WO2022270446A1 - ポリビニルアルコール樹脂、ポリビニルアセタール樹脂、ポリビニルアルコール樹脂の製造方法及びポリビニルアセタール樹脂の製造方法 - Google Patents
ポリビニルアルコール樹脂、ポリビニルアセタール樹脂、ポリビニルアルコール樹脂の製造方法及びポリビニルアセタール樹脂の製造方法 Download PDFInfo
- Publication number
- WO2022270446A1 WO2022270446A1 PCT/JP2022/024444 JP2022024444W WO2022270446A1 WO 2022270446 A1 WO2022270446 A1 WO 2022270446A1 JP 2022024444 W JP2022024444 W JP 2022024444W WO 2022270446 A1 WO2022270446 A1 WO 2022270446A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- polyvinyl alcohol
- polyvinyl
- alcohol resin
- resin
- Prior art date
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 217
- 239000011347 resin Substances 0.000 title claims abstract description 217
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 142
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 142
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 58
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000011354 acetal resin Substances 0.000 title claims abstract description 55
- 229920006324 polyoxymethylene Polymers 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- 239000004094 surface-active agent Substances 0.000 claims abstract description 37
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 16
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims abstract description 15
- 125000003368 amide group Chemical group 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 12
- 125000002636 imidazolinyl group Chemical group 0.000 claims abstract description 12
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims abstract description 8
- 125000003277 amino group Chemical group 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 56
- 238000007127 saponification reaction Methods 0.000 claims description 53
- 229920001290 polyvinyl ester Polymers 0.000 claims description 50
- -1 dialkylamine compound Chemical class 0.000 claims description 45
- 239000000178 monomer Substances 0.000 claims description 36
- 239000002002 slurry Substances 0.000 claims description 36
- 239000003505 polymerization initiator Substances 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 29
- 125000004432 carbon atom Chemical group C* 0.000 claims description 27
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 25
- 229920001567 vinyl ester resin Polymers 0.000 claims description 22
- 239000003093 cationic surfactant Substances 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 239000005340 laminated glass Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 125000001174 sulfone group Chemical group 0.000 claims description 13
- 238000011084 recovery Methods 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 8
- 239000011229 interlayer Substances 0.000 claims description 8
- 150000001875 compounds Chemical group 0.000 claims description 6
- 125000005270 trialkylamine group Chemical group 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 238000000034 method Methods 0.000 description 37
- 229920002689 polyvinyl acetate Polymers 0.000 description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- 239000011118 polyvinyl acetate Substances 0.000 description 31
- 239000000243 solution Substances 0.000 description 22
- 239000002904 solvent Substances 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000006359 acetalization reaction Methods 0.000 description 15
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 150000001299 aldehydes Chemical class 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 238000005227 gel permeation chromatography Methods 0.000 description 11
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 10
- 229910001873 dinitrogen Inorganic materials 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000002270 dispersing agent Substances 0.000 description 8
- 239000000975 dye Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000007870 radical polymerization initiator Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000004014 plasticizer Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000003377 acid catalyst Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 229920006280 packaging film Polymers 0.000 description 6
- 239000012785 packaging film Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 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 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 125000005265 dialkylamine group Chemical group 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 5
- 229920001225 polyester resin Polymers 0.000 description 5
- 229920005672 polyolefin resin Polymers 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- BSXGCUHREZFSRY-UHFFFAOYSA-N 3-[[1-amino-2-[[1-amino-1-(2-carboxyethylimino)-2-methylpropan-2-yl]diazenyl]-2-methylpropylidene]amino]propanoic acid;tetrahydrate Chemical compound O.O.O.O.OC(=O)CCNC(=N)C(C)(C)N=NC(C)(C)C(=N)NCCC(O)=O BSXGCUHREZFSRY-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 4
- LWMFAFLIWMPZSX-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene Chemical compound N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 LWMFAFLIWMPZSX-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 4
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 4
- LGYNIFWIKSEESD-UHFFFAOYSA-N 2-ethylhexanal Chemical compound CCCCC(CC)C=O LGYNIFWIKSEESD-UHFFFAOYSA-N 0.000 description 3
- 239000001431 2-methylbenzaldehyde Substances 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000987 azo dye Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- UREZNYTWGJKWBI-UHFFFAOYSA-M benzethonium chloride Chemical compound [Cl-].C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 UREZNYTWGJKWBI-UHFFFAOYSA-M 0.000 description 3
- 229960001950 benzethonium chloride Drugs 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000003985 ceramic capacitor Substances 0.000 description 3
- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 239000000693 micelle Substances 0.000 description 3
- RVRFYZGKUZFYAH-UHFFFAOYSA-N n',n'-dimethylpropane-1,3-diamine;octadecanoic acid Chemical compound CN(C)CCCN.CCCCCCCCCCCCCCCCCC(O)=O RVRFYZGKUZFYAH-UHFFFAOYSA-N 0.000 description 3
- WVFLGSMUPMVNTQ-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-[[1-(2-hydroxyethylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCO WVFLGSMUPMVNTQ-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 150000004714 phosphonium salts Chemical class 0.000 description 3
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 239000011112 polyethylene naphthalate Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical class CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- BMQZYMYBQZGEEY-UHFFFAOYSA-M 1-ethyl-3-methylimidazolium chloride Chemical compound [Cl-].CCN1C=C[N+](C)=C1 BMQZYMYBQZGEEY-UHFFFAOYSA-M 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- IAQQDIGGISSSQO-UHFFFAOYSA-N 2-(4-fluorophenyl)piperidine Chemical compound C1=CC(F)=CC=C1C1NCCCC1 IAQQDIGGISSSQO-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- UMESNHVJZFCGBV-UHFFFAOYSA-N 2-methyl-4-[(2-methylphenyl)methylidene]-1,3-oxazol-5-one Chemical compound O=C1OC(C)=NC1=CC1=CC=CC=C1C UMESNHVJZFCGBV-UHFFFAOYSA-N 0.000 description 2
- IAVREABSGIHHMO-UHFFFAOYSA-N 3-hydroxybenzaldehyde Chemical compound OC1=CC=CC(C=O)=C1 IAVREABSGIHHMO-UHFFFAOYSA-N 0.000 description 2
- YGCZTXZTJXYWCO-UHFFFAOYSA-N 3-phenylpropanal Chemical compound O=CCCC1=CC=CC=C1 YGCZTXZTJXYWCO-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- STOOUUMSJPLRNI-UHFFFAOYSA-N 5-amino-4-hydroxy-3-[[4-[4-[(4-hydroxyphenyl)diazenyl]phenyl]phenyl]diazenyl]-6-[(4-nitrophenyl)diazenyl]naphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC2=CC(S(O)(=O)=O)=C(N=NC=3C=CC(=CC=3)C=3C=CC(=CC=3)N=NC=3C=CC(O)=CC=3)C(O)=C2C(N)=C1N=NC1=CC=C([N+]([O-])=O)C=C1 STOOUUMSJPLRNI-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical class CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 150000003934 aromatic aldehydes Chemical class 0.000 description 2
- 239000002635 aromatic organic solvent Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 229960001716 benzalkonium Drugs 0.000 description 2
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 description 2
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 229960001927 cetylpyridinium chloride Drugs 0.000 description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- HXWGXXDEYMNGCT-UHFFFAOYSA-M decyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)C HXWGXXDEYMNGCT-UHFFFAOYSA-M 0.000 description 2
- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 2
- KQPPJWHBSYEOKV-UHFFFAOYSA-M dodecyl-ethyl-dimethylazanium;ethyl sulfate Chemical compound CCOS([O-])(=O)=O.CCCCCCCCCCCC[N+](C)(C)CC KQPPJWHBSYEOKV-UHFFFAOYSA-M 0.000 description 2
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- JYVPKRHOTGQJSE-UHFFFAOYSA-M hexyl(trimethyl)azanium;bromide Chemical compound [Br-].CCCCCC[N+](C)(C)C JYVPKRHOTGQJSE-UHFFFAOYSA-M 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 description 2
- BTFQKIATRPGRBS-UHFFFAOYSA-N o-tolualdehyde Chemical compound CC1=CC=CC=C1C=O BTFQKIATRPGRBS-UHFFFAOYSA-N 0.000 description 2
- GIDDQKKGAYONOU-UHFFFAOYSA-N octylazanium;bromide Chemical compound Br.CCCCCCCCN GIDDQKKGAYONOU-UHFFFAOYSA-N 0.000 description 2
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- SSEGNMJSEROZIF-UHFFFAOYSA-M trimethyl(nonyl)azanium;bromide Chemical compound [Br-].CCCCCCCCC[N+](C)(C)C SSEGNMJSEROZIF-UHFFFAOYSA-M 0.000 description 2
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- MWEXRLZUDANQDZ-RPENNLSWSA-N (2s)-3-hydroxy-n-[11-[4-[4-[4-[11-[[2-[4-[(2r)-2-hydroxypropyl]triazol-1-yl]acetyl]amino]undecanoyl]piperazin-1-yl]-6-[2-[2-(2-prop-2-ynoxyethoxy)ethoxy]ethylamino]-1,3,5-triazin-2-yl]piperazin-1-yl]-11-oxoundecyl]-2-[4-(3-methylsulfanylpropyl)triazol-1-y Chemical compound N1=NC(CCCSC)=CN1[C@@H](CO)C(=O)NCCCCCCCCCCC(=O)N1CCN(C=2N=C(N=C(NCCOCCOCCOCC#C)N=2)N2CCN(CC2)C(=O)CCCCCCCCCCNC(=O)CN2N=NC(C[C@@H](C)O)=C2)CC1 MWEXRLZUDANQDZ-RPENNLSWSA-N 0.000 description 1
- NNJRPZZMNBNRFJ-UHFFFAOYSA-N (3-ethoxy-3-oxo-2-phenylpropyl)azanium;chloride Chemical compound Cl.CCOC(=O)C(CN)C1=CC=CC=C1 NNJRPZZMNBNRFJ-UHFFFAOYSA-N 0.000 description 1
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- VPBZZPOGZPKYKX-UHFFFAOYSA-N 1,2-diethoxypropane Chemical compound CCOCC(C)OCC VPBZZPOGZPKYKX-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical class O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- KVGOXGQSTGQXDD-UHFFFAOYSA-N 1-decane-sulfonic-acid Chemical class CCCCCCCCCCS(O)(=O)=O KVGOXGQSTGQXDD-UHFFFAOYSA-N 0.000 description 1
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical class CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 description 1
- GKQHIYSTBXDYNQ-UHFFFAOYSA-M 1-dodecylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+]1=CC=CC=C1 GKQHIYSTBXDYNQ-UHFFFAOYSA-M 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- YCMFMSOTJOUSLI-UHFFFAOYSA-M 1-hexadecyl-4-methylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=C(C)C=C1 YCMFMSOTJOUSLI-UHFFFAOYSA-M 0.000 description 1
- VWNAITWBRLKIIS-UHFFFAOYSA-N 1-sulfanylpropane-1,1-diol Chemical compound CCC(O)(O)S VWNAITWBRLKIIS-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- UNNGUFMVYQJGTD-UHFFFAOYSA-N 2-Ethylbutanal Chemical compound CCC(CC)C=O UNNGUFMVYQJGTD-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- JEYLQCXBYFQJRO-UHFFFAOYSA-N 2-[2-[2-(2-ethylbutanoyloxy)ethoxy]ethoxy]ethyl 2-ethylbutanoate Chemical compound CCC(CC)C(=O)OCCOCCOCCOC(=O)C(CC)CC JEYLQCXBYFQJRO-UHFFFAOYSA-N 0.000 description 1
- IZBZQUREHISXFJ-UHFFFAOYSA-N 2-[4-chloro-5-methyl-3-(trifluoromethyl)pyrazol-1-yl]acetic acid Chemical compound CC1=C(Cl)C(C(F)(F)F)=NN1CC(O)=O IZBZQUREHISXFJ-UHFFFAOYSA-N 0.000 description 1
- YTVQIZRDLKWECQ-UHFFFAOYSA-N 2-benzoylcyclohexan-1-one Chemical compound C=1C=CC=CC=1C(=O)C1CCCCC1=O YTVQIZRDLKWECQ-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- BVKRDNIULHRLCO-UHFFFAOYSA-N 2-carboxyethyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCC(=O)O)C1=CC=CC=C1 BVKRDNIULHRLCO-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- JLSJEUQOXVVCPN-UHFFFAOYSA-N 3-sulfanylpropanamide Chemical compound NC(=O)CCS JLSJEUQOXVVCPN-UHFFFAOYSA-N 0.000 description 1
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 1
- AVERNFJXXRIVQN-XSDYUOFFSA-N 5-[(4-ethoxyphenyl)diazenyl]-2-[(e)-2-[4-[(4-ethoxyphenyl)diazenyl]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound C1=CC(OCC)=CC=C1N=NC(C=C1S(O)(=O)=O)=CC=C1\C=C\C1=CC=C(N=NC=2C=CC(OCC)=CC=2)C=C1S(O)(=O)=O AVERNFJXXRIVQN-XSDYUOFFSA-N 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- UFUQRRYHIHJMPB-DUCFOALUSA-L Sirius red 4B Chemical compound [Na+].[Na+].OS(=O)(=O)c1cc2cc(NC(=O)c3ccccc3)ccc2c([O-])c1\N=N\c1ccc(cc1)\N=N\c1ccc(cc1)S([O-])(=O)=O UFUQRRYHIHJMPB-DUCFOALUSA-L 0.000 description 1
- DPOPAJRDYZGTIR-UHFFFAOYSA-N Tetrazine Chemical compound C1=CN=NN=N1 DPOPAJRDYZGTIR-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 125000004054 acenaphthylenyl group Chemical class C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 229960001413 acetanilide Drugs 0.000 description 1
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Chemical class C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 1
- 229940072049 amyl acetate Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- GDCXBZMWKSBSJG-UHFFFAOYSA-N azane;4-methylbenzenesulfonic acid Chemical compound [NH4+].CC1=CC=C(S([O-])(=O)=O)C=C1 GDCXBZMWKSBSJG-UHFFFAOYSA-N 0.000 description 1
- AERRGWRSYANDQB-UHFFFAOYSA-N azanium;dodecane-1-sulfonate Chemical compound [NH4+].CCCCCCCCCCCCS([O-])(=O)=O AERRGWRSYANDQB-UHFFFAOYSA-N 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- YSJGOMATDFSEED-UHFFFAOYSA-M behentrimonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCCCCCC[N+](C)(C)C YSJGOMATDFSEED-UHFFFAOYSA-M 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229960000686 benzalkonium chloride Drugs 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- KHSLHYAUZSPBIU-UHFFFAOYSA-M benzododecinium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 KHSLHYAUZSPBIU-UHFFFAOYSA-M 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 1
- OCBHHZMJRVXXQK-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 OCBHHZMJRVXXQK-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 229960000228 cetalkonium chloride Drugs 0.000 description 1
- DVBJBNKEBPCGSY-UHFFFAOYSA-M cetylpyridinium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 DVBJBNKEBPCGSY-UHFFFAOYSA-M 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 1
- 229940117916 cinnamic aldehyde Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- KSMVZQYAVGTKIV-UHFFFAOYSA-N decanal Chemical compound CCCCCCCCCC=O KSMVZQYAVGTKIV-UHFFFAOYSA-N 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- HDTUMIMTZDKTPD-UHFFFAOYSA-N dimethyl(17-phenylheptadecyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CCCCCCCCCCCCCCCCCC1=CC=CC=C1 HDTUMIMTZDKTPD-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- PBOIUUROGJVVNC-UHFFFAOYSA-L disodium 2-hydroxy-5-[[4-[[2-methoxy-4-[(3-sulfonatophenyl)diazenyl]phenyl]carbamoylamino]phenyl]diazenyl]benzoate Chemical compound [Na+].[Na+].COc1cc(ccc1NC(=O)Nc1ccc(cc1)N=Nc1ccc(O)c(c1)C([O-])=O)N=Nc1cccc(c1)S([O-])(=O)=O PBOIUUROGJVVNC-UHFFFAOYSA-L 0.000 description 1
- OYUZMQYZGSMPII-UHFFFAOYSA-L disodium 4-hydroxy-7-[(5-hydroxy-6-phenyldiazenyl-7-sulfonatonaphthalen-2-yl)amino]-3-phenyldiazenylnaphthalene-2-sulfonate Chemical compound [Na+].[Na+].Oc1c(N=Nc2ccccc2)c(cc2cc(Nc3ccc4c(O)c(N=Nc5ccccc5)c(cc4c3)S([O-])(=O)=O)ccc12)S([O-])(=O)=O OYUZMQYZGSMPII-UHFFFAOYSA-L 0.000 description 1
- DSARWKALPGYFTA-UHFFFAOYSA-L disodium 4-hydroxy-7-[(5-hydroxy-6-phenyldiazenyl-7-sulfonatonaphthalen-2-yl)carbamoylamino]-3-phenyldiazenylnaphthalene-2-sulfonate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=CC2=CC(NC(=O)NC=3C=C4C=C(C(N=NC=5C=CC=CC=5)=C(O)C4=CC=3)S([O-])(=O)=O)=CC=C2C(O)=C1N=NC1=CC=CC=C1 DSARWKALPGYFTA-UHFFFAOYSA-L 0.000 description 1
- PHBXSOKXCTZJBO-UHFFFAOYSA-L disodium 7-amino-4-hydroxy-3-[[4-[4-[(1-hydroxy-4-sulfonatonaphthalen-2-yl)diazenyl]-3-methoxyphenyl]-2-methoxyphenyl]diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].COc1cc(ccc1N=Nc1cc(c2ccccc2c1O)S([O-])(=O)=O)-c1ccc(N=Nc2c(O)c3ccc(N)cc3cc2S([O-])(=O)=O)c(OC)c1 PHBXSOKXCTZJBO-UHFFFAOYSA-L 0.000 description 1
- LARMRMCFZNGNNX-UHFFFAOYSA-L disodium 7-anilino-3-[[4-[(2,4-dimethyl-6-sulfonatophenyl)diazenyl]-2-methoxy-5-methylphenyl]diazenyl]-4-hydroxynaphthalene-2-sulfonate Chemical compound [Na+].[Na+].COc1cc(N=Nc2c(C)cc(C)cc2S([O-])(=O)=O)c(C)cc1N=Nc1c(O)c2ccc(Nc3ccccc3)cc2cc1S([O-])(=O)=O LARMRMCFZNGNNX-UHFFFAOYSA-L 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 239000004664 distearyldimethylammonium chloride (DHTDMAC) Substances 0.000 description 1
- VZXFEELLBDNLAL-UHFFFAOYSA-N dodecan-1-amine;hydrobromide Chemical compound [Br-].CCCCCCCCCCCC[NH3+] VZXFEELLBDNLAL-UHFFFAOYSA-N 0.000 description 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 1
- NUFVQEIPPHHQCK-UHFFFAOYSA-N ethenyl-methoxy-dimethylsilane Chemical compound CO[Si](C)(C)C=C NUFVQEIPPHHQCK-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- FYORGSHNBIUQDZ-UHFFFAOYSA-N ethyl 2-sulfanylethanesulfinate Chemical compound CCOS(=O)CCS FYORGSHNBIUQDZ-UHFFFAOYSA-N 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 125000006125 ethylsulfonyl group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- TTXDNWCDEIIMDP-UHFFFAOYSA-M heptadecyl(trimethyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCC[N+](C)(C)C TTXDNWCDEIIMDP-UHFFFAOYSA-M 0.000 description 1
- FXHGMKSSBGDXIY-UHFFFAOYSA-N heptanal Chemical compound CCCCCCC=O FXHGMKSSBGDXIY-UHFFFAOYSA-N 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- UCRJJNVFJGKYQT-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;hydron;sulfate Chemical compound OS([O-])(=O)=O.CCCCCCCCCCCCCCCC[N+](C)(C)C UCRJJNVFJGKYQT-UHFFFAOYSA-M 0.000 description 1
- WJLUBOLDZCQZEV-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCCCCCC[N+](C)(C)C WJLUBOLDZCQZEV-UHFFFAOYSA-M 0.000 description 1
- KXNZYPBRSATHKV-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCCCCCCCCCCCCCC[N+](C)(C)C KXNZYPBRSATHKV-UHFFFAOYSA-M 0.000 description 1
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- RNYJXPUAFDFIQJ-UHFFFAOYSA-N hydron;octadecan-1-amine;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[NH3+] RNYJXPUAFDFIQJ-UHFFFAOYSA-N 0.000 description 1
- PHFDTSRDEZEOHG-UHFFFAOYSA-N hydron;octan-1-amine;chloride Chemical compound Cl.CCCCCCCCN PHFDTSRDEZEOHG-UHFFFAOYSA-N 0.000 description 1
- 125000005191 hydroxyalkylamino group Chemical group 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- OVWYEQOVUDKZNU-UHFFFAOYSA-N m-tolualdehyde Chemical compound CC1=CC=CC(C=O)=C1 OVWYEQOVUDKZNU-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000005439 maleimidyl group Chemical class C1(C=CC(N1*)=O)=O 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-UHFFFAOYSA-N 0.000 description 1
- DCBBWYIVFRLKCD-UHFFFAOYSA-N n-[2-(dimethylamino)ethyl]-2-methylprop-2-enamide Chemical class CN(C)CCNC(=O)C(C)=C DCBBWYIVFRLKCD-UHFFFAOYSA-N 0.000 description 1
- WWVIUVHFPSALDO-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCCN(C)C WWVIUVHFPSALDO-UHFFFAOYSA-N 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- WLGDAKIJYPIYLR-UHFFFAOYSA-N octane-1-sulfonic acid Chemical class CCCCCCCCS(O)(=O)=O WLGDAKIJYPIYLR-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000005385 peroxodisulfate group Chemical group 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229940100595 phenylacetaldehyde Drugs 0.000 description 1
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- KYPIULIVYSQNNT-UHFFFAOYSA-N prop-2-enylsulfonylbenzene Chemical compound C=CCS(=O)(=O)C1=CC=CC=C1 KYPIULIVYSQNNT-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- CZPZWMPYEINMCF-UHFFFAOYSA-N propaneperoxoic acid Chemical compound CCC(=O)OO CZPZWMPYEINMCF-UHFFFAOYSA-N 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- WPPDXAHGCGPUPK-UHFFFAOYSA-N red 2 Chemical compound C1=CC=CC=C1C(C1=CC=CC=C11)=C(C=2C=3C4=CC=C5C6=CC=C7C8=C(C=9C=CC=CC=9)C9=CC=CC=C9C(C=9C=CC=CC=9)=C8C8=CC=C(C6=C87)C(C=35)=CC=2)C4=C1C1=CC=CC=C1 WPPDXAHGCGPUPK-UHFFFAOYSA-N 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYGBQXDNOUHIBZ-UHFFFAOYSA-L sodium formaldehyde sulphoxylate Chemical group [Na+].[Na+].O=C.[O-]S[O-] VYGBQXDNOUHIBZ-UHFFFAOYSA-L 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- FRTIVUOKBXDGPD-UHFFFAOYSA-M sodium;3-sulfanylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCS FRTIVUOKBXDGPD-UHFFFAOYSA-M 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001370 static light scattering Methods 0.000 description 1
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- LIXPXSXEKKHIRR-UHFFFAOYSA-M tetraethylphosphanium;bromide Chemical compound [Br-].CC[P+](CC)(CC)CC LIXPXSXEKKHIRR-UHFFFAOYSA-M 0.000 description 1
- YIEDHPBKGZGLIK-UHFFFAOYSA-L tetrakis(hydroxymethyl)phosphanium;sulfate Chemical compound [O-]S([O-])(=O)=O.OC[P+](CO)(CO)CO.OC[P+](CO)(CO)CO YIEDHPBKGZGLIK-UHFFFAOYSA-L 0.000 description 1
- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 description 1
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 1
- WAGFXJQAIZNSEQ-UHFFFAOYSA-M tetraphenylphosphonium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WAGFXJQAIZNSEQ-UHFFFAOYSA-M 0.000 description 1
- QTTDXDAWQMDLOF-UHFFFAOYSA-J tetrasodium 3-[[4-[[4-[(6-amino-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl]-6-sulfonatonaphthalen-1-yl]diazenyl]naphthalen-1-yl]diazenyl]naphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].Nc1ccc2c(O)c(N=Nc3ccc(N=Nc4ccc(N=Nc5cc(c6cccc(c6c5)S([O-])(=O)=O)S([O-])(=O)=O)c5ccccc45)c4ccc(cc34)S([O-])(=O)=O)c(cc2c1)S([O-])(=O)=O QTTDXDAWQMDLOF-UHFFFAOYSA-J 0.000 description 1
- WNQPPENQFWLADQ-UHFFFAOYSA-J tetrasodium;4-hydroxy-5-[[4-[[4-[(8-hydroxy-3,6-disulfonatonaphthalen-1-yl)diazenyl]-2-methoxy-5-methylphenyl]carbamoylamino]-5-methoxy-2-methylphenyl]diazenyl]naphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]S(=O)(=O)C1=CC(O)=C2C(N=NC3=C(C)C=C(C(=C3)OC)NC(=O)NC3=CC(C)=C(N=NC=4C5=C(O)C=C(C=C5C=C(C=4)S([O-])(=O)=O)S([O-])(=O)=O)C=C3OC)=CC(S([O-])(=O)=O)=CC2=C1 WNQPPENQFWLADQ-UHFFFAOYSA-J 0.000 description 1
- 238000001107 thermogravimetry coupled to mass spectrometry Methods 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- JCHWNYYARSRCKZ-UHFFFAOYSA-M tributyl(cyanomethyl)phosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CC#N JCHWNYYARSRCKZ-UHFFFAOYSA-M 0.000 description 1
- ABJGUZZWSKMTEI-UHFFFAOYSA-M tributyl(dodecyl)phosphanium;bromide Chemical compound [Br-].CCCCCCCCCCCC[P+](CCCC)(CCCC)CCCC ABJGUZZWSKMTEI-UHFFFAOYSA-M 0.000 description 1
- RYVBINGWVJJDPU-UHFFFAOYSA-M tributyl(hexadecyl)phosphanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[P+](CCCC)(CCCC)CCCC RYVBINGWVJJDPU-UHFFFAOYSA-M 0.000 description 1
- ZBZFETNHIRABGK-UHFFFAOYSA-M tributyl(hexyl)phosphanium;bromide Chemical compound [Br-].CCCCCC[P+](CCCC)(CCCC)CCCC ZBZFETNHIRABGK-UHFFFAOYSA-M 0.000 description 1
- UJMLRSWRUXXZEW-UHFFFAOYSA-M tributyl(octyl)phosphanium;bromide Chemical compound [Br-].CCCCCCCC[P+](CCCC)(CCCC)CCCC UJMLRSWRUXXZEW-UHFFFAOYSA-M 0.000 description 1
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 description 1
- OOACLPDZHDFCQP-LLIZZRELSA-L triphenyl-[(e)-4-triphenylphosphaniumylbut-2-enyl]phosphanium;dichloride Chemical compound [Cl-].[Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C\C=C\C[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 OOACLPDZHDFCQP-LLIZZRELSA-L 0.000 description 1
- VRVDFJOCCWSFLI-UHFFFAOYSA-K trisodium 3-[[4-[(6-anilino-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl]-5-methoxy-2-methylphenyl]diazenyl]naphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].[Na+].COc1cc(N=Nc2cc(c3cccc(c3c2)S([O-])(=O)=O)S([O-])(=O)=O)c(C)cc1N=Nc1c(O)c2ccc(Nc3ccccc3)cc2cc1S([O-])(=O)=O VRVDFJOCCWSFLI-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009463 water soluble packaging Methods 0.000 description 1
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
- C08F18/00—Homopolymers and 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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F18/02—Esters of monocarboxylic acids
- C08F18/04—Vinyl esters
- C08F18/08—Vinyl acetate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
-
- 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
- C08F216/00—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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/38—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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an acetal or ketal radical
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/28—Oxygen or compounds releasing free oxygen
- C08F4/30—Inorganic compounds
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/28—Oxygen or compounds releasing free oxygen
- C08F4/32—Organic compounds
-
- 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
- C08F8/12—Hydrolysis
-
- 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
- C08F8/28—Condensation with aldehydes or ketones
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- 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
-
- 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
- C08K5/20—Carboxylic acid amides
Definitions
- the present invention relates to a polyvinyl alcohol resin, a polyvinyl acetal resin, a method for producing a polyvinyl alcohol resin, and a method for producing a polyvinyl acetal resin.
- Polyvinyl alcohol resin obtained by saponifying polyvinyl acetate resin (hereinafter referred to as PVAc) is colorless and transparent and has strong mechanical properties, and is used in various applications.
- Polyvinyl acetal resin obtained by acetalizing PVA is colorless and transparent, and has higher mechanical strength than PVA.
- PVAc Polyvinyl alcohol resin
- PVB Polyvinyl acetal resin
- PVAc polyvinyl acetal resin
- it is necessary to increase the degree of polymerization of PVAc which is a raw material.
- PVAc obtained by a solution polymerization method is used. However, it is difficult to control the amount of heat generated by the solution polymerization method, and the upper limit of the weight-average molecular weight of the resulting resin is about 700,000.
- the molecular weight obtained using the above empirical formula is called the viscosity average molecular weight
- the viscosity average molecular weight is the average molecular weight obtained by the osmotic pressure method or the light scattering method, that is, the intermediate value of the values obtained by the number average molecular weight and the weight average molecular weight, respectively. show. This is because the value of the constant a takes an intermediate value between 0.5 and 1.
- Patent Document 1 states that PVA with an ultra-high degree of polymerization can be obtained by using a solution in which a polyvinyl ester polymer emulsion having a particle size of 5 ⁇ m or less is mixed with a predetermined amount of methanol. Further, in Patent Document 2, by using a specific solvent and setting the solvent composition and the polymerization temperature to predetermined conditions, a polyvinyl ester-based polymer having a limiting viscosity of 2.3 dl/g or more is produced. , and a method of saponifying this to obtain a polyvinyl alcohol resin with a high degree of polymerization.
- Patent Document 3 a vinyl ester monomer is subjected to photoemulsion polymerization at a low polymerization temperature of ⁇ 60° C. or higher and 10° C. or lower to prepare a polyvinyl ester with a high degree of polymerization having an intrinsic viscosity of 1.5 dl / g or more. is disclosed to obtain a polyvinyl alcohol resin with a high degree of polymerization by saponifying.
- At least one molecular end of the main chain is selected from the group consisting of a sulfone group, an alkylsulfonyl group, an aromatic sulfonyl group, a sulphine group, an imidazoline group, a carboxyl group, an amide group, an amino group, and a hydroxyl group.
- It is a polyvinyl alcohol resin having at least one of the above, having a weight average molecular weight (Mw) of 1,000,000 or more, and having a water-soluble surfactant content of 0.02% by weight or less.
- the present disclosure (2) is the polyvinyl alcohol resin of the present disclosure (1) containing 0.0000001% by weight or more of the cationic surfactant.
- the present disclosure (3) is the polyvinyl alcohol of the present disclosure (1) or (2), wherein the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.0 to 3.0 Resin.
- the present disclosure (4) is a polyvinyl alcohol resin in any combination with any one of the present disclosures (1) to (3) having a degree of saponification of 70 mol % or more and 99 mol % or less.
- (5) of the present disclosure is a polyvinyl alcohol resin in any combination with any of (1) to (4) of the present disclosure having a cloud point of 30° C. or higher.
- the present disclosure (6) is the present disclosure containing at least one selected from the group consisting of a dialkylamine compound having an alkyl group having 1 to 10 carbon atoms and a trialkylamine compound having an alkyl group having 1 to 10 carbon atoms
- (7) of the present disclosure is a polyvinyl acetal resin which is an acetalized product of the polyvinyl alcohol resin of any one of (1) to (6) of the present disclosure.
- This start (8) is an interlayer film for laminated glass containing the polyvinyl acetal resin of the present disclosure (7).
- This disclosure (9) is a binder composition comprising the polyvinyl acetal resin of this disclosure (7).
- the present disclosure (10) includes a polymerization step of adding a polymerization initiator to polymerize a vinyl ester to produce a polyvinyl ester, and a saponification catalyst to saponify the polyvinyl ester to produce a water-soluble polyvinyl alcohol resin.
- the polymerization initiator is at least selected from the group consisting of a sulfone group, an alkylsulfonyl group, an aromatic sulfonyl group, a sulphine group, an imidazoline group, a carboxyl group, an amide group, an amino group and a hydroxyl group.
- 1 is a method for producing a polyvinyl alcohol resin.
- the present disclosure (11) is a method for producing a polyvinyl alcohol resin according to the present disclosure (10), wherein the amount of the water-soluble surfactant added in the polymerization step is 0.02 parts by weight or less per 100 parts by weight of the vinyl ester.
- the polymerization step is to prepare an aqueous emulsion polymerization slurry containing polyvinyl ester by adding a polymerization initiator to an aqueous monomer solution containing vinyl ester and water, and
- the polyvinyl ester has an average particle size of 0.01 ⁇ m or more and 10 ⁇ m or less
- the saponification step includes saponifying the polyvinyl ester by directly adding a saponification catalyst to the aqueous emulsion polymerization slurry, and the saponification catalyst is (10) or (11) of the present disclosure, which is at least one selected from the group consisting of a dialkylamine compound having an alkyl group having 1 to 10 carbon atoms and a trialkylamine compound having an alkyl group having 1 to 10 carbon atoms.
- the polymerization step is to prepare an aqueous emulsion polymerization slurry containing polyvinyl ester by adding a polymerization initiator to an aqueous monomer solution containing vinyl ester and water, and further, the aqueous emulsion polymerization slurry
- the present disclosure (10) or ( 11) is a method for producing a polyvinyl alcohol resin.
- the present disclosure (14) is the present disclosure (10) to (13), wherein the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polyvinyl ester is 1.0 to 3.0
- a method for producing a polyvinyl alcohol resin in any combination with any of The present disclosure (15) is a polyvinyl acetal resin obtained by adding aldehyde to the polyvinyl alcohol resin obtained by the method for producing a polyvinyl alcohol resin according to any one of the present disclosure (10) to (14) to acetalize the polyvinyl alcohol resin. manufacturing method.
- the present invention will be described in detail below.
- an ultra-high molecular weight polyvinyl alcohol resin having a specific substituent at the molecular end and having a predetermined amount of water-soluble surfactant content relative to the weight of the entire resin is acetal
- the present inventors have found that a molded article having excellent strength can be obtained by reducing the amount of the resin, and a resin film having excellent transparency can be obtained, and have completed the present invention.
- the polyvinyl alcohol resin of the present invention is selected from the group consisting of a sulfone group, an alkylsulfonyl group, an aromatic sulfonyl group, a sulphine group, an imidazoline group, a carboxyl group, an amide group, an amino group and a hydroxyl group at at least one molecular end of the main chain. have at least one
- the polyvinyl alcohol resin having the above-described substituent has a strong mechanical strength, and when the polyvinyl acetal resin obtained by acetalization is molded, a molded product having high strength and excellent transparency can be produced. can be done.
- the above polyvinyl alcohol resin may have the above functional group at at least one molecular end of the main chain. It may have a carboxyalkylamidine group such as a carboxyethylamidine group at the molecular end. In addition to the hydroxyl group, those having a hydroxyl group may also have a hydroxyalkylamino group such as a hydroxyethylamino group or a hydroxyalkylamide group such as a hydroxyethylamide group at the molecular end. Furthermore, the sulfone group may be a salt or an ester. Examples of the above salts include ammonium salts, sodium salts, potassium salts and the like.
- ester examples include esters having an aliphatic group having 1 to 12 carbon atoms and an aromatic group having 6 to 12 carbon atoms, and alkyl esters are more preferable.
- alkylsulfonyl group examples include sulfonyl groups having alkyl having 1 to 12 carbon atoms, and specific examples include methylsulfonyl, ethylsulfonyl, propylsulfonyl and the like.
- aromatic sulfonyl group examples include sulfonyl groups having an aromatic group having 12 or less carbon atoms, and specific examples include a phenylsulfonyl group.
- the sulphine group may be a salt or an ester.
- the above salts include ammonium salts, sodium salts, potassium salts and the like.
- the ester include esters having an aliphatic group having 1 to 12 carbon atoms and an aromatic group having 6 to 12 carbon atoms, and alkyl esters are more preferable.
- the amino group may be a monoamino group, diamino group or triamino group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms).
- the polyvinyl alcohol resin preferably has a sulfone group at the molecular end.
- the specific substituent at at least one molecular terminal of the main chain of the polyvinyl alcohol resin is preferably derived from a polymerization initiator.
- the polyvinyl alcohol resin of the present invention has a weight average molecular weight (Mw) of 1,000,000 or more.
- Mw weight average molecular weight
- the polyvinyl alcohol resin of the present invention preferably has a weight average molecular weight (Mw) of 1,500,000 or more, more preferably 2,000,000 or more, preferably 4,000,000 or less, and preferably 3,000,000 or less. more preferred.
- the polyvinyl alcohol resin of the present invention preferably has a number average molecular weight (Mn) of 500,000 or more, more preferably 1,000,000 or more, preferably 2,000,000 or less, and 1,500,000 or less. is more preferable.
- Mn number average molecular weight
- the ratio (Mw/Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polyvinyl alcohol resin of the present invention is preferably 1.0 or more, more preferably 1.5 or more. It is preferably 3.0 or less, more preferably 2.0 or less. By setting it as the said range, the toughness of resin can be improved more.
- the weight average molecular weight (Mw) and number average molecular weight (Mn) are, for example, measured by gel permeation chromatography (GPC), measuring polyvinyl ester before saponification by GPC, and polyvinyl alcohol resin. It can be obtained by measuring the polyvinyl ester obtained by re-esterification by the GPC method and by measuring the viscosity of the aqueous solution according to JIS K6726. For example, columns such as TSKgel (Tosoh Corporation), PLgel (AMR Corporation), KF-806, KF-807 (Shodex Corporation) and the like can be used with polystyrene as a standard.
- the degree of saponification of the polyvinyl alcohol resin of the present invention is preferably 70 mol % or more, and preferably 99.9 mol % or less. By setting it as the said range, the toughness of resin can be improved more. Moreover, when it is made into a polyvinyl alcohol resin film, both water resistance and gas barrier properties can be improved in a well-balanced manner.
- the degree of saponification is more preferably 80 mol% or more, still more preferably 85% or more, even more preferably 90 mol% or more, particularly preferably 92 mol% or more, particularly preferably 93 mol% or more, and 94 mol% or more.
- the degree of saponification can be measured according to JIS K6726.
- the degree of saponification indicates the ratio of units actually converted to vinyl alcohol units among units that can be converted to vinyl alcohol units by saponification.
- the degree of saponification can be appropriately adjusted by saponification conditions, that is, hydrolysis conditions.
- the polyvinyl alcohol resin of the present invention preferably has a cloud point of 30°C or higher. By setting it as the said range, the toughness of resin can be improved more.
- the cloud point is more preferably 35° C. or higher, still more preferably 40° C. or higher, and for example 90° C. or lower.
- the cloud point can be visually confirmed, and can also be measured by a haze meter, static light scattering method, or the like.
- the proportion of undissolved components is preferably 10% by weight or less, more preferably 1% by weight or less.
- the lower limit is not particularly limited, and is preferably 0% by weight.
- the proportion of the undissolved component can be measured by mesh filtration. For example, a resin aqueous solution with a concentration of 4% by weight is allowed to stand for 12 hours or more, the temperature is raised to 80 ° C., and then allowed to stand to lower the temperature to room temperature. Water and water-absorbed and swollen resin are separated, the separated resin is dried at 60° C.
- the degree of polymerization of the polyvinyl alcohol resin of the present invention is preferably 10,000 or more, and preferably 30,000 or less.
- the degree of polymerization of the polyvinyl alcohol resin for example, is obtained by measuring the polyvinyl acetate resin before saponification by gel permeation chromatography (GPC) or by measuring the viscosity of the aqueous solution in accordance with JIS K6726. be able to.
- the polyvinyl alcohol resin of the present invention has a water-soluble surfactant content of 0.02% by weight or less. That is, when the polyvinyl alcohol resin of the present invention contains a water-soluble surfactant and other components, the polyvinyl alcohol resin of the present invention can be said to be a polyvinyl alcohol resin composition containing the polyvinyl alcohol resin.
- the content of the water-soluble surfactant in the compatibility of the composition is 0.02% by weight or less. By setting it as the said range, it can be set as resin with high transparency.
- the content of the water-soluble surfactant is preferably 0.002% by weight or less.
- the lower limit is not particularly limited, and is preferably 0% by weight, more preferably 0.0005% by weight or more.
- the method for measuring the content of the water-soluble surfactant is not particularly limited, it can be measured, for example, by a method using liquid chromatography such as HPLC, or a method of extraction using methanol or the like.
- the water-soluble surfactant is preferably a surfactant having a solubility of 10 g/100 g or more in water at 25°C.
- the water-soluble surfactant is used as a dispersant added during emulsion polymerization.
- examples include anionic surfactants such as alkylsulfonates and polymeric surfactants such as polyalkylene glycol. mentioned.
- examples of the alkylsulfonate include sodium, potassium and ammonium salts of octylsulfonic acid, decylsulfonic acid, dodecylsulfonic acid and p-toluenesulfonic acid.
- the polyvinyl alcohol resin of the present invention When the polyvinyl alcohol resin of the present invention is made into a resin solution, even if the amount of the resin solution is very small, it becomes cloudy due to the content of the water-soluble surfactant. Further, since the polyvinyl alcohol resin of the present invention has a very high molecular weight, the resin solution becomes cloudy even if the solubility in the solvent is poor.
- the water-soluble surfactant is usually an anionic surfactant.
- the polyvinyl alcohol resin of the present invention may contain a cationic surfactant.
- a cationic surfactant By containing the above cationic surfactant, the resin can be made more excellent in transparency.
- the cationic surfactant is different from the water-soluble surfactant, and preferably has a solubility in water of 0.05 g/100 g or more at 25°C.
- cationic surfactant examples include amine salts such as quaternary ammonium salts, aliphatic amine salts, aromatic amine salts and heterocyclic amine salts, and phosphonium salts.
- quaternary ammonium salts include tetraethylammonium chloride, tetraethylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium chloride, hexyltrimethylammonium bromide, n-octyltrimethylammonium bromide, n-octyltrimethylammonium chloride, nonyltrimethyl Ammonium bromide, decyltrimethylammonium chloride, decyltrimethylammonium bromide, dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, tetrade
- amine salt examples include stearic acid dimethylaminopropylamide, n-octylammonium chloride, n-octylammonium bromide, dodecylamine hydrochloride, dodecyl ammonium bromide, octadecylamine hydrochloride and the like.
- Examples of the phosphonium salts include trans-2-butene-1,4-bis(triphenylphosphonium chloride), tributyl(cyanomethyl)phosphonium chloride, (2-carboxyethyl)triphenylphosphonium bromide, tributyldodecylphosphonium bromide, tributyl Hexadecylphosphonium bromide, tributyl-n-octylphosphonium bromide, tetrakis(hydroxymethyl)phosphonium chloride, tetraphenylphosphonium bromide, tetrakis(hydroxymethyl)phosphonium sulfate, tetrabutylphosphonium bromide, tetraphenylphosphonium chloride, tetraethylphosphonium bromide, tetra butylphosphonium chloride, tetra-n-octylphosphonium bromide, tetrae
- quaternary ammonium salts, amine salts and phosphonium salts are preferred, quaternary ammonium salts and amine salts are more preferred, 1-ethyl-3-methylimidazolium chloride, cetylpyridinium chloride, tetrabutylammonium bromide, tetra butylammonium chloride, hexyltrimethylammonium bromide, n-octyltrimethylammonium bromide, n-octyltrimethylammonium chloride, nonyltrimethylammonium bromide, decyltrimethylammonium chloride, decyltrimethylammonium bromide, dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, tetradecyl trimethylammonium bromide, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, cet
- the content of the cationic surfactant in the polyvinyl alcohol resin of the present invention is preferably 0% by weight or more. By setting it as the said range, it can be set as resin with higher transparency.
- the content of the cationic surfactant is more preferably greater than 0% by weight, more preferably 0.0000001% by weight or more, and more preferably 0.0001% by weight or more. It is particularly preferably 0.002% by weight or less, more preferably 0.0015% by weight or less, and even more preferably 0.001% by weight or less.
- the content of the cationic surfactant can be measured by HPLC method or GC-MS method.
- the polyvinyl alcohol resin of the present invention contains at least one compound selected from the group consisting of a dialkylamine compound having an alkyl group of 1 to 10 carbon atoms and a trialkylamine compound having an alkyl group of 1 to 10 carbon atoms.
- a dialkylamine compound having an alkyl group of 1 to 10 carbon atoms and a trialkylamine compound having an alkyl group of 1 to 10 carbon atoms may be containing the above compound, the toughness of the resin can be further enhanced.
- dialkylamines having an alkyl group of 1 to 10 carbon atoms and trialkylamines of 1 to 10 carbon atoms are preferred.
- Dialkylamine compounds having an alkyl group having 1 to 10 carbon atoms include, for example, dimethylamine and diethylamine.
- Trialkylamines having an alkyl group of 1 to 10 carbon atoms include, for example, trimethylamine, triethylamine, tributylamine and the like.
- the content of the dialkylamine compound and the trialkylamine compound in the polyvinyl alcohol resin of the present invention is preferably 0.00001% by weight or more, more preferably 0.0001% by weight or more, and 0.1% by weight or more. % by weight or less is preferable, and 0.05% by weight or less is more preferable.
- the above content can be measured by HPLC method or GC-MS method.
- a polymerization step of adding a polymerization initiator having a specific substituent to polymerize a vinyl ester to produce a polyvinyl ester, and a saponification catalyst to add a polyvinyl A method having a saponification step of saponifying the ester is preferred. It has a polymerization step of adding a polymerization initiator to polymerize a vinyl ester to produce a polyvinyl ester, and a saponification step of adding a saponification catalyst to saponify the polyvinyl ester to produce a water-soluble polyvinyl alcohol resin.
- the polymerization initiator has at least one selected from the group consisting of a sulfone group, an alkylsulfonyl group, an aromatic sulfonyl group, a sulphine group, an imidazoline group, a carboxyl group, an amide group and a hydroxyl group. is also one of the present invention.
- a polymerization initiator is added to an aqueous monomer solution containing vinyl ester and water to prepare an aqueous emulsion polymerization slurry containing polyvinyl ester.
- vinyl ester is not particularly limited, examples thereof include vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, etc. Among them, vinyl acetate is preferable.
- the polyvinyl ester may be copolymerized with a vinyl-based monomer as long as the polymerization degree and saponification degree of the resulting polyvinyl alcohol resin are not affected.
- the vinyl-based monomer include ethylene, butadiene, 1,3-butadiene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, isoprene, acrylic acid ester, methacrylic acid ester, maleic acid, Higher fatty acid vinyl esters such as fumaric acid and itaconic acid, alkyl vinyl ethers, N-(2-dimethylaminoethyl) methacrylamides or quaternized products thereof, N-vinylimidazole or quaternized products thereof, N-vinylpyrrolidone, N -n-butoxymethylacrylamide, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, acrylonitrile, methacryl
- the polyvinyl ester preferably has a weight average molecular weight of 1,000,000 or more. Normally, it is very difficult to increase the degree of polymerization to about 1,000,000. Since the polymerized resin has a high Tg, the mobility of the molecular ends is poor and the probability of collision with radicals is very low. Therefore, it is usually difficult to obtain a high molecular weight polyvinyl ester having a weight average molecular weight of 1,000,000 or more. Normally, in emulsion polymerization, monomer polymerization proceeds in dispersant micelles, but in order to obtain a high-molecular-weight resin, it is necessary to form huge micelles.
- the resin contains a large amount of dispersant as a foreign substance, the transparency and strength of the resin are also low.
- the dispersant used in ordinary emulsion polymerization is not used.
- a water-soluble radical polymerization initiator having a sulfone group, a sulfonyl group, a sulphine group, an imidazoline group, a carboxyl group, an amide group, and a hydroxyl group is used as a base point to initiate polymerization of a vinyl ester monomer dispersed in water, and each monomer domain collides. , dispersion polymerization is carried out at a low concentration so as not to coalesce.
- a polymer in which the size of each domain is uniform and the particle size is uniform can be obtained.
- the growth of molecules in the particles is the same, the molecular weight is very high, and a resin having a weight average molecular weight of 4,000,000 or more can be synthesized.
- the reason why the weight average molecular weight increases is that by polymerizing a water-soluble radical polymerization initiator having a sulfone group, a sulfonyl group, a sulphine group, an imidazoline group, a carboxyl group, an amide group, and a hydroxyl group at a low concentration, unevenness such as hydrogen abstraction is caused. This is because multiple polymers are less likely to grow within the domain because the polymerization reaction can be minimized.
- a water-soluble radical polymerization initiator having at least one selected from the group consisting of a sulfone group, a sulfonyl group, a sulphine group, an imidazoline group, a carboxyl group, an amide group and a hydroxyl group can be used.
- a high-molecular-weight polyvinyl ester can be produced without adding a large amount of a dispersant as in normal emulsion polymerization. .
- water-soluble radical polymerization initiator examples include 2,2′-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2′-azobis[2-(2-imidazoline-2 -yl)propane]sulfatohydrate, 2,2′-azobis[2-(2-imidazolin-2-yl)propane] acid mixtures of imidazole azo compounds, 2,2′-azobis(2-methyl propionamidine) dihydrochloride, 2,2′-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]tetrahydrate, 2,2′-azobis[2-methyl-N-(2-hydroxyethyl) ) propionamide], water-soluble azo compounds such as 4,4′-azobis-4-cyanovaleric acid, potassium persulfate (potassium peroxodisulfate), ammonium persulfate (ammonium peroxodisulfate), sodium persulfate
- acid mixtures of imidazole-based azo compounds, water-soluble azo compounds, and oxoacids are preferred.
- a polyvinyl ester having a weight average molecular weight within a predetermined range can be produced, but the weight average molecular weight of the polyvinyl ester may be adjusted by adding a chain transfer agent or a polymerization terminator.
- the chain transfer agent and polymerization terminator are not particularly limited, but sodium 3-mercapto-1-propanesulfonate, mercaptosuccinic acid, mercaptopropanediol, (allylsulfonyl)benzene, ethyl 2-mercaptoethanesulfinate, 3 - mercaptopropionamide and the like.
- At least one selected from the group consisting of a sulfone group, a sulfonyl group, a sulphine group, an imidazoline group, a carboxyl group, an amide group and a hydroxyl group is added to at least one molecular end of the main chain.
- Polyvinyl ester having one type and having a weight average molecular weight within a predetermined range can be produced.
- These water-soluble radical polymerization initiators may be used alone, or two or more of them may be used in combination.
- the amount of the water-soluble radical polymerization initiator added is preferably 0.03 to 0.2 parts by weight, more preferably 0.05 to 0.15 parts by weight, with respect to 100 parts by weight of the raw material monomer. preferable. By setting the amount to be added to 0.03 parts by weight or more, the reaction rate of the raw material monomer can be sufficiently increased. By setting the amount to be added to 0.2 parts by weight or less, the molecular weight of the polyvinyl ester can be sufficiently increased.
- the polyvinyl ester having at least one selected from a sulfone group, a sulfonyl group, a sulphine group, an imidazoline group, a carboxyl group, an amide group and a hydroxyl group at the molecular terminal ( ⁇ position) is low in water. It is possible to obtain a resin with a uniform particle size by dispersing it at a concentration. Furthermore, in general emulsion polymerization, 1 part by weight or more of a water-soluble surfactant is added to 100 parts by weight of raw material monomers. Less is better. However, it is difficult to polymerize a resin having a high molecular weight simply by reducing the water-soluble surfactant.
- the amount of the raw material monomer to be added is preferably 50 to 300 parts by weight per 1000 parts by weight of water. When the content is within the above range, aggregation during polymerization and adhesion of the resin to the reaction vessel can be prevented. Further, the addition amount of the raw material monomer is more preferably 70 to 200 parts by weight per 1000 parts by weight of water. By setting the amount within the above range, it is possible to reduce the amount of residual monomers and achieve uniform polymerization.
- a high-speed rotating mixer or the like is not required. After charging the monomer, it is only necessary to rotate the blade at 100 to 250 rpm to disperse the monomer in the water.
- the reaction temperature in the polymerization step is preferably 50° C. or higher and preferably 70° C. or lower. Since vinyl acetate, which is a vinyl ester monomer, has a high reaction heat, it is not preferable to react at a very high temperature. By setting the temperature to 50° C. or higher, radicals can be sufficiently generated and the reaction can proceed sufficiently. Moreover, by setting the temperature to 70° C. or lower, adhesion of scale to the reaction vessel can be suppressed, and poor polymerization can be prevented.
- a small amount of water-soluble surfactant may be added.
- the water-soluble surfactant is used as a dispersant to be added during emulsion polymerization, and includes those mentioned above.
- the amount of the water-soluble surfactant added is preferably 0 to 0.02 parts by weight, more preferably 0.002 to 0.01 parts by weight, per 100 parts by weight of the raw material monomer.
- a polymerization initiator is added to an aqueous monomer solution containing vinyl ester and water to prepare an aqueous emulsion polymerization slurry containing polyvinyl ester, and a cationic surfactant is added to the aqueous emulsion polymerization slurry. It is preferable to have a recovery step of filtering the slurry to which the is added to recover the polyvinyl ester. Examples of the cationic surfactant include those described above.
- the amount of the cationic surfactant added is preferably 1 ⁇ 10 ⁇ 6 to 10000 ⁇ 10 ⁇ 6 parts by weight with respect to 100 parts by weight of the raw material monomer. By setting it as the said range, it can fully adsorb
- the average particle size of the polyvinyl ester in the aqueous emulsion polymerization slurry is preferably 0.001 ⁇ m or more, and preferably 50 ⁇ m or less. By setting it as the said range, the transparency of resin obtained can be improved more.
- the average particle size is more preferably 0.005 ⁇ m or more, still more preferably 0.01 ⁇ m or more, even more preferably 0.1 ⁇ m or more, more preferably 30 ⁇ m or less, and 10 ⁇ m It is more preferably 5 ⁇ m or less, particularly preferably 1 ⁇ m or less, particularly preferably 0.8 ⁇ m or less, and most preferably 0.5 ⁇ m or less.
- the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polyvinyl ester is preferably 1.0 or more and preferably 3.0 or less. By setting it as the said range, the transparency of resin obtained can be improved more.
- the above ratio is more preferably 1.5 or more, and more preferably 2.0 or less.
- Examples of the saponification step include a method of directly adding a saponification catalyst to the aqueous emulsion polymerization slurry obtained in the polymerization step, and a method of saponifying the polyvinyl ester recovered in the recovery step.
- the saponification catalyst examples include alkali catalysts such as sodium hydroxide, potassium hydroxide, sodium alcoholate, and sodium carbonate, and acid catalysts such as sulfuric acid, phosphoric acid, and hydrochloric acid.
- Alkaline catalysts are preferred, and sodium hydroxide is particularly preferred, since they can improve the properties.
- amines such as dialkylamine compounds and trialkylamine compounds as the saponification catalyst.
- the dialkylamine compounds include dialkylamine compounds having an alkyl group having 1 to 10 carbon atoms
- the trialkylamine compounds include trialkylamine compounds having an alkyl group having 1 to 10 carbon atoms. Specific examples include dimethylamine, diethylamine, trimethylamine, triethylamine, tributylamine and the like.
- the polyvinyl ester recovered in the recovery step it is preferable to add the polyvinyl ester to an organic solvent and further add a saponification catalyst.
- the saponification catalyst in the above method include alkali catalysts such as sodium hydroxide, potassium hydroxide, sodium alcoholate and sodium carbonate, and acid catalysts such as sulfuric acid, phosphoric acid and hydrochloric acid.
- alkali catalysts such as sodium hydroxide, potassium hydroxide, sodium alcoholate and sodium carbonate
- acid catalysts such as sulfuric acid, phosphoric acid and hydrochloric acid.
- an alkali catalyst is preferable, and sodium hydroxide is particularly preferable, because it can improve productivity.
- the amount of the saponification catalyst used is preferably 0.002 to 0.50, more preferably 0.003 to 0.30, in terms of molar ratio to the vinyl ester monomer unit of the vinyl ester copolymer. , 0.004 to 0.10 is particularly preferred.
- the saponification catalyst may be added all at once at the beginning of the saponification reaction, or may be partially added at the beginning of the saponification reaction and the rest may be additionally added during the saponification reaction. .
- the saponification reaction is preferably carried out at a temperature of 5-80°C, more preferably 20-70°C.
- the saponification reaction is preferably carried out for 5 minutes to 10 hours, more preferably 10 minutes to 5 hours.
- the saponification reaction can be carried out by either batch method or continuous method.
- the remaining catalyst may be neutralized, if desired.
- Usable neutralizing agents include organic acids such as acetic acid and lactic acid, and ester compounds such as methyl acetate.
- a step of washing the PVA resin may be provided if necessary.
- a solution containing a lower alcohol such as methanol as a main component and further containing water and/or an ester such as methyl acetate produced in the saponification step can be used.
- organic solvent examples include methanol, ethanol, propanol, butanol, tertiary butanol, isobutanol, isopropyl alcohol, n-propyl alcohol, hexanol, 2-ethylhexanol, benzyl alcohol, ethylene glycol, propylene glycol, glycerin, diethylene glycol, and the like.
- esters such as methyl acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, hydrocarbons such as toluene, xylene, cyclohexane, isooctane, isopentane, acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketones such as ketones, cyclohexanone and diacetone alcohol; ethers such as methyl cellosolve, ethyl cellosolve, butyl cellosolve and 1,4-dioxane; and tetrahydrofuran, 2-pyrrolidone, NMP and DMF.
- a polymerization initiator is added to an aqueous monomer solution containing vinyl ester and water to prepare an aqueous emulsion polymerization slurry containing polyvinyl ester, and the average particle size of polyvinyl ester in the aqueous emulsion polymerization slurry is is 0.01 ⁇ m or more and 0.5 ⁇ m or less
- the saponification step is to saponify the polyvinyl ester by directly adding a saponification catalyst to the aqueous emulsion polymerization slurry, and the saponification catalyst has 1 to 10 carbon atoms. and a trialkylamine compound having an alkyl group having 1 to 10 carbon atoms. .
- a polymerization initiator is added to an aqueous monomer solution containing vinyl ester and water to prepare an aqueous emulsion polymerization slurry containing polyvinyl ester.
- the method for producing a polyvinyl alcohol resin includes a recovery step of filtering the slurry to which the activator is added to recover the polyvinyl ester, and the saponification step includes saponifying the polyvinyl ester recovered in the recovery step. is one.
- the polyvinyl alcohol resin has an ultrahigh molecular weight, it can be preferably used for film applications and the like.
- the gas barrier property can be effectively improved, and a uniform film can be obtained.
- the film contains the polyvinyl alcohol resin. Moreover, the film may contain a surface tension modifier, an antifoaming agent, a surfactant, an antiseptic, a water-soluble plasticizer such as glycerin or polyethylene glycol, and the like, if necessary.
- the film may be a laminated film laminated on a support member.
- the material of the support member is not particularly limited, examples thereof include polyolefin resins, polyester resins, acrylic resins, and the like.
- the polyolefin resin include polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer and the like.
- the polyester-based resin include polyethylene terephthalate and polyethylene naphthalate.
- the material of the support member is preferably not polyvinyl alcohol resin.
- the film may have a dichroic dye adsorbed on its surface.
- a dichroic dye adsorbed on its surface By having the above structure, it can be suitably used as a polarizing layer of a polarizing plate.
- the dichroic dyes include iodine and dichroic dyes such as azo dyes, anthraquinone dyes, and tetrazine dyes. Azo dyes are preferred from the viewpoint of the optical properties and durability of the polarizing plate.
- the azo dye include C.I. I. Direct Yellow 12, C.I. I. Direct Yellow 28, C.I. I. Direct Yellow 44, C.I. I. Direct Yellow 142, C.I. I. Direct Orange 26, C.I. I. Direct Orange 39, C.I. I.
- Direct Orange 71 C.I. I. Direct Orange 107, C.I. I. Direct Red 2, C.I. I. Direct Red 31, C.I. I. Direct Red 79, C.I. I. Direct Red 81, C.I. I. Direct Red 117, C.I. I. Direct Red 247, C.I. I. Direct Green 80, C.I. I. Direct Green 59, C.I. I. Direct Blue 71, C.I. I. Direct Blue 78, C.I. I. Direct Blue 168, C.I. I. Direct Blue 202, C.I. I. Direct Violet 9, C.I. I. Direct Violet 51, C.I. I. Direct Brown 106, C.I. I. Direct Brown 223 and the like.
- dyes produced by known methods include the method described in JP-A-3-12606 and the method described in JP-A-59-145255.
- the thickness of the film is preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less, still more preferably 15 ⁇ m or less, and particularly preferably 10 ⁇ m or less. Within the above range, gas barrier properties can be further enhanced. Moreover, transparency can be made still higher. Furthermore, the drying time during production can be shortened to improve productivity.
- the lower limit of the thickness of the film is not particularly limited, and is, for example, 1 ⁇ m or more.
- the polyvinyl alcohol resin is suitably used for obtaining a packaging film or a stretched film having a thickness of 30 ⁇ m or less, and in particular, for obtaining a packaging film or a stretched film having a thickness of 20 ⁇ m or less.
- thin packaging films and stretching films having a thickness of 30 ⁇ m or less are likely to break during stretching due to air bubbles or liquid droplets.
- the polyvinyl alcohol resin even when obtaining a packaging film or a stretched film having a thickness of 30 ⁇ m or less, the inclusion of air bubbles and droplets in the film can be sufficiently suppressed during stretching. film breakage can be prevented.
- the thickness of the polarizing layer in the polarizing plate can be appropriately set according to the purpose and application of the LCD in which the polarizing plate is used, but is generally 5 ⁇ m or more. 80 ⁇ m or less.
- the polarizing layer made of stretched and dyed polyvinyl alcohol resin is vulnerable to heat and moisture, so it is preferable to provide a protective layer on the surface.
- the material of the protective layer is not particularly limited, examples thereof include cellulose resins such as triacetyl cellulose, polyester resins such as polyethylene naphthalate, cyclic polyolefin resins such as cycloolefin polymer, and acrylic resins.
- the method of forming a film using the polyvinyl alcohol resin is not particularly limited, and for example, a method of applying an aqueous polyvinyl alcohol resin solution and drying can be used.
- coating methods include solution casting method (casting method), roll coating method, spin coating method, screen coating method, fountain coating method, dipping method, and spray method.
- roll coating method include wire bar coating method, reverse coating method, gravure coating method and the like.
- drying method include a method of natural drying, a method of drying by heating at a temperature not higher than the glass transition temperature of the polyvinyl alcohol resin, and the like.
- composition of the polyvinyl alcohol resin aqueous solution is not particularly limited, and if necessary, surface tension modifiers, antifoaming agents, surfactants, preservatives, water-soluble plasticizers such as glycerin and polyethylene glycol, etc. may be added. good.
- the film may be provided in a state of being laminated on a support member. It is preferable that the supporting member can maintain the polyvinyl alcohol resin aqueous solution on the surface when the polyvinyl alcohol resin aqueous solution is applied and can support the obtained polyvinyl alcohol resin film.
- the material of the support member is not particularly limited, examples thereof include polyolefin resins, polyester resins, acrylic resins, and the like.
- the polyolefin resin include polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer and the like.
- the polyester-based resin include polyethylene terephthalate and polyethylene naphthalate.
- the material of the support member is preferably not polyvinyl alcohol resin.
- the above film can be suitably used as a packaging film such as a water-soluble packaging film for packaging medicines such as agricultural chemicals, a stretching film, and the like.
- a polarizing plate can be produced by dyeing the film after stretching.
- the method for dyeing the film include a method in which the film is uniaxially stretched and a dichroic dye such as iodine is adsorbed and oriented.
- the polarizing layer is preferably a polarizing film obtained by stretching the film uniaxially about 2 to 8 times to adsorb and align the dichroic dye.
- a polyvinyl acetal resin can be obtained by adding an aldehyde to the polyvinyl alcohol resin in the presence of an acid catalyst to proceed with the acetalization reaction.
- a polyvinyl acetal resin, which is an acetalized product of the polyvinyl alcohol resin of the present invention, is also one aspect of the present invention.
- the degree of polymerization of the polyvinyl acetal resin is preferably 10,000 or more, and preferably 40,000 or less. By setting it as the said range, the intensity
- the degree of polymerization is more preferably 15,000 or more, and more preferably 25,000 or less.
- the degree of acetalization of the polyvinyl acetal resin is preferably 50 mol % or more, and preferably 80 mol % or less. By setting it as the said range, the solubility to a solvent can fully be improved. In addition, the compatibility with the plasticizer is sufficiently enhanced to facilitate molding of the polyvinyl acetal resin.
- the degree of acetalization is more preferably 60 mol % or more, and more preferably 75 mol % or less.
- the hydroxyl group content of the polyvinyl acetal resin is preferably 16 mol % or more, and preferably 50 mol % or less. When the content is within the above range, the dispersibility of the inorganic powder is improved when the ceramics dispersed sheet is produced, and the compatibility with the plasticizer can be enhanced.
- the amount of hydroxyl groups is more preferably 20 mol % or more, and more preferably 33 mol % or less.
- a method for producing a polyvinyl acetal resin in which an aldehyde is added to the polyvinyl alcohol resin obtained by the above method for producing a polyvinyl alcohol resin to acetalize the polyvinyl alcohol resin is also one aspect of the present invention.
- the polyvinyl alcohol resin of the present invention has an ultra-high molecular weight and is excellent in toughness and transparency. By acetalization, it is made into a polyvinyl acetal resin with an ultra-high molecular weight and excellent toughness and transparency. can be done.
- a known method can be used for the acetalization, and it is preferably carried out in a water solvent, in a mixed solvent of water and an organic solvent having compatibility with water, or in an organic solvent.
- an organic solvent compatible with water for example, an alcohol-based organic solvent can be used.
- the organic solvent include alcohol-based organic solvents, aromatic organic solvents, aliphatic ester-based solvents, ketone-based solvents, lower paraffin-based solvents, ether-based solvents, amide-based solvents, and amine-based solvents.
- the alcohol-based organic solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and the like.
- Examples of the aromatic organic solvent include xylene, toluene, ethylbenzene, and methyl benzoate.
- Examples of the aliphatic ester solvent include methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl acetoacetate, and ethyl acetoacetate.
- Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methylcyclohexanone, benzophenone, and acetophenone.
- Examples of the lower paraffin solvents include hexane, pentane, octane, cyclohexane, and decane.
- Examples of the ether solvent include diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol diethyl ether and the like.
- Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethyltesetamide, N-methylpyrrolidone, acetanilide and the like.
- amine solvent examples include ammonia, trimethylamine, triethylamine, n-butylamine, di-n-butylamine, tri-n-butylamine, aniline, N-methylaniline, N,N-dimethylaniline and pyridine. These can be used alone, or two or more solvents can be used in combination. Among these, ethanol, n-propanol, isopropanol, and tetrahydrofuran are particularly preferred from the viewpoints of solubility in resins and ease of purification.
- the acetalization is preferably carried out in the presence of an acid catalyst.
- the acid catalyst is not particularly limited, and includes mineral acids such as sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid, carboxylic acids such as formic acid, acetic acid and propionic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid and paratoluenesulfone. sulfonic acids such as acids.
- These acid catalysts may be used alone or in combination of two or more compounds. Among them, hydrochloric acid, nitric acid and sulfuric acid are preferred, and hydrochloric acid is particularly preferred.
- Aldehydes used in the acetalization include aldehydes having a chain aliphatic group, a cycloaliphatic group or an aromatic group having 1 to 10 carbon atoms. Conventionally known aldehydes can be used as these aldehydes.
- the aldehyde used in the acetalization reaction is not particularly limited, and examples thereof include aliphatic aldehydes and aromatic aldehydes.
- Examples of the aliphatic aldehyde include formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, n-hexylaldehyde, 2-ethylbutyraldehyde, 2-ethylhexylaldehyde, n-heptylaldehyde, n- octylaldehyde, n-nonylaldehyde, n-decylaldehyde, amylaldehyde and the like.
- the aromatic aldehydes include benzaldehyde, cinnamaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, phenylacetaldehyde, ⁇ -phenylpropionaldehyde and the like. These aldehydes may be used individually by 1 type, and may use 2 or more types together.
- aldehydes formaldehyde, acetaldehyde, butyraldehyde, 2-ethylhexylaldehyde, 2-ethylhexylaldehyde, etc., which are excellent in acetalization reactivity, bring about a sufficient internal plasticizing effect on the resin to be produced, and as a result impart good flexibility.
- n-nonylaldehyde is preferred. More preferred are formaldehyde, acetaldehyde, and butyraldehyde, since an adhesive composition having particularly excellent impact resistance and adhesiveness to metal can be obtained.
- the amount of the aldehyde to be added can be appropriately set according to the desired degree of acetalization of the polyvinyl acetal resin.
- the acetalization reaction is efficiently performed, and unreacted aldehyde It is also preferable because it is easy to remove.
- the holding time after the reaction is preferably 1.5 hours or longer, more preferably 2 hours or longer, although it depends on other conditions.
- the acetalization reaction can be allowed to proceed sufficiently by setting the holding time as described above.
- the holding temperature after the reaction is preferably 15° C. or higher, more preferably 20° C. or higher. By setting it as the said holding temperature, an acetalization reaction can fully be advanced.
- the polyvinyl acetal resin is excellent in toughness and transparency, and can be used for applications that take advantage of these properties.
- the polyvinyl acetal resin can be used as an interlayer film for laminated glass.
- An interlayer film for laminated glass containing the polyvinyl acetal resin is also one aspect of the present invention.
- the interlayer film for laminated glass can be obtained by forming the polyvinyl acetal resin and the plasticizer into a sheet by an extruder. Also, a laminated glass can be obtained by sandwiching the interlayer film for laminated glass between two glass plates and hot-pressing them. Since the polyvinyl acetal resin is excellent in toughness and transparency, even when it is used as an intermediate film having another resin layer for imparting characteristics to laminated glass, it can have sufficient strength. Also, the laminated glass can be thinner.
- the polyvinyl acetal resin can be suitably used in binder compositions such as binders for manufacturing laminated ceramic capacitors, binders for paints, and binders for secondary batteries.
- binder compositions such as binders for manufacturing laminated ceramic capacitors, binders for paints, and binders for secondary batteries.
- many multilayer ceramic capacitors are mounted in electronic devices such as smartphones, but miniaturization is required, and by using the polyvinyl acetal resin, ceramic sheets with higher strength can be obtained.
- the binder is thermally decomposed, and if there is a large amount of firing residue, the reliability of the capacitor is lowered.
- the polyvinyl acetal resin it is possible to reduce the amount of the binder to be added and reduce the baking residue.
- the present invention it is possible to provide an ultra-high molecular weight polyvinyl alcohol resin that can be acetalized to form a resin film having high strength and transparency. Moreover, the manufacturing method of polyvinyl acetal resin and polyvinyl alcohol resin, and the manufacturing method of polyvinyl acetal resin can be provided.
- Example 1 Preparation of polyvinyl acetate resin (PVAc)) (Polymerization process)
- PVAc polyvinyl acetate resin
- Example 2 Preparation of polyvinyl acetate resin (PVAc) (Polymerization process)
- a 2 L separable flask equipped with a stirrer, a cooler, a thermometer, a hot water bath and a nitrogen gas inlet was prepared, and 900 parts by weight of water and 100 parts by weight of vinyl acetate (VAc) as a monomer were added to the 2 L separable flask. put in. Thereafter, the mixture was stirred with a stirring blade at 150 rpm to disperse the monomers in water to obtain a monomer mixture.
- VAc vinyl acetate
- a polymerization initiator solution was added to the monomer mixed solution to initiate polymerization, and 12 hours after the initiation of polymerization, the polymerization was terminated by cooling to room temperature to obtain a polyvinyl acetate resin (
- An aqueous solution (polymerization slurry) containing PVAc) was obtained. 2 g of the resulting aqueous solution was dried in an oven at 150° C., and the resin solid content was evaluated.
- the polymerization slurry was evaluated by a zetatizer, the polyvinyl acetate resin had an average particle size of 0.2 ⁇ m and a CV value of the particle size of 4%.
- polyvinyl alcohol resin (Preparation of polyvinyl alcohol resin (PVA))
- the resulting polyvinyl acetate resin was added to methanol (MeOH) as a solvent so as to have a concentration of 6% by weight.
- a methanol solution of sodium hydroxide was added so as to be mol/1 mol of resin, and saponified at 40°C. After that, it was washed with ethyl acetate and dried in a vacuum oven to obtain a polyvinyl alcohol resin (PVA).
- the degree of saponification was 87.7 mol % when measured according to JIS K6726. Moreover, when the clouding point was measured visually, the clouding point was 90° C. or higher.
- the ratio of undissolved components when added to water at a concentration of 4% by weight was measured by a filtration method
- the ratio of undissolved components was 0% by weight.
- the ratio of undissolved components was measured by the following method. First, an aqueous resin solution having a concentration of 4% by weight was allowed to stand still for 12 hours or more, the temperature was raised to 80° C., and then the temperature was lowered to normal temperature by allowing the solution to stand. After that, using a metal mesh (opening #100 mesh), the water and the resin that has absorbed water and swollen are separated, the separated resin is dried at 60 ° C. for 3 hours, and the metal mesh after drying is used.
- Weight average molecular weight (Mw) and number average molecular weight (Mn) were calculated based on a calibration curve prepared using high molecular weight standard polystyrene EasiVial PS-H manufactured by GL Sciences as a standard substance.
- a polyvinyl acetal resin (PVB) was obtained.
- the weight-average molecular weight of the obtained polyvinyl acetal resin was measured by gel permeation chromatography using LF-804 (manufactured by SHOKO) as a column, in terms of polystyrene, and found to be 1.82 million.
- Example 2 to 10 Polyvinyl acetate resin and polyvinyl alcohol resin were obtained in the same manner as in Example 1 except that the water-soluble surfactant and the polymerization initiator were added so that the types and formulations shown in Table 1 were obtained.
- a polyvinyl acetal resin was obtained in the same manner as in Example 1, except that n-butyraldehyde was added so as to obtain a composition as shown in Table 3.
- the following water-soluble surfactants and polymerization initiators were used.
- VA-057 2,2′-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]tetrahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Tetramethylammonium peroxodisulfate P-toluenesulfonic acid peroxide Peroxodisulfinic acid
- VA-61 2,2'-azobis[2-(2-imidazolin-2-yl)propane]
- V-50 2,2′-azobis(2-methylpropionamidine) dihydrochloride
- VA-086 2,2′-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
- Example 11 to 16 Vinyl acetate, water, a water-soluble surfactant, and a polymerization initiator were added so that the formulations as shown in Table 1 were obtained, and polyvinyl acetate resin (PVAc) was prepared in the same manner as in Example 1, except that the recovery step was not performed. ) was obtained (polymerization slurry).
- a polyvinyl alcohol resin was obtained in the same manner as in Example 1, except that the compound shown in Table 2 was added as a saponification catalyst to the obtained polymerization slurry.
- a polyvinyl acetal resin was obtained in the same manner as in Example 1, except that the obtained polyvinyl alcohol resin was used.
- a saponification catalyst the following was used.
- Dialkylamine compound diethylamine
- Trialkylamine compound triethylamine: solubility in water at 25° C. 8 g/100 g
- Tributylamine solubility in water at 25° C. 0.3 g/100 g
- Example 17-23 A polyvinyl acetate resin was obtained in the same manner as in Example 1 except that vinyl acetate, water, a water-soluble surfactant, a polymerization initiator, and a cationic surfactant were added so as to have the formulation shown in Table 1. rice field.
- a polyvinyl alcohol resin was obtained in the same manner as in Example 1, except that the type of solvent and the blending amount of the saponification catalyst were changed.
- a polyvinyl acetal resin was obtained in the same manner as in Example 1, except that the obtained polyvinyl alcohol resin was used.
- the following cationic surfactants were used.
- the mixture is cooled to 20° C. under a nitrogen atmosphere, and 0.03% hydrogen peroxide solution prepared with separately deaerated ion-exchanged water is uniformly dropped continuously at 12 parts/hr for polymerization. started. After 2 hours, when the polymerization rate reached 48%, the addition of the hydrogen peroxide solution was stopped, and 1.0 part of hydroquinone was added to stop the polymerization, thereby obtaining an aqueous solution (polymerization slurry) containing a polyvinyl acetate resin.
- the polymerization slurry was evaluated by a zetatizer, the polyvinyl acetate resin had an average particle size of 0.2 ⁇ m and a CV value of 20%.
- the obtained polymerization slurry was spray-dried to obtain a polyvinyl acetate resin composition.
- the obtained polyvinyl acetate resin dissolved in acetone and methanol. Moreover, the molecular weight of the obtained polyvinyl acetate resin was 1,000,000.
- a polyvinyl alcohol resin and a polyvinyl acetal resin were obtained in the same manner as in Example 1, except that the obtained polyvinyl acetate resin was used.
- Example 2 A 2 L separable flask equipped with a stirrer, condenser, thermometer, hot water bath and nitrogen gas inlet was prepared. A 2-L separable flask was charged with 900 parts by weight of water and 100 parts by weight of vinyl acetate as a monomer. Thereafter, 2.0 parts by weight of azobisisobutyronitrile (AIBN) was added as a polymerization initiator, 12 parts by weight of sodium dodecylsulfonate was added as an emulsifier, and the reaction system was emulsified using a homogenizer.
- AIBN azobisisobutyronitrile
- aqueous solution (polymerization slurry) containing a polyvinyl acetate resin having an isobutyrolonitrile group at one molecular end of the main chain. 2 g of the obtained aqueous solution was dried in an oven at 150° C., and the solid resin content was evaluated.
- the polyvinyl acetate resin When the polymerization slurry was evaluated by a zetatizer, the polyvinyl acetate resin had an average particle size of 10 ⁇ m and a CV value of 40%.
- the resulting polymerized slurry was dehydrated using a filter cloth and dried for 18 hours in a vacuum dryer set at 27° C. to obtain a polyvinyl acetate resin.
- the obtained polyvinyl acetate resin dissolved in acetone and methanol.
- the molecular weight of the obtained polyvinyl acetate resin was 150,000.
- a polyvinyl alcohol resin was obtained in the same manner as in Example 1, except that the obtained polyvinyl acetate resin was used.
- a polyvinyl acetal resin was obtained in the same manner as in Example 1 except that the obtained polyvinyl alcohol resin was used and the amounts of polyvinyl alcohol resin, water and aldehyde added were as shown in Table 3.
- a polyvinyl acetate resin was obtained in the same manner as in Example 1, except that the type and amount of the water-soluble surfactant were as shown in Table 1.
- a polyvinyl alcohol resin was obtained in the same manner as in Example 1 except that the type of solvent and the amount of saponification catalyst added were as shown in Table 2.
- a polyvinyl acetal resin was obtained in the same manner as in Example 1, except that the obtained polyvinyl alcohol resin was used. The following water-soluble surfactants were used. ⁇ Water-soluble surfactant> Polycarboxylic acid: Demol P (Kao Corporation)
- a polymerization initiator solution was prepared by dissolving 1.2 parts by weight of ammonium persulfate (APS) as a polymerization initiator in 200 parts by weight of water. After removing dissolved oxygen by bubbling the emulsified monomer mixture for 20 minutes with nitrogen gas, the inside of the separable flask is replaced with nitrogen gas, and the water bath is heated to 60°C while stirring. Then, a polymerization initiator solution was added dropwise to initiate polymerization.
- APS ammonium persulfate
- aqueous solution (polymerization slurry) containing a polyvinyl acetate resin having a sulfonic acid group at one molecular end of the main chain.
- 2 g of the obtained aqueous solution was dried in an oven at 150° C., and the solid resin content was evaluated.
- the polymerization slurry was evaluated by a zetatizer, the polyvinyl acetate resin had an average particle size of 0.2 ⁇ m and a CV value of 20%.
- the resulting polymerized slurry was dehydrated using a filter cloth and dried for 18 hours in a vacuum dryer set at 27° C. to obtain a polyvinyl acetate resin.
- the obtained polyvinyl acetate resin dissolved in acetone and methanol.
- the molecular weight of the obtained polyvinyl acetate resin was 900,000.
- a polyvinyl alcohol resin was obtained in the same manner as in Example 1, except that the obtained polyvinyl acetate resin was used.
- a polyvinyl acetal resin was obtained in the same manner as in Example 1 except that the obtained polyvinyl alcohol resin was used and the amounts of polyvinyl alcohol resin, water and aldehyde added were as shown in Table 3.
- PVA film To 190 parts by weight of water, 10 parts by weight of the obtained polyvinyl alcohol resin, 40 parts by weight of glycerin as a plasticizer, and 0.4 parts by weight of polyether silicone (KF-642 manufactured by Shin-Etsu Chemical Co., Ltd.) as an antifoaming agent are added. Then, a polyvinyl alcohol resin aqueous solution was prepared. The obtained aqueous solution was coated on a release PET film to form a liquid coating, which was cast on a chromium plating drum heated to 80° C. and dried for 3 minutes to obtain a 40 ⁇ m PVA film.
- KF-642 manufactured by Shin-Etsu Chemical Co., Ltd.
- the film was cut into a size of 100 mm ⁇ 15 mm to prepare a measurement sample (PVA film).
- the resulting measurement sample was subjected to a tensile test in accordance with JIS K7113 at a temperature of 23° C., a humidity of 50%, and a peel speed of 100 mm /min. was measured.
- PVB resin sheet 10 parts by weight of the obtained polyvinyl acetal resin was added to 90 parts by weight of an ethanol/toluene mixed solvent (weight ratio: 1:1), and dissolved by stirring to obtain a resin sheet composition.
- a measurement sample is prepared by applying the obtained resin sheet composition on a release-treated PET film using a coater so that the thickness after drying becomes 20 ⁇ m, followed by heating and drying. did.
- the resulting measurement sample was stretched at a tensile speed of 20 mm/min using AUTOGRAPH (AGS-J, manufactured by Shimadzu Corporation) according to JIS K7113, and the breaking stress was measured.
- the strength was evaluated according to the standard. ⁇ : Breaking stress is 100 MPa or more ⁇ : Breaking stress is less than 100 MPa
- Interlayer film for laminated glass 100 parts by weight of the obtained polyvinyl acetal resin and 40 parts by weight of triethylene glycol-di-2-ethylbutyrate as a plasticizer are mixed, and the mixture is thoroughly melt-kneaded with a mixing roll and then molded with a press molding machine. Press molding was performed at 150° C. for 30 minutes to obtain a resin (interlayer film for laminated glass) having a thickness of 0.3 mm. The resulting resin film was sandwiched between two sheets of transparent float glass (30 cm long x 30 cm wide x 3 mm thick), placed in a rubber bag, degassed at a vacuum of 20 torr for 20 minutes, and then heated to 90°C. A laminated glass was obtained by transferring to an oven and vacuum pressing while holding for 30 minutes.
- the transparency of the obtained laminated glass was confirmed according to JIS R3205.
- the falling ball impact peeling property was confirmed in accordance with JIS R3205, the height of visible cracks was measured in the falling ball test, and the strength was evaluated according to the following criteria. ⁇ : 6.0 m or more ⁇ : less than 6.0 m
- the present invention it is possible to provide an ultra-high molecular weight polyvinyl alcohol resin that can be acetalized to form a resin film having high strength and transparency. Moreover, the manufacturing method of polyvinyl acetal resin and polyvinyl alcohol resin, and the manufacturing method of polyvinyl acetal resin can be provided.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
PVAやPVBの強靭性を更に高めるには、原料であるPVAcの重合度を高めることが必要であるが、通常PVAを製造する際には、溶液重合法により得られたPVAcが用いられているが、溶液重合法は発熱量の制御が難しく、得られる樹脂の重量平均分子量の上限は70万程度である。
固有粘度[η]と分子量Mとの間には、Mark-Houwinkの実験式が成り立つことが知られている。すなわち、[η]=kMaにより分子量が評価される。ここで、k及びaは高分子の種類、溶媒の種類及び測定温度によって決まる定数であり、高分子の重合度には依存しない定数である。高分子の種類、溶媒の種類及び測定温度が決まれば、k、aは実験的にその値を知ることができる。上記実験式を用いて求められた分子量を粘度平均分子量といい、粘度平均分子量は、浸透圧法又は光散乱法による平均分子量、すなわちそれぞれ数平均分子量、重量平均分子量によって求められた値の中間値を示す。これは、定数aの値が0.5~1で中間値をとっているからである。
また、特許文献2には、特定の溶媒を用い、溶媒組成と重合温度とを所定の条件とすることで、極限粘度が2.3dl/g以上の高重合度ポリビニルエステル系重合体を作製し、これをケン化して高重合度ポリビニルアルコール樹脂を得る方法が開示されている。
更に、特許文献3には、ビニルエステルモノマーを重合温度-60℃以上10℃以下の低温で光乳化重合することで、極限粘度1.5dl/g以上の高重合度ポリビニルエステルを作製し、これをケン化して高重合度ポリビニルアルコール樹脂を得る方法が開示されている。
本開示(2)は、陽イオン界面活性剤を0.0000001重量%以上含有する、本開示(1)のポリビニルアルコール樹脂である。
本開示(3)は、重量平均分子量(Mw)と数平均分子量(Mn)との比(Mw/Mn)が1.0~3.0である本開示(1)又は(2)のポリビニルアルコール樹脂である。
本開示(4)は、ケン化度が70モル%以上99モル%以下である本開示(1)~(3)の何れかとの任意の組み合わせのポリビニルアルコール樹脂である。
本開示(5)は、曇点が30℃以上である本開示(1)~(4)の何れかとの任意の組み合わせのポリビニルアルコール樹脂である。
本開示(6)は、炭素数1~10のアルキル基を有するジアルキルアミン化合物及び炭素数1~10のアルキル基を有するトリアルキルアミン化合物からなる群から選ばれる少なくとも1種を含有する本開示(1)~(5)の何れかとの任意の組み合わせのポリビニルアルコール樹脂である。
本開示(7)は、本開示(1)~(6)の何れかのポリビニルアルコール樹脂のアセタール化物であるポリビニルアセタール樹脂である。
本開始(8)は、本開示(7)のポリビニルアセタール樹脂を含む合わせガラス用中間膜である。
本開示(9)は、本開示(7)のポリビニルアセタール樹脂を含むバインダー組成物である。
本開示(10)は、重合開始剤を添加してビニルエステルを重合させてポリビニルエステルを作製する重合工程、及び、ケン化触媒を添加してポリビニルエステルをケン化して水溶性ポリビニルアルコール樹脂を作製するケン化工程を有し、前記重合開始剤は、スルホン基、アルキルスルホニル基、芳香族スルホニル基、スルフィン基、イミダゾリン基、カルボキシル基、アミド基、アミノ基及び水酸基からなる群から選択される少なくとも1種を有するポリビニルアルコール樹脂の製造方法である。
本開示(11)は、重合工程における水溶性界面活性剤の添加量がビニルエステル100重量部に対して0.02重量部以下である本開示(10)のポリビニルアルコール樹脂の製造方法である。
本開示(12)は、重合工程は、ビニルエステル及び水を含有するモノマー水溶液に重合開始剤を添加してポリビニルエステルを含む水系乳化重合スラリーを作製するものであり、前記水系乳化重合スラリー中のポリビニルエステルの平均粒子径が0.01μm以上10μm以下であり、ケン化工程は、前記水系乳化重合スラリーにケン化触媒を直接添加してポリビニルエステルをケン化するものであり、前記ケン化触媒は炭素数1~10のアルキル基を有するジアルキルアミン化合物及び炭素数1~10のアルキル基を有するトリアルキルアミン化合物からなる群から選択される少なくとも1種である本開示(10)又は(11)のポリビニルアルコール樹脂の製造方法である。
本開示(13)は、重合工程は、ビニルエステル及び水を含有するモノマー水溶液に重合開始剤を添加してポリビニルエステルを含む水系乳化重合スラリーを作製するものであり、更に、前記水系乳化重合スラリーに陽イオン界面活性剤を添加したスラリーをろ過してポリビニルエステルを回収する回収工程を有し、ケン化工程は、前記回収工程において回収されたポリビニルエステルをケン化する本開示(10)又は(11)のポリビニルアルコール樹脂の製造方法である。
本開示(14)は、ポリビニルエステルの重量平均分子量(Mw)と数平均分子量(Mn)との比(Mw/Mn)が1.0~3.0である本開示(10)~(13)の何れかとの任意の組み合わせのポリビニルアルコール樹脂の製造方法である。
本開示(15)は、本開示(10)~(14)の何れかのポリビニルアルコール樹脂の製造方法により得られたポリビニルアルコール樹脂にアルデヒドを添加してポリビニルアルコール樹脂をアセタール化するポリビニルアセタール樹脂の製造方法である。
以下に本発明を詳述する。
上記置換基を有するポリビニルアルコール樹脂は、強靭な機械的強度を有し、アセタール化して得られるポリビニルアセタール樹脂を成形した際、高い強度を有しつつ、透明性にも優れる成形体を作製することができる。
上記ポリビニルアルコール樹脂は、主鎖の少なくとも一方の分子末端に上記官能基を有していればよく、カルボキシル基を有するものとしては、カルボキシル基の他、カルボキシエチルアミノ基等のカルボキシアルキルアミノ基、カルボキシエチルアミジン基等のカルボキシアルキルアミジン基を分子末端に有するものであってもよい。
また、水酸基を有するものとしては、水酸基の他、ヒドロキシエチルアミノ基等のヒドロキシアルキルアミノ基、ヒドロキシエチルアミド基等のヒドロキシアルキルアミド基を分子末端に有するものであってもよい。
更に、上記スルホン基は、塩、エステルであってもよい。上記塩としては、アンモニウム塩、ナトリウム塩、カリウム塩等が挙げられる。上記エステルとしては、炭素数1~12の脂肪族基、炭素数6~12の芳香族基を有するエステル等が挙げられ、アルキルエステルがより好ましい。
上記アルキルスルホニル基としては、炭素数1~12のアルキルを有するスルホニル基が挙げられ、具体的には、メチルスルホニル基、エチルスルホニル基、プロピルスルホニル基等が挙げられる。
上記芳香族スルホニル基としては、炭素数12以下の芳香族基を有するスルホニル基が挙げられ、具体的にはフェニルスルホニル基等が挙げられる。
上記スルフィン基は、塩、エステルであってもよい。上記塩としては、アンモニウム塩、ナトリウム塩、カリウム塩等が挙げられる。上記エステルとしては、炭素数1~12の脂肪族基、炭素数6~12の芳香族基を有するエステル等が挙げられ、アルキルエステルがより好ましい。
上記アミノ基としては、炭素数1~10(好ましくは炭素数1~5、より好ましくは1~3)のモノアミノ基、ジアミノ基、トリアミノ基であってよい。
上記ポリビニルアルコール樹脂は、なかでも、分子末端にスルホン基を有することが好ましい。
本発明の好適な実施態様においては、上記ポリビニルアルコール樹脂の主鎖の少なくとも一方の分子末端における上記特定の置換基は、好ましくは重合開始剤由来である。
重量平均分子量が100万以上であることにより、樹脂の強靭性を高めることができ、アセタール化して得られるポリビニルアセタール樹脂を成形することで、高い強度を有する成形体を得ることができる。
本発明のポリビニルアルコール樹脂は、重量平均分子量(Mw)が150万以上であることが好ましく、200万以上であることがより好ましく、400万以下であることが好ましく、300万以下であることがより好ましい。
更に、本発明のポリビニルアルコール樹脂の重量平均分子量(Mw)と数平均分子量(Mn)との比(Mw/Mn)は1.0以上であることが好ましく、1.5以上であることがより好ましく、3.0以下であることが好ましく、2.0以下であることがより好ましい。
上記範囲とすることで、樹脂の強靭性をより向上させることができる。
上記重量平均分子量(Mw)、数平均分子量(Mn)は、例えば、ゲルパーミエーションクロマトグラフィー(GPC)法により測定すること、ケン化前のポリビニルエステルをGPC法により測定すること、ポリビニルアルコール樹脂を再エステル化して得られたポリビニルエステルをGPC法により測定すること、JIS K6726に準拠して水溶液の粘度を測定することで求めることができる。例えば、ポリスチレンを標準とし、TSKgel(東ソー社)、PLgel(AMR社)、KF-806,KF-807(Shodex社)等のカラムを使用することができる。
上記範囲とすることで、樹脂の強靭性をより高めることができる。また、ポリビニルアルコール樹脂フィルムとした際、耐水性とガスバリア性との双方をバランスよく高めることができる。
上記ケン化度は、80モル%以上がより好ましく、85%以上が更に好ましく、90モル%以上が更により好ましく、92モル%以上が特に好ましく、93モル%以上がとりわけ好ましく、94モル%以上が最も好ましく、99モル%以下が好ましく、98.5モル%以下がより好ましく、98モル%以下が更に好ましく、97モル%以下が特に好ましく、95モル%以下が最も好ましい。
上記ケン化度は、JIS K6726に準拠して測定することができる。上記ケン化度は、ケン化によりビニルアルコール単位に変換され得る単位のうち、実際にビニルアルコール単位に変換された単位の割合を示す。
上記ケン化度は、ケン化条件、すなわち加水分解条件により適宜調整可能である。
上記範囲とすることで、樹脂の強靭性をより向上させることができる。
上記曇点は、35℃以上であることがより好ましく、40℃以上であることが更に好ましく、例えば90℃以下である。
上記曇点は、目視により確認できる他、ヘイズメーターや静的光散乱方等で測定することができる。
上記未溶解成分の割合は、メッシュ濾過により測定することができる。例えば、4重量%の濃度の樹脂水溶液を12時間以上静置し、80℃まで昇温し、その後放置することで常温まで降温し、その後、金属メッシュ(目開き#100メッシュ)を用いて、水と水を吸収し膨潤した樹脂を分離し、分離後の樹脂を60℃の条件下で3時間乾燥し、乾燥後の金属メッシュを含む樹脂の重量を測定し、下記式を用いて未溶解成分の割合を算出することができる。
未溶解成分の割合(重量%)=100×(W1-W2)/W0
(W0:初期樹脂重量、W1:乾燥後の金属メッシュを含む樹脂重量、W2:金属メッシュの初期重量)
すなわち、本発明のポリビニルアルコール樹脂が水溶性界面活性剤やその他の成分を含有する場合、本発明のポリビニルアルコール樹脂は、ポリビニルアルコール樹脂を含むポリビニルアルコール樹脂組成物ということができ、上記ポリビニルアルコール樹脂組成物の相溶に占める水溶性界面活性剤の含有量は0.02重量%以下である。
上記範囲とすることで、透明性が高い樹脂とすることができる。
上記水溶性界面活性剤の含有量は、0.002重量%以下であることが好ましい。また、下限は特に限定されず、0重量%であることが好ましく、0.0005重量%以上であることがより好ましい。
上記水溶性界面活性剤の含有量の測定方法は特に限定されないが、例えば、HPLCをはじめとする液体クロマトグラフィーを用いる方法やメタノール等を用いて抽出する方法により測定することができる。
上記水溶性界面活性剤は、乳化重合の際に添加される分散剤として用いられるものであり、例えば、アルキルスルホン酸塩等のアニオン性界面活性剤、ポリアルキレングリコール等の高分子界面活性剤が挙げられる。
上記アルキルスルホン酸塩としては、オクチルスルホン酸、デシルスルホン酸、ドデシルスルホン酸、p-トルエンスルホン酸等のナトリウム塩、カリウム塩、アンモニウム塩等が挙げられる。
本発明のポリビニルアルコール樹脂を樹脂溶液化した場合、上記水溶性界面活性剤の含有量によって樹脂溶液が極わずかであっても白濁する。また、本発明のポリビニルアルコール樹脂は非常に分子量が高いため、溶媒への溶解性が悪くなっても樹脂溶液が白濁する。なお、本発明において、水溶性界面活性剤は通常陰イオン界面活性剤である。
上記陽イオン界面活性剤を含有することで、透明性により優れた樹脂とすることができる。
なお、上記陽イオン界面活性剤は、上記水溶性界面活性剤とは異なるものであり、25℃における水への溶解度が0.05g/100g以上の界面活性剤であることが好ましい。
上記第4級アンモニウム塩としては、例えば、テトラエチルアンモニウムクロリド、テトラエチルアンモニウムブロミド、テトラブチルアンモニウムブロミド、テトラブチルアンモニウムクロリド、ヘキシルトリメチルアンモニウムブロミド、n-オクチルトリメチルアンモニウムブロミド、n-オクチルトリメチルアンモニウムクロリド、ノニルトリメチルアンモニウムブロミド、デシルトリメチルアンモニウムクロリド、デシルトリメチルアンモニウムブロミド、ドデシルトリメチルアンモニウムクロリド、ドデシルトリメチルアンモニウムブロミド、テトラデシルトリメチルアンモニウムブロミド、テトラデシルトリメチルアンモニウムクロリド、ヘキサデシルトリメチルアンモニウムクロリド、ヘキサデシルトリメチルアンモニウムブロミド、ヘキサデシルトリメチルアンモニウムヘキサフルオロホスファート、ヘキサデシルトリメチルアンモニウムテトラフルオロボラート、過塩素酸ヘキサデシルトリメチルアンモニウム、ヘキサデシルトリメチルアンモニウムヒドロキシド、ヘキサデシルトリメチルアンモニウム硫酸水素塩、ヘプタデシルトリメチルアンモニウムブロミド、オクタデシルトリメチルアンモニウムクロリド、オクタデシルトリメチルアンモニウムブロミド、ベンジルドデシルジメチルアンモニウムクロリド、ベンジルドデシルジメチルアンモニウムブロミド、ベンジルジメチルテトラデシルアンモニウムクロリド、ベンジルヘキサデシルジメチルアンモニウムクロリド、ベンジルジメチルオクタデシルアンモニウムクロリド、塩化ベンザルコニウム、ベンゼトニウムクロリド、ドデカン-1-イル(エチル)(ジメチル)アンモニウム=エチル=スルファート、ジステアリルジメチルアンモニウムクロライド、ドコシルトリメチルアンモニウムクロライド、1-ドデシルピリジニウムクロリド、ヘキサデシルピリジニウムクロリド、ヘキサデシルピリジニウムブロミド、1-ヘキサデシル-4-メチルピリジニウムクロリド、塩化1-エチル-3-メチルイミダゾリウム、塩化セチルピリジニウム、塩化ベンゼトニウム等が挙げられる。
上記アミン塩としては、ステアリン酸ジメチルアミノプロピルアミド、n-オクチルアンモニウムクロリド、n-オクチルアンモニウムブロミド、ドデシルアミン塩酸塩、ドデシルアンモニウムブロミド、オクタデシルアミン塩酸塩等が挙げられる。
上記ホスホニウム塩としては、例えば、trans-2-ブテン-1,4-ビス(トリフェニルホスホニウムクロリド)、トリブチル(シアノメチル)ホスホニウムクロリド、(2-カルボキシエチル)トリフェニルホスホニウムブロミド、トリブチルドデシルホスホニウムブロミド、トリブチルヘキサデシルホスホニウムブロミド、トリブチル-n-オクチルホスホニウムブロミド、テトラキス(ヒドロキシメチル)ホスホニウムクロリド、テトラフェニルホスホニウムブロミド、テトラキス(ヒドロキシメチル)ホスホニウムスルファート、テトラブチルホスホニウムブロミド、テトラフェニルホスホニウムクロリド、テトラエチルホスホニウムブロミド、テトラブチルホスホニウムクロリド、テトラ-n-オクチルホスホニウムブロミド、テトラエチルホスホニウムヘキサフルオロホスファート、テトラエチルホスホニウムテトラフルオロボラート、テトラブチルホスホニウムテトラフルオロボラート、テトラブチルホスホニウムヘキサフルオロホスファート、テトラブチルホスホニウムテトラフェニルボラート、トリブチルヘキシルホスホニウムブロミド等が挙げられる。
なかでも、第4級アンモニウム塩、アミン塩、ホスホニウム塩が好ましく、第4級アンモニウム塩、アミン塩がより好ましく、塩化1-エチル-3-メチルイミダゾリウム、塩化セチルピリジニウム、テトラブチルアンモニウムブロミド、テトラブチルアンモニウムクロリド、ヘキシルトリメチルアンモニウムブロミド、n-オクチルトリメチルアンモニウムブロミド、n-オクチルトリメチルアンモニウムクロリド、ノニルトリメチルアンモニウムブロミド、デシルトリメチルアンモニウムクロリド、デシルトリメチルアンモニウムブロミド、ドデシルトリメチルアンモニウムクロリド、ドデシルトリメチルアンモニウムブロミド、テトラデシルトリメチルアンモニウムブロミド、テトラデシルトリメチルアンモニウムクロリド、ヘキサデシルトリメチルアンモニウムクロリド、オクタデシルトリメチルアンモニウムクロリド、ベンジルドデシルジメチルアンモニウムクロリド、ドデカン-1-イル(エチル)(ジメチル)アンモニウム=エチル=スルファート、ヘキサデシルトリメチルアンモニウムブロミド、テトラエチルアンモニウムブロミド、塩化ベンゼトニウム、ステアリン酸ジメチルアミノプロピルアミドが更に好ましく、テトラブチルアンモニウムブロミド、ステアリン酸ジメチルアミノプロピルアミドが更により好ましい。
上記範囲とすることで、透明性がより高い樹脂とすることができる。
ポリビニルアルコール樹脂が陽イオン界面活性剤を含む場合、上記陽イオン界面活性剤の含有量は、0重量%より大きいことがより好ましく、0.0000001重量%以上であることが更に好ましく、0.0001重量%以上であることが特に好ましく、0.002重量%以下であることが好ましく、0.0015重量%以下であることがより好ましく、0.001重量%以下であることが更に好ましい。
上記陽イオン界面活性剤の含有量は、HPLC法やGC-MS法により測定することができる。
上記化合物を含有することで、樹脂の強靭性をより高めることができる。
なかでも、炭素数1~10のアルキル基を有するジアルキルアミン、炭素数1~10のトリアルキルアミンが好ましい。
炭素数1~10のアルキル基を有するトリアルキルアミンとしては、例えば、トリメチルアミン、トリエチルアミン、トリブチルアミン等が挙げられる。
上記含有量は、HPLC法やGC-MS法により測定することができる。
重合開始剤を添加してビニルエステルを重合させてポリビニルエステルを作製する重合工程、及び、ケン化触媒を添加してポリビニルエステルをケン化して水溶性ポリビニルアルコール樹脂を作製するケン化工程を有し、前記重合開始剤は、スルホン基、アルキルスルホニル基、芳香族スルホニル基、スルフィン基、イミダゾリン基、カルボキシル基、アミド基及び水酸基からなる群から選択される少なくとも1種を有するポリビニルアルコール樹脂の製造方法もまた本発明の1つである。
上記ビニル系モノマーとしては、例えば、エチレン、ブタジエン、1,3-ブタジエン、プロピレン、1-ブテン、1-ヘキセン、4-メチル-1-ペンテン、イソプレン、アクリル酸エステル、メタクリル酸エステル、マレイン酸、フマル酸、イタコン酸等の高級脂肪酸ビニルエステル、アルキルビニルエーテル、N-(2-ジメチルアミノエチル)メタクリルアミド類あるいはその4級化物、N-ビニルイミダゾール、あるいはその4級化物、N-ビニルピロリドン、N-n・ブトキシメチルアクリルアミド、ビニルトリメトキシシラン、ビニルメチルジメトキシシラン、ビニルジメチルメトキシシラン、アクリロニトリル、メタクリルアミド誘導体、アクリルアミド誘導体、フッ化ビニリデン、α-メチルスチレン、N-アルキル置換マレイミド、アセナフチレン、ビニレンカーボネート等が挙げられる。
通常は100万位の高重合度化させることは非常に難しい。重合された樹脂はTgが高いため、分子末端の運動性に乏しく、ラジカルとの衝突確率が非常に低いため、通常、重量平均分子量が100万以上の高分子量のポリビニルエステルを得ることは難しい。
通常、乳化重合では分散剤ミセル中でモノマーの重合を進行させるが、高分子量の樹脂を得るためには巨大なミセルを形成する必要があり、そのため、多量の分散剤が必要となり、得られた樹脂は多量の分散剤を異物として含むため、樹脂透明や樹脂強度も低い。上記ポリビニルエステルを作製する重合工程では、通常の乳化重合で用いる分散剤は用いない。水中に分散させたビニルエステルモノマーをスルホン基、スルホニル基、スルフィン基、イミダゾリン基、カルボキシル基、アミド基、水酸基を有する水溶性ラジカル重合開始剤を基点として重合を開始させ、それぞれのモノマードメインが衝突、合着しないよう低濃度で分散重合させる。
そうすることにより、各ドメインの大きさが均一で粒子径のそろった重合体が得られる。
上記重合工程では、粒子内の分子の成長が同一で分子量が非常に高く、重量平均分子量が400万以上の樹脂も合成することができる。重量平均分子量が高くなる理由はスルホン基、スルホニル基、スルフィン基、イミダゾリン基、カルボキシル基、アミド基、水酸基を有する水溶性ラジカル重合開始剤を低濃度で重合することにより、水素引き抜き等の不均化反応を最低限化することができるため、ドメイン内に複数のポリマーが成長しにくいためである。
上記重合開始剤を用いた重合では、上記水溶性ラジカル重合開始剤を用いることで、通常の乳化重合のように分散剤を多量に添加することなく、高分子量のポリビニルエステルを作製することができる。
なかでも、イミダゾール系アゾ化合物の酸混合物、水溶性アゾ化合物、オキソ酸類が好ましい。また、2,2’-アゾビス[2-(2-イミダゾリン-2-イル)プロパン]ジヒドロクロライド、2,2’-アゾビス(2-メチルプロピオンアミジン)ジハイドロクロライド、2,2’-アゾビス[N-(2-カルボキシエチル)-2-メチルプロピオンアミジン]テトラハイドレート、2,2’-アゾビス[2-メチル-N-(2-ヒドロキシエチル)プロピオンアミド]、過硫酸カリウム、過硫酸アンモニウム、過硫酸ナトリウムがより好ましい。更に、残渣を少なくできることから、過硫酸カリウム、過硫酸アンモニウムが更に好ましい。
上記連鎖移動剤、重合停止剤としては、特に限定されないが、3-メルカプト-1-プロパンスルホン酸ナトリウム、メルカプトコハク酸、メルカプトプロパンジオール、(アリルスルホニル)ベンゼン、2-メルカプトエタンスルフィン酸エチル、3-メルカプトプロピオンアミド等が挙げられる。
上記連鎖移動剤、重合停止剤を添加することで、主鎖の少なくとも一方の分子末端にスルホン基、スルホニル基、スルフィン基、イミダゾリン基、カルボキシル基、アミド基及び水酸基からなる群から選択される少なくとも1種を有し、重量平均分子量が所定範囲のポリビニルエステルを作製することができる。
これらの水溶性ラジカル重合開始剤は単独で用いてもよいし、2種以上を併用してもよい。
上記添加量を0.03重量部以上とすることで、原料モノマーの反応率を充分に高めることができる。上記添加量を0.2重量部以下とすることで、ポリビニルエステルの分子量を充分に高めることができる。
また、上記範囲とすることで、分子末端(ω位)にスルホン基、スルホニル基、スルフィン基、イミダゾリン基、カルボキシル基、アミド基及び水酸基から選択される少なくとも1種を有するポリビニルエステルが水中に低濃度で分散して均一な粒径の樹脂を得ることができる。
更に、一般的な乳化重合においては、原料モノマー100重量部に対して水溶性界面活性剤を1重量部以上添加するが、水溶性界面活性剤は樹脂シートを成形する場合、異物として振る舞うため、より少ない方が望ましい。しかしながら、単に水溶性界面活性剤を減らしただけでは、分子量が高い樹脂の重合は難しい。水溶性ラジカル重合開始剤の添加量を上記範囲とすることで、乳化剤をほとんど添加しなくても、水中で重合ドメインが分散状態を維持し、非常に高い分子量を有するポリビニルエステルを作製することができる。
上記範囲とすることで、重合途中での凝集や反応容器への樹脂の付着を防止することができる。
また、原料モノマーの添加量は、水1000重量部に対して70~200重量部とすることがより好ましい。
上記範囲とすることで、残留モノマーを少なくして、均一に重合することが可能となる。
ビニルエステルモノマーである酢酸ビニルは反応熱が高いため、あまり高温での反応は好ましくない。50℃以上とすることでラジカルを充分に発生させて、反応を充分に進行できる。また、70℃以下とすることで、反応容器へのスケール付着を抑制して、重合不良を防止することができる。
水溶性界面活性剤は、乳化重合の際に添加される分散剤として用いられるものであり、上述したものが挙げられる。
上記水溶性界面活性剤の添加量は、原料モノマー100重量部に対して、0~0.02重量部とすることが好ましく、0.002~0.01重量部とすることがより好ましい。
上記陽イオン界面活性剤としては、上述したものが挙げられる。
上記範囲とすることで、得られるポリビニルエステルに充分に吸着して、得られる樹脂の再溶解性を向上させることができる。
上記範囲とすることで、得られる樹脂の透明性をより高めることができる。
上記平均粒子径は、0.005μm以上であることがより好ましく、0.01μm以上であることが更に好ましく、0.1μm以上であることが更により好ましく、30μm以下であることがより好ましく、10μm以下であることが更に好ましく、5μm以下であることが更により好ましく、1μm以下であることが特に好ましく、0.8μm以下であることがとりわけ好ましく、0.5μm以下であることが最も好ましい。
上記範囲とすることで、得られる樹脂の透明性をより高めることができる。
上記比は、1.5以上であることがより好ましく、2.0以下であることがより好ましい。
また、上記水系乳化重合スラリーに直接添加する場合、ケン化触媒としては、ジアルキルアミン化合物、トリアルキルアミン化合物等のアミンを用いることが好ましい。
ジアルキルアミン化合物としては、炭素数1~10のアルキル基を有するジアルキルアミン化合物が挙げられ、トリアルキルアミン化合物としては炭素数1~10のアルキル基を有するトリアルキルアミン化合物等が挙げられる。具体的には、例えば、ジメチルアミン、ジエチルアミン、トリメチルアミン、トリエチルアミン、トリブチルアミン等が挙げられる。
上記方法におけるケン化触媒としては、例えば、水酸化ナトリウム、水酸化カリウム、ナトリウムアルコラート、炭酸ナトリウム等のアルカリ触媒、硫酸、燐酸、塩酸等の酸触媒が挙げられ、なかでも、ケン化速度を速くし、生産性を向上できることから、アルカリ触媒が好ましく、水酸化ナトリウムが特に好ましい。
更に、上記重合工程は、ビニルエステル及び水を含有するモノマー水溶液に重合開始剤を添加してポリビニルエステルを含む水系乳化重合スラリーを作製するものであり、更に、上記水系乳化重合スラリーに陽イオン界面活性剤を添加したスラリーをろ過してポリビニルエステルを回収する回収工程を有し、ケン化工程は、上記回収工程において回収されたポリビニルエステルをケン化するポリビニルアルコール樹脂の製造方法もまた本発明の1つである。
上記ポリビニルアルコール樹脂を用いて包装用フィルムや延伸加工用フィルムを作製した場合、ガスバリア性を効果的に高めることができ、また、均一なフィルムとすることができる。
また、上記フィルムは、必要に応じて、表面張力調整剤、消泡剤、界面活性剤、防腐剤、グリセリンやポリエチレングリコール等の水溶性可塑剤等を含んでいてもよい。
上記支持部材の材料は特に限定されないが、例えば、ポリオレフィン系樹脂、ポリエステル系樹脂、アクリル樹脂等が挙げられる。上記ポリオレフィン系樹脂としては、ポリエチレン、ポリプロピレン、エチレン-酢酸ビニル共重合体、エチレン-ビニルアルコール共重合体等が挙げられる。上記ポリエステル系樹脂としては、ポリエチレンテレフタレート、ポリエチレンナフタレート等が挙げられる。上記支持部材の材料は、ポリビニルアルコール樹脂ではないことが好ましい。
上記二色性色素としては、例えば、ヨウ素の他、アゾ系染料、アントラキノン系染料、テトラジン系染料等の二色性染料等が挙げられる。偏光板の光学特性及び耐久性の観点から、アゾ系染料が好ましい。
上記アゾ系染料としては、例えば、C.I.Direct Yellow 12、C.I.Direct Yellow 28、C.I.Direct Yellow 44、C.I.Direct Yellow 142、C.I.Direct Orange 26、C.I.Direct Orange 39、C.I.Direct Orange 71、C.I.Direct Orange 107、C.I.Direct Red 2、C.I.Direct Red 31、C.I.Direct Red 79、C.I.Direct Red 81、C.I.Direct Red 117、C.I.Direct Red 247、C.I.Direct Green 80、C.I.Direct Green 59、C.I.Direct Blue 71、C.I.Direct Blue 78、C.I.Direct Blue 168、C.I.Direct Blue 202、C.I.Direct Violet 9、C.I.Direct Violet 51、C.I.Direct Brown 106、C.I.Direct Brown 223等が挙げられる。
上記染料は、公知の方法により製造された染料を使用できる。製造方法としては、例えば、特開平3-12606号公報に記載の方法や特開昭59-145255号公報に記載の方法等が挙げられる。
上記範囲であるとガスバリア性をより一層高めることができる。また、透明性をより一層高くできる。更に、製造時の乾燥時間を短くして生産性を向上できる。
上記フィルムの厚みの下限は特に限定されず、例えば、1μm以上である。
上記ポリビニルアルコール樹脂は、厚さが30μm以下である包装用フィルムや延伸加工用フィルムを得るために好適に用いられ、特に、厚さが20μm以下である包装用フィルムや延伸加工用フィルムを得るために好適に用いられる。通常、厚さが30μm以下である薄い包装用フィルムや延伸加工用フィルムは気泡や液滴により延伸時のフィルムの破断を引き起こしやすい。これに対して、上記ポリビニルアルコール樹脂を用いることで、厚さが30μm以下の包装用フィルムや延伸加工用フィルムを得る場合でも、フィルムに気泡や液滴が含まれることを充分に抑えて延伸時のフィルムの破断を防止できる。
上記偏光板において、延伸、染色されたポリビニルアルコール樹脂からなる偏光層は、熱や水分に対して脆弱であるため、表面に保護層を設けることが好ましい。
上記保護層の材料は特に限定されないが、例えば、トリアセチルセルロース等のセルロース系樹脂、ポリエチレンナフタレート等のポリエステル系樹脂、シクロオレフィンポリマー等の環状ポリオレフィン系樹脂、アクリル樹脂等が挙げられる。
塗工する方法としては、溶液流延法(キャスト法)、ロールコーティング法、スピンコーティング法、スクリーンコーティング法、ファウンテンコーティング法、ディッピング法、スプレー法等が挙げられる。上記ロールコーティング法としては、ワイヤーバーコーティング法、リバースコーティング法、グラビアコーティング法等が挙げられる。
また、乾燥する方法としては、自然乾燥する方法、ポリビニルアルコール樹脂のガラス転移温度以下の温度で加熱乾燥する方法等が挙げられる。
上記支持部材は、ポリビニルアルコール樹脂水溶液を塗工した際、ポリビニルアルコール樹脂水溶液を表面に維持でき、かつ、得られたポリビニルアルコール樹脂フィルムを支持可能であることが好ましい。
上記支持部材の材料は特に限定されないが、例えば、ポリオレフィン系樹脂、ポリエステル系樹脂、アクリル樹脂等が挙げられる。上記ポリオレフィン系樹脂としては、ポリエチレン、ポリプロピレン、エチレン-酢酸ビニル共重合体、エチレン-ビニルアルコール共重合体等が挙げられる。上記ポリエステル系樹脂としては、ポリエチレンテレフタレート、ポリエチレンナフタレート等が挙げられる。上記支持部材の材料は、ポリビニルアルコール樹脂ではないことが好ましい。
上記フィルムを染色する方法としては、例えば、フィルムを一軸方向に延伸しヨウ素等二色性色素を吸着配向させる方法等が挙げられる。
上記偏光板において、偏光層は、上記フィルムを一軸方向に2~8倍程度に延伸し二色性色素を吸着配向させた偏光膜であることが好ましい。
本発明のポリビニルアルコール樹脂のアセタール化物であるポリビニルアセタール樹脂もまた本発明の1つである。
上記範囲とすることで、スラリー組成物を塗工して得られる塗膜の強度を充分に向上させることができる。
上記重合度は15000以上であることがより好ましく、25000以下であることがより好ましい。
このようなポリビニルアセタール樹脂とすることで、これまでにない高強度を有するポリビニルアセタール樹脂を得ることができ、合わせガラスの強度をより高めたり、より薄いセラミックスシートを生産することが可能となる。
上記範囲とすることで、溶剤への溶解性を充分に高めることができる。また、可塑剤との相溶性を充分に高めて、ポリビニルアセタール樹脂を成形しやすくなる。
上記アセタール化度は60モル%以上であることがより好ましく、75モル%以下であることがより好ましい。
上記範囲とすることで、セラミックス分散シート作製の際に無機粉の分散性が良好となり、また、可塑剤との相溶性を高めることができる。
上記水酸基量は20モル%以上であることがより好ましく、33モル%以下であることがより好ましい。
本発明のポリビニルアルコール樹脂は超高分子量であり、また、強靭性、透明性に優れるものであり、アセタール化することで、超高分子量で、強靭性、透明性に優れるポリビニルアセタール樹脂とすることができる。
上記水との相溶性のある有機溶剤としては、例えば、アルコール系有機溶剤を用いることができる。
上記有機溶剤としては、例えば、アルコール系有機溶剤、芳香族有機溶剤、脂肪族エステル系溶剤、ケトン系溶剤、低級パラフィン系溶剤、エーテル系溶剤、アミド系溶剤、アミン系溶剤等が挙げられる。
上記アルコール系有機溶剤としては、例えば、メタノール、エタノール、n-プロパノール、イソプロパノール、n-ブタノール、tert-ブタノール等が挙げられる。
上記芳香族有機溶剤としては、例えば、キシレン、トルエン、エチルベンゼン、安息香酸メチル等が挙げられる。
上記脂肪族エステル系溶剤としては、例えば、酢酸メチル、酢酸エチル、酢酸ブチル、プロピオン酸メチル、プロピオン酸エチル、酪酸メチル、酪酸エチル、アセト酢酸メチル、アセト酢酸エチル等が挙げられる。
上記ケトン系溶剤としては、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、メチルシクロヘキサノン、ベンゾフェノン、アセトフェノン等が挙げられる。
上記低級パラフィン系溶剤としては、ヘキサン、ペンタン、オクタン、シクロヘキサン、デカン等が挙げられる。
上記エーテル系溶剤としては、ジエチルエーテル、テトラヒドロフラン、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、プロピレングリコールジエチルエーテル等が挙げられる。
上記アミド系溶剤としては、N,N-ジメチルホルムアミド、N,N-ジメチルテセトアミド、N-メチルピロリドン、アセトアニリド等が挙げられる。
上記アミン系溶剤としては、アンモニア、トリメチルアミン、トリエチルアミン、n-ブチルアミン、ジn-ブチルアミン、トリn-ブチルアミン、アニリン、N-メチルアニリン、N,N-ジメチルアニリン、ピリジン等が挙げられる。
これらは、単体で用いることもできるし、2種以上の溶剤を混合で用いることもできる。これらのなかでも、樹脂に対する溶解性及び精製時の簡易性の観点から、エタノール、n-プロパノール、イソプロパノール、テトラヒドロフランが特に好ましい。
上記酸触媒は特に限定されず、硫酸、塩酸、硝酸、リン酸等の鉱酸や、ギ酸、酢酸、プロピオン酸等のカルボン酸や、メタンスルホン酸、エタンスルホン酸、ベンゼンスルホン酸、パラトルエンスルホン酸等のスルホン酸が挙げられる。これらの酸触媒は、単独で用いられてもよく、2種以上の化合物を併用してもよい。なかでも、塩酸、硝酸、硫酸が好ましく、塩酸が特に好ましい。
、特に限定されるものではなく、例えば、脂肪族アルデヒド、芳香族アルデヒド等が挙げられる。
上記脂肪族アルデヒドとしては、ホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、n-ブチルアルデヒド、イソブチルアルデヒド、n-バレルアルデヒド、n-ヘキシルアルデヒド、2-エチルブチルアルデヒド、2-エチルヘキシルアルデヒド、n-ヘプチルアルデヒド、n-オクチルアルデヒド、n-ノニルアルデヒド、n-デシルアルデヒド、アミルアルデヒド等が挙げられる。
上記芳香族アルデヒドとしては、ベンズアルデヒド、シンナムアルデヒド、2-メチルベンズアルデヒド、3-メチルベンズアルデヒド、4-メチルベンズアルデヒド、p-ヒドロキシベンズアルデヒド、m-ヒドロキシベンズアルデヒド、フェニルアセトアルデヒド、β-フェニルプロピオンアルデヒド等が挙げられる。
これらのアルデヒドは、1種を単独で使用してもよく、2種以上を併用してもよい。アルデヒドとしては、なかでも、アセタール化反応性に優れ、生成する樹脂に充分な内部可塑効果をもたらし、結果として良好な柔軟性を付与することができるホルムアルデヒド、アセトアルデヒド、ブチルアルデヒド、2-エチルヘキシルアルデヒド、n-ノニルアルデヒドが好ましい。また、耐衝撃性及び金属との接着性に特に優れる接着剤組成物を得られることから、ホルムアルデヒド、アセトアルデヒド、ブチルアルデヒドがより好ましい。
反応後の保持温度は、15℃以上であることが好ましく、20℃以上であることがより好ましい。上記保持温度とすることで、アセタール化反応を充分に進行させることができる。
例えば、上記ポリビニルアセタール樹脂は、合わせガラス用中間膜用途に用いることができる。上記ポリビニルアセタール樹脂を含む合わせガラス用中間膜もまた本発明の1つである。
また、上記合わせガラス用中間膜を2枚のガラス板で挟み込み、熱プレスすることで合わせガラスを得ることができる。
上記ポリビニルアセタール樹脂は、強靭性、透明性に優れるため、合わせガラスに特性を付与するために他の樹脂層を有する中間膜とした場合でも、充分な強度を有するものとできる。また、より薄い合わせガラスとすることができる。
例えば、積層セラミックスコンデンサはスマートフォン等の電子機器に多数搭載されるが、小型化が必要となっており、上記ポリビニルアセタール樹脂を用いることでより高強度のセラミックスシートを得ることができる。
また、積層セラミックスコンデンサではバインダーは熱分解されるが、焼成残渣が多いとコンデンサの信頼性が低下する。上記ポリビニルアセタール樹脂を用いることで、バインダーの添加量を少なくして、焼成残渣を少なくすることができる。
(ポリ酢酸ビニル樹脂(PVAc)の作製)
(重合工程)
撹拌機、冷却器、温度計、湯浴及び窒素ガス導入口を備えた2Lセパラブルフラスコを用意し、2Lセパラブルフラスコに、水900重量部、モノマーとして酢酸ビニル(VAc)を100重量部を投入した。その後、攪拌翼により150rpmの条件で攪拌し、モノマーを水中に分散させてモノマー混合液を得た。
得られた水溶液2gを150℃オーブンで乾燥させ、樹脂固形分を評価したところ、水溶液中の樹脂固形分濃度は10重量%であり、用いたモノマーがすべて反応したことを確認した。
重合スラリーをゼータタイザーで評価したところ、ポリ酢酸ビニル樹脂の平均粒子径は0.2μm、粒子径のCV値は4%であった。
得られたポリ酢酸ビニル樹脂を含む水溶液に、更に、陽イオン界面活性剤としてn-オクチルアンモニウムブロミド(TOAB、25℃の水への溶解度0.005g/100g、東京化成工業社製)0.01重量部を加えて樹脂水溶液を得た。
得られた樹脂水溶液をろ布を用いて脱水し、27℃に設定した真空乾燥機で18時間乾燥させポリ酢酸ビニル樹脂を回収した。
得られたポリ酢酸ビニル樹脂を濃度6重量%となるように溶媒としてのメタノール(MeOH)に加え、このメタノール溶液に樹脂に対するケン化触媒である水酸化ナトリウム(NaOH)の添加量が0.05モル/樹脂1モルとなるように水酸化ナトリウムのメタノール溶液を加え、40℃でケン化した。その後、酢酸エチルによる洗浄、真空オーブンでの乾燥を行い、ポリビニルアルコール樹脂(PVA)を得た。
JIS K6726に準拠して測定したところ、ケン化度は87.7モル%であった。
また、目視により曇点を測定したところ、曇点は90℃以上であった。
更に、水に4重量%の濃度で添加した際の未溶解成分の割合を濾過法により測定したところ、未溶解成分の割合は0重量%であった。未溶解成分の割合は、具体的には、以下の方法により測定した。まず、4重量%の濃度の樹脂水溶液を12時間以上静置し、80℃まで昇温し、その後放置することで常温まで降温した。その後、金属メッシュ(目開き#100メッシュ)を用いて、水と水を吸収し膨潤した樹脂を分離し、分離後の樹脂を60℃の条件下で3時間乾燥し、乾燥後の金属メッシュを含む樹脂の重量を測定し、下記式を用いて未溶解成分の割合を算出した。
未溶解成分の割合(重量%)=100×(W1-W2)/W0
(W0:初期樹脂重量、W1:乾燥後の金属メッシュを含む樹脂重量、W2:金属メッシュの初期重量)
また、GPCにより同様にして重量平均分子量(Mw)、数平均分子量(Mn)を測定しところ、Mwは180万、Mnは90万であった。
GPC分析は分離カラムに昭和電工社製Shodex KF-807を用いる。サンプルは0.01~0.05wt%THF希釈したものを評価する。標準物質としてジーエルサイエンス社製高分子量標準ポリスチレンEasiVial PS-Hを用いて作成した検量線をもとに重量平均分子量(Mw)ならびに数平均分子量(Mn)を算出した。
純水2890重量部に、得られたポリビニルアルコール樹脂275重量部を加えて加温溶解した。反応系を12℃に調節し、35重量%の塩酸触媒201重量部とn-ブチルアルデヒド148重量部を加え、この温度を保持しながら反応物を析出させた。
その後、反応系を45℃として3時間保持して反応を完了させ、過剰の水で洗浄して未反応のn-ブチルアルデヒドを洗い流し、塩酸触媒を中和し、水洗及び乾燥を経て、白色粉末状のポリビニルアセタール樹脂(PVB)を得た。
得られたポリビニルアセタール樹脂について、カラムとしてLF-804(SHOKO社製)を用い、ゲルパーミエーションクロマトグラフィーにより、ポリスチレン換算による重量平均分子量を測定したところ、重量平均分子量は182万であった。
表1に示す通りの種類及び配合となるように水溶性界面活性剤及び重合開始剤を添加した以外は実施例1と同様にしてポリ酢酸ビニル樹脂、ポリビニルアルコール樹脂を得た。
表3に示す通りの配合となるようにn-ブチルアルデヒドを添加した以外は実施例1と同様にしてポリビニルアセタール樹脂を得た。
なお、水溶性界面活性剤、重合開始剤としては、以下のものを用いた。
<水溶性界面活性剤>
P-トルエンスルホン酸アンモニウム、25℃の水への溶解度63g/100g
<重合開始剤>
VA-057:2,2’-アゾビス[N-(2-カルボキシエチル)-2-メチルプロピオンアミジン]テトラハイドレート(富士フイルム和光純薬社製)
ペルオキソ二硫酸テトラメチルアンモニウム
P-トルエンスルホン酸過酸化物
ペルオキソ二スルフィン酸
VA-61:2,2’-アゾビス[2-(2-イミダゾリン-2-イル)プロパン]
V-50:2,2’-アゾビス(2-メチルプロピオンアミジン)ジヒドロクロライド(富士フイルム和光純薬社製)
VA-086:2,2’-アゾビス[2-メチル-N-(2-ヒドロキシエチル)プロピオンアミド](富士フイルム和光純薬社製)
表1に示す通りの配合となるように酢酸ビニル、水、水溶性界面活性剤、重合開始剤を添加し、回収工程を行わなかった以外は実施例1と同様にしてポリ酢酸ビニル樹脂(PVAc)を含む水溶液(重合スラリー)を得た。
得られた重合スラリーにケン化触媒として表2に示す化合物を添加した以外は実施例1と同様にして、ポリビニルアルコール樹脂を得た。
得られたポリビニルアルコール樹脂を用いた以外は実施例1と同様にして、ポリビニルアセタール樹脂を得た。
なお、ケン化触媒としては、以下のものを用いた。
<ケン化触媒>
ジアルキルアミン化合物:ジエチルアミン
トリアルキルアミン化合物:トリエチルアミン:25℃の水への溶解度8g/100g
トリブチルアミン:25℃の水への溶解度0.3g/100g
表1に示す通りの配合となるように酢酸ビニル、水、水溶性界面活性剤、重合開始剤、陽イオン界面活性剤を添加した以外は実施例1と同様にして、ポリ酢酸ビニル樹脂を得た。
表2に示す通り、溶媒の種類、ケン化触媒の配合量を変更した以外は実施例1と同様にして、ポリビニルアルコール樹脂を得た。
得られたポリビニルアルコール樹脂を用いた以外は実施例1と同様にして、ポリビニルアセタール樹脂を得た。
なお、陽イオン界面活性剤としては、以下のものを用いた。
<陽イオン界面活性剤>
ステアリン酸ジメチルアミノプロピルアミド:25℃の水への溶解度1mg/100g
撹拌機、冷却器、温度計、湯浴及び窒素ガス導入口を備えた2Lセパラブルフラスコを用意した。イオン交換水300重量部、界面活性剤としてノニポール400(三洋化成工業社製)を12重量部、硫酸鉄(II)七水和物を0.05重量部及びナトリウムホルムアルデヒドスルホキシレートを0.5重量部を加えて攪拌しながら溶解した。窒素流下に60℃で脱気した酢酸ビニル300重量部とメタノール100重量部を添加し、室温で30分攪拌した。その後、窒素雰囲気下で混合液が20℃になるまで冷却し、別途脱気したイオン交換水で調整した0.03%の過酸化水素水を12部/hrで均一に連続滴下することで重合を開始した。2時間後重合率48%に達したところで過酸化水素水の添加を停止し、ヒドロキノン1.0部を加えて重合を停止して、ポリ酢酸ビニル樹脂を含む水溶液(重合スラリー)を得た。
重合スラリーをゼータタイザーで評価したところ、ポリ酢酸ビニル樹脂の平均粒子径は0.2μm、CV値は20%であった。
得られた重合スラリーを噴霧乾燥し、ポリ酢酸ビニル樹脂組成物を得た。
得られたポリ酢酸ビニル樹脂はアセトン、メタノールには溶解した。また、得られたポリ酢酸ビニル樹脂の分子量は100万であった。
撹拌機、冷却器、温度計、湯浴及び窒素ガス導入口を備えた2Lセパラブルフラスコを用意した。2Lセパラブルフラスコに、水900重量部、モノマーとして、酢酸ビニルを100重量部を投入した。その後、重合開始剤としてアゾビスイソブチロニトリル(AIBN)2.0重量部添加し、乳化剤としてドデシルスルホン酸ナトリウムを12重量部を添加し、ホモジナイザーを用いて反応系を乳化させた。
得られた水溶液2gを150℃オーブンで乾燥させ、樹脂固形分を評価したところ、水溶液中の樹脂固形分濃度は3重量%であり、用いたモノマーの一部が反応したことを確認した。
重合スラリーをゼータタイザーで評価したところ、ポリ酢酸ビニル樹脂の平均粒子径は10μm、CV値は40%であった。
得られた重合スラリーをろ布を用いて脱水し、27℃に設定した真空乾燥機で18時間乾燥させポリ酢酸ビニル樹脂を得た。
得られたポリ酢酸ビニル樹脂はアセトン、メタノールには溶解した。得られたポリ酢酸ビニル樹脂の分子量は15万であった。
得られたポリビニルアルコール樹脂を用い、ポリビニルアルコール樹脂、水、アルデヒドの添加量を表3に示す通りとした以外は実施例1と同様にして、ポリビニルアセタール樹脂を得た。
水溶性界面活性剤の種類及び添加量を表1に示す通りとした以外は実施例1と同様にして、ポリ酢酸ビニル樹脂を得た。
溶媒の種類及びケン化触媒の添加量を表2に示す通りとした以外は実施例1と同様にして、ポリビニルアルコール樹脂を得た。
得られたポリビニルアルコール樹脂を用いた以外は実施例1と同様にして、ポリビニルアセタール樹脂を得た。
なお、水溶性界面活性剤としては、以下のものを用いた。
<水溶性界面活性剤>
ポリカルボン酸:デモール P(花王社)
撹拌機、冷却器、温度計、湯浴及び窒素ガス導入口を備えた2Lセパラブルフラスコを用意した。2Lセパラブルフラスコに、水700重量部、モノマーとして、酢酸ビニルを100重量部を投入した。その後、乳化剤としてドデシルスルホン酸ナトリウムを2.3重量部を添加し、ホモジナイザーを用いて反応系を乳化させた。
得られた水溶液2gを150℃オーブンで乾燥させ、樹脂固形分を評価したところ、水溶液中の樹脂固形分濃度は3重量%であり、用いたモノマーの一部が反応したことを確認した。
重合スラリーをゼータタイザーで評価したところ、ポリ酢酸ビニル樹脂の平均粒子径は0.2μm、CV値は20%であった。
得られた重合スラリーをろ布を用いて脱水し、27℃に設定した真空乾燥機で18時間乾燥させポリ酢酸ビニル樹脂を得た。
得られたポリ酢酸ビニル樹脂はアセトン、メタノールには溶解した。得られたポリ酢酸ビニル樹脂の分子量は90万であった。
得られたポリビニルアルコール樹脂を用い、ポリビニルアルコール樹脂、水、アルデヒドの添加量を表3に示す通りとした以外は実施例1と同様にして、ポリビニルアセタール樹脂を得た。
(ポリビニルアルコール樹脂の測定)
得られたポリビニルアルコール樹脂について、熱重量質量分析装置(TG-MS装置、Netzsch社製)を用いて、水溶性界面活性剤の燃焼に起因する400~600℃の分解ガス量とポリビニルアルコール樹脂自体の分解に起因する200~300℃の分解ガス量に基づき、水溶性界面活性剤の含有量を算出した。
また、GC-MSにより、陽イオン界面活性剤の含有量、ジアルキルアミン化合物、トリアルキルアミン化合物の含有量を算出した。
水190重量部に対して、得られたポリビニルアルコール樹脂10重量部、可塑剤としてグリセリン40重量部、消泡剤としてポリエーテルシリコーン(信越化学工業社製KF-642)0.4重量部を添加してポリビニルアルコール樹脂水溶液を作製した。得られた水溶液を離形PETフィルム上に塗工し液状被膜を形成し、80℃まで加熱したクロムメッキドラム上に液状被膜を流延して3分間乾燥し、40μmのPVAフィルムを得た。
得られたポリビニルアセタール樹脂10重量部を、エタノール/トルエン混合溶剤(重量比1:1)90重量部に加え、攪拌溶解し樹脂シート用組成物を得た。
得られた樹脂シート用組成物を、コーターを用いて乾燥後の厚みが20μmとなるように離型処理したPETフィルム上に塗工、加熱乾燥させることにより、測定用サンプル(樹脂シート)を作製した。
〇:破断応力が100MPa以上
×:破断応力が100MPa未満
得られたポリビニルアセタール樹脂100重量部と、可塑剤としてトリエチレングリコール-ジ-2-エチルブチレート40重量部とを混合し、これをミキシングロールで充分に溶融混錬した後、プレス成型機で150℃の条件で30分間プレス成型し、厚さ0.3mmの樹脂(合わせガラス用中間膜)を得た。
得られた樹脂膜を2枚の透明なフロートガラス(縦30cm×横30cm×厚さ3mm)で挟み込み、これをゴムバック内に入れ、20torrの真空度で20分間脱気した後、90℃のオーブンに移し、30分間保持しつつ真空プレスすることにより、合わせガラスを得た。
〇:6.0m以上
×:6.0m未満
Claims (15)
- 主鎖の少なくとも一方の分子末端にスルホン基、アルキルスルホニル基、芳香族スルホニル基、スルフィン基、イミダゾリン基、カルボキシル基、アミド基、アミノ基及び水酸基からなる群から選択される少なくとも1種を有し、重量平均分子量(Mw)が100万以上であり、
水溶性界面活性剤の含有量が0.02重量%以下である、ポリビニルアルコール樹脂。 - 陽イオン界面活性剤を0.0000001重量%以上含有する、請求項1に記載のポリビニルアルコール樹脂。
- 重量平均分子量(Mw)と数平均分子量(Mn)との比(Mw/Mn)が1.0~3.0である、請求項1又は2に記載のポリビニルアルコール樹脂。
- ケン化度が70モル%以上99モル%以下である、請求項1~3の何れかに記載のポリビニルアルコール樹脂。
- 曇点が30℃以上である、請求項1~4の何れかに記載のポリビニルアルコール樹脂。
- 炭素数1~10のアルキル基を有するジアルキルアミン化合物及び炭素数1~10のアルキル基を有するトリアルキルアミン化合物からなる群から選ばれる少なくとも1種を含有する、請求項1~5の何れかに記載のポリビニルアルコール樹脂。
- 請求項1~6の何れかに記載のポリビニルアルコール樹脂のアセタール化物である、ポリビニルアセタール樹脂。
- 請求項7に記載のポリビニルアセタール樹脂を含む、合わせガラス用中間膜。
- 請求項7に記載のポリビニルアセタール樹脂を含む、バインダー組成物。
- 重合開始剤を添加してビニルエステルを重合させてポリビニルエステルを作製する重合工程、及び、ケン化触媒を添加してポリビニルエステルをケン化して水溶性ポリビニルアルコール樹脂を作製するケン化工程を有し、
前記重合開始剤は、スルホン基、アルキルスルホニル基、芳香族スルホニル基、スルフィン基、イミダゾリン基、カルボキシル基、アミド基、アミノ基及び水酸基からなる群から選択される少なくとも1種を有する、ポリビニルアルコール樹脂の製造方法。 - 重合工程における水溶性界面活性剤の添加量がビニルエステル100重量部に対して0.02重量部以下である、請求項10に記載のポリビニルアルコール樹脂の製造方法。
- 重合工程は、ビニルエステル及び水を含有するモノマー水溶液に重合開始剤を添加してポリビニルエステルを含む水系乳化重合スラリーを作製するものであり、前記水系乳化重合スラリー中のポリビニルエステルの平均粒子径が0.01μm以上10μm以下であり、
ケン化工程は、前記水系乳化重合スラリーにケン化触媒を直接添加してポリビニルエステルをケン化するものであり、前記ケン化触媒は炭素数1~10のアルキル基を有するジアルキルアミン化合物及び炭素数1~10のアルキル基を有するトリアルキルアミン化合物からなる群から選択される少なくとも1種である、請求項10又は11に記載のポリビニルアルコール樹脂の製造方法。 - 重合工程は、ビニルエステル及び水を含有するモノマー水溶液に重合開始剤を添加してポリビニルエステルを含む水系乳化重合スラリーを作製するものであり、
更に、前記水系乳化重合スラリーに陽イオン界面活性剤を添加したスラリーをろ過してポリビニルエステルを回収する回収工程を有し、
ケン化工程は、前記回収工程において回収されたポリビニルエステルをケン化する、請求項10又は11に記載のポリビニルアルコール樹脂の製造方法。 - ポリビニルエステルの重量平均分子量(Mw)と数平均分子量(Mn)との比(Mw/Mn)が1.0~3.0である、請求項10~13の何れかに記載のポリビニルアルコール樹脂の製造方法。
- 請求項10~14の何れかに記載のポリビニルアルコール樹脂の製造方法により得られたポリビニルアルコール樹脂にアルデヒドを添加してポリビニルアルコール樹脂をアセタール化する、ポリビニルアセタール樹脂の製造方法。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE112022003265.0T DE112022003265T5 (de) | 2021-06-24 | 2022-06-20 | Polyvinylalkoholharz, Polyvinylacetalharz, Verfahren zur Herstellung von Polyvinylalkoholharz und Verfahren zur Herstellung von Polyvinylacetalharz |
CN202280038616.0A CN117412995A (zh) | 2021-06-24 | 2022-06-20 | 聚乙烯醇树脂、聚乙烯醇缩醛树脂、聚乙烯醇树脂的制造方法及聚乙烯醇缩醛树脂的制造方法 |
JP2022541966A JPWO2022270446A1 (ja) | 2021-06-24 | 2022-06-20 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2021104860 | 2021-06-24 | ||
JP2021-104860 | 2021-06-24 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022270446A1 true WO2022270446A1 (ja) | 2022-12-29 |
Family
ID=84545658
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2022/024444 WO2022270446A1 (ja) | 2021-06-24 | 2022-06-20 | ポリビニルアルコール樹脂、ポリビニルアセタール樹脂、ポリビニルアルコール樹脂の製造方法及びポリビニルアセタール樹脂の製造方法 |
Country Status (4)
Country | Link |
---|---|
JP (1) | JPWO2022270446A1 (ja) |
CN (1) | CN117412995A (ja) |
DE (1) | DE112022003265T5 (ja) |
WO (1) | WO2022270446A1 (ja) |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08188620A (ja) * | 1995-01-09 | 1996-07-23 | Kuraray Co Ltd | ポリビニルアルコール系重合体微粒子の製造方法 |
JP2534294B2 (ja) * | 1988-01-29 | 1996-09-11 | 株式会社クラレ | 高重合度ポリビニルエステル系重合体の製法及び高重合度ポリビニルアルコ―ル系重合体の製法 |
JP2599716B2 (ja) * | 1987-05-14 | 1997-04-16 | 株式会社クラレ | 高重合度ポリビニルエステル系重合体の製造方法及び高重合度ポリビニルアルコール系重合体の製造方法 |
JP2001342202A (ja) * | 2000-06-01 | 2001-12-11 | Kuraray Co Ltd | ビニルアルコール系重合体の製造方法 |
WO2003033548A1 (en) * | 2001-10-16 | 2003-04-24 | Sekisui Chemical Co., Ltd. | Process for producing modified polymer, apparatus for producing modified polymer, and modified polymer |
JP2011207762A (ja) * | 2009-12-25 | 2011-10-20 | Sekisui Chem Co Ltd | 合わせガラス用中間膜、合わせガラス用多層中間膜及び合わせガラス |
JP2013177570A (ja) * | 2012-01-31 | 2013-09-09 | Daikin Industries Ltd | 含フッ素重合体及びその製造方法 |
JP2019066533A (ja) * | 2017-09-28 | 2019-04-25 | 株式会社クラレ | 光学フィルム製造用原反フィルム及びそれを用いた光学フィルムの製造方法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59145255A (ja) | 1983-02-07 | 1984-08-20 | Nippon Kayaku Co Ltd | 水溶性ジスアゾ化合物 |
JP2622748B2 (ja) | 1989-06-12 | 1997-06-18 | 日本化薬株式会社 | 水溶性アゾ染料及びこれを含有する偏光膜 |
-
2022
- 2022-06-20 WO PCT/JP2022/024444 patent/WO2022270446A1/ja active Application Filing
- 2022-06-20 DE DE112022003265.0T patent/DE112022003265T5/de active Pending
- 2022-06-20 CN CN202280038616.0A patent/CN117412995A/zh active Pending
- 2022-06-20 JP JP2022541966A patent/JPWO2022270446A1/ja active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2599716B2 (ja) * | 1987-05-14 | 1997-04-16 | 株式会社クラレ | 高重合度ポリビニルエステル系重合体の製造方法及び高重合度ポリビニルアルコール系重合体の製造方法 |
JP2534294B2 (ja) * | 1988-01-29 | 1996-09-11 | 株式会社クラレ | 高重合度ポリビニルエステル系重合体の製法及び高重合度ポリビニルアルコ―ル系重合体の製法 |
JPH08188620A (ja) * | 1995-01-09 | 1996-07-23 | Kuraray Co Ltd | ポリビニルアルコール系重合体微粒子の製造方法 |
JP2001342202A (ja) * | 2000-06-01 | 2001-12-11 | Kuraray Co Ltd | ビニルアルコール系重合体の製造方法 |
WO2003033548A1 (en) * | 2001-10-16 | 2003-04-24 | Sekisui Chemical Co., Ltd. | Process for producing modified polymer, apparatus for producing modified polymer, and modified polymer |
JP2011207762A (ja) * | 2009-12-25 | 2011-10-20 | Sekisui Chem Co Ltd | 合わせガラス用中間膜、合わせガラス用多層中間膜及び合わせガラス |
JP2013177570A (ja) * | 2012-01-31 | 2013-09-09 | Daikin Industries Ltd | 含フッ素重合体及びその製造方法 |
JP2019066533A (ja) * | 2017-09-28 | 2019-04-25 | 株式会社クラレ | 光学フィルム製造用原反フィルム及びそれを用いた光学フィルムの製造方法 |
Also Published As
Publication number | Publication date |
---|---|
DE112022003265T5 (de) | 2024-04-04 |
CN117412995A (zh) | 2024-01-16 |
JPWO2022270446A1 (ja) | 2022-12-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR102070011B1 (ko) | 폴리비닐아세탈계 수지 조성물 | |
TWI639618B (zh) | 乙烯醇系聚合物薄膜及使用其之光學薄膜之製造方法 | |
KR101902025B1 (ko) | 변성 폴리비닐알코올, 변성 폴리비닐아세탈 및 세라믹 슬러리 조성물 | |
US20060205871A1 (en) | Crosslinked polyvinyl acetals | |
EP0389833A1 (en) | Vinyl alcohol polymers and a process for their production | |
TW201241077A (en) | Polyoxyalkylene modified vinyl acetal polymer and composition comprising the same | |
TWI825084B (zh) | 聚乙烯醇膜、及偏光膜之製造方法 | |
WO2022270446A1 (ja) | ポリビニルアルコール樹脂、ポリビニルアセタール樹脂、ポリビニルアルコール樹脂の製造方法及びポリビニルアセタール樹脂の製造方法 | |
JP2013242341A (ja) | ポリビニルアルコール樹脂フィルム材料、偏光フィルム及び偏光フィルムの製造方法 | |
JP6629496B1 (ja) | ポリビニルアルコールフィルム、延伸フィルム、及びポリビニルアルコールフィルムの製造方法 | |
KR20150109479A (ko) | 수용성 고 교대 배열 폴리비닐 알코올 | |
TW202006055A (zh) | 聚乙烯醇薄膜、延伸薄膜、偏光薄膜、及聚乙烯醇薄膜之製造方法 | |
TW201434615A (zh) | 光學薄膜 | |
JP7496355B2 (ja) | ポリビニルアルコールフィルム、延伸フィルム、偏光フィルム、及びポリビニルアルコールフィルムの製造方法 | |
JP5667533B2 (ja) | アクリル系熱可塑性樹脂組成物 | |
WO2017195735A1 (ja) | ビニルアルコール-酢酸ビニル共重合体 | |
TWI636086B (zh) | Ethylene acetal polymer | |
JP2019066533A (ja) | 光学フィルム製造用原反フィルム及びそれを用いた光学フィルムの製造方法 | |
JPH08188624A (ja) | ポリビニルアルコールフィルム | |
TWI842798B (zh) | 組成物、皮膜、薄膜及基材 | |
WO2023127874A1 (ja) | ポリビニルアルコールフィルム、及びポリビニルアルコールフィルムの製造方法 | |
JPH04296302A (ja) | 乳化重合用安定剤 | |
KR20180059643A (ko) | 폴리아세트산비닐/폴리메틸메타크릴레이트 블렌드 필름의 불균일계 비누화에 의해 제조된 폴리비닐알코올/폴리메틸메타크릴레이트 블렌드 필름 및 그의 제조방법 | |
JP2022152832A (ja) | 樹脂組成物及び成形物 | |
TW202340279A (zh) | 乙烯醇共聚物、以及包含其之樹脂組成物、及樹脂成形體 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2022541966 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22828363 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 202280038616.0 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 18569739 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 112022003265 Country of ref document: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 22828363 Country of ref document: EP Kind code of ref document: A1 |