient of the glutarimide resin according to the present disclosure is preferably 20 ⁇ 10-12 m 2 / N or less, more preferably 10 ⁇ 10-12 m 2 / N or less, and 5 ⁇ 10 ⁇ . It is more preferably 12 m 2 / N or less.
- the absolute value of the photoelastic coefficient is larger than 20 ⁇ 10-12 m 2 / N, light leakage is likely to occur, and the tendency becomes remarkable especially in a high temperature and high humidity environment.
- the photoelastic coefficient is that when an external force is applied to an isotropic solid to cause stress ( ⁇ F), it temporarily exhibits optical anisotropy and exhibits birefringence ( ⁇ n).
- the photoelastic coefficient is a value measured by the Senalmon method at a wavelength of 515 nm at 23 ° C. and 50% RH.
- the acid value of the resin represents the content of the carboxylic acid unit and the acid anhydride unit in the resin.
- the acid value can be calculated by, for example, the titration method described in International Publication No. 2005/054311.
- the acid value of the glutarimide resin according to the present disclosure is preferably 0.10 to 1.00 mmol / g. When the acid value is within the above range, a glutarimide resin having an excellent balance of heat resistance, mechanical properties, and molding processability can be obtained.
- the content of the carboxylic acid is preferably 1 mmol / g or less, more preferably 0.50 mmol / g or less, from the viewpoint of molding processability.
- the method for measuring the amount of carboxylic acid can be calculated by using the acid value (DMSO acid value) obtained by changing the solvent of the titration method described in International Publication No. 2005/054311 from methanol to dimethyl sulfoxide.
- (amount of carboxylic acid) 2 ⁇ (acid value)-(DMSO acid value)
- (amount of carboxylic acid) 2 ⁇ (acid value)-(DMSO acid value)
- the glutarimide resin may be further copolymerized with other units other than the repeating unit represented by the formulas (1) to (4), the carboxylic acid unit and the carboxylic acid anhydride unit, if necessary. ..
- Examples of other units include nitrile-based monomer units such as acrylonitrile and methacrylonitrile, and maleimide-based monomers such as maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. These other units may be directly copolymerized or graft-copolymerized in the glutarimide resin.
- the weight average molecular weight of the glutarimide resin is not particularly limited, but is preferably 1 ⁇ 10 4 to 5 ⁇ 10 5 , and more preferably 5 ⁇ 10 4 to 3 ⁇ 105. Within the above range, the moldability and the mechanical strength at the time of film processing can be good.
- a raw material resin having a repeating unit represented by the general formula (3) and a repeating unit represented by the general formula (4) (hereinafter referred to as a methacrylic raw material resin). It is preferable to react with ammonia (sometimes called).
- the methacrylic acid raw material resin is not particularly limited, but a methacrylic acid ester-aromatic vinyl monomer copolymer is preferable, and a methacrylic acid alkyl ester-aromatic vinyl monomer copolymer is preferable. More preferably, a methyl methacrylate-styrene copolymer is particularly preferable.
- the methacrylic acid ester-aromatic vinyl monomer copolymer preferably has a methacrylic acid ester monomer unit (formula (3)) as a main unit, and specifically, the methacrylic acid ester monomer.
- the molar ratio of the unit (the formula (3)) to the aromatic vinyl monomer unit (the formula (4)) is preferably 97/3 to 77/23.
- Such a copolymer polymerizes a monomer mixture containing 97 to 77 mol% of a methacrylic acid ester monomer and 3 to 23 mol% of an aromatic vinyl monomer in 100 mol% of all the monomers. Can be obtained.
- the molar ratio is preferably 95/5 to 80/20, more preferably 93/7 to 85/15.
- the content (mol%) of the repeating unit represented by the general formula (3) or (4) in the methacrylic raw material resin can be identified by a known method such as NMR measurement.
- the methacrylic acid ester monomer preferably has 1 to 12 carbon atoms in the ester moiety from the viewpoint of polymerization reactivity and cost, and the ester moiety may be linear or branched. Specific examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate and the like. These monomers may be used alone or in combination of two or more. Of these, methyl methacrylate is preferable from the viewpoint of cost and physical characteristics.
- the content of methyl methacrylate in the methacrylate ester monomer is preferably 50 to 100 mol%. It is more preferably 70 to 100 mol%, further preferably 80 to 100 mol%, and particularly preferably 90 to 100 mol%.
- aromatic vinyl monomer examples include aromatic vinyl derivatives such as vinyltoluene, vinylnaphthalene, styrene, and ⁇ -methylstyrene. These monomers may be used alone or in combination of two or more. Of these, styrene is preferable from the viewpoint of cost and physical properties.
- the method for producing the methacrylic raw material resin is not particularly limited, and known emulsification polymerization methods, emulsification-suspension polymerization methods, suspension polymerization methods, bulk polymerization methods, solution polymerization methods and the like can be applied, but in the field of optics. From the viewpoint of having few impurities, a bulk polymerization method and a solution polymerization method are particularly preferable.
- an initiator In the production of the methacrylic resin, an initiator, a chain transfer agent, a polymerization solvent and the like can be used, if necessary.
- Examples of the manufacturing method include JP-A-57-149311, JP-A-57-153009, JP-A-10-152505, JP-A-2004-27191, and International Publication No. 2009/41693. Is exemplified, but the present invention is not limited to these.
- the method for producing a glutarimide resin according to the present disclosure includes a step (imidization step) of heating and melting the methacrylic raw material resin and treating it with an imidizing agent. This makes it possible to produce a glutarimide resin.
- Ammonia is used as the imidizing agent. By performing imidization using ammonia, two types of glutarimide ring structures (units represented by the above formula (1) and units represented by the above formula (2)) can be introduced together.
- the imidization step In the conventional imidization using methylamine, it is necessary to increase the imidization rate in order to improve the heat resistance, the imidization step requires a long time, and the productivity tends to decrease. Further, if the imidization ratio is increased too much, the glutarimide resin may become brittle when it is formed into a film. On the other hand, in imidization using ammonia, the heat resistance of the obtained glutarimide resin can be improved even if the imidization ratio (M1 + M2) is low, as compared with the conventional imidization using methylamine. .. Since the imidization rate may be low, the reaction time in the imidization step can be shortened, and brittleness at the time of film formation can be avoided.
- ammonia liquefied ammonia or ammonia water may be used. Since it has good compatibility with the methacrylic raw material resin and has high reaction efficiency, it is preferable to use liquid ammonia from the viewpoint of productivity. Liquid ammonia has a higher concentration than the case of using ammonia water diluted with water, and can be reacted with a small amount of addition.
- concentration of the ammonia water is not particularly limited, but is preferably about 25 to 35% by weight in consideration of availability and reactivity.
- the ratio of the repeating unit represented by (2) and the repeating unit represented by the above formula (3) can be adjusted.
- the degree of imidization and the ratio of the monomer unit represented by the above formula (4) the physical properties of the glutarimide resin obtained and the optical film obtained by molding the glutarimide resin composition are formed.
- the optical characteristics of the above can be adjusted.
- the amount of the imidizing agent used can be appropriately adjusted according to the required characteristics, but is required, for example, if it is 0.5 parts by weight or more with respect to 100 parts by weight of the methacrylic raw material resin. It can be adjusted as appropriate according to the characteristics. It is preferably 1 part by weight or more, and more preferably 3 parts by weight or more. If it is less than 0.5 parts by weight, the heat resistance of the obtained glutarimide resin composition may decrease.
- the upper limit can be appropriately selected in relation to moldability and physical properties, but is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, still more preferably 15 parts by weight or less, from the viewpoint of ease of handling.
- the amount of the imidizing agent used refers to the amount of the imidizing agent used in terms of ammonia contained in the aqueous ammonia.
- a ring closure accelerator (catalyst) may be added, if 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 methacrylic raw material resin can be imidized by a method using an extruder, a batch type reaction vessel (pressure vessel), or the like.
- the extruder used is not particularly limited, and various extruders can be used. Specifically, for example, a single-screw extruder, a twin-screw extruder, a multi-screw extruder, or the like can be used.
- twin-screw extruder it is possible to promote the mixing of the imidizing agent (in the case of using a ring closure accelerator, the imidizing agent and the ring closure accelerator) with the methacrylic raw material resin.
- twin-screw extruder examples include a non-meshing type same-direction rotation type, a meshing type same-direction rotation type, a non-meshing type different-direction rotation type, and a meshing type different-direction rotation type. Above all, it is preferable to use the meshing type co-directional rotation type. Since the meshing-type co-rotating twin-screw extruder can rotate at high speed, the imidizing agent (in the case of using a ring-closing accelerator, the imidizing agent and the ring-closing accelerator) is further mixed with the raw material resin. Can be promoted.
- the above-exemplified extruder may be used alone or may be used by connecting a plurality of extruders in series.
- the tandem type reaction extruder described in JP-A-2008-273140 can be used.
- a methacrylic raw material resin is charged from the raw material input section of the extruder, the resin is melted, the inside of the cylinder is filled, and then an imidizing agent is used using an addition pump. Can be injected into the extruder to allow the imidization reaction to proceed in the extruder.
- the temperature (resin temperature) of the reaction zone in the extruder is preferably 180 ° C to 300 ° C, more preferably 200 to 290 ° C.
- the temperature of the reaction zone (resin temperature) is less than 180 ° C., the imidization reaction hardly proceeds and the heat resistance tends to decrease.
- the reaction zone temperature exceeds 300 ° C., the resin is significantly decomposed, so that the bending resistance of the film that can be formed from the obtained glutarimide resin tends to decrease.
- the reaction zone in the extruder means a region in the cylinder of the extruder from the injection position of the imidizing agent to the resin discharge port (die portion).
- reaction time in the reaction zone of the extruder By lengthening the reaction time in the reaction zone of the extruder, imidization can be further promoted.
- the reaction time in the reaction zone of the extruder is preferably longer than 10 seconds, more preferably longer than 30 seconds. Imidization may hardly proceed with a reaction time of 10 seconds or less.
- the resin pressure in the extruder is preferably in the range of atmospheric pressure to 50 MPa, and more preferably in the range of 1 MPa to 30 MPa. If it is less than 1 MPa, the solubility of the imidizing agent is low, and the progress of the reaction tends to be suppressed. Further, if it is 50 MPa or more, the limit of the mechanical pressure resistance of a normal extruder is exceeded, and a special device is required, which is not preferable in terms of cost.
- a vent hole that can reduce the pressure below atmospheric pressure in order to remove unreacted imidizing agents and by-products.
- unreacted imidizing agents, by-products such as methanol, and monomers can be removed.
- a horizontal twin-screw reactor such as Vivolac manufactured by Sumitomo Heavy Industries, Ltd. or a vertical twin-screw stirrer such as Super Blend has a high viscosity. Corresponding reactors can also be suitably used.
- the structure of the batch type reaction vessel is not particularly limited.
- the structure has a structure in which a methacrylic raw material resin can be melted by heating and stirred, and an imidizing agent (in the case of using a ring closure accelerator, an imidizing agent and a ring closure accelerator) can be added.
- an imidizing agent in the case of using a ring closure accelerator, an imidizing agent and a ring closure accelerator
- the structure has a good stirring efficiency.
- a batch type reaction vessel pressure vessel
- imidization method examples include known methods such as those described in JP-A-2008-273140 and JP-A-2008-274187.
- the glutarimide resin according to the present disclosure may be used as a raw material resin and the step of reacting with ammonia may be performed again. That is, the imidization step may be repeated a plurality of times. This makes it possible to increase the imidization rate.
- the method for producing a glutarimide resin according to the present disclosure may 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 acid value of the glutarimide resin obtained in the imidization step can be adjusted within a desired range.
- the esterifying agent include dimethyl carbonate, 2,2-dimethoxypropane, dimethyl sulfoxide, triethyl orthoformate, trimethyl orthoacetate, trimethyl orthoformate, diphenyl carbonate, dimethyl sulfate, methyl toluene sulfonate, and methyl trifluoromethyl sulfonate.
- the amount of the esterifying agent used is preferably 0 to 12 parts by weight, more preferably 0 to 8 parts by weight, based on 100 parts by weight of the methacrylic raw material resin.
- the acid value can be adjusted to an appropriate range.
- an unreacted esterifying agent may remain in the resin, which may cause foaming or odor generation when molding is performed using the resin.
- a catalyst can also be used in combination.
- the type of catalyst is not particularly limited, and examples thereof include aliphatic tertiary amines such as trimethylamine, triethylamine, and tributylamine. Among these, triethylamine is preferable from the viewpoint of cost, reactivity and the like.
- (D) Volatilization step, filtration step In the glutarimide resin that has undergone the imidization step and any esterification step, an unreacted imidizing agent, an unreacted esterifying agent, and volatilization by-produced by the reaction. Since it contains components and resin decomposition products, it is possible to install a vent hole that can be depressurized below atmospheric pressure in the latter half of the extruder.
- a filter at the end of the extruder for the purpose of reducing foreign matter in the glutarimide resin. It is preferable to install a gear pump in front of the filter to boost the glutarimide resin.
- a type of filter it is preferable to use a stainless leaf disc filter capable of removing foreign substances from the molten polymer, and as the filter element, it is preferable to use a fiber type, a powder type, or a composite type thereof.
- the glutarimide resin according to the present disclosure can be blended with other resins or additives as needed to form a glutarimide resin composition.
- Additives include commonly used weather resistant stabilizers such as antioxidants, heat stabilizers, light stabilizers, UV absorbers and radical scavengers, catalysts, plasticizers, lubricants, antistatic agents, colorants and shrinkage agents.
- An inhibitor, an antibacterial / deodorant, or the like may be added alone or in combination of two or more as long as the object of the invention is not impaired. Further, these additives can also be added at the time of molding the glutarimide resin or the glutarimide resin composition described later.
- the glutarimide resin composition according to the present disclosure preferably contains an ultraviolet absorber.
- the glutarimide resin according to the present disclosure has good compatibility with an ultraviolet absorber and can be used in a wide range of applications.
- the ultraviolet absorber include triazine compounds, benzotriazole compounds, benzophenone compounds, cyanoacrylate compounds, benzoxazine compounds, oxadiazole compounds and the like.
- triazine compounds are preferable from the viewpoint of ultraviolet absorption performance with respect to the amount added. Any commercially available triazine compound can be used.
- the ultraviolet absorber preferably has a maximum absorption wavelength of 300 nm or more and 370 nm or less.
- the glutarimide resin composition containing such an ultraviolet absorber efficiently suppresses deterioration of ultraviolet A waves (wavelength 320 nm or more and 400 nm or less) due to light. Therefore, the amount of the ultraviolet absorber added may be relatively small, and bleed-out due to the increase in the amount of the ultraviolet absorber is unlikely to occur.
- the ultraviolet absorber preferably has a 1% weight loss temperature of 350 ° C. or higher in a nitrogen atmosphere.
- a triazine compound is preferable from the viewpoint of high heat resistance and a large molar extinction coefficient.
- the amount of addition can be suppressed, and mold (roll, etc.) contamination during processing can also be suppressed.
- the ultraviolet absorber uses a triazine compound, the thermal stability can be enhanced without adding a general thermal stabilizer as described in JP-A-2014-95926.
- Examples of the ultraviolet absorber using such a triazine compound include Tinuvin1577, Tinuvin460, Tinuvin477, Tinuvin479 (all manufactured by BASF) and LA-F70 (manufactured by ADEKA).
- the amount added is 0.1 part by weight or more and 5.0 parts by weight or less with respect to 100 parts by weight of the glutarimide resin. It is preferable, and it is more preferably 0.4 parts by weight or more and 2.0 parts by weight or less.
- the amount of UV absorber is less than 0.1 parts by weight, sufficient effect may not be obtained in applications that require UV absorption, and if it is more than 2.0 parts by weight, bleed out during film formation. Etc. may occur.
- the number of foreign substances having a size of 20 ⁇ m or more is preferably 30 or less, more preferably 20 or less, and particularly preferably 10 or less.
- the number of foreign substances of 10 ⁇ m or more and less than 20 ⁇ m is preferably 300 or less, more preferably 200 or less, and particularly preferably 100 or less.
- the number of foreign substances of 5 ⁇ m or more and less than 10 ⁇ m is preferably 1000 or less, more preferably 800 or less, and particularly preferably 500 or less.
- the glutarimide resin composition For the amount of foreign matter in the glutarimide resin composition, weigh 10.0 to 10.5 g of the glutarimide resin composition, prepare 5 samples dissolved in a mixed solution of 230 to 245 g of methylene chloride and 15 g of cleansolve, and prepare 5 foreign substances. Was counted. The total number of foreign substances in these foreign substances is the amount of foreign substances in the glutarimide resin composition referred to in the present application.
- an automatic fine particle measuring instrument for liquids HIAC Royco System 8011-100 (measuring instrument body: Model 8000A Counter, sampling device: Model ABS-2 Sampler, sensor: Model HRLD-100 Sensor) can be used.
- the glutarimide resin composition according to the present disclosure preferably has good bending resistance.
- a glutarimide resin is formed by a melt extrusion method and stretched twice vertically and horizontally by a biaxial stretching device (IMC-1905, Imoto Seisakusho) to produce a film having a predetermined thickness.
- IMC-1905 Imoto Seisakusho
- a bending resistance test is carried out using a DMLHB-FS-C type test device manufactured by an instrument, it is preferable that there is no breakage even when visually observed. Further, it is preferable that no cracks or obvious bending streaks are observed, and it is more preferable that no whitening occurs.
- the above-mentioned glutarimide resin composition may contain a crosslinked elastic body in order to improve the mechanical strength of the glutarimide resin.
- the crosslinked elastic body can be produced by a known polymerization method such as suspension polymerization, dispersion polymerization, emulsion polymerization, solution polymerization and bulk polymerization.
- a polymerization method such as suspension polymerization, dispersion polymerization, or emulsion polymerization.
- 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 (hard polymer) is preferable.
- the core layer made of a rubber-like polymer may have one or more layers made of a glass-like polymer as the innermost layer or the intermediate layer.
- the glass transition temperature Tg of the rubber-like polymer constituting the core layer is preferably 20 ° C. or lower, more preferably -60 to 20 ° C., and even more preferably -60 to 10 ° C. If the Tg of the rubber-like polymer constituting the core layer exceeds 20 ° C., the mechanical strength of the glutarimide resin may not be sufficiently improved.
- the Tg of the glassy polymer (hard polymer) constituting the shell layer is preferably 50 ° C. or higher, more preferably 50 to 140 ° C., and even more preferably 60 to 130 ° C. If the Tg of the glassy polymer constituting the shell layer is lower than 50 ° C., the heat resistance of the glutarimide resin may decrease.
- the glass transition temperature of the "rubber-like polymer” and the polymer of the "glass-like polymer” is Fox using the value described in the Polymer Handbook [Polymer Hand Book (J. Brandrup, Interscience 1989)].
- polymethylmethacrylate is 105 ° C.
- polybutylacrylate is ⁇ 54 ° C.
- the content ratio 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 ratio of the glassy polymer layer in the core layer is 0 to 60%, preferably 0 to 45%, and more preferably 10 to 40% with respect to 100% by weight of the total amount of the core layer.
- the content ratio of the shell layer in the core-shell type elastic body is preferably 5 to 70% by weight, more preferably 10 to 50% by weight.
- the core-shell elastic body may contain any suitable other components as long as the effects of the invention are not impaired.
- Any suitable polymerizable monomer may be used as the polymerizable monomer that forms the rubber-like polymer constituting the core layer.
- the polymerizable monomer forming the rubbery polymer preferably contains an alkyl (meth) acrylate.
- the alkyl (meth) acrylate is preferably contained in an amount of 50% by weight or more, more preferably 50 to 99.9% by weight, and 60 to 99% by weight in 100% by weight of the polymerizable monomer forming the rubber-like polymer. It is more preferably contained in an amount of 9% by weight.
- alkyl (meth) acrylate examples include ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, and lauroyl.
- alkyl (meth) acrylates having an alkyl group having 2 to 20 carbon atoms such as (meth) acrylate and stearyl (meth) acrylate.
- These alkyl groups may have an alicyclic or aromatic cyclic substituent, a branched structure, or a functional group.
- butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate and the like are preferable, and butyl acrylate, 2-Ethylhexyl acrylate and isononyl acrylate are more preferable. Only one of these may be used, or two or more thereof may be used in combination.
- the polymerizable monomer forming the rubbery polymer preferably contains a polyfunctional monomer having two or more polymerizable functional groups in the molecule.
- the polyfunctional monomer having two or more polymerizable functional groups in the molecule is preferably contained in an amount of 0.01 to 20% by weight, preferably 0.1 to 20% by weight. % Is more preferable, 0.1 to 10% by weight is more preferable, and 0.2 to 5% by weight is particularly preferable.
- polyfunctional monomer having two or more polymerizable functional groups in the molecule examples include aromatic divinyl monomers such as divinylbenzene, ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, and hexanediol.
- Alcan polyol poly (meth) acrylates such as di (meth) acrylates, oligoethylene glycol di (meth) acrylates, trimerol propanedi (meth) acrylates, and trimerol propanetri (meth) acrylates, urethane di (meth) acrylates, etc. Examples thereof include epoxydi (meth) acrylate and triallyl isocyanurate.
- examples of the polyfunctional monomer having different reactive polymerizable functional groups include allyl (meth) acrylate, diallyl maleate, diallyl fumarate, diallyl itaconate and the like. Of these, ethylene glycol dimethacrylate, butylene glycol diacrylate, and allyl methacrylate are preferable. Only one of these may be used, or two or more thereof may be used in combination.
- the polymerizable monomer forming the rubbery polymer includes the alkyl (meth) acrylate and another polymerizable monomer copolymerizable with the polyfunctional monomer having two or more polymerizable functional groups in the molecule. But it's okay.
- the other polymerizable monomers are preferably contained in an amount of 0 to 49.9% by weight, more preferably 0 to 39.9% by weight.
- the other polymerizable monomer examples include aromatic vinyl such as styrene, vinyltoluene and ⁇ -methylstyrene, vinyl cyanide such as aromatic vinylidene, acrylonitrile and methacrylonitrile, vinylidene cyanide, methyl methacrylate and urethane acrylate. , Urethane methacrylate and the like.
- the other polymerizable monomer may be a monomer having a functional group such as an epoxy group, a carboxyl group, a hydroxyl group or an amino group.
- examples of the monomer having an epoxy group include glycidyl methacrylate and the like, and examples of the monomer having a carboxyl group include methacrylic acid, acrylic acid, maleic acid, itaconic acid and the like.
- examples of the monomer having a hydroxyl group include 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate, and examples of the monomer having an amino group include diethylaminoethyl methacrylate and diethylaminoethyl acrylate. Only one of these may be used, or two or more thereof may be used in combination.
- the polymerizable monomer forming the rubber-like polymer may be used in combination with a chain transfer agent in a small amount.
- a chain transfer agent widely known ones can be used, and examples thereof include alkyl mercaptans such as octyl mercaptan, dodecyl mercaptan, and t-dodecyl mercaptan, and thioglycolic acid derivatives.
- Any suitable polymerizable monomer may be used as the polymerizable monomer forming the glassy polymer constituting the shell layer and the glassy polymer layer in the core layer.
- the polymerizable monomer forming the glassy polymer preferably contains at least one monomer selected from an alkyl (meth) acrylate and an aromatic vinyl monomer. In 100% by weight of the polymerizable monomer forming the glassy polymer, at least one selected from alkyl (meth) acrylate and aromatic vinyl monomer is preferably contained in an amount of 50 to 100% by weight, preferably 60 to 100% by weight. Is more preferable.
- the alkyl (meth) acrylate preferably has an alkyl group having 1 to 8 carbon atoms. Further, these alkyl groups may have an alicyclic or aromatic cyclic substituent, a branched structure, or a functional group.
- alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. And so on. Of these, methyl methacrylate is particularly preferable. Only one of these may be used, or two or more thereof may be used in combination.
- aromatic vinyl monomer examples include styrene, vinyltoluene, ⁇ -methylstyrene, and the like, and among these, styrene is preferable. Only one of these may be used, or two or more thereof may be used in combination.
- the polymerizable monomer forming the glassy polymer may contain a polyfunctional monomer having two or more polymerizable functional groups in the molecule. In 100% by weight of the polymerizable monomer forming the glassy polymer, 0 to 10% by weight, preferably 0 to 8% by weight, of the polyfunctional monomer having two or more polymerizable functional groups in the molecule is contained. It is more preferably contained, and further preferably 0 to 5% by weight.
- polyfunctional monomer having two or more polymerizable functional groups in the molecule include the same as those described above.
- the polymerizable monomer forming the glassy polymer contains the alkyl (meth) acrylate and another polymerizable monomer copolymerizable with the polyfunctional monomer having two or more polymerizable functional groups in the molecule. You may stay.
- the other polymerizable monomer is preferably contained in an amount of 0 to 50% by weight, more preferably 0 to 40% by weight, based on 100% by weight of the polymerizable monomer forming the glassy polymer.
- Examples of the other polymerizable monomer include vinyl cyanide such as acrylonitrile and methacrylonitrile, vinylidene cyanide, and alkyl (meth) acrylates, urethane acrylates, and urethane methacrylates other than those described above. Further, it may have a functional group such as an epoxy group, a carboxyl group, a hydroxyl group and an amino group. Examples of the monomer having an epoxy group include glycidyl methacrylate and the like, and examples of the monomer having a carboxyl group include methacrylic acid, acrylic acid, maleic acid, itaconic acid and the like, which have a hydroxyl group.
- Examples of the monomer include 2-hydroxymethacrylate and 2-hydroxyacrylate, and examples of the monomer having an amino group include diethylaminoethyl methacrylate and diethylaminoethyl acrylate. Only one of these may be used, or two or more thereof may be used in combination.
- the polymerizable monomer forming the glassy polymer it is also preferable to use a small amount of a known chain transfer agent similar to that used for the rubber-like polymer layer.
- any appropriate method capable of producing core-shell type particles can be adopted.
- the polymerizable monomer forming the rubber-like polymer constituting the core layer is suspended or emulsified to produce a suspension or emulsified dispersion containing the rubber-like polymer particles, followed by the suspension.
- a core-shell type having a multilayer structure in which the surface of the rubber-like polymer particles is coated with the glass-like polymer by adding a polymerizable monomer forming the glass-like polymer constituting the shell layer to the emulsified dispersion and radically polymerizing the rubber-like polymer particles.
- a method of obtaining an elastic body can be mentioned.
- the polymerizable monomer forming the rubber-like polymer and the polymerizable monomer forming the glassy polymer may be polymerized in one stage, or may be polymerized in two or more stages by changing the composition ratio. May be good.
- Preferred structures of the core-shell type elastic body include, for example, (a) a soft and rubber-like core layer and a hard and glass-like shell layer, and the core layer is a (meth) acrylic crosslinked elastic polymer layer.
- the rubber-like core layer has a multilayer structure having one or more glass-like layers inside thereof, and further has a glass-like shell layer on the outside of the core layer. ..
- the shell layer of the core-shell type elastic body contains alkyl acrylate in an amount of 3% by weight or more, more preferably 10% by weight or more, still more preferably 15% by weight.
- a non-crosslinked methacrylic resin containing the above (B) the shell layer of the core-shell type elastic body is composed of two or more layers having different alkyl acrylate contents, and the total alkyl acrylate is 10% by weight or more, more preferably.
- the core layer of the core-shell type elastic body is a glassy weight obtained by polymerizing a mixture of alkyl methacrylate, polyfunctional monomer, alkyl mercaptan, and other monomers as appropriate.
- Those having a multilayer structure in which a rubber-like polymer layer obtained by polymerizing a mixture of alkyl acrylate, polyfunctional monomer, alkyl mercaptan, and other monomers as appropriate in the presence of a coalesced layer is formed (D) the core-shell type elastic body.
- the core layer uses a peracid (persulfate, perphosphate, etc.) as a thermal decomposition initiator in the presence of a glassy polymer layer polymerized using an organic peroxide as a redox-type polymerization initiator.
- a peracid persulfate, perphosphate, etc.
- examples thereof include those having a multi-layer structure in which a rubber-like polymer layer polymerized in the process is formed.
- the structural design element of such a preferable core-shell type elastic body may have only one, or a plurality of two or more design elements may be used in combination.
- the core-shell type elastic body can be easily dispersed well in the glutarimide resin, there are few defects due to undispersion and aggregation when the film is formed, and the strength, toughness, and heat resistance are small. It has excellent transparency and appearance, and whitening due to temperature changes and stress is suppressed, so that a film with excellent quality can be obtained.
- polymerization initiator When the core-shell type elastic body is produced by emulsion polymerization, suspension polymerization, etc., a known polymerization initiator can be used.
- Particularly preferable polymerization initiators include persulfates such as potassium persulfate, ammonium persulfate and ammonium persulfate, perphosphates such as sodium perphosphate, and organic azo compounds such as 2,2-azobisisobutyronitrile.
- Hydroperoxide compounds such as cumene hydroperoxide, tertiary butyl hydroperoxide, 1,1-dimethyl-2-hydroxyethyl hydroperoxide, and peresters such as tertiary butyl isopropyl oxycarbonate and tertiary butyl peroxybutyrate.
- examples thereof include organic peroxide compounds such as benzoyl peroxide, dibutyl peroxide and lauryl peroxide.
- thermal decomposition type polymerization initiator may be used as a thermal decomposition type polymerization initiator, and may be used as a redox type polymerization initiator in the presence of a catalyst such as ferrous sulfate and a water-soluble reducing agent such as ascorbic acid and sodium formaldehyde sulfoxylate. It may be appropriately selected depending on the monomer composition to be polymerized, the layer structure, the polymerization temperature conditions and the like.
- the core-shell type elastic body When the core-shell type elastic body is produced by emulsion polymerization, it can be produced by ordinary emulsion polymerization using a known emulsifier.
- Known emulsifiers include anionics such as phosphate ester salts such as sodium alkyl sulphonate, sodium alkylbenzene sulphonate, sodium dioctyl sulphosuccinate, sodium lauryl sulfate, fatty acid sodium, sodium polyoxyethylene lauryl ether phosphate and the like.
- Surfactants, nonionic surfactants such as alkylphenols, aliphatic alcohols and propylene oxide, reaction products of ethylene oxide and the like are shown. These surfactants may be used alone or in combination of two or more.
- a cationic surfactant such as an alkylamine salt may be used.
- polymerization is carried out using a phosphate ester salt (alkali metal or alkaline earth metal) such as polyoxyethylene lauryl ether sodium phosphate. It is preferable to do so.
- a phosphate ester salt alkali metal or alkaline earth metal
- the core-shell type elastic latex obtained by emulsion polymerization is spray-dried, or, as is generally known, the polymer component is coagulated by adding an electrolyte or an organic solvent as a coagulant to the latex, and the polymer is appropriately heated, washed, and washed.
- An operation such as separation of the aqueous phase is carried out to dry the polymer component, and a lumpy or powdery core-shell type elastic body is obtained.
- the coagulant known substances such as a water-soluble electrolyte and an organic solvent can be used, but from the viewpoint of improving the thermal stability of the obtained copolymer during molding and from the viewpoint of productivity, magnesium chloride or sulfuric acid can be used. It is preferable to use a magnesium salt such as magnesium or a calcium salt such as calcium acetate or calcium chloride.
- the glutarimide resin composition according to the present disclosure contains a core-shell type elastic body
- the glutarimide resin composition contains 1 to 40 parts by weight, more preferably 2 to 35 parts by weight, based on 100 parts by weight of the glutarimide resin. It is by weight, more preferably 3 to 25 parts by weight. If the content of the core-shell type elastic body is less than 1 part by weight, the mechanical strength of the glutarimide resin is not sufficiently improved, and if it exceeds 40 parts by weight, the heat resistance of the glutarimide resin may decrease.
- the particle size of the soft core layer is preferably 1 to 500 nm, more preferably 10 to 400 nm, further preferably 50 to 300 nm, and 70. It is particularly preferably at ⁇ 300 nm. If the particle size of the core layer of the core-shell type elastic body is less than 1 nm, the mechanical strength of the glutarimide resin is not sufficiently improved, and if it is larger than 500 nm, the heat resistance and transparency of the glutarimide resin are impaired. There is a risk.
- the particle size of the core layer of the core-shell type elastic body is a film obtained by molding a compound obtained by blending a core-shell cross-linked elastic body and Sumipex EX at a weight ratio of 50:50.
- 100 rubber particle images were randomly selected from the obtained photographs taken by the RuO4 stained ultrathin section method with an acceleration voltage of 80 kV, and the average value of their particle diameters can be obtained.
- the glutarimide resin composition can be molded into a film containing the glutarimide resin composition by a known molding method.
- the film containing the glutarimide resin composition preferably has a haze value of 2.0% or less, and more preferably 1.0% or less.
- the transmittance is preferably 85% or more, more preferably 90% or more. When both the haze value and the transmittance are within the above ranges, it is preferable because the range of applications that can be used is widened.
- the optical anisotropy is not particularly limited, but it may be preferable that not only the optical anisotropy in the in-plane direction (length direction, width direction) but also the optical anisotropy in the thickness direction is small. In other words, it may be preferable that both the in-plane phase difference and the thickness direction phase difference are small.
- the in-plane phase difference at a wavelength of 590 nm is preferably 10 nm or less, more preferably 5 nm or less, and further preferably 1 nm or less.
- the phase difference in the thickness direction at a wavelength of 590 nm is preferably 40 nm or less, more preferably 15 nm or less, and further preferably 3 nm or less.
- the in-plane phase difference (Re) and the thickness direction phase difference (Rth) can be calculated by the following equations, respectively.
- nx, ny, and nz each have an X-axis in the direction in which the in-plane refractive index is maximized, a Y-axis in the direction perpendicular to the X-axis, and a Z-axis in the film thickness direction.
- d represents the thickness of the film, and
- the film obtained from the glutarimide resin composition according to the present disclosure has a small amount of foreign matter.
- the number of foreign substances is preferably 50 pieces / m 2 or less, more preferably 40 pieces / m 2 , and particularly preferably 30 pieces / m 2 or less.
- the foreign matter is the total number of foreign matter obtained by cutting out 1 m and 2 minutes from the obtained stretched film and counting the number of foreign matter of 20 ⁇ m or more by microscopic observation or the like.
- the film containing the glutarimide resin composition according to the present disclosure can be used as a substrate for an electronic material.
- Display peripherals viewpoint adjustment film, image adjustment film, image projection screen, retroreflective film, lens sheet, dust cover
- brightness improvement film cover glass substitute, glass substrate substitute, reflective film, antireflection film, antiglare film
- Double-sided / single-sided tape for electronic devices, adhesive film base material, AR Glass optical waveguide, dimming device substrate, light-shielding device substrate, high-frequency circuit substrate film, transparent flexible printed substrate, battery separator film, smartphone back cover It can be used for various purposes such as a release film or a detector substrate of an X-ray inspection device.
- video fields such as shooting lenses and finder for cameras, VTRs and projectors, filters, prisms, and Fresnel lenses, lens fields such as pickup lenses for optical disks such as CD players, DVD players, and MD players, and CD players and DVD players.
- lens fields such as pickup lenses for optical disks such as CD players, DVD players, and MD players, and CD players and DVD players.
- Optical recording field for optical disks such as MD players, light guide plate for liquid crystal, liquid crystal display film such as polarizing element protection film and retardation film, information equipment field such as surface protection film, optical fiber, optical switch, optical connector, etc.
- Optical communication field automobile headlight and tail lamp lens, inner lens, instrument cover, sun roof and other vehicle fields, eyeglasses and contact lenses, internal vision lenses, medical equipment fields such as medical supplies that require sterilization, road transparency It can be suitably used for plates, lenses for paired glasses, light-collecting windows and carports, lighting lenses and lighting covers, construction and building materials fields such as sizing for building materials, and microwave cooking containers (tableware).
- the film according to the present disclosure is excellent in optical properties such as optical homogeneity and transparency. Therefore, by utilizing these optical characteristics, it can be particularly suitably used for known optical applications such as an optically isotropic film, a polarizing element protective film, a transparent conductive film, and the like around a liquid crystal display device.
- the film according to the present disclosure can be attached to a polarizing element and used as a polarizing plate. That is, the film can be used as a polarizing element protective film for a polarizing plate.
- the substituent is not particularly limited, and any conventionally known polarizing element can be used. Specifically, for example, a polarizing element obtained by containing iodine in stretched polyvinyl alcohol can be mentioned.
- the film can be produced by a solution casting method or a spin coating method in which the glutarimide resin 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 manufacturing cost and the load on the global environment and the working environment due to the solvent.
- the film manufacturing method a method of molding the glutarimide resin by a melt extrusion method to manufacture a film will be described in detail.
- the film obtained by the melt extrusion method is referred to as a "melt extrusion film" to distinguish it from the film obtained by another method such as a solution casting method.
- the glutarimide resin is formed into a film by a melt extrusion method, first, the glutarimide resin is supplied to an extruder and the glutarimide resin is heated and melted.
- the glutarimide resin is preferably pre-dried before being supplied to the extruder. By performing such pre-drying, it is possible to prevent foaming of the resin extruded from the extruder.
- the method of pre-drying is not particularly limited, but for example, the raw material (that is, the glutarimide resin) can be in the form of pellets or the like and used in a hot air dryer, a vacuum dryer, or the like.
- the glutarimide resin heated and melted in the extruder is supplied to the T-die through a gear pump and a filter.
- a gear pump is used, the uniformity of the extrusion amount of the resin can be improved and the thickness unevenness in the film longitudinal direction can be reduced.
- a filter is used, foreign substances in the glutarimide resin can be removed, and a film having no defects and having an excellent appearance can be obtained.
- the glutarimide resin supplied to the T-die is extruded from the T-die as a sheet-shaped molten resin. Then, the sheet-shaped molten resin is sandwiched between two cooling rolls and cooled to form a film.
- the film forming temperature is preferably 310 ° C. or lower, preferably 300 ° C. or lower, and even more preferably 280 ° C. or lower.
- one is a rigid metal roll having a smooth surface, and the other is provided with an elastically deformable metal elastic outer cylinder having a smooth surface.
- Flexible rolls are preferred.
- cooling roll is used in the meaning including “touch roll” and “cooling roll”.
- each cooling roll is metal, if the film to be formed is thin, the surfaces of the cooling rolls come into contact with each other and the cooling rolls are used. The outer surface of the body may be scratched or the cooling roll itself may be damaged.
- the sheet-shaped molten resin is sandwiched between the two cooling rolls as described above to form a film
- the sheet-shaped molten resin is sandwiched between the two cooling rolls to cool the film, and the thickness is relatively thick. Obtain the original film once. After that, it is preferable to uniaxially stretch or biaxially stretch the raw film to produce a film having a predetermined thickness.
- a sheet-shaped molten resin is sandwiched between the two cooling rolls and cooled to once obtain an original film having a thickness of 150 ⁇ m. Then, the raw film may be stretched by biaxial stretching in the vertical and horizontal directions to produce a film having a thickness of 40 ⁇ m.
- the glutarimide resin is once formed into an unstretched raw film, and then uniaxially stretched or biaxially stretched to produce a stretched film. Can be done.
- a film after forming the glutarimide resin into a film and before stretching that is, a film in an unstretched state is referred to as a "raw film”.
- the raw fabric film When the raw fabric film is stretched, the raw fabric film may be continuously stretched immediately after the raw fabric film is molded, or after the raw fabric film is molded, it is temporarily stored or moved to be stored or moved.
- the anti-film may be stretched.
- the raw film When the raw film is stretched immediately after being formed into the raw film, if the raw film is in a very short time (in some cases, instantaneously) in the film manufacturing process, it is stretched. It does not have to be in a perfect film state as long as it maintains a sufficient degree of film form. Further, the raw film may not have the performance as a finished film.
- the method for stretching the raw film is not particularly limited, and any conventionally known stretching method may be used. Specifically, for example, lateral stretching using a tenter, longitudinal stretching using a roll, and sequential biaxial stretching in which these are sequentially combined can be used.
- the raw film When stretching the raw film, it is preferable to preheat the raw film to a temperature 0.5 ° C to 5 ° C, preferably 1 ° C to 3 ° C higher than the stretching temperature, and then cool to the stretching temperature for stretching. ..
- the thickness of the raw film in the width direction can be maintained with high accuracy, and the thickness accuracy of the stretched film does not decrease or unevenness of thickness does not occur.
- the original film does not stick to the roll or loosen due to its own weight.
- the preheating temperature of the raw film if the preheating temperature of the raw film is too high, the raw film tends to stick to the roll or loosen due to its own weight. Further, if the difference between the preheating temperature and the stretching temperature of the raw film is small, it tends to be difficult to maintain the thickness accuracy of the raw film before stretching, the thickness unevenness becomes large, and the thickness accuracy tends to decrease. be.
- the stretching temperature when stretching the raw film is not particularly limited, and may be changed according to the mechanical strength, surface properties, thickness accuracy, etc. required for the stretched film to be manufactured.
- the glass transition temperature of the raw film (glutarimide resin composition) obtained by the DSC method is Tg
- it is preferably in the temperature range of (Tg-30 ° C) to (Tg + 30 ° C).
- the temperature range is more preferably (Tg-20 ° C.) to (Tg + 30 ° C.), further preferably (Tg-10 ° C.) to (Tg + 30 ° C.), and the temperature range is (Tg) to (Tg + 30 ° C.).
- the stretching temperature of the biaxial stretching of the optical film is preferably in the temperature range of Tg-30 ° C. or higher and Tg + 30 ° C. or lower when the glass transition temperature of the glutarimide resin composition is Tg.
- the stretching temperature is within the above temperature range, the thickness unevenness of the obtained stretched film can be reduced, and the mechanical properties of elongation rate, tear propagation strength, and MIT bending resistance can be improved. In addition, it is possible to prevent the occurrence of troubles such as the film sticking to the roll.
- the stretching temperature is higher than the above temperature range, the thickness unevenness of the obtained stretched film becomes large, and the mechanical properties such as elongation rate, tear propagation strength, and kneading fatigue resistance cannot be sufficiently improved. There is. Further, there is a tendency that troubles such as the film sticking to the roll are likely to occur.
- the draw ratio thereof is not particularly limited, and may be determined according to the mechanical strength, surface properties, thickness accuracy, etc. of the stretched film to be manufactured. Although it depends on the stretching temperature, it is generally preferable to select the stretching ratio in the range of 1.1 times to 3 times, and more preferably in the range of 1.3 times to 2.5 times. It is preferable to select in the range of 1.5 times to 2.3 times, more preferably.
- the draw ratio is within the above range, the mechanical properties such as the elongation rate of the film, the tear propagation strength, and the kneading fatigue resistance can be significantly improved. Therefore, it is possible to produce a stretched film having a thickness unevenness of 5 ⁇ m or less and an internal haze of 1.0% or less.
- any of unstretched film, uniaxially stretched film, and biaxially stretched film can be suitably used because the film is excellent in mechanical strength.
- a film-molded glutarimide resin composition according to the present disclosure can be used as a substrate.
- the substrate Due to its excellent dielectric properties, heat resistance, weather resistance, and transparency, the substrate can be used for antennas, vehicle windowpanes, building windowpanes, industrial machine displays, in-house electronic devices and displays. It can be used for the display of the device and the like.
- the dielectric loss tangent Df value is preferably 0.010 or less, and more preferably 0.007 or less. When the Df value is in this range, the loss is low.
- the relative permittivity Dk value is preferably 3.2 or less, and more preferably 3.0 or less.
- the antenna part formed by the conductor is also pulled by the contraction and expansion of the base material, and the antenna size changes. Since the antenna size is uniquely determined by the length of the wavelength of the resonating frequency, it is not preferable that the antenna size changes due to an increase in temperature or the like. Therefore, the coefficient of linear expansion is preferably 100 ppm or less, preferably 80 ppm or less. Is particularly preferred.
- a transparent conductive film can be formed by using a substrate containing the glutarimide resin composition according to the present disclosure.
- the transparent conductive film is obtained by laminating an optical adjustment layer on the substrate and further laminating a transparent conductive layer on the optical adjustment layer.
- the optical adjustment layer is a layer having a refractive index different from that of the substrate, and the refractive index and the film thickness can be designed to match the desired optical characteristics.
- the material of the optical adjustment layer is not particularly limited, and a material having the desired characteristics can be arbitrarily selected. Examples thereof include an ultraviolet curable resin and a thermosetting resin having a refractive index different from that of the substrate, and an ultraviolet curable resin and a thermosetting resin in which high refractive index particles and low refractive index particles are dispersed.
- a photosensitive resin such as an ultraviolet curable resin is preferable because high productivity can be obtained.
- acrylic resins examples include acrylic resins, urethane resins, fluororesins, silicone compounds, silane compounds, imide compounds, magnesium, calcium, titanium, yttrium, zirconium, niobium, zinc, aluminum, indium, etc.
- Elements such as silicon, tin, and carbon, compounds such as oxides, nitrides, and fluorides containing these elements, and compounds obtained by combining these elements can be preferably used.
- the transparent conductive layer is a material containing indium oxide as a main component, a material in which fine particles of zirconium oxide or titanium oxide are dispersed in an ultraviolet curable resin can be particularly preferably used.
- the thickness of the optical adjustment layer can be designed according to the refractive index and thickness of the optical adjustment layer and the transparent conductive layer, and is preferably about 40 to 150 nm in order to positively utilize the interference. In some cases, the desired characteristics can be obtained without positively utilizing interference, and in such cases, the thickness is preferably 0.5 to 5 ⁇ m in order to reduce the influence of film thickness fluctuations.
- the method for forming the optical adjustment layer is not particularly limited, and a wet coating that obtains a film by drying or curing a coating liquid containing a solvent after application may be used, or a solvent such as sputtering, vapor deposition, or ion plating is not used.
- a dry coating may be used. Either dry coating or wet coating may be used alone, or may be used in combination. In particular, the wet coating can be preferably used because of its high productivity.
- the material for forming the transparent conductive layer examples include inorganic materials mainly composed of oxides such as indium, tin, zinc, titanium and aluminum and nitrides, graphene, carbon nanotubes, fullerene and diamond-like carbon. It can be used without particular limitation, such as a carbon-based material, an organic transparent conductive material such as PEDOT, a material in which conductive nanowires are dispersed, and a material made transparent by thinning an opaque conductive material.
- forming the transparent conductive layer with an oxide containing at least one element selected from the group consisting of indium, zinc, and tin can impart conductivity uniformly to the entire surface, and also. It is preferable from the viewpoint of the balance between transparency and resistance value.
- the transparent conductive layer may be formed from a single material or layer, or may be formed by combining a plurality of materials or layers.
- ITO which is a mixture of indium oxide and tin oxide
- the transparent conductive layer is formed on the optical adjustment layer.
- the transparent conductive layer may be formed on one side of the substrate or may be formed on both sides. When the transparent conductive layer is formed on both sides, the optical adjustment layer is also formed on both sides.
- the method for forming the transparent conductive layer is not particularly limited, and a known method can be preferably used.
- a method of forming a transparent conductive material by a method such as sputtering, vapor deposition, ion plating, aerosol deposition, or coating, or a method of making an opaque conductive material transparent by thinning it into wires can be mentioned.
- a method for forming a transparent conductive layer a method for forming a transparent conductive material by sputtering can be particularly preferably used.
- the area of the peak derived from 3 protons is B
- the area of the peak derived from the NH proton of the above formula (1) is C around 10.2 to 10.8 ppm
- the aromatic ring of styrene around 6.8 to 7.3 ppm.
- the area of the peak of origin was defined as D.
- the area of the proton-derived peak contained in CH 2 and CH 3 of methyl methacrylate is represented by A ⁇ (10C + 10B / 3 + 2D / 5). That is, the molar ratio M1: M2: M3: M4 of the monomer units represented by the above formulas (1) to (4) in the glutarimide resin is C: B / 3: ⁇ A- (10C + 10B / 3 + 2D / / 5) ⁇ / 5: Represented by D / 5.
- M1 + M2 + M3 + M4 100.
- monomer units and impurities other than the above formulas (1) to (4) are not taken into consideration.
- FIG. 2 is an NMR chart measured using heavy DMF
- FIG. 3 is an NMR chart measured using heavy methylene chloride.
- the area B cannot be calculated because the peak derived from N—CH 3 proton of the above formula (2) and the peak derived from heavy DMF overlap at around 3 ppm.
- the area B can be calculated.
- the solvent used may be changed to calculate the peak area.
- the areas of other peaks can be corrected based on the area of the peak derived from the aromatic ring of styrene in the vicinity of, for example, 6.8 to 7.3 ppm.
- TGA thermogravimetric measuring device
- This test piece was subjected to an in-plane phase difference Re at a wavelength of 590 nm and an incident angle of 0 ° at a temperature of 23 ⁇ 2 ° C and a humidity of 50 ⁇ 5% using an automatic birefringence meter (KOBRA-WR manufactured by Oji Measurement Co., Ltd.). It was measured.
- orientation birefringence The value obtained by dividing the in-plane phase difference Re by the thickness of the test piece measured using a Mitutoyo digital indicator at a temperature of 23 ° C. ⁇ 2 ° C. and a humidity of 60% ⁇ 5% was defined as orientation birefringence.
- Acid value 0.3 g of glutarimide resin was dissolved in 37.5 mL of methylene chloride, and 37.5 mL of methanol was further added. Next, 5 mL of a 0.1 mmol% sodium hydroxide aqueous solution and a few drops of an ethanol solution of phenolphthalein were added. Next, back titration was performed using 0.1 mmol% hydrochloric acid, and the acid value was determined from the amount of hydrochloric acid required for neutralization.
- a film having a thickness of 160 ⁇ m was produced from a glutarimide resin by a melt extrusion method (film formation temperature: 275 ° C.). The obtained film was stretched 2 ⁇ 2 times at 160 ° C. using a biaxial stretching machine (stretching machine: Imoto Seisakusho IMC-1905). The thickness was measured at 40 ⁇ m. The room temperature was 23 ° C., the humidity was controlled to 60% RH, and the bending resistance test was carried out using the Yuasa system equipment DMLHB-FS-C type test equipment. The test conditions were as follows.
- Example 1 A glutarimide resin was produced using a 40 mm ⁇ fully meshed co-rotating twin-screw extruder.
- a co-directional meshing twin-screw extruder with a diameter of 40 mm and an L / D (ratio of the length L and diameter D of the extruder) of 90 is used, and a constant weight feeder (CE-T- manufactured by Kubota Co., Ltd.) is used.
- CE-T- manufactured by Kubota Co., Ltd. Using 2E), the raw material resin was charged into the raw material supply port of the extruder. The degree of pressure reduction of the vent in the extruder was set to ⁇ 0.10 MPa.
- the resin (strand) discharged from the extruder was cooled in a cooling water tank and then cut with a pelletizer to form pellets.
- a resin pressure gauge was provided at the outlet of the extruder in order to check the pressure inside the extruder or to determine the extrusion fluctuation.
- a copolymer of methyl methacrylate monomer unit and styrene monomer unit (Mw: 105,000, styrene unit 11 mol%) was used as the methacrylic raw material resin, and 28% by weight was used as the imidizing agent.
- a glutarimide resin was produced using aqueous ammonia. At this time, the maximum temperature of the extruder is 280 ° C., the screw rotation speed is 100 rpm, the raw material resin supply amount is 10 kg / hour, and the amount of ammonia water added is 10.0 parts by weight (pure ammonia) with respect to 100 parts by weight of the raw material resin. The minute was 2.8 parts by weight).
- the glass transition temperature of the glutarimide resin obtained as described above was 127.6 ° C.
- M1 was 5.3 mol%
- M2 was 11.0 mol%
- M3 was 71.5 mol%
- M4 was 12.2 mol%.
- the acid value was 0.23 mmol / g.
- the orientation birefringence was ⁇ 0.71 ⁇ 10 -3 .
- Example 2 The glutarimide resin obtained in Example 1 was used as a raw material resin, and the second stage imidization was carried out using 28% by weight of aqueous ammonia as an imidizing agent to produce a glutarimide resin.
- the maximum temperature of the extruder is 280 ° C.
- the screw rotation speed is 100 rpm
- the raw material resin supply amount is 10 kg / hour
- the amount of ammonia water added is 20.0 parts by weight (pure ammonia) with respect to 100 parts by weight of the raw material resin.
- the minute was 5.6 parts by weight).
- the glass transition temperature of the glutarimide resin obtained as described above was 146.1 ° C., M1 was 17.1 mol%, M2 was 16.0 mol%, M3 was 52.5 mol%, and M4 was 14.4 mol%.
- the acid value was 0.29 mmol / g.
- the orientation birefringence was 0.54 ⁇ 10 -3 .
- Example 3 The glutarimide resin obtained in Example 2 was used as a raw material resin, and a third stage imidization was carried out using 28% by weight of aqueous ammonia as an imidizing agent to produce a glutarimide resin.
- the maximum temperature of the extruder is 280 ° C.
- the screw rotation speed is 100 rpm
- the raw material resin supply amount is 10 kg / hour
- the amount of ammonia water added is 20.0 parts by weight (pure ammonia) with respect to 100 parts by weight of the raw material resin.
- the minute was 5.6 parts by weight).
- the glass transition temperature of the glutarimide resin obtained here was 173.7 ° C., M1 was 34.9 mol%, M2 was 26.3 mol%, M3 was 19.4 mol%, and M4 was 19.4 mol%.
- the acid value was 0.39 mmol / g.
- the orientation birefringence was 2.0 ⁇ 10 -3 .
- Example 6 Liquefied ammonia was used instead of ammonia water, and the amount of liquefied ammonia added was the same as in Example 1 except that the number of parts shown in Table 1 was set with respect to 100 parts by weight of the raw material resin to obtain a glutarimide resin. .. The evaluation results are shown in Table 1.
- a glutarimide resin was produced using a tandem type reaction extruder in which two extrusion reactors were arranged in series.
- both the first extruder and the second extruder have a diameter of 75 mm and an L / D (ratio of the length L of the extruder to the diameter D) of 74 in the same direction meshing twin-screw extruder.
- the raw material resin was supplied to the raw material supply port of the first extruder using a constant weight feeder (manufactured by Kubota Co., Ltd.).
- the degree of decompression of each vent in the first extruder and the second extruder was set to ⁇ 0.095 MPa.
- a pressure control mechanism inside the component that connects the first extruder and the second extruder with a pipe having a diameter of 38 mm and a length of 2 m, and connects the resin discharge port of the first extruder and the raw material supply port of the second extruder. Used a constant flow pressure valve.
- the resin (strand) discharged from the second extruder was cooled by a cooling conveyor and then cut with a pelletizer to obtain pellets.
- the outlet of the first extruder, the first extruder and the second extruder are used.
- a resin pressure gauge was provided at the outlet of the second extruder at the center of the extruder connection component.
- polymethylmethacrylate resin (Mw: 105,000, acrylic acid ester unit less than 0.1% by weight) is used as a raw material resin, and monomethylamine is used as an imidizing agent to make an imide resin.
- the intermediate was manufactured.
- the maximum temperature of the extruder was 280 ° C.
- the screw rotation speed was 55 rpm
- the supply amount of the raw material resin was 450 kg / hour
- the amount of monomethylamine added was 2.0 parts by weight with respect to 100 parts by weight of the raw material resin.
- the constant flow pressure valve was installed immediately before the raw material supply port of the second extruder, and the pressure of the monomethylamine press-fitting portion of the first extruder was adjusted to 8 MPa.
- the imidizing agent and by-products remaining in the rear vent and the vacuum vent were devolatile, and then a mixed solution of dimethyl carbonate and triethylamine was added as an esterifying agent to produce a glutarimide resin.
- the temperature of each barrel of the extruder was 260 ° C.
- the screw rotation speed was 55 rpm
- the amount of dimethyl carbonate added was 3.2 parts with respect to 100 parts of the raw material resin
- the amount of triethylamine added was with respect to 100 parts by weight of the raw material resin.
- the weight was 0.8 parts by weight.
- the esterifying agent was removed by venting, extruded from the strand die, cooled in a water tank, and then pelletized with a pelletizer to obtain a resin composition.
- Example 2 The physical characteristics of the methacrylic raw material resin used in Example 1 were evaluated.
- Table 1 shows the results obtained in Examples 1 to 6 and Comparative Examples 1 and 2.
- the glutarimide resins of Examples 1 to 6 containing the repeating units represented by the formulas (1) to (4) have a sufficiently low value of orientation birefringence, and Comparative Examples 1 to 1. It can be seen that the glass transition temperature is higher than that of the resin of No. 2 and the heat resistance is excellent.
- Table 2 shows the bending resistance test results for Examples 2 and 3 and Comparative Example 3.
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Abstract
Description
特許文献2記載のグルタルイミド樹脂は、位相差は小さいものの、耐熱性に改善の余地があった。
本発明は、前記現状に鑑み、耐熱性が良好で、かつ配向複屈折が小さいグルタルイミド樹脂を提供することを目的とする。
即ち、本発明は、下記一般式(1)で表される繰り返し単位、
下記一般式(2)で表される繰り返し単位、
下記一般式(3)で表される繰り返し単位、
及び、下記一般式(4)で表される繰り返し単位、
を含有するグルタルイミド樹脂に関する。
好ましくは、前記グルタルイミド樹脂の配向複屈折が、-3.0×10-3~3.0×10-3であり、より好ましくは、-1.5×10-3~1.5×10-3である。
好ましくは、前記グルタルイミド樹脂は、下記式(a)及び(b)を満たす。
10≦M1+M2≦70 (a)
5≦M4≦25 (b)
(式中、M1は、前記グルタルイミド樹脂中の前記式(1)で表される繰り返し単位の含有量(モル%)、M2は、前記グルタルイミド樹脂中の前記式(2)で表される繰り返し単位の含有量(モル%)、M4は、前記グルタルイミド樹脂中の前記式(4)で表される繰り返し単位の含有量(モル%)である。M1>0、及びM2>0である。)
好ましくは、前記グルタルイミド樹脂のガラス転移温度が124℃以上である。
好ましくは、前記グルタルイミド樹脂のTGA測定における5%重量減少温度が350℃以上である。
また本発明は、前記グルタルイミド樹脂を含有する、グルタルイミド樹脂組成物;前記グルタルイミド樹脂組成物を含有するフィルム又は基板;当該基板、光学調整層、及び透明導電層がこの順で積層されている、透明導電フィルムにも関する。
さらに本発明は、前記一般式(3)で表される繰り返し単位と、前記一般式(4)で表される繰り返し単位とを含有する原料樹脂と、アンモニアを反応させる工程を含む、グルタルイミド樹脂の製造方法であって、前記原料樹脂中の前記一般式(4)で表される繰り返し単位の含有量が、前記原料樹脂中の前記一般式(3)で表される繰り返し単位と前記一般式(4)で表される繰り返し単位の合計含有量に対して、3モル%以上、23モル%以下である、グルタルイミド樹脂の製造方法にも関する。
さらにまた、本発明は、前記製造方法で得られたグルタルイミド樹脂をさらにアンモニアと反応させる工程を含む、グルタルイミド樹脂の製造方法にも関する。
本発明の好適な態様によれば、良好な耐折り曲げ性も有するグルタルイミド樹脂を提供することができる。
更に、本発明に係るグルタルイミド樹脂は、製造で使用するイミド化剤の使用量を減らしても耐熱性が良好であるため、イミド化工程での反応時間を短縮できるため、生産性の向上を図ることができ、また、イミド化工程でのガス排出量を低減できるという利点がある。
本開示に係るグルタルイミド樹脂は、下記一般式(1)で表される繰り返し単位、
耐熱性と配向複屈折のバランスに優れることから、メタクリル酸メチル単位が好ましい。前記式(3)で表される繰り返し単位のうち、前記メタクリル酸メチル単位の割合は、50~100モル%が好ましく、70~100モル%がより好ましく、80~100モル%がさらに好ましく、90~100モル%が特に好ましい。
前記式(4)で表される繰り返し単位を構成するモノマーとしては、例えば、スチレン、α-メチルスチレン、ビニルトルエン、ビニルナフタレン等が挙げられる。なかでも、スチレンが特に好ましい。
なお、本明細書において、特に断りのない限り、「配向複屈折」とは、グルタルイミド樹脂をフィルム化し、当該樹脂のガラス転移温度より5~8℃高い温度で、前記フィルムを100%延伸して得た延伸フィルムについて測定した複屈折が意図される。配向複屈折(△n)は、△n=nx-ny=Re/dで定義され、位相差計により測定することができる。延伸する際の温度は、前記樹脂のガラス転移温度より5℃高い温度であってもよいし、前記樹脂のガラス転移温度より8℃高い温度であってもよい。
10≦M1+M2≦70 (a)
式中、M1は、前記グルタルイミド樹脂中の前記式(1)で表される繰り返し単位の含有量(モル%)、M2は、前記グルタルイミド樹脂中の前記式(2)で表される繰り返し単位の含有量(モル%)である。M1>0、及びM2>0である。
本開示に係るグルタルイミド樹脂では、M1+M2が比較的小さい値であっても耐熱性が良好である。M1+M2が大きい値になるとグルタルイミド樹脂をフィルム化した時に脆くなり得るが、M1+M2が前記範囲にあるグルタルイミド樹脂ではフィルムの脆さを回避することができる。
5≦M4≦25 (b)
式中、M4は、前記グルタルイミド樹脂中の前記式(4)で表される繰り返し単位の含有量(モル%)である。
M1>M2 (c)
M1がM2よりも大きい場合、高い耐熱性と小さい配向複屈折をより高度のレベルで両立可能である。より好ましくは、M1>M2+0.2である。
M2の値は、耐熱性と配向複屈折の両立の観点から、好ましくは3モル%以上であり、より好ましくは5モル%以上であり、さらに好ましくは7モル%以上であり、さらに好ましくは8モル%以上であり、より更に好ましくは10モル%以上であり、特に好ましくは12モル%以上である。
イミド化率(%)=100×(S1+S2)/(S1+S2+S3)
c=Δn/ΔF
で示される。
本願において、光弾性係数は、セナルモン法により、波長515nmにて、23℃、50%RHにおいて測定した値である。
本開示に係るグルタルイミド樹脂の酸価は0.10~1.00mmol/gであることが好ましい。酸価が前記範囲内であれば、耐熱性、機械物性、成形加工性のバランスに優れたグルタルイミド樹脂を得ることができる。
カルボン酸量の測定方法は、国際公開第2005/054311号公報に記載の滴定法の溶媒をメタノールからジメチルスルホキシドに変えた酸価(DMSO酸価)を用いることにより算出できる。具体的には
(カルボン酸量)=2×(酸価)-(DMSO酸価)
により算出できる。メタノールを用いた滴定では1分子の酸無水物を1分子とカウントするのに対して、ジメチルスルホキシドを用いた滴定では1分子の酸無水物を2分子とカウントするため、前記式が適用できる。
本開示に係るグルタルイミド樹脂を製造するには、前記一般式(3)で表される繰り返し単位及び前記一般式(4)で表される繰り返し単位を有する原料樹脂(以下、メタクリル系原料樹脂と呼ぶ場合がある)とアンモニアを反応させることが好ましい。
前記メタクリル系原料樹脂としては特に制限されないが、メタクリル酸エステル-芳香族ビニル単量体共重合体が好ましく、メタクリル酸アルキルエステル-芳香族ビニル単量体共重合体がより好ましく、メタクリル酸メチル-スチレン共重合体が特に好ましい。
前記メタクリル酸エステル-芳香族ビニル単量体共重合体は、メタクリル酸エステル単量体単位(前記式(3))を主要単位とすることが好ましく、具体的には、メタクリル酸エステル単量体単位(前記式(3))と芳香族ビニル単量体単位(前記式(4))のモル比が97/3~77/23であることが好ましい。このような共重合体は、全ての単量体100モル%中、メタクリル酸エステル単量体97~77モル%と芳香族ビニル単量体3~23モル%を含有する単量体混合物を重合して得ることができる。前記モル比は、95/5~80/20が好ましく、93/7~85/15がより好ましい。
前記メタクリル系原料樹脂中の一般式(3)又は(4)で表される繰り返し単位の含有量(モル%)は、NMR測定等、公知の方法で同定することができる。
特に、メタクリル酸エステル単量体中、メタクリル酸メチルの含有量が50~100モル%であることが好ましい。より好ましくは70~100モル%であり、さらに好ましくは80~100モル%であり、特に好ましくは90~100モル%である。
本開示に係るグルタルイミド樹脂の製造方法は、前記メタクリル系原料樹脂を加熱溶融して、イミド化剤で処理する工程(イミド化工程)を含む。これによりグルタルイミド樹脂が製造できる。
前記イミド化剤としては、アンモニアを用いる。アンモニアを用いてイミド化を行うことで、二種類のグルタルイミド環構造(前記式(1)で表される単位及び前記式(2)で表される単位)を共に導入することができる。
これに対して、アンモニアを用いたイミド化では、従来のメチルアミンを用いたイミド化と比較して、イミド化率(M1+M2)が低くても、得られるグルタルイミド樹脂の耐熱性が良好となり得る。イミド化率が低くてよいので、イミド化工程での反応時間を短縮でき、また、フィルム化した時の脆さを回避することができる。
本開示に係るグルタルイミド樹脂の製造方法では、前記イミド化工程に加え、エステル化剤で処理する工程を含むことができる。このエステル化工程によって、イミド化工程で得られたグルタルイミド樹脂の酸価を所望の範囲内に調整することができる。エステル化剤としては、例えば、ジメチルカーボネート、2,2-ジメトキシプロパン、ジメチルスルホキシド、トリエチルオルトホルメート、トリメチルオルトアセテート、トリメチルオルトホルメート、ジフェニルカーボネート、ジメチルサルフェート、メチルトルエンスルホネート、メチルトリフルオロメチルスルホネート、メチルアセテート、メタノール、エタノール、メチルイソシアネート、p-クロロフェニルイソシアネート、ジメチルカルボジイミド、ジメチル-t-ブチルシリルクロライド、イソプロペニルアセテート、ジメチルウレア、テトラメチルアンモニウムハイドロオキサイド、ジメチルジエトキシシラン、テトラ-N-ブトキシシラン、ジメチル(トリメチルシラン)フォスファイト、トリメチルフォスファイト、トリメチルフォスフェート、トリクレジルフォスフェート、ジアゾメタン、エチレンオキサイド、プロピレンオキサイド、シクロヘキセンオキサイド、2-エチルヘキシルグリシジルエーテル、フェニルグリシジルエーテル、ベンジルグリシジルエーテルなどが挙げられる。これらの中でも、コスト、反応性などの観点から、ジメチルカーボネート、トリメチルオルトアセテートが好ましく、コストの観点からジメチルカーボネートが好ましい。
このエステル化工程において、エステル化剤の使用量は、メタクリル系原料樹脂100重量部に対して0~12重量部であることが好ましく、0~8重量部であることがより好ましい。
イミド化工程および任意のエステル化工程を経たグルタルイミド樹脂中には、未反応のイミド化剤や、未反応のエステル化剤、反応により副生した揮発成分および樹脂分解物等を含んでいるため、大気圧以下に減圧可能なベント孔を押出機の後半に装着することが可能である。
本開示に係るグルタルイミド樹脂に、必要に応じて他の樹脂や添加剤を配合して、グルタルイミド樹脂組成物を構成することができる。添加剤としては、一般に用いられる酸化防止剤、熱安定剤、光安定剤、紫外線吸収剤、ラジカル捕捉剤などの耐候性安定剤や、触媒、可塑剤、滑剤、帯電防止剤、着色剤、収縮防止剤、抗菌・脱臭剤等を単独または2種以上組み合わせて、発明の目的を損なわない範囲で添加してもよい。また、これらの添加剤は、後述するグルタルイミド樹脂またはグルタルイミド樹脂組成物を成形加工する際に添加することも可能である。
D=2mm(r=1mm)、60rpm、1時間=3600回
サンプルサイズ:100mm×20mm
試験方向:長軸=MD(TD軸で折り曲げ)
前述のグルタルイミド樹脂組成物は、グルタルイミド樹脂の機械的強度を向上させるために架橋弾性体を含んでもよい。架橋弾性体は、公知の懸濁重合、分散重合、乳化重合、溶液重合、塊状重合等の重合方法によって製造できる。特に以下に記載するようなコアシェル型構造を有する架橋弾性体を製造するには、懸濁重合、分散重合、乳化重合等の重合方法を用いることが好ましい。
また、他の重合性モノマーとしては、エポキシ基、カルボキシル基、水酸基、アミノ基等の官能基を有するモノマーでもよい。具体的には、エポキシ基を有するモノマーとして、例えば、グリシジルメタクリレート等を挙げることができ、カルボキシル基を有するモノマーとして、例えば、メタクリル酸、アクリル酸、マレイン酸、イタコン酸等を挙げることができ、水酸基を有するモノマーとして、例えば、2-ヒドロキシエチルメタクリレート、2-ヒドロキシエチルアクリレート等を挙げることができ、アミノ基を有するモノマーとして、例えば、ジエチルアミノエチルメタクリレート、ジエチルアミノエチルアクリレート等を挙げることができる。これらは1種のみ用いても良いし、2種以上を併用しても良い。
前記グルタルイミド樹脂組成物は、公知の成形方法で、グルタルイミド樹脂組成物を含有するフィルムに成形することができる。
Rth=|(nx+ny)/2-nz|×d
前記式中において、nx、ny、およびnzは、それぞれ、面内屈折率が最大となる方向をX軸、X軸に垂直な方向をY軸、フィルムの厚さ方向をZ軸とし、それぞれの軸方向の屈折率を表す。また、dはフィルムの厚さ、||は絶対値を表す。
また、カメラやVTR、プロジェクター用の撮影レンズやファインダー、フィルター、プリズム、フレネルレンズなどの映像分野、CDプレイヤーやDVDプレイヤー、MDプレイヤーなどの光ディスク用ピックアップレンズなどのレンズ分野、CDプレイヤーやDVDプレイヤー、MDプレイヤーなどの光ディスク用の光記録分野、液晶用導光板、偏光子保護フィルムや位相差フィルムなどの液晶ディスプレイ用フィルム、表面保護フィルムなどの情報機器分野、光ファイバ、光スイッチ、光コネクターなどの光通信分野、自動車ヘッドライトやテールランプレンズ、インナーレンズ、計器カバー、サンルーフなどの車両分野、眼鏡やコンタクトレンズ、内視境用レンズ、滅菌処理の必要な医療用品などの医療機器分野、道路透光板、ペアガラス用レンズ、採光窓やカーポート、照明用レンズや照明カバー、建材用サイジングなどの建築・建材分野、電子レンジ調理容器(食器)等にも好適に用いることができる。
本開示に係る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、前記グルタルイミド樹脂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。
原反フィルムを延伸する方法は、特に限定されるものではなく、従来公知の任意の延伸方法を用いればよい。具体的には、例えば、テンターを用いた横延伸、ロールを用いた縦延伸、及びこれらを逐次組み合わせた逐次二軸延伸等を用いることができる。
本開示に係るグルタルイミド樹脂組成物をフィルム成形したものを基板として用いることができる。
本開示に係るグルタルイミド樹脂組成物を含有する基板を用いて、透明導電フィルムを構成することができる。前記透明導電フィルムは、前記基板の上に、光学調整層が積層され、当該光学調整層の上に、透明導電層が更に積層されたものである。
光学調整層の材料としては特に限定されず、目的とする特性の得られる材料を任意に選択できる。例えば、基板と異なる屈折率を持った紫外線硬化樹脂や熱硬化性樹脂、高屈折率粒子や低屈折率粒子を分散した紫外線硬化樹脂や熱硬化性樹脂が挙げられる。高い生産性を得ることができることから、紫外線硬化樹脂などの感光性樹脂が好ましい。具体的な例を挙げると、アクリル系樹脂、ウレタン系樹脂、フッ素樹脂、シリコーン系化合物、シラン化合物、イミド化合物等の他、マグネシウム、カルシウム、チタン、イットリウム、ジルコニウム、ニオブ、亜鉛、アルミニウム、インジウム、シリコン、スズ、炭素などの元素、及びこれらの元素を含む酸化物、窒化物、フッ化物等の化合物、及びこれらの組み合わせによって得られる化合物などを好ましく用いることができる。中でも、屈折率調整が容易であることから無機粒子を含むことが好ましく、酸化ジルコニウム、酸化チタン、酸化ニオブ、酸化アルミニウム、窒化アルミニウム、酸化インジウム、酸化ケイ素よりなる群から選択される少なくとも1種の無機粒子を含んでいることがより好ましい。透明導電層が酸化インジウムを主成分とする材料の場合は、紫外線硬化樹脂に酸化ジルコニウムや酸化チタンの微粒子を分散させたものを特に好ましく用いることができる。
光学調整層の厚みは、光学調整層や透明導電層の屈折率や厚みに応じて設計することができ、干渉を積極的に利用するためには40~150nm程度とすることが好ましい。干渉を積極的に利用せずとも目的とする特性が得られる場合もあり、その場合は膜厚変動の影響を受けにくくするため0.5~5μmとすることも好ましい。
光学調整層の形成方法は特に限定されず、溶媒を含む塗液を塗布後に乾燥や硬化させることで膜を得るウエットコーティングを用いても良いし、スパッタリング、蒸着、イオンプレーティングといった溶剤を使わないドライコーティングを用いても良い。ドライコーティングとウエットコーティングのどちらかのみを用いても良いし、組み合わせて用いても良い。特にウエットコーティングは生産性の高さから、好ましく用いることができる。
透明導電層は光学調整層上に形成する。透明導電層は基板の片面に形成されても良いし、両面に形成されても良い。両面に透明導電層を形成する場合、光学調整層も両面に形成される。
透明導電層の形成方法は特に制限されず、公知の方法を好ましく用いることができる。例えば、透明導電性材料をスパッタリング、蒸着、イオンプレーティング、エアロゾルデポジション、塗布などの方法によって形成する方法や、不透明な導電性材料を細線化することで透明化する方法、が挙げられる。これらの透明導電層の形成方法の中でも、特にスパッタリングによって透明導電性材料を形成する方法を好ましく用いることができる。
1H-NMR BRUKER社製 AvanceIII(400MHz)を用いて、樹脂30mgを重DMSO、重DMF、または重塩化メチレンに溶解し、樹脂の1H-NMR測定を行った。0.5から2.3ppm付近のメタクリル酸メチルおよびスチレンのCH2およびCH3に含まれるプロトン由来のピークの面積をA、2.7から3.2ppm付近の前記式(2)のN-CH3プロトン由来のピークの面積をB、10.2~10.8ppm付近の前記式(1)のN-Hプロトン由来のピークの面積をC、6.8から7.3ppm付近のスチレンの芳香環由来のピークの面積をDとした。
1H-NMR BRUKER社性 AvanceIII(400MHz)を用いて、樹脂30mgを重クロロホルムに溶解し、樹脂の1H-NMR測定を行った。2.7から3.1ppm付近と3.4~3.7ppm付近の2つのピークからなるメタクリル酸メチルのOCH3プロトン由来のピークの面積を3で割った値Eと、6.8から7.3ppm付近のスチレンの芳香環由来のピークの面積を5で割った値Fより次式で求めた。
フーリエ変換赤外分光光度計(JASCO社製FI/IR-4100)を用いて、樹脂のIRスペクトルを測定した。N-Hのイミドカルボニル基に由来する1700cm-1付近の吸収の強度(ピーク高さ)S1、N-CH3のイミドカルボニル基に由来する1680cm-1付近の吸収の強度S2、エステルカルボニル基に由来する1720cm-1付近の吸収の強度S3から、次式によりイミド化率を決定した。
イミド化率(%)=100×(S1+S2)/(S1+S2+S3)
樹脂10mgを用いて、示差走査熱量計(DSC、日立ハイテクサイエンス社製 示差走査熱量計DSC7000X)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。
熱重量測定装置(TGA:日立ハイテクサイエンス社製:STA7200)を用いて、グルタルイミド樹脂15mgを、窒素雰囲気下、室温から10℃/minで昇温させ、グルタルイミド樹脂の熱減量(重量%)が5%になるときの温度を測定した。
前記(6)で作製したフィルムから、幅50mm、長さ150mmのサンプルを切り出し、延伸倍率100%で、ガラス転移温度より5℃(実施例1~3、比較例1、2)又は8℃(実施例4~6)高い温度で、延伸フィルムを作製した。この1軸2倍延伸フィルムのTD方向の中央部から40mm×40mmの試験片を切り出した。この試験片を、自動複屈折計(王子計測株式会社製 KOBRA-WR)を用いて、温度23±2℃、湿度50±5%において、波長590nm、入射角0゜で面内位相差Reを測定した。
グルタルイミド樹脂0.3gを塩化メチレン37.5mLに溶解し、さらにメタノール37.5mLを加えた。次に0.1mmol%の水酸化ナトリウム水溶液5mLとフェノールフタレインのエタノール溶液数滴を加えた。次に0.1mmol%の塩酸を用いて逆滴定を行い、中和に要する塩酸の量から酸価を求めた。
グルタルイミド樹脂から、溶融押出法(製膜温度275℃)により160μmのフィルムを製造した。得られたフィルムを二軸延伸機(延伸機:井元製作所 IMC-1905)を用いて160℃で2×2倍延伸した。厚みは40μmで測定した。室温23℃、湿度を60%RHにコントロールし、ユアサシステム機器性DMLHB-FS-C型の試験装置を用いて耐折り曲げ試験を実施した。試験条件は以下の通り実施した。
D=2mm(r=1mm)、60rpm、1時間=3600回
サンプルサイズ:100mm×20mm
試験方向:長軸=MD(TD軸で折り曲げ)
耐折り曲げ試験の結果は下記の2段階で示した。
〇:変化なし
×:フィルム破断
40mmΦ完全噛合型同方向回転二軸押出反応機を用いて、グルタルイミド樹脂を製造した。押出機に関しては直径40mm、L/D(押出機の長さLと直径Dの比)が90の同方向噛合型二軸押出機を使用し、定重量フィーダー(クボタ株式会社製CE-T-2E)を用いて、押出機原料供給口に原料樹脂を投入した。押出機に於けるベントの減圧度は-0.10MPaとした。押出機から吐出された樹脂(ストランド)は、冷却水槽で冷却した後、ペレタイザーでカッティングしペレットとした。ここで、押出機の内部の圧力確認、又は押出変動を見極める為に、押出機出口に樹脂圧力計を設けた。
以上により得られたグルタルイミド樹脂のガラス転移温度は127.6℃、M1は5.3モル%、M2は11.0モル%、M3は71.5モル%、M4は12.2モル%、酸価は0.23mmol/gであった。配向複屈折は-0.71×10-3であった。
実施例1で得られたグルタルイミド樹脂を原料樹脂として使用し、イミド化剤として、28重量%のアンモニア水を用いて二段目のイミド化を実施して、グルタルイミド樹脂を製造した。この際、押出機最高温部温度を280℃、スクリュー回転数は100rpm、原料樹脂供給量は10kg/時間、アンモニア水の添加量は原料樹脂100重量部に対して20.0重量部(アンモニア純分としては5.6重量部)とした。
以上により得られたグルタルイミド樹脂のガラス転移温度は146.1℃、M1は17.1モル%、M2は16.0モル%、M3は52.5モル%、M4は14.4モル%、酸価は0.29mmol/gであった。配向複屈折は0.54×10-3であった。
実施例2で得られたグルタルイミド樹脂を原料樹脂として使用し、イミド化剤として、28重量%のアンモニア水を用いて三段目のイミド化を実施して、グルタルイミド樹脂を製造した。この際、押出機最高温部温度を280℃、スクリュー回転数は100rpm、原料樹脂供給量は10kg/時間、アンモニア水の添加量は原料樹脂100重量部に対して20.0重量部(アンモニア純分としては5.6重量部)とした。
ここで得られたグルタルイミド樹脂のガラス転移温度は173.7℃、M1は34.9モル%、M2は26.3モル%、M3は19.4モル%、M4は19.4モル%、酸価は0.39mmol/gであった。配向複屈折は2.0×10-3であった。
アンモニア水の代わりに液化アンモニアを使用し、液化アンモニアの添加量は原料樹脂100重量部に対して表1に記載の部数とした以外は実施例1と同様に実施し、グルタルイミド樹脂を得た。評価結果を表1に記載する。
押出反応機を2台直列に並べたタンデム型反応押出機を用いて、グルタルイミド樹脂を製造した。タンデム型反応押出機に関しては、第1押出機、第2押出機共に、直径75mm、L/D(押出機の長さLと直径Dの比)が74の同方向噛合型二軸押出機を使用し、定重量フィーダー(クボタ株式会社製)を用いて、第1押出機原料供給口に原料樹脂を供給した。第1押出機、第2押出機における各ベントの減圧度は-0.095MPaとした。更に、直径38mm、長さ2mの配管で第1押出機と第2押出機を接続し、第1押出機の樹脂吐出口と第2押出機の原料供給口を接続する部品内圧力制御機構には定流圧力弁を用いた。第2押出機から吐出された樹脂(ストランド)は、冷却コンベアで冷却した後、ペレタイザーでカッティングし、ペレットとした。ここで、第1押出機の樹脂吐出口と第2押出機の原料供給口を接続する部品内圧力調整、又は押出変動を抑制する為に、第1押出機出口、第1押出機と第2押出機接続部品の中央部、第2押出機出口に樹脂圧力計を設けた。
実施例1で使用したメタクリル系原料樹脂について、各物性を評価した。
ZF14フィルム(日本ゼオン社製)を用いて、耐折り曲げ性試験を実施した。サンプルは破断した。
Claims (12)
- 下記一般式(1)で表される繰り返し単位、
下記一般式(2)で表される繰り返し単位、
下記一般式(3)で表される繰り返し単位、
及び、下記一般式(4)で表される繰り返し単位、
を含有するグルタルイミド樹脂。 - 配向複屈折が、-3.0×10-3~3.0×10-3である、請求項1に記載のグルタルイミド樹脂。
- 配向複屈折が-1.5×10-3~1.5×10-3である、請求項1に記載のグルタルイミド樹脂。
- 下記式(a)及び(b)を満たす、請求項1~3のいずれか1項に記載のグルタルイミド樹脂。
10≦M1+M2≦70 (a)
5≦M4≦25 (b)
(式中、M1は、前記グルタルイミド樹脂中の前記式(1)で表される繰り返し単位の含有量(モル%)、M2は、前記グルタルイミド樹脂中の前記式(2)で表される繰り返し単位の含有量(モル%)、M4は、前記グルタルイミド樹脂中の前記式(4)で表される繰り返し単位の含有量(モル%)である。M1>0、及びM2>0である。) - ガラス転移温度が124℃以上である、請求項1~4のいずれか1項に記載のグルタルイミド樹脂。
- TGA測定における5%重量減少温度が350℃以上である、請求項1~5のいずれか1項に記載のグルタルイミド樹脂。
- 請求項1~6のいずれか1項に記載のグルタルイミド樹脂を含有する、グルタルイミド樹脂組成物。
- 請求項7に記載のグルタルイミド樹脂組成物を含有するフィルム。
- 請求項7に記載のグルタルイミド樹脂組成物を含有する基板。
- 請求項9に記載の基板、光学調整層、及び透明導電層がこの順で積層されている、透明導電フィルム。
- 下記一般式(3)で表される繰り返し単位と、
下記一般式(4)で表される繰り返し単位とを含有する原料樹脂と、アンモニアを反応させる工程を含む、グルタルイミド樹脂の製造方法であって、
前記原料樹脂中の前記一般式(4)で表される繰り返し単位の含有量が、前記原料樹脂中の前記一般式(3)で表される繰り返し単位と前記一般式(4)で表される繰り返し単位の合計含有量に対して、3モル%以上、23モル%以下である、グルタルイミド樹脂の製造方法。 - 請求項11に記載の製造方法で得られたグルタルイミド樹脂をさらにアンモニアと反応させる工程を含む、グルタルイミド樹脂の製造方法。
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4595727A (en) * | 1985-05-02 | 1986-06-17 | Doak Kenneth W | Blends of a polyglutarimide with a rubber-modified vinyl chloride resin |
JPH04331209A (ja) * | 1990-02-01 | 1992-11-19 | Roehm Gmbh | メタクリル酸のアルキルエステルのポリマーをイミド化する方法 |
JPH08325326A (ja) * | 1995-05-29 | 1996-12-10 | Kuraray Co Ltd | イミド化アクリル樹脂の製造方法 |
JPH0948819A (ja) * | 1995-05-29 | 1997-02-18 | Kuraray Co Ltd | イミド化アクリル樹脂の製造法 |
JP2016155956A (ja) * | 2015-02-25 | 2016-09-01 | 株式会社日本触媒 | グルタルイミド樹脂の製造方法 |
WO2017169931A1 (ja) * | 2016-03-29 | 2017-10-05 | 旭化成株式会社 | メタクリル系樹脂組成物、及び成形体 |
JP2019048965A (ja) * | 2016-10-13 | 2019-03-28 | 旭化成株式会社 | メタクリル系樹脂組成物、成形体 |
WO2021193922A1 (ja) * | 2020-03-26 | 2021-09-30 | 株式会社クラレ | アクリル系組成物及び成形体 |
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Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4595727A (en) * | 1985-05-02 | 1986-06-17 | Doak Kenneth W | Blends of a polyglutarimide with a rubber-modified vinyl chloride resin |
JPH04331209A (ja) * | 1990-02-01 | 1992-11-19 | Roehm Gmbh | メタクリル酸のアルキルエステルのポリマーをイミド化する方法 |
JPH08325326A (ja) * | 1995-05-29 | 1996-12-10 | Kuraray Co Ltd | イミド化アクリル樹脂の製造方法 |
JPH0948819A (ja) * | 1995-05-29 | 1997-02-18 | Kuraray Co Ltd | イミド化アクリル樹脂の製造法 |
JP2016155956A (ja) * | 2015-02-25 | 2016-09-01 | 株式会社日本触媒 | グルタルイミド樹脂の製造方法 |
WO2017169931A1 (ja) * | 2016-03-29 | 2017-10-05 | 旭化成株式会社 | メタクリル系樹脂組成物、及び成形体 |
JP2019048965A (ja) * | 2016-10-13 | 2019-03-28 | 旭化成株式会社 | メタクリル系樹脂組成物、成形体 |
WO2021193922A1 (ja) * | 2020-03-26 | 2021-09-30 | 株式会社クラレ | アクリル系組成物及び成形体 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2024128122A1 (ja) * | 2022-12-13 | 2024-06-20 | 株式会社クラレ | 延伸フィルムとその製造方法、光学フィルム、および加飾フィルム |
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