JP5501345B2 - Water-based adhesive - Google Patents
Water-based adhesive Download PDFInfo
- Publication number
- JP5501345B2 JP5501345B2 JP2011507055A JP2011507055A JP5501345B2 JP 5501345 B2 JP5501345 B2 JP 5501345B2 JP 2011507055 A JP2011507055 A JP 2011507055A JP 2011507055 A JP2011507055 A JP 2011507055A JP 5501345 B2 JP5501345 B2 JP 5501345B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- hydrogen atom
- poa
- polyoxyalkylene
- adhesive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000853 adhesive Substances 0.000 title claims description 89
- 230000001070 adhesive effect Effects 0.000 title claims description 89
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title description 32
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 67
- 238000006116 polymerization reaction Methods 0.000 claims description 45
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 32
- 239000000178 monomer Substances 0.000 claims description 31
- 239000000839 emulsion Substances 0.000 claims description 30
- 238000007127 saponification reaction Methods 0.000 claims description 22
- 229920001567 vinyl ester resin Polymers 0.000 claims description 20
- 229920001577 copolymer Polymers 0.000 claims description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 230000004048 modification Effects 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 9
- 239000008346 aqueous phase Substances 0.000 claims description 8
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 8
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Polymers OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 6
- 239000011256 inorganic filler Substances 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 239000012766 organic filler Substances 0.000 claims description 4
- 150000001993 dienes Chemical class 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Chemical group 0.000 claims 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
- 125000000914 phenoxymethylpenicillanyl group Chemical group CC1(S[C@H]2N([C@H]1C(=O)*)C([C@H]2NC(COC2=CC=CC=C2)=O)=O)C 0.000 description 87
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 63
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 59
- 239000004372 Polyvinyl alcohol Substances 0.000 description 58
- -1 polyoxyethylene groups Polymers 0.000 description 46
- 238000000034 method Methods 0.000 description 35
- 239000007787 solid Substances 0.000 description 32
- 229920002689 polyvinyl acetate Polymers 0.000 description 29
- 239000011118 polyvinyl acetate Substances 0.000 description 29
- 238000003860 storage Methods 0.000 description 28
- 238000004519 manufacturing process Methods 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000004927 clay Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 20
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 19
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 17
- 239000000123 paper Substances 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 238000004062 sedimentation Methods 0.000 description 11
- 238000007334 copolymerization reaction Methods 0.000 description 9
- 239000003999 initiator Substances 0.000 description 9
- 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 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000002023 wood Substances 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
- 229910052622 kaolinite Inorganic materials 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- 239000011975 tartaric acid Substances 0.000 description 4
- 235000002906 tartaric acid Nutrition 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000011111 cardboard Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 235000013808 oxidized starch Nutrition 0.000 description 3
- 239000001254 oxidized starch Substances 0.000 description 3
- 239000012966 redox initiator Substances 0.000 description 3
- 235000010413 sodium alginate Nutrition 0.000 description 3
- 239000000661 sodium alginate Substances 0.000 description 3
- 229940005550 sodium alginate Drugs 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 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
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical group 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 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
- 238000005406 washing Methods 0.000 description 2
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- LAYAKLSFVAPMEL-UHFFFAOYSA-N 1-ethenoxydodecane Chemical compound CCCCCCCCCCCCOC=C LAYAKLSFVAPMEL-UHFFFAOYSA-N 0.000 description 1
- QJJDJWUCRAPCOL-UHFFFAOYSA-N 1-ethenoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOC=C QJJDJWUCRAPCOL-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- DRYJUBPIARAFOC-UHFFFAOYSA-N 2,5-dimethyl-4-oxohexa-2,5-dienoic acid Chemical compound CC(=C)C(=O)C=C(C)C(O)=O DRYJUBPIARAFOC-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- PGYJSURPYAAOMM-UHFFFAOYSA-N 2-ethenoxy-2-methylpropane Chemical compound CC(C)(C)OC=C PGYJSURPYAAOMM-UHFFFAOYSA-N 0.000 description 1
- UPZFLZYXYGBAPL-UHFFFAOYSA-N 2-ethyl-2-methyl-1,3-dioxolane Chemical compound CCC1(C)OCCO1 UPZFLZYXYGBAPL-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- LVCMKNCJDCTPIB-UHFFFAOYSA-N 2-methyl-1-pyrrolidin-1-ylprop-2-en-1-one Chemical compound CC(=C)C(=O)N1CCCC1 LVCMKNCJDCTPIB-UHFFFAOYSA-N 0.000 description 1
- FVSAFCHCUDOKSI-UHFFFAOYSA-N 2-methylprop-2-enamide;propane-1-sulfonic acid Chemical compound CC(=C)C(N)=O.CCCS(O)(=O)=O FVSAFCHCUDOKSI-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- NXVGUNGPINUNQN-UHFFFAOYSA-N 2-phenylpropan-2-yl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C1=CC=CC=C1 NXVGUNGPINUNQN-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
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- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- PWBBJVOEXJCLDB-UHFFFAOYSA-N C(C(=C)C)(=O)N(CO)C(=O)C(=C)C Chemical class C(C(=C)C)(=O)N(CO)C(=O)C(=C)C PWBBJVOEXJCLDB-UHFFFAOYSA-N 0.000 description 1
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
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- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
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- 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 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- HETCEOQFVDFGSY-UHFFFAOYSA-N Isopropenyl acetate Chemical compound CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-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
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 229940064004 antiseptic throat preparations Drugs 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- DBUPOCYLUHVFHU-UHFFFAOYSA-N carboxyoxy 2,2-diethoxyethyl carbonate Chemical compound CCOC(OCC)COC(=O)OOC(O)=O DBUPOCYLUHVFHU-UHFFFAOYSA-N 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- BSVQJWUUZCXSOL-UHFFFAOYSA-N cyclohexylsulfonyl ethaneperoxoate Chemical compound CC(=O)OOS(=O)(=O)C1CCCCC1 BSVQJWUUZCXSOL-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical group C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 description 1
- LPUZTLKYAOOFDX-QXMHVHEDSA-N ethenyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC=C LPUZTLKYAOOFDX-QXMHVHEDSA-N 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
- WNMORWGTPVWAIB-UHFFFAOYSA-N ethenyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC=C WNMORWGTPVWAIB-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- UJRIYYLGNDXVTA-UHFFFAOYSA-N ethenyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OC=C UJRIYYLGNDXVTA-UHFFFAOYSA-N 0.000 description 1
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- QBDADGJLZNIRFQ-UHFFFAOYSA-N ethenyl octanoate Chemical compound CCCCCCCC(=O)OC=C QBDADGJLZNIRFQ-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
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229940005740 hexametaphosphate Drugs 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 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
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 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
- 239000011259 mixed solution Substances 0.000 description 1
- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- YMDZGJOTVBKZQK-UHFFFAOYSA-N n,n-dimethylpropan-1-amine;2-methylprop-2-enamide Chemical compound CCCN(C)C.CC(=C)C(N)=O YMDZGJOTVBKZQK-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- NYUSKIVSFXNJTN-UHFFFAOYSA-N n-(hydroxymethyl)prop-2-enamide;prop-2-enamide Chemical class NC(=O)C=C.OCNC(=O)C=C NYUSKIVSFXNJTN-UHFFFAOYSA-N 0.000 description 1
- ADTJPOBHAXXXFS-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]prop-2-enamide Chemical compound CN(C)CCCNC(=O)C=C ADTJPOBHAXXXFS-UHFFFAOYSA-N 0.000 description 1
- ZIWDVJPPVMGJGR-UHFFFAOYSA-N n-ethyl-2-methylprop-2-enamide Chemical compound CCNC(=O)C(C)=C ZIWDVJPPVMGJGR-UHFFFAOYSA-N 0.000 description 1
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001290 polyvinyl ester Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- AAYRWMCIKCRHIN-UHFFFAOYSA-N propane-1-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CCCS(O)(=O)=O AAYRWMCIKCRHIN-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000019830 sodium polyphosphate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- WKEWCYHGACEYTR-UHFFFAOYSA-N tert-butyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(C)(C)C WKEWCYHGACEYTR-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
- C09J129/02—Homopolymers or copolymers of unsaturated alcohols
- C09J129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、特定の官能基を有するビニルアルコール系重合体を水相に含有する水性接着剤に関する。 The present invention relates to an aqueous adhesive containing a vinyl alcohol polymer having a specific functional group in an aqueous phase.
従来、水性接着剤は澱粉、カゼイン、ゼラチン、グアーガム、アラビアガム、アルギン酸ソーダ類などの天然糊剤；ＣＭＣ、酸化澱粉、メチルセルロースなどの加工天然糊剤；アクリルエマルジョン、ポリ酢酸ビニルエマルジョン、エチレン−酢酸ビニル共重合体エマルジョンなどの合成樹脂系エマルジョン；ＳＢＲラテックスなどのゴムラテックス；ビニルアルコール系重合体（以下「ＰＶＡ」と略記することがある）を主成分としたものが単独またはこれらを組み合わせて広く用いられている。 Conventionally, water-based adhesives are natural pastes such as starch, casein, gelatin, guar gum, gum arabic and sodium alginate; processed natural pastes such as CMC, oxidized starch and methylcellulose; acrylic emulsion, polyvinyl acetate emulsion, ethylene-acetic acid Synthetic resin emulsions such as vinyl copolymer emulsions; rubber latexes such as SBR latex; vinyl alcohol polymers (hereinafter sometimes abbreviated as “PVA”) as main components are widely used alone or in combination. It is used.
しかし、天然糊剤やその加工糊剤には接着力不足や接着剤溶液の粘度安定性に欠けることや腐敗するなどの問題があるうえに、品質の一定したものを長期間継続的に得ることが難しいなどの欠点がある。一方、エマルジョンやラテックスは接着力には優れているものの、機械安定性に欠ける、表面の皮張りが激しいなどの問題点を抱えているものが多い。 However, natural glues and processed pastes have problems such as insufficient adhesive strength, lack of viscosity stability of the adhesive solution, and spoilage, as well as obtaining products with consistent quality over a long period of time. There are disadvantages such as difficult. On the other hand, emulsions and latexes are excellent in adhesive strength but often have problems such as lack of mechanical stability and severe surface skinning.
一方、ＰＶＡ系の水性接着剤はコスト的に安価で優れた接着性を有しており、板紙の接着、段ボールの接着、紙管の接着、襖や壁紙の接着に使用されたり、各種エマルジョンと混合したものは木工用、繊維加工用、紙用の接着などに使用されている。このようにＰＶＡ系の水性接着剤は広く使用されており、バランスの取れた接着剤として賞用されてきた。しかしながらＰＶＡ系の水性接着剤においても、近年は特にコストダウンや生産性の向上を目指した水性接着剤の高速塗工化が進み、また、ハンドリング性（塗布量の安定化、粘度安定性、沈降安定性など）の向上による作業効率の改善を目指した水性接着剤の要求も増えているのが現状である。 On the other hand, PVA-based water-based adhesives are inexpensive and have excellent adhesion, and are used for bonding paperboard, corrugated cardboard, paper tube, paper and wallpaper, and various emulsions. The mixture is used for woodworking, textile processing, paper bonding, and the like. Thus, PVA-based water-based adhesives are widely used and have been awarded as balanced adhesives. However, PVA-based water-based adhesives have recently been rapidly applied to water-based adhesives with the aim of reducing costs and improving productivity, and handling properties (coating stability, viscosity stability, sedimentation) At present, there is an increasing demand for water-based adhesives aimed at improving work efficiency by improving stability and the like.
これらの要求に対する改善策として、例えば特開昭６２−１９５０７０号（特許文献１）で提案されているＰＶＡ、クレーおよび水溶性ホウ素化合物を主成分とする接着剤がある。この種の接着剤は、高速接着性、初期接着性が改善でき、これまで段ボールの製造などで工業的に広く使用されてきた。しかし、環境への影響が懸念されるホウ酸の使用は近年制限される流れにあり、その代替品が強く求められている。また、同様に、ＰＶＡの架橋剤となるような化合物（例えば、尿素−ホルマリン系樹脂等）を使用し、初期接着性を改善する試みが多数なされているが、実質的に架橋剤として使用する化合物の安全性に問題があるケースが多く、また、組成物の粘度安定性にも問題がある場合が多かったのが現状である。 As an improvement measure for these requirements, for example, there is an adhesive mainly composed of PVA, clay and water-soluble boron compound proposed in JP-A-62-195070 (Patent Document 1). This type of adhesive can improve high-speed adhesion and initial adhesion and has been widely used industrially in the production of corrugated cardboard. However, the use of boric acid, whose environmental impact is a concern, has been restricted in recent years, and there is a strong demand for alternatives. Similarly, many attempts have been made to improve the initial adhesion by using a compound (for example, urea-formalin resin, etc.) that can be used as a cross-linking agent for PVA, but it is substantially used as a cross-linking agent. There are many cases where there is a problem with the safety of the compound, and there are many cases where there is also a problem with the viscosity stability of the composition.
特開平０４−２３９０８５号（特許文献２）では、特定の金属塩を含有する接着剤が提案されているが、高速塗工性や初期接着力は改善されるものの、溶液の安定性に問題があり、工業的に十分満足するものではなかった。さらに、特開平１１−０２１５３０号（特許文献３）には、エチレン単位を１〜２０モル％含有する変性ポリビニルアルコール（Ａ）、澱粉（Ｂ）および糖類（Ｃ）からなる接着剤が提案されており、接着力、耐水接着力および保存安定性が改良されているが、高速塗工性や耐熱性、耐クリープ性という観点で不十分な場合があった。また、特開２００１−１６４２１９号（特許文献４）には、分子中に１，２−グリコール結合を１．８〜３．５モル％含有し、かつけん化度が９０モル％以上のビニルアルコール系重合体（ａ）および無機充填剤（ｂ）を必須成分とする接着剤が提案されており、粘度安定性、高速塗工性および初期接着力は改良されてはいるものの、無機充填剤の長期保存における沈降などの問題があった。 In Japanese Patent Laid-Open No. 04-239085 (Patent Document 2), an adhesive containing a specific metal salt is proposed. However, although the high-speed coating property and the initial adhesive force are improved, there is a problem in the stability of the solution. Yes, it was not industrially satisfactory. Further, JP-A-11-021530 (Patent Document 3) proposes an adhesive comprising modified polyvinyl alcohol (A), starch (B) and saccharide (C) containing 1 to 20 mol% of ethylene units. However, although the adhesive strength, water-resistant adhesive strength, and storage stability have been improved, there are cases where it is insufficient in terms of high-speed coating property, heat resistance, and creep resistance. Japanese Patent Application Laid-Open No. 2001-164219 (Patent Document 4) contains 1.8 to 3.5 mol% of 1,2-glycol bond in the molecule and has a caking degree of 90 mol% or more. An adhesive comprising a polymer (a) and an inorganic filler (b) as essential components has been proposed, and although the viscosity stability, high-speed coating property and initial adhesive force have been improved, the long-term use of the inorganic filler has been improved. There were problems such as sedimentation during storage.
特開昭５９−１５５４０８号（特許文献５）には、オキシアルキレン基を含有する不飽和単量体と酢酸ビニルとの共重合体をケン化することを特徴とする変性ＰＶＡの製造方法が開示されている。該変性ＰＶＡの製造に用いる不飽和単量体中のオキシアルキレン基としては、、繰り返し単位数が１〜５０程度のポリオキシエチレン基、ポリオキシプロピレン基、ポリオキシブチレン基等が例示されている。また、該変性ＰＶＡの用途として多数例示されているものなかに、接着剤が記載されている。 JP 59-155408 (Patent Document 5) discloses a process for producing a modified PVA characterized by saponifying a copolymer of an unsaturated monomer containing an oxyalkylene group and vinyl acetate. Has been. Examples of the oxyalkylene group in the unsaturated monomer used for the production of the modified PVA include polyoxyethylene groups, polyoxypropylene groups, polyoxybutylene groups having about 1 to 50 repeating units. . In addition, adhesives are described in many examples of uses of the modified PVA.
また、上記の水性接着剤は、各種の被着体に対する接着性改善や固形分濃度増加よる初期接着性向上の目的で各種の水性エマルジョンと混合使用されるケースがあるが、その場合でも上記の問題点は十分に解決されるものではなかった。 In addition, the above-mentioned aqueous adhesive may be used in combination with various aqueous emulsions for the purpose of improving adhesion to various adherends and improving initial adhesiveness by increasing the solid content concentration. The problem was not fully resolved.
本発明は、上記従来の技術における問題点を解消し、水性接着剤として使用する場合に重要な性能の一つである初期接着性が高く、高速生産が可能で、しかも保存安定性（粘度安定性、沈降安定性）に優れる水性接着剤を提供するものである。 The present invention solves the above-mentioned problems in the prior art, has high initial adhesiveness, which is one of the important performances when used as a water-based adhesive, enables high-speed production, and has storage stability (viscosity stability). It is intended to provide an aqueous adhesive having excellent properties and sedimentation stability.
本発明者らは、“高い安全性”と“環境にやさしい”という水性接着剤の特徴を損なうことなく、初期接着性が高く高速生産が可能であり、しかも保存安定性（粘度安定性、沈降安定性）に優れた水性接着剤を工業的な規模で得ることについて鋭意検討した結果、下記一般式（Ｉ）で示されるポリオキシアルキレン（以下、ＰＯＡと略すことがある）基を側鎖に含有するビニルアルコール系重合体であり、ビニルアルコール系重合体の粘度平均重合度が２００〜３０００であり、けん化度が８０〜９９．９９モル％であり、ＰＯＡ基変性量が０．１〜１０モル％であるポリオキシアルキレン変性ビニルアルコール系重合体（以下、ＰＯＡ変性ＰＶＡと略すことがある）を水相に含有する水性接着剤が、目的の水性接着剤として適していることを見出し、本発明を完成するに至った。 The inventors of the present invention have high initial adhesiveness and high-speed production without impairing the characteristics of water-based adhesives such as “high safety” and “environmentally friendly”, and storage stability (viscosity stability, sedimentation). As a result of intensive studies on obtaining an aqueous adhesive having excellent stability on an industrial scale, a polyoxyalkylene (hereinafter sometimes abbreviated as POA) group represented by the following general formula (I) is used as a side chain. It is a vinyl alcohol polymer to be contained, the viscosity average polymerization degree of the vinyl alcohol polymer is 200 to 3000, the saponification degree is 80 to 99.99 mol%, and the POA group modification amount is 0.1 to 10 A water-based adhesive containing a mol% polyoxyalkylene-modified vinyl alcohol polymer (hereinafter sometimes abbreviated as POA-modified PVA) in the aqueous phase is suitable as the target water-based adhesive. Heading, which resulted in the completion of the present invention.
式中、Ｒ１は水素原子またはメチル基、Ｒ２は水素原子または炭素数１〜８のアルキル基を表す。ｍとｎはそれぞれのオキシアルキレンユニットの繰り返し単位数を表し、１≦ｍ≦１０、３≦ｎ≦２０である。ここで、繰り返し単位数ｍで表されるユニットをユニット１と呼び、繰り返し単位数ｎで表されるユニットをユニット２と呼ぶことにする。ユニット１とユニット２の配置は、ランダム状、ブロック状のどちらの形態になっても良い。 In the formula, R1 represents a hydrogen atom or a methyl group, and R2 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. m and n represent the number of repeating units of each oxyalkylene unit, and 1 ≦ m ≦ 10 and 3 ≦ n ≦ 20. Here, a unit represented by the number m of repeating units is referred to as unit 1, and a unit represented by the number of repeating units n is referred to as unit 2. The arrangement of the unit 1 and the unit 2 may be random or block.
前記ポリオキシアルキレン変性ビニルアルコール系重合体が、下記一般式（II）で示されるポリオキシアルキレン基を有するマクロモノマーとビニルエステルとを共重合した後、けん化することによって得られたものであることが好ましい。 The polyoxyalkylene-modified vinyl alcohol polymer is obtained by copolymerizing a macromonomer having a polyoxyalkylene group represented by the following general formula (II) and a vinyl ester and then saponifying the copolymer. Is preferred.
式中、Ｒ１は水素原子またはメチル基、Ｒ２は水素原子または炭素数１〜８のアルキル基を表す。ｍとｎはそれぞれのオキシアルキレンユニットの繰り返し単位数を表し、１≦ｍ≦１０、３≦ｎ≦２０である。Ｒ３は水素原子または−ＣＯＯＭ基を表し、ここでＭは水素原子、アルカリ金属またはアンモニウム基を表す。Ｒ４は水素原子、メチル基または−ＣＨ２−ＣＯＯＭ基を示し、ここでＭは前記定義どおりである。Ｘは−Ｏ−、−ＣＨ２−Ｏ−、−（ＣＨ２）ｋ−、−ＣＯ−、−ＣＯ−Ｏ−または−ＣＯ−ＮＲ５−を表す。ここでＲ５は水素原子または炭素数１〜４の飽和アルキル基を表す。ｋはメチレンユニットの繰り返し単位数を表し、１≦ｋ≦１５である。In the formula, R1 represents a hydrogen atom or a methyl group, and R2 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. m and n represent the number of repeating units of each oxyalkylene unit, and 1 ≦ m ≦ 10 and 3 ≦ n ≦ 20. R3 represents a hydrogen atom or a -COOM group, where M represents a hydrogen atom, an alkali metal or an ammonium group. R4 represents a hydrogen atom, a methyl group or a —CH 2 —COOM group, where M is as defined above. X is -O -, - CH 2 -O - , - (CH 2) k -, - CO -, - represents a CO-O- or -CO-NR5-. Here, R5 represents a hydrogen atom or a saturated alkyl group having 1 to 4 carbon atoms. k represents the number of repeating units of methylene units, and 1 ≦ k ≦ 15.
前記ポリオキシアルキレン変性ビニルアルコール系重合体が、下記一般式（III）で示されるポリオキシアルキレン基を有するマクロモノマーとビニルエステルとを共重合した後、けん化することによって得られたものであることがより好ましい。 The polyoxyalkylene-modified vinyl alcohol polymer is obtained by copolymerization of a macromonomer having a polyoxyalkylene group represented by the following general formula (III) and a vinyl ester and then saponifying. Is more preferable.
式中、Ｒ１は水素原子またはメチル基、Ｒ２は水素原子または炭素数１〜８のアルキル基を表す。ｍとｎはそれぞれのオキシアルキレンユニットの繰り返し単位数を表し、１≦ｍ≦１０、３≦ｎ≦２０である。Ｒ４は水素原子、メチル基または−ＣＨ２−ＣＯＯＭ基を示し、ここでＭは水素原子、アルカリ金属またはアンモニウム基を表す。Ｒ５は水素原子または炭素数１〜４の飽和アルキル基を表す。In the formula, R1 represents a hydrogen atom or a methyl group, and R2 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. m and n represent the number of repeating units of each oxyalkylene unit, and 1 ≦ m ≦ 10 and 3 ≦ n ≦ 20. R4 represents a hydrogen atom, a methyl group or a —CH 2 —COOM group, where M represents a hydrogen atom, an alkali metal or an ammonium group. R5 represents a hydrogen atom or a saturated alkyl group having 1 to 4 carbon atoms.
本発明の水性接着剤は、さらにエチレン系不飽和単量体およびジエン系単量体から選ばれる一種以上の単量体からなる（共）重合体エマルジョンを含有することが好ましく、さらに無機系あるいは有機系のフィラーを含有することも好ましい。 The aqueous adhesive of the present invention preferably further contains a (co) polymer emulsion composed of one or more monomers selected from ethylenically unsaturated monomers and diene monomers, and is further inorganic or It is also preferable to contain an organic filler.
また、紙用又は木工用接着剤が本発明の水性接着剤の好適な実施態様である。 Also, a paper or woodworking adhesive is a preferred embodiment of the aqueous adhesive of the present invention.
本発明の水性接着剤は、従来の水性接着剤に比べて、初期接着性が高いため、高速生産が可能である。さらに、本発明の水性接着剤は、従来の水性接着剤に比べて、保存安定性にも優れる。 Since the water-based adhesive of the present invention has high initial adhesiveness compared to conventional water-based adhesives, high-speed production is possible. Furthermore, the water-based adhesive of the present invention is excellent in storage stability as compared with conventional water-based adhesives.
以下、本発明について詳しく説明する。本発明は、上記の一般式（Ｉ）で示されるＰＯＡ基を側鎖に含有するＰＶＡであり、該ＰＶＡの粘度平均重合度が２００〜３０００であり、けん化度が８０〜９９．９９モル％であり、ＰＯＡ基変性量が０．１〜１０モル％であるＰＯＡ変性ＰＶＡを水相に含有する水性接着剤である。本発明において、水性接着剤の水相に含有されるＰＶＡの側鎖に存在するＰＯＡ基のユニット１の繰り返し単位数ｍは１≦ｍ≦１０であり、ユニット２の繰り返し単位数ｎは３≦ｎ≦２０である必要がある。ｍ及びｎがこのような範囲であることで水性接着剤の優れた接着力、特に初期接着力が発現する。ｍは２以上であることが好ましい。ｍは５以下であることが好ましく、３以下であることがより好ましい。ｎは５以上であることが好ましく、８以上であることがより好ましい。ｎは１８以下であることが好ましく、１５以下であることがより好ましい。 The present invention will be described in detail below. The present invention is a PVA containing a POA group represented by the above general formula (I) in the side chain, the PVA has a viscosity average polymerization degree of 200 to 3000, and a saponification degree of 80 to 99.99 mol%. And an aqueous adhesive containing POA-modified PVA having a POA group modification amount of 0.1 to 10 mol% in an aqueous phase. In the present invention, the repeating unit number m of the unit 1 of the POA group present in the side chain of the PVA contained in the aqueous phase of the aqueous adhesive is 1 ≦ m ≦ 10, and the repeating unit number n of the unit 2 is 3 ≦ It is necessary that n ≦ 20. When m and n are within such ranges, the excellent adhesive strength of the water-based adhesive, particularly the initial adhesive strength, is exhibited. m is preferably 2 or more. m is preferably 5 or less, and more preferably 3 or less. n is preferably 5 or more, and more preferably 8 or more. n is preferably 18 or less, and more preferably 15 or less.
上記の一般式（Ｉ）で示されるＰＯＡ基を側鎖に含有するＰＶＡにおいて、ＰＯＡ基変性量は０．１〜１０モル％であることが必要であり、好ましくは０．１５〜８モル％、より好ましくは０．２〜６モル％である。ＰＯＡ基の変性量が０．１モル％よりも小さい場合には、本発明の目的である該ＰＯＡ変性ＰＶＡを水相に含有する水性接着剤の初期接着性が発現しない。一方、１０モル％を超える場合には、該ＰＯＡ変性ＰＶＡの疎水性が増加し、保存安定性の低下や水溶性の低下が起こることがあるため不適である。 In the PVA containing the POA group represented by the general formula (I) in the side chain, the POA group modification amount needs to be 0.1 to 10 mol%, preferably 0.15 to 8 mol%. More preferably, it is 0.2-6 mol%. When the modification amount of the POA group is smaller than 0.1 mol%, the initial adhesiveness of the aqueous adhesive containing the POA-modified PVA, which is the object of the present invention, in the aqueous phase does not appear. On the other hand, if it exceeds 10 mol%, the hydrophobicity of the POA-modified PVA increases, which may be unsuitable because storage stability and water solubility may decrease.
ＰＯＡ基変性量とは、ＰＶＡの主鎖メチレン基に対するＰＯＡ基のモル分率で表される。ＰＯＡ変性ＰＶＡのＰＯＡ基変性量は、例えば、該ＰＶＡの前駆体であるＰＯＡ変性ポリビニルエステル、具体的な一例としては、ＰＯＡ変性ポリ酢酸ビニル（以下、ポリ酢酸ビニルをＰＶＡｃと略記することがある）のプロトンＮＭＲから求めることができる。具体的には、ｎ−ヘキサン／アセトンでＰＯＡ変性ＰＶＡｃの再沈精製を３回以上十分に行った後、５０℃の減圧下で乾燥を２日間行い、分析用のＰＯＡ変性ＰＶＡｃを作成する。該ＰＶＡｃをＣＤＣｌ３に溶解させ、５００ＭＨｚのプロトンＮＭＲ（ＪＥＯＬ ＧＸ−５００）を室温で測定する。ビニルエステルの主鎖メチンに由来するピークα（４．７〜５．２ｐｐｍ）とユニット２の末端メチル基に由来するピークβ（０．８〜１．０ｐｐｍ）から下記式を用いてＰＯＡ基変性量Ｓを算出する。
Ｓ（モル％）＝｛（βのプロトン数／３ｎ）／（αのプロトン数＋（βのプロトン数／３ｎ））｝×１００
ｎはユニット２の繰り返し単位数を表す。The POA group modification amount is represented by the mole fraction of the POA group with respect to the main chain methylene group of PVA. The POA group modification amount of the POA-modified PVA is, for example, a POA-modified polyvinyl ester that is a precursor of the PVA. As a specific example, POA-modified polyvinyl acetate (hereinafter, polyvinyl acetate may be abbreviated as PVAc). ) Proton proton NMR. Specifically, after re-precipitation purification of POA-modified PVAc with n-hexane / acetone three times or more sufficiently, drying is performed under reduced pressure at 50 ° C. for 2 days to prepare POA-modified PVAc for analysis. The PVAc is dissolved in CDCl 3 and 500 MHz proton NMR (JEOL GX-500) is measured at room temperature. POA group modification from the peak α derived from the main chain methine of vinyl ester (4.7 to 5.2 ppm) and the peak β derived from the terminal methyl group of unit 2 (0.8 to 1.0 ppm) using the following formula The quantity S is calculated.
S (mol%) = {(number of protons of β / 3n) / (number of protons of α + (number of protons of β / 3n))} × 100
n represents the number of repeating units of unit 2.
また、本発明において、ＰＯＡ変性ＰＶＡ中のＰＯＡ基の含有量は、２．０〜５０重量部であることが好ましく、この範囲内において、本発明の水性接着剤の初期接着性が特に良好となる。ここで、ＰＯＡ基の含有量とは、ＰＶＡの主鎖１００重量部に対するＰＯＡ基の重量部（重量分率）で表される。ＰＯＡ基の含有量はＰＯＡ基変性量Ｓ、ユニット１の繰り返し単位数ｍ、ユニット２の繰り返し単位数ｎ、ＰＯＡ変性ＰＶＡのけん化度を用いて計算される値である。前述のＰＯＡ基変性量Ｓが同等であっても、けん化度が高くなるにつれ、あるいはｍ又はｎが大きくなるにつれ、ＰＯＡ変性ＰＶＡ中のＰＯＡ基の含有量は大きくなる。 In the present invention, the POA group content in the POA-modified PVA is preferably 2.0 to 50 parts by weight. Within this range, the initial adhesiveness of the aqueous adhesive of the present invention is particularly good. Become. Here, the content of the POA group is represented by the weight part (weight fraction) of the POA group with respect to 100 parts by weight of the main chain of PVA. The content of the POA group is a value calculated using the POA group modification amount S, the number of repeating units m of unit 1, the number of repeating units n of unit 2, and the degree of saponification of POA modified PVA. Even if the above-mentioned POA group modification amount S is equivalent, the POA group content in the POA-modified PVA increases as the degree of saponification increases or as m or n increases.
上記の一般式（Ｉ）で示されるＰＯＡ基を側鎖に含有するＰＶＡの粘度平均重合度は、２００〜３０００であることが必要であり、２５０〜２８００が好ましく、３００〜２６００がより好ましい。ここで、粘度平均重合度Ｐは、ＪＩＳ−Ｋ６７２６に準じて測定される。すなわち、該ＰＯＡ変性ＰＶＡを再けん化し、精製した後、３０℃の水中で測定した極限粘度[η]から次式により求められる。
Ｐ＝（[η]×１０３／８．２９）（１／０．６２）
なお、粘度平均重合度は、単に重合度と呼ぶことがある。The viscosity average degree of polymerization of the PVA containing the POA group represented by the general formula (I) in the side chain needs to be 200 to 3000, preferably 250 to 2800, and more preferably 300 to 2600. Here, the viscosity average polymerization degree P is measured according to JIS-K6726. That is, after the POA-modified PVA is re-saponified and purified, the intrinsic viscosity [η] measured in water at 30 ° C. is obtained by the following formula.
P = ([η] × 10 3 /8.29) (1 / 0.62)
The viscosity average degree of polymerization may be simply referred to as the degree of polymerization.
重合度が２００より小さい場合には、該ＰＶＡを含有する水性接着剤が十分な初期接着力を発現しない。また、重合度が３０００よりも大きい場合には、水性接着剤の保存安定性が悪化することがあるので不適である。 When the degree of polymerization is less than 200, the aqueous adhesive containing the PVA does not exhibit sufficient initial adhesive force. On the other hand, when the degree of polymerization is larger than 3000, the storage stability of the aqueous adhesive may be deteriorated, which is not suitable.
上記の一般式（Ｉ）で示されるＰＯＡ基を側鎖に含有するＰＶＡのけん化度は８０〜９９．９９モル％であることが必要であり、８３〜９９．５モル％が好ましく、８５〜９９モル％がより好ましい。けん化度が８０よりも小さい場合には該ＰＶＡの水溶性が失われるため保存安定性に問題が生じる場合がある上、初期接着力が低下する問題がある。一方、けん化度が９９．９９モル％を超える場合には、保存安定性が悪化することがある。 The saponification degree of the PVA containing the POA group represented by the general formula (I) in the side chain needs to be 80 to 99.99 mol%, preferably 83 to 99.5 mol%, 99 mol% is more preferable. When the degree of saponification is less than 80, the water solubility of the PVA is lost, so that there may be a problem in storage stability and there is a problem that initial adhesive strength is lowered. On the other hand, when the degree of saponification exceeds 99.99 mol%, the storage stability may deteriorate.
上記一般式（Ｉ）で示されるＰＯＡ基を側鎖に含有するＰＶＡは、各種の方法により製造される。一般式（Ｉ）で表されるＰＯＡ基とＰＶＡの水酸基などと反応しうる官能基（カルボキシル基、イソシアネート基など）とを有する化合物とＰＶＡとを反応させることにより得ることも可能であるが、一般的および工業的には、一般式（Ｉ）で示されるＰＯＡ基を含有する不飽和単量体（マクロモノマー）とビニルエステルとを共重合した後、けん化することにより得られる。ここで、ＰＯＡ基を有するマクロモノマーとしては、上記の一般式（II）で示されるものが好ましい。 PVA containing the POA group represented by the general formula (I) in the side chain is produced by various methods. Although it is also possible to obtain by reacting a compound having a functional group (carboxyl group, isocyanate group, etc.) capable of reacting with the POA group represented by the general formula (I) and the hydroxyl group of PVA with PVA, In general and industrially, it is obtained by copolymerizing an unsaturated monomer (macromonomer) containing a POA group represented by the general formula (I) with a vinyl ester and then saponifying it. Here, as a macromonomer which has POA group, what is shown by said general formula (II) is preferable.
例えば、一般式（II）のＲ１が水素原子、Ｒ２が水素原子、Ｒ３が水素原子の場合、一般式（II）で示されるマクロモノマーとして具体的には、ポリオキシエチレンポリオキシブチレンモノアクリレート、ポリオキシエチレンポリオキシブチレンモノメタクリレート、ポリオキシエチレンポリオキシブチレンモノアクリル酸アミド、ポリオキシエチレンポリオキシブチレンモノメタクリル酸アミド、ポリオキシエチレンポリオキシブチレンモノアリルエーテル、ポリオキシエチレンポリオキシブチレンモノメタアリルエーテル、ポリオキシエチレンポリオキシブチレンモノビニルエーテルなどが挙げられる。なかでも、ポリオキシエチレンポリオキシブチレンモノアクリル酸アミド、ポリオキシエチレンポリオキシブチレンモノメタクリル酸アミド、ポリオキシエチレンポリオキシブチレンモノビニルエーテルが好適に用いられ、ポリオキシエチレンポリオキシブチレンモノメタクリル酸アミド、ポリオキシエチレンポリオキシブチレンモノビニルエーテルが特に好適に用いられる。 For example, when R1 in the general formula (II) is a hydrogen atom, R2 is a hydrogen atom, and R3 is a hydrogen atom, specifically, as a macromonomer represented by the general formula (II), polyoxyethylene polyoxybutylene monoacrylate, Polyoxyethylene polyoxybutylene monomethacrylate, polyoxyethylene polyoxybutylene monoacrylic amide, polyoxyethylene polyoxybutylene monomethacrylamide, polyoxyethylene polyoxybutylene monoallyl ether, polyoxyethylene polyoxybutylene monomethallyl Examples include ether and polyoxyethylene polyoxybutylene monovinyl ether. Among them, polyoxyethylene polyoxybutylene monoacrylic acid amide, polyoxyethylene polyoxybutylene monomethacrylic acid amide, polyoxyethylene polyoxybutylene monovinyl ether are preferably used, polyoxyethylene polyoxybutylene monomethacrylic acid amide, Polyoxyethylene polyoxybutylene monovinyl ether is particularly preferably used.
一般式（II）のＲ２が炭素数１〜８のアルキル基の場合、具体的には、一般式（II）のＲ１が水素原子、Ｒ２が水素原子、Ｒ３が水素原子の場合の例として上記に例示したマクロモノマーの末端のＯＨ基が炭素数１〜８のアルコキシ基に置換されたものが挙げられる。なかでも、ポリオキシエチレンポリオキシブチレンモノメタクリル酸アミド、ポリオキシエチレンポリオキシブチレンモノビニルエーテルの末端のＯＨ基がメトキシ基に置換されたマクロモノマーが好適に用いられ、ポリオキシエチレンポリオキシブチレンモノメタクリル酸アミドの末端のＯＨ基がメトキシ基に置換されたマクロモノマーが特に好適に用いられる。 When R2 in the general formula (II) is an alkyl group having 1 to 8 carbon atoms, specifically, as an example in which R1 in the general formula (II) is a hydrogen atom, R2 is a hydrogen atom, and R3 is a hydrogen atom, In which the OH group at the end of the macromonomer exemplified in the above is substituted with an alkoxy group having 1 to 8 carbon atoms. Of these, a macromonomer in which the OH group at the terminal of polyoxyethylene polyoxybutylene monomethacrylamide or polyoxyethylene polyoxybutylene monovinyl ether is substituted with a methoxy group is preferably used. A macromonomer in which the OH group at the terminal of the acid amide is substituted with a methoxy group is particularly preferably used.
また、本発明の水性接着剤の水相に含有されるＰＯＡ変性ＰＶＡを、上記の一般式（II）で示されるマクロモノマーとビニルエステルとの共重合体をけん化して得る場合には、共重合性を考慮して、Ｘが−ＣＯ−ＮＲ５−である上記の一般式（III）で示されるマクロモノマーを用いることがさらに好適である。 When the POA-modified PVA contained in the aqueous phase of the aqueous adhesive of the present invention is obtained by saponifying the copolymer of the macromonomer represented by the general formula (II) and the vinyl ester, In consideration of polymerizability, it is more preferable to use a macromonomer represented by the above general formula (III) in which X is -CO-NR5-.
上記の一般式（III）で示されるマクロモノマーとしては、ポリオキシエチレンポリオキシブチレンモノアクリル酸アミド、およびその末端のＯＨ基がメトキシ基に置換された不飽和単量体、ポリオキシエチレンポリオキシブチレンモノメタクリル酸アミド、およびその末端のＯＨ基がメトキシ基に置換された不飽和単量体が代表的である。 Examples of the macromonomer represented by the general formula (III) include polyoxyethylene polyoxybutylene monoacrylic acid amide, an unsaturated monomer in which the terminal OH group is substituted with a methoxy group, polyoxyethylene polyoxy Typical are butylene monomethacrylamide and unsaturated monomers in which the terminal OH group is substituted with a methoxy group.
本発明で使用するＰＯＡ変性ＰＶＡを製造するには、ＰＯＡ基を有するマクロモノマーとビニルエステル系単量体との共重合をアルコール系溶媒中または無溶媒で行い、得られたＰＯＡ変性ビニルエステル系共重合体をけん化する方法が好ましい。ＰＯＡ基を有するマクロモノマーとビニルエステル系単量体との共重合を行う際に採用される温度は０〜２００℃が好ましく、３０〜１４０℃がより好ましい。共重合を行う温度が０℃より低い場合は、十分な重合速度が得られにくい。また、重合を行う温度が２００℃より高い場合、本発明で規定するＰＯＡ基変性量を有するＰＯＡ変性ＰＶＡを得られにくい。共重合を行う際に採用される温度を０〜２００℃に制御する方法としては、例えば、重合速度を制御することで、重合により生成する発熱と反応器の表面からの放熱とのバランスをとる方法や、適当な熱媒を用いた外部ジャケットにより制御する方法等があげられるが、安全性の面からは後者の方法が好ましい。 In order to produce the POA-modified PVA used in the present invention, copolymerization of a macromonomer having a POA group and a vinyl ester monomer is carried out in an alcohol solvent or without solvent, and the resulting POA modified vinyl ester system is obtained. A method of saponifying the copolymer is preferred. The temperature employed when copolymerizing the macromonomer having a POA group and the vinyl ester monomer is preferably 0 to 200 ° C, more preferably 30 to 140 ° C. When the copolymerization temperature is lower than 0 ° C., it is difficult to obtain a sufficient polymerization rate. Moreover, when the temperature which superposes | polymerizes is higher than 200 degreeC, it is difficult to obtain POA modified PVA which has the POA group modification amount prescribed | regulated by this invention. As a method for controlling the temperature employed in the copolymerization to 0 to 200 ° C., for example, by controlling the polymerization rate, the heat generated by the polymerization is balanced with the heat released from the surface of the reactor. Examples thereof include a method and a method of controlling by an external jacket using an appropriate heating medium, but the latter method is preferable from the viewpoint of safety.
ＰＯＡ基を有するマクロモノマーとビニルエステル系単量体との共重合を行うのに用いられる重合方式としては、回分重合、半回分重合、連続重合、半連続重合のいずれでもよい。重合方法としては、塊状重合法、溶液重合法、懸濁重合法、乳化重合法など公知の任意の方法を用いることができる。その中でも、無溶媒またはアルコール系溶媒中で重合を行う塊状重合法や溶液重合法が好適に採用され、高重合度の共重合体の製造を目的とする場合は乳化重合法が採用される。アルコール系溶媒としては、メチルアルコール、エチルアルコール、プロピルアルコールなどを用いることができるが、これらに限定されるものではない。またこれらの溶媒は２種類以上を混合して用いることができる。 As a polymerization method used for copolymerization of a macromonomer having a POA group and a vinyl ester monomer, any of batch polymerization, semi-batch polymerization, continuous polymerization, and semi-continuous polymerization may be used. As the polymerization method, any known method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, or an emulsion polymerization method can be used. Among them, a bulk polymerization method or a solution polymerization method in which polymerization is performed in the absence of a solvent or an alcohol solvent is preferably employed, and an emulsion polymerization method is employed for the purpose of producing a copolymer having a high degree of polymerization. As the alcohol solvent, methyl alcohol, ethyl alcohol, propyl alcohol, and the like can be used, but are not limited thereto. These solvents can be used as a mixture of two or more.
共重合に使用される開始剤としては、重合方法に応じて従来公知のアゾ系開始剤、過酸化物系開始剤、レドックス系開始剤などが適宜選ばれる。アゾ系開始剤としては、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（２，４−ジメチルバレロニトリル）、２，２’−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）などが挙げられ、過酸化物系開始剤としては、ジイソプロピルパーオキシジカーボネート、ジ−２−エチルヘキシルパーオキシジカーボネート、ジエトキシエチルパーオキシジカーボネートなどのパーカーボネート化合物；ｔ−ブチルパーオキシネオデカネート、α−クミルパーオキシネオデカネート、ｔ−ブチルパーオキシデカネートなどのパーエステル化合物；アセチルシクロヘキシルスルホニルパーオキシド；２，４，４−トリメチルペンチル−２−パーオキシフェノキシアセテートなどが挙げられる。さらには、上記開始剤に過硫酸カリウム、過硫酸アンモニウム、過酸化水素などを組み合わせて開始剤とすることもできる。また、レドックス系開始剤としては、上記の過酸化物と亜硫酸水素ナトリウム、炭酸水素ナトリウム、酒石酸、Ｌ−アスコルビン酸、ロンガリットなどの還元剤とを組み合わせたものが挙げられる。 As the initiator used for copolymerization, conventionally known azo initiators, peroxide initiators, redox initiators and the like are appropriately selected according to the polymerization method. As the azo initiator, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4- Dimethyl valeronitrile) and the like. Peroxide compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, diethoxyethyl peroxydicarbonate; t-butyl Perester compounds such as peroxyneodecanate, α-cumylperoxyneodecanate, t-butylperoxydecanate; acetylcyclohexylsulfonyl peroxide; 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate, etc. Is mentioned. Furthermore, the initiator can be combined with potassium persulfate, ammonium persulfate, hydrogen peroxide, or the like to form an initiator. Examples of the redox initiator include a combination of the above-described peroxide and a reducing agent such as sodium hydrogen sulfite, sodium hydrogen carbonate, tartaric acid, L-ascorbic acid, or longalite.
また、ＰＯＡ基を有するマクロモノマーとビニルエステル系単量体との共重合を高い温度で行った場合、ビニルエステル系単量体の分解に起因するＰＶＡの着色等が見られることがあるため、その場合には着色防止の目的で重合系に酒石酸のような酸化防止剤を１〜１００ｐｐｍ（ビニルエステル系単量体に対して）程度添加することはなんら差し支えない。 In addition, when copolymerization of a macromonomer having a POA group and a vinyl ester monomer is carried out at a high temperature, coloring of PVA due to decomposition of the vinyl ester monomer may be seen. In that case, an antioxidant such as tartaric acid may be added to the polymerization system in an amount of 1 to 100 ppm (relative to the vinyl ester monomer) for the purpose of preventing coloring.
ビニルエステル系単量体としては、ギ酸ビニル、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、イソ酪酸ビニル、ピバリン酸ビニル、バーサチック酸ビニル、カプロン酸ビニル、カプリル酸ビニル、ラウリル酸ビニル、パルミチン酸ビニル、ステアリン酸ビニル、オレイン酸ビニル、安息香酸ビニルなどが挙げられるが、中でも酢酸ビニルが最も好ましい。 Examples of vinyl ester monomers include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl palmitate, Examples include vinyl stearate, vinyl oleate, and vinyl benzoate. Among them, vinyl acetate is most preferable.
ＰＯＡ基を有するマクロモノマーとビニルエステル系単量体との共重合に際して、本発明の主旨を損なわない範囲で他の単量体を共重合しても差し支えない。使用しうる単量体として、例えば、エチレン、プロピレン、ｎ−ブテン、イソブチレンなどのα−オレフィン；アクリル酸およびその塩；アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ−プロピル、アクリル酸ｉ−プロピル、アクリル酸ｎ−ブチル、アクリル酸ｉ−ブチル、アクリル酸ｔ−ブチル、アクリル酸２−エチルヘキシル、アクリル酸ドデシル、アクリル酸オクタデシルなどのアクリル酸エステル類；メタクリル酸およびその塩；メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ−プロピル、メタクリル酸ｉ−プロピル、メタクリル酸ｎ−ブチル、メタクリル酸ｉ−ブチル、メタクリル酸ｔ−ブチル、メタクリル酸２−エチルヘキシル、メタクリル酸ドデシル、メタクリル酸オクタデシルなどのメタクリル酸エステル類；アクリルアミド；Ｎ−メチルアクリルアミド、Ｎ−エチルアクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、ジアセトンアクリルアミド、アクリルアミドプロパンスルホン酸およびその塩、アクリルアミドプロピルジメチルアミンおよびその塩またはその４級塩、Ｎ−メチロールアクリルアミドおよびその誘導体などのアクリルアミド誘導体；メタクリルアミド；Ｎ−メチルメタクリルアミド、Ｎ−エチルメタクリルアミド、メタクリルアミドプロパンスルホン酸およびその塩、メタクリルアミドプロピルジメチルアミンおよびその塩またはその４級塩、Ｎ−メチロールメタクリルアミドおよびその誘導体などのメタクリルアミド誘導体；メチルビニルエーテル、エチルビニルエーテル、ｎ−プロピルビニルエーテル、ｉ−プロピルビニルエーテル、ｎ−ブチルビニルエーテル、ｉ−ブチルビニルエーテル、ｔ−ブチルビニルエーテル、ドデシルビニルエーテル、ステアリルビニルエーテルなどのビニルエーテル類；アクリロニトリル、メタクリロニトリルなどのニトリル類；塩化ビニル、フッ化ビニルなどのハロゲン化ビニル類；塩化ビニリデン、フッ化ビニリデンなどのハロゲン化ビニリデン類；酢酸アリル、塩化アリルなどのアリル化合物；マレイン酸、イタコン酸、フマル酸などの不飽和ジカルボン酸およびその塩またはそのエステル；ビニルトリメトキシシランなどのビニルシリル化合物；酢酸イソプロペニルなどが挙げられる。 When the macromonomer having a POA group and the vinyl ester monomer are copolymerized, other monomers may be copolymerized within a range not impairing the gist of the present invention. Examples of monomers that can be used include α-olefins such as ethylene, propylene, n-butene, and isobutylene; acrylic acid and salts thereof; methyl acrylate, ethyl acrylate, n-propyl acrylate, and i-propyl acrylate. Acrylates such as n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate; methacrylic acid and salts thereof; methyl methacrylate, methacryl Methacrylic acid such as ethyl acetate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate Beauty treatment Acrylamide; N-methyl acrylamide, N-ethyl acrylamide, N, N-dimethyl acrylamide, diacetone acrylamide, acrylamide propane sulfonic acid and its salt, acrylamidopropyldimethylamine and its salt or quaternary salt thereof, N-methylol acrylamide Acrylamide derivatives such as and derivatives thereof; methacrylamide; N-methyl methacrylamide, N-ethyl methacrylamide, methacrylamide propane sulfonic acid and salts thereof, methacrylamide propyldimethylamine and salts thereof or quaternary salts thereof, N-methylol methacryl Methacrylamide derivatives such as amides and derivatives thereof; methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl Vinyl ethers such as nyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, dodecyl vinyl ether, stearyl vinyl ether; nitriles such as acrylonitrile and methacrylonitrile; vinyl halides such as vinyl chloride and vinyl fluoride; Vinylidene halides such as vinylidene chloride and vinylidene fluoride; allyl compounds such as allyl acetate and allyl chloride; unsaturated dicarboxylic acids such as maleic acid, itaconic acid and fumaric acid, and salts or esters thereof; vinyltrimethoxysilane, etc. Vinylsilyl compounds; isopropenyl acetate and the like.
また、ＰＯＡ基を有するマクロモノマーとビニルエステル系単量体との共重合に際し、得られる共重合体の重合度を調節することなどを目的として、本発明の主旨を損なわない範囲で連鎖移動剤の存在下で共重合を行っても差し支えない。連鎖移動剤としては、アセトアルデヒド、プロピオンアルデヒド、などのアルデヒド類；アセトン、メチルエチルケトンなどのケトン類；２−ヒドロキシエタンチオールなどのメルカプタン類；トリクロロエチレン、パークロロエチレンなどのハロゲン化炭化水素類が挙げられ、中でもアルデヒド類およびケトン類が好適に用いられる。連鎖移動剤の添加量は、添加する連鎖移動剤の連鎖移動定数および目的とするビニルエステル系重合体の重合度に応じて決定されるが、一般にビニルエステル系単量体に対して０．１〜１０重量％が望ましい。 In addition, in the copolymerization of a macromonomer having a POA group and a vinyl ester monomer, a chain transfer agent is used within the range not impairing the gist of the present invention for the purpose of adjusting the degree of polymerization of the resulting copolymer. Copolymerization may be carried out in the presence of. Examples of chain transfer agents include aldehydes such as acetaldehyde and propionaldehyde; ketones such as acetone and methyl ethyl ketone; mercaptans such as 2-hydroxyethanethiol; and halogenated hydrocarbons such as trichloroethylene and perchloroethylene. Of these, aldehydes and ketones are preferably used. The addition amount of the chain transfer agent is determined according to the chain transfer constant of the chain transfer agent to be added and the degree of polymerization of the target vinyl ester polymer, but is generally 0.1% relative to the vinyl ester monomer. -10 wt% is desirable.
ＰＯＡ変性ビニルエステル系共重合体のけん化反応には、従来公知の水酸化ナトリウム、水酸化カリウム、ナトリウムメトキシドなどの塩基性触媒またはＰ−トルエンスルホン酸などの酸性触媒を用いた加アルコール分解反応ないし加水分解反応を適用することができる。この反応に使用しうる溶媒としては、メタノール、エタノールなどのアルコール類；酢酸メチル、酢酸エチルなどのエステル類；アセトン、メチルエチルケトンなどのケトン類；ベンゼン、トルエンなどの芳香族炭化水素などが挙げられ、これらは単独で、または２種以上を組み合わせて用いることができる。中でもメタノールまたはメタノール／酢酸メチル混合溶液を溶媒とし、水酸化ナトリウムを触媒に用いてけん化反応を行うのが簡便であり好ましい。 In the saponification reaction of the POA-modified vinyl ester copolymer, an alcoholysis reaction using a conventionally known basic catalyst such as sodium hydroxide, potassium hydroxide or sodium methoxide or an acidic catalyst such as P-toluenesulfonic acid. Alternatively, a hydrolysis reaction can be applied. Examples of the solvent that can be used for this reaction include alcohols such as methanol and ethanol; esters such as methyl acetate and ethyl acetate; ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as benzene and toluene; These can be used alone or in combination of two or more. Among them, it is convenient and preferable to perform the saponification reaction using methanol or a methanol / methyl acetate mixed solution as a solvent and sodium hydroxide as a catalyst.
本発明の水性接着剤に含有されるＰＯＡ変性ＰＶＡは、水溶性を維持し、かつ、本発明の効果を損なわない範囲であれば、従来公知の方法でＰＯＡ変性ＰＶＡをさらに変性したＰＯＡ変性ＰＶＡを用いることも可能である。このようなＰＯＡ変性ＰＶＡは、例えば、ＰＯＡ変性ＰＶＡをブチルアルデヒド等のアルデヒドで変性したり、ジケテンで変性したりして得られたものが挙げられる。 The POA-modified PVA contained in the aqueous adhesive of the present invention is a POA-modified PVA obtained by further modifying the POA-modified PVA by a conventionally known method as long as it maintains water solubility and does not impair the effects of the present invention. It is also possible to use. Examples of such POA-modified PVA include those obtained by modifying POA-modified PVA with an aldehyde such as butyraldehyde or with diketene.
本発明の水性接着剤は、基本的に上記のＰＯＡ変性ＰＶＡを水相中に有するものであれば良いが、各種基材への接着性や固形分増加による乾燥負荷低減などを目的に、エチレン系不飽和単量体およびジエン系単量体から選ばれる一種以上の単量体からなる（共）重合体エマルジョンを含有することができる。該エマルジョンとしては、酢酸ビニル系エマルジョン（酢酸ビニル重合体、酢酸ビニル−エチレン共重合体、酢酸ビニル−バーサチック酸ビニル共重合体、酢酸ビニル−(メタ)アクリル酸エステル共重合体等）、(メタ)アクリル酸エステル系エマルジョン、スチレン系エマルジョン、ブタジエン系エマルジョン（スチレン−ブタジエン共重合体、メタクリル酸メチルーブタジエン共重合体等）等が使用できる。このとき、エマルジョンの分散安定剤としては、ビニルアルコール系重合体、ヒドロキシエチルセルロースなどの水溶性セルロース誘導体、各種の界面活性剤などが使用できる。中でも分散安定剤としてビニルアルコール系重合体を使用した酢酸ビニル系エマルジョン又は(メタ)アクリル酸エステル系エマルジョンが本発明の水性接着剤の初期接着性および保存安定性の観点から好ましい。これらのエマルジョンは、固形分基準でＰＯＡ変性ＰＶＡ１００重量部に対し、通常、５００重量部以下、好ましくは３００重量部以下、さらに好ましくは２５０重量部以下使用することができる。 The water-based adhesive of the present invention may basically have any of the above-mentioned POA-modified PVA in the aqueous phase, but for the purpose of reducing the drying load due to the adhesiveness to various substrates and the increase in the solid content. A (co) polymer emulsion composed of one or more monomers selected from a series unsaturated monomer and a diene monomer can be contained. Examples of the emulsion include vinyl acetate emulsions (vinyl acetate polymer, vinyl acetate-ethylene copolymer, vinyl acetate-vinyl versatate copolymer, vinyl acetate- (meth) acrylic acid ester copolymer, etc.), (meta ) Acrylic ester emulsion, styrene emulsion, butadiene emulsion (styrene-butadiene copolymer, methyl methacrylate-butadiene copolymer, etc.) can be used. At this time, as a dispersion stabilizer for the emulsion, vinyl alcohol polymers, water-soluble cellulose derivatives such as hydroxyethyl cellulose, various surfactants, and the like can be used. Among these, a vinyl acetate emulsion or a (meth) acrylic ester emulsion using a vinyl alcohol polymer as a dispersion stabilizer is preferable from the viewpoint of initial adhesiveness and storage stability of the aqueous adhesive of the present invention. These emulsions can be used usually in an amount of 500 parts by weight or less, preferably 300 parts by weight or less, more preferably 250 parts by weight or less based on 100 parts by weight of POA-modified PVA on a solid basis.
また、本発明の水性接着剤は、固形分増加による乾燥負荷低減や形成される接着層の強度および硬度の上昇を目的に、無機系あるいは有機系のフィラーを含有することができる。無機系のフィラーとしては、カオリナイト、ハロイサイト、パイロフェライトまたはセリサイトなどのクレー、重質、軽質、または表面処理された炭酸カルシウム、水酸化アルミニウム、酸化アルミニウム、石膏類、タルク、酸化チタン等があげられる。有機系フィラーとしては、澱粉、酸化澱粉、小麦粉、木紛等があげられる。なかでも、各種クレーと各種澱粉が好適に使用できる。これらのフィラーは、固形分基準で水性接着剤中のＰＯＡ変性ＰＶＡ１００重量部に対して１０００重量部以下、好ましくは、５００重量部以下、より好ましくは４００重量部以下使用することができる。１０００重量部よりもフィラーが多い場合には、保存中にフィラーの沈降などの問題が起こることがある。 The aqueous adhesive of the present invention can contain an inorganic or organic filler for the purpose of reducing the drying load due to an increase in solid content and increasing the strength and hardness of the formed adhesive layer. Inorganic fillers include clays such as kaolinite, halloysite, pyroferrite or sericite, heavy, light or surface treated calcium carbonate, aluminum hydroxide, aluminum oxide, gypsum, talc, titanium oxide, etc. can give. Examples of the organic filler include starch, oxidized starch, wheat flour, wood powder and the like. Of these, various clays and various starches can be suitably used. These fillers can be used in an amount of 1000 parts by weight or less, preferably 500 parts by weight or less, more preferably 400 parts by weight or less based on 100 parts by weight of the POA-modified PVA in the aqueous adhesive on a solid basis. When there are more fillers than 1000 weight part, problems, such as sedimentation of a filler, may occur during storage.
本発明の水性接着剤には、本発明の効果を損なわない範囲であれば、各種添加剤を加えても差し支えない。これら添加剤の例としては、ポリリン酸ソーダやヘキサメタリン酸ソーダなどのリン酸化合物の金属塩や水ガラスなどの無機物の分散剤、ポリアクリル酸およびその塩、アルギン酸ソーダ、α−オレフィン−無水マレイン酸共重合物などのアニオン性高分子化合物とその金属塩、高級アルコールのエチレンオキサイド付加物、エチレンオキサイドとプロピレンオキサイドとの共重合体などのノニオン界面活性剤、カルボキシメチルセルロース、メチルセルロース、アルギン酸ソーダ、ポリエチレンオキサイド、各種消泡剤、防腐剤、防黴剤、着色顔料、消臭剤、香料などが挙げられる。 Various additives may be added to the aqueous adhesive of the present invention as long as the effects of the present invention are not impaired. Examples of these additives include metal salts of phosphate compounds such as sodium polyphosphate and hexametaphosphate, inorganic dispersants such as water glass, polyacrylic acid and its salts, sodium alginate, α-olefin-maleic anhydride Nonionic surfactants such as anionic polymer compounds such as copolymers and their metal salts, ethylene oxide adducts of higher alcohols, copolymers of ethylene oxide and propylene oxide, carboxymethylcellulose, methylcellulose, sodium alginate, polyethylene oxide And various antifoaming agents, antiseptics, antifungal agents, coloring pigments, deodorants, and fragrances.
本発明の水性接着剤の調製方法としては特に制限はない。例えば、ＰＯＡ変性ＰＶＡとフィラーなどの他の添加剤を予め混合したものを水中に撹拌しながら投入するか、または、各種添加剤、フィラー、ＰＯＡ変性ＰＶＡを逐次水中に撹拌しながら投入してスラリー液を調製した後、加熱溶解する等の方法があげられる。このときの加熱方法としては、スラリー液に蒸気を直接吹き込む加熱方式、あるいはジャケットによる間接加熱方式のような任意の加熱方式が採用される。この調製はバッチ方式あるいは連続方式のどちらで行ってもよい。 There is no restriction | limiting in particular as a preparation method of the water-based adhesive of this invention. For example, a mixture in which POA-modified PVA and other additives such as a filler are mixed in advance is added to water while stirring, or various additives, filler, and POA-modified PVA are sequentially added to water while stirring. Examples of the method include preparing the solution and then dissolving it by heating. As a heating method at this time, an arbitrary heating method such as a heating method in which steam is directly blown into the slurry liquid or an indirect heating method using a jacket is employed. This preparation may be carried out either batchwise or continuously.
本発明の水性接着剤は、初期接着性が高く、高速生産が可能であり、しかも保存安定性（粘度安定性、沈降安定性）に優れる。そのため、このような水性接着剤は段ボール、紙袋、紙箱、紙管、壁紙等の製造時又は使用時などに用いる紙用接着剤、木材同士、木材と繊維、木材と紙、木材とプラスチックスを接着する木工用接着剤として好適に使用される。また、布や不職布などの繊維、コンクリートなどのセメント成形物、各種プラスチックス、アルミ箔等を被着材とする用途にも使用できる。しかしながら、本発明の水性接着剤の用途は、これらに限定されるものではない。 The aqueous adhesive of the present invention has high initial adhesiveness, enables high-speed production, and is excellent in storage stability (viscosity stability and sedimentation stability). Therefore, such water-based adhesives include paper adhesives used in the manufacture or use of cardboard, paper bags, paper boxes, paper tubes, wallpaper, etc., wood-to-wood, wood-to-fiber, wood-to-paper, wood-to-plastics. It is suitably used as an adhesive for woodwork to be bonded. Further, it can also be used for applications using fibers such as cloth and unemployed cloth, cement moldings such as concrete, various plastics, aluminum foil and the like. However, the use of the aqueous adhesive of the present invention is not limited to these.
本発明の水性接着剤の粘度は、用途によって任意に選ぶことができる。高速塗工性を意図した場合には、その貼り合わせ温度での粘度は、Ｂ型粘度で１００〜１００００ｍＰａ・Ｓが多く用いられる。本発明の水性接着剤に含有されるＰＯＡ変性ＰＶＡは、水中において、特定のＰＯＡ基間の疎水性相互作用により擬似会合体を形成し、それにより高粘度で、濃度上昇に対する大きい粘度上昇を示すという初期接着力発現に重要な特性を発現するものと考えられる。さらに、ＰＯＡ変性ＰＶＡはＰＯＡ基の温度上昇による脱水に起因して疎水性相互作用が増加することによる感温増粘性を有する。そのため、通常温度上昇により低下する系粘度の低下が抑えられ、分離安定性、フィラーの沈降安定性等の保存安定性がよくなるものと考えられる。 The viscosity of the aqueous adhesive of the present invention can be arbitrarily selected depending on the application. When high-speed coating property is intended, the viscosity at the bonding temperature is often B-type viscosity of 100 to 10,000 mPa · S. The POA-modified PVA contained in the water-based adhesive of the present invention forms a pseudo-aggregate in water due to hydrophobic interaction between specific POA groups, thereby exhibiting a high viscosity and a large viscosity increase with increasing concentration. It is thought that it expresses an important characteristic for the expression of initial adhesive strength. Furthermore, the POA-modified PVA has a temperature-sensitive thickening due to an increase in hydrophobic interaction due to dehydration due to an increase in temperature of the POA group. For this reason, it is considered that a decrease in system viscosity, which usually decreases due to an increase in temperature, is suppressed, and storage stability such as separation stability and sedimentation stability of the filler is improved.
以下、実施例を挙げて本発明をより具体的に説明するが本発明はこれらによって何ら制限されるものではない。なお、実施例中の「％」および「部」は特に断りのない限り、それぞれ「重量％」および「重量部」を表す。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the examples, “%” and “parts” represent “% by weight” and “parts by weight”, respectively, unless otherwise specified.
［ＰＯＡ変性ＰＶＡの製造］
製造例１（ＰＶＡ１の製造）
撹拌機、還流冷却管、窒素導入管、コモノマー滴下口および開始剤の添加口を備えた３Ｌの反応器に、酢酸ビニル７５０ｇ、メタノール２５０ｇ、ＰＯＡ基を有するマクロモノマー（単量体Ａ）１７．６ｇを仕込み、窒素バブリングをしながら３０分間系内を窒素置換した。また、ディレー溶液としてＰＯＡ基を有するマクロモノマー（単量体Ａ）をメタノールに溶解して濃度２０％としたコモノマー溶液を調製し、窒素ガスのバブリングにより窒素置換した。反応器の昇温を開始し、内温が６０℃となったところで、２，２’−アゾビスイソブチロニトリル（ＡＩＢＮ）０．２５ｇを添加し重合を開始した。ディレー溶液を滴下して重合溶液中のモノマー組成（酢酸ビニルと単量体Ａの比率）が一定となるようにしながら、６０℃で３時間重合した後冷却して重合を停止した。重合を停止するまで加えたコモノマー溶液の総量は７５ｍｌであった。また重合停止時の固形分濃度は２４．４％であった。続いて３０℃、減圧下でメタノールを時々添加しながら未反応の酢酸ビニルモノマーの除去を行い、ＰＯＡ変性ＰＶＡｃのメタノール溶液（濃度３５％）を得た。さらに、これにメタノールを加えて調製したＰＯＡ変性ＰＶＡｃのメタノール溶液４５３．４ｇ（溶液中のＰＯＡ変性ＰＶＡｃ１００．０ｇ）に、５５．６ｇのアルカリ溶液（水酸化ナトリウムの１０％メタノール溶液）を添加してけん化を行った（けん化溶液のＰＯＡ変性ＰＶＡｃ濃度２０％、ＰＯＡ変性ＰＶＡｃ中の酢酸ビニルユニットに対する水酸化ナトリウムのモル比０．１モル％）。アルカリ溶液を添加後約１分でゲル状物が生成したので、これを粉砕器にて粉砕し、４０℃で１時間放置してけん化を進行させた後、酢酸メチル５００ｇを加えて残存するアルカリを中和した。フェノールフタレイン指示薬を用いて中和が終了したことを確認した後、濾別して白色固体を得、これにメタノール２０００ｇを加えて室温で３時間放置洗浄した。上記の洗浄操作を３回繰り返した後、遠心脱液して得られた白色固体を乾燥機中６５℃で２日間放置してＰＯＡ変性ＰＶＡ（ＰＶＡ１）を得た。ＰＶＡ１の重合度は１７６０、けん化度は９８．７モル％、ＰＯＡ基変性量（Ｓ）は０．４モル％であった。[Production of POA-modified PVA]
Production Example 1 (Production of PVA1)
Macromonomer (monomer A) having 750 g of vinyl acetate, 250 g of methanol and POA group in a 3 L reactor equipped with a stirrer, reflux condenser, nitrogen inlet, comonomer dropping port and initiator addition port 6 g was charged, and the system was purged with nitrogen for 30 minutes while bubbling nitrogen. Further, a comonomer solution having a concentration of 20% was prepared by dissolving a macromonomer having a POA group (monomer A) in methanol as a delay solution, and nitrogen substitution was performed by bubbling nitrogen gas. The temperature of the reactor was increased, and when the internal temperature reached 60 ° C., 0.25 g of 2,2′-azobisisobutyronitrile (AIBN) was added to initiate polymerization. While the delay solution was added dropwise so that the monomer composition (ratio of vinyl acetate and monomer A) in the polymerization solution was constant, polymerization was performed at 60 ° C. for 3 hours and then cooled to stop the polymerization. The total amount of comonomer solution added until the polymerization was stopped was 75 ml. The solid content concentration when the polymerization was stopped was 24.4%. Subsequently, unreacted vinyl acetate monomer was removed while occasionally adding methanol under reduced pressure at 30 ° C. to obtain a methanol solution (concentration 35%) of POA-modified PVAc. Furthermore, 55.6 g of an alkali solution (10% methanol solution of sodium hydroxide) was added to 453.4 g of POA-modified PVAc methanol solution prepared by adding methanol to this (100.0 g of POA-modified PVAc in the solution). Saponification was carried out (POA-modified PVAc concentration of saponified solution 20%, molar ratio of sodium hydroxide to vinyl acetate unit in POA-modified PVAc 0.1 mol%). A gel-like product was formed in about 1 minute after the addition of the alkaline solution. This was pulverized with a pulverizer and allowed to stand at 40 ° C. for 1 hour to proceed with saponification. Neutralized. After confirming that the neutralization was completed using a phenolphthalein indicator, a white solid was obtained by filtration, 2000 g of methanol was added thereto, and the mixture was allowed to stand and washed at room temperature for 3 hours. After the above washing operation was repeated three times, the white solid obtained by centrifugal drainage was left in a dryer at 65 ° C. for 2 days to obtain POA-modified PVA (PVA1). The degree of polymerization of PVA1 was 1760, the degree of saponification was 98.7 mol%, and the POA group modification amount (S) was 0.4 mol%.
製造例２〜２２（ＰＶＡ２〜２２の製造）
酢酸ビニルおよびメタノールの仕込み量、重合時に使用するＰＯＡ基を有する不飽和単量体の種類（表２）や添加量等の重合条件、けん化時におけるＰＯＡ変性ＰＶＡｃの濃度、酢酸ビニルユニットに対する水酸化ナトリウムのモル比等のけん化条件を表１および表２に示すように変更した以外は、製造例１と同様の方法により各種のＰＯＡ変性ＰＶＡ（ＰＶＡ２〜２２）を製造した。Production Examples 2 to 22 (Production of PVA 2 to 22)
Charge amount of vinyl acetate and methanol, type of unsaturated monomer having POA group used during polymerization (Table 2), polymerization conditions such as addition amount, concentration of POA-modified PVAc during saponification, hydroxylation to vinyl acetate unit Various POA-modified PVAs (PVA2-22) were produced in the same manner as in Production Example 1 except that the saponification conditions such as the molar ratio of sodium were changed as shown in Tables 1 and 2.
製造例２３（ＰＶＡ２３の製造）
撹拌機、還流冷却管、窒素導入管、開始剤の添加口を備えた３Ｌの反応器に、酢酸ビニル７００ｇ、メタノール３００ｇを仕込み、窒素バブリングをしながら３０分間系内を窒素置換した。反応器の昇温を開始し、内温が６０℃となったところで、２，２’−アゾビスイソブチロニトリル（ＡＩＢＮ）０．２５ｇを添加し重合を開始し、６０℃で３時間重合した後冷却して重合を停止した。重合停止時の固形分濃度は１７．０％であった。続いて３０℃、減圧下でメタノールを時々添加しながら未反応の酢酸ビニルモノマーの除去を行い、ポリ酢酸ビニル（ＰＶＡｃ）のメタノール溶液（濃度３０％）を得た。さらに、これにメタノールを加えて調製したＰＶＡｃのメタノール溶液５４４．１ｇ（溶液中のＰＶＡｃ１２０．０ｇ）に、５５．８ｇのアルカリ溶液（水酸化ナトリウムの１０％メタノール溶液）を添加してけん化を行った（けん化溶液のＰＶＡｃ濃度２０％、ＰＶＡｃ中の酢酸ビニルユニットに対する水酸化ナトリウムのモル比０．１）。アルカリ溶液を添加後約１分でゲル状物が生成したので、これを粉砕器にて粉砕し、４０℃で１時間放置してけん化を進行させた後、酢酸メチル５００ｇを加えて残存するアルカリを中和した。フェノールフタレイン指示薬を用いて中和が終了したことを確認した後、濾別して白色固体を得、これにメタノール２０００ｇを加えて室温で３時間放置洗浄した。上記の洗浄操作を３回繰り返した後、遠心脱液して得られた白色固体を乾燥機中６５℃で２日間放置して無変性ＰＶＡ（ＰＶＡ２３）を得た。ＰＶＡ２３の重合度は１７００、けん化度は９８．５モル％であった。Production Example 23 (Production of PVA23)
700 g of vinyl acetate and 300 g of methanol were charged into a 3 L reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet, and an initiator addition port, and the system was purged with nitrogen for 30 minutes while bubbling nitrogen. The temperature of the reactor was increased, and when the internal temperature reached 60 ° C., 0.25 g of 2,2′-azobisisobutyronitrile (AIBN) was added to start polymerization, and polymerization was performed at 60 ° C. for 3 hours. After cooling, the polymerization was stopped. The solid content concentration when the polymerization was stopped was 17.0%. Subsequently, unreacted vinyl acetate monomer was removed while sometimes adding methanol under reduced pressure at 30 ° C. to obtain a methanol solution (concentration 30%) of polyvinyl acetate (PVAc). Furthermore, saponification was performed by adding 55.8 g of an alkaline solution (sodium hydroxide in 10% methanol) to 544.1 g of PVAc methanol solution prepared by adding methanol thereto (120.0 g of PVAc in the solution). (PVAc concentration of saponification solution 20%, molar ratio of sodium hydroxide to vinyl acetate unit in PVAc 0.1). A gel-like product was formed in about 1 minute after the addition of the alkaline solution. This was pulverized with a pulverizer and allowed to stand at 40 ° C. for 1 hour to proceed with saponification. Neutralized. After confirming that the neutralization was completed using a phenolphthalein indicator, a white solid was obtained by filtration, 2000 g of methanol was added thereto, and the mixture was allowed to stand and washed at room temperature for 3 hours. After repeating the above washing operation three times, the white solid obtained by centrifugal drainage was allowed to stand in a dryer at 65 ° C. for 2 days to obtain unmodified PVA (PVA23). The polymerization degree of PVA23 was 1700, and the saponification degree was 98.5 mol%.
製造例２４〜２６（ＰＶＡ２４〜２６の製造）
酢酸ビニルおよびメタノールの仕込み量、けん化時におけるＰＶＡｃの濃度、酢酸ビニルユニットに対する水酸化ナトリウムのモル比等のけん化条件を表１に示すように変更した以外は、製造例２３と同様の方法により各種の無変性ＰＶＡ（ＰＶＡ２４〜２６）を製造した。Production Examples 24-26 (Production of PVA 24-26)
Various methods were used in the same manner as in Production Example 23 except that the saponification conditions such as the amount of vinyl acetate and methanol, the concentration of PVAc during saponification, and the molar ratio of sodium hydroxide to vinyl acetate unit were changed as shown in Table 1. Of unmodified PVA (PVA 24-26).
実施例および比較例において、各種のＰＶＡを用いて調製された水性接着剤について、以下の方法にしたがって評価した。
［保存安定性］
水性接着剤溶液を４０℃で７日間放置した場合の状態を観察し、保存前後の状態変化を以下の指標で評価した。
○；分離、沈降なく、粘度変化もなし。
△；分離、沈降がわずかに認められるが、流動性はあり。
×；分離、沈降が認められる。あるいは、流動性がない。
［初期接着性］
日本たばこ産業社製の初期接着試験機を用いて、以下の条件で初期接着力を測定した。
条件；クラフト紙／クラフト紙接着
塗布速度 ０．５ｍ／秒
せん断速度 ３００ｍｍ／秒
オープンタイム １秒
圧着時間 ２秒
養生時間 1秒、３秒、５秒、１０秒
接着面積 １ｍｍ×２５ｍｍ×８ヶ所（計２ｃｍ２）
温湿度２０℃、６５％ＲＨIn Examples and Comparative Examples, aqueous adhesives prepared using various PVA were evaluated according to the following methods.
[Storage stability]
The state when the aqueous adhesive solution was allowed to stand at 40 ° C. for 7 days was observed, and the state change before and after storage was evaluated by the following indices.
○: No separation or sedimentation, no change in viscosity.
Δ: Separation and sedimentation are slightly observed, but fluidity exists.
X: Separation and sedimentation are observed. Or there is no fluidity.
[Initial adhesion]
The initial adhesion strength was measured under the following conditions using an initial adhesion tester manufactured by Nippon Tobacco Inc.
Conditions: Kraft paper / craft paper bonding Application speed 0.5m / sec Shear speed 300mm / sec Open time 1sec Crimping time 2sec Curing time 1sec, 3sec, 5sec, 10sec Adhesive area 1mm x 25mm x 8 locations ( 2cm 2 in total)
Temperature and humidity 20 ° C, 65% RH
実施例１
７６９部のイオン交換水に１００部のＰＶＡ１を常温で添加し、攪拌しながら１時間で９５℃まで昇温した。９５℃で２時間保持した後、攪拌しながら常温まで冷却し、１３％のＰＶＡ１水溶液を得た。これを接着剤とし、前記の方法に従い、保存安定性および初期接着性の評価を行った。結果を表３に示す。Example 1
100 parts of PVA1 was added to 769 parts of ion-exchanged water at room temperature, and the temperature was raised to 95 ° C. over 1 hour while stirring. After maintaining at 95 ° C. for 2 hours, the mixture was cooled to room temperature while stirring to obtain a 13% PVA1 aqueous solution. This was used as an adhesive, and storage stability and initial adhesiveness were evaluated according to the method described above. The results are shown in Table 3.
実施例２〜１２、比較例１〜１４
実施例１のＰＶＡ１に代えて製造例２〜２６で得られたＰＶＡ２〜２６を用いる以外は実施例１と同様にして接着剤を得た。これらを用い、前記の方法に従い、保存安定性および初期接着性を評価した。結果を表３に示す。Examples 2-12, Comparative Examples 1-14
An adhesive was obtained in the same manner as in Example 1 except that PVA 2 to 26 obtained in Production Examples 2 to 26 were used in place of PVA 1 in Example 1. Using these, the storage stability and the initial adhesiveness were evaluated according to the above-described method. The results are shown in Table 3.
実施例１３
還流冷却器、滴下ロート、温度計、窒素吹込口、イカリ型攪拌翼を備えたガラス製重合容器に、イオン交換水４５０部と製造例２３で得られたＰＶＡ２３を３２部仕込み、９５℃で溶解した。次に、このＰＶＡ２３の水溶液を冷却、窒素置換後、１４０ｒｐｍで撹拌しながら酢酸ビニル４０部を仕込み、６０℃に昇温した後、過酸化水素／酒石酸のレドックス開始剤系の存在下で重合を開始した。重合開始１５分後から酢酸ビニル３６０部を３時間にわたって連続的に添加し、重合を完結させた。使用した開始剤は、１％過酸化水素水３０ｇ、５％酒石酸水溶液１０ｇであった。得られたＰＶＡｃエマルジョンは、固形分濃度４６．８％であった。実施例１で得られた１３％のＰＶＡ１水溶液１００部とＰＶＡｃエマルジョン２７．７部とを混合し接着剤を調製した（固形分２０．３％：ＰＶＡ１とＰＶＡｃの固形分重量比は１００：１００）。これを用い、前記の方法に従い、保存安定性および初期接着性を評価した。結果を表４に示す。Example 13
In a glass polymerization vessel equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen inlet, and a squid type stirring blade, 450 parts of ion-exchanged water and 32 parts of PVA 23 obtained in Production Example 23 were charged and dissolved at 95 ° C. did. Next, this aqueous solution of PVA23 was cooled, purged with nitrogen, charged with 40 parts of vinyl acetate while stirring at 140 rpm, heated to 60 ° C., and then polymerized in the presence of a redox initiator system of hydrogen peroxide / tartaric acid. Started. From 15 minutes after the start of the polymerization, 360 parts of vinyl acetate was continuously added over 3 hours to complete the polymerization. The initiator used was 30 g of 1% hydrogen peroxide solution and 10 g of 5% aqueous tartaric acid solution. The obtained PVAc emulsion had a solid content concentration of 46.8%. An adhesive was prepared by mixing 100 parts of the 13% PVA1 aqueous solution obtained in Example 1 and 27.7 parts of PVAc emulsion (solid content 20.3%: solid weight ratio of PVA1 and PVAc is 100: 100). ). Using this, storage stability and initial adhesiveness were evaluated according to the method described above. The results are shown in Table 4.
比較例１５
実施例１３においてＰＶＡ１水溶液に代えて比較例１１で得られたＰＶＡ２３水溶液を用いる以外は実施例１３と同様にＰＶＡｃエマルジョンと混合し接着剤を調製した（固形分２０．３％：ＰＶＡ２３とＰＶＡｃの固形分重量比は１００：１００）。これを用い、前記の方法に従い、保存安定性および初期接着性を評価した。結果を表４に示す。Comparative Example 15
An adhesive was prepared by mixing with a PVAc emulsion in the same manner as in Example 13 except that the PVA23 aqueous solution obtained in Comparative Example 11 was used instead of the PVA1 aqueous solution in Example 13 (solid content 20.3%: PVA23 and PVAc Solids weight ratio is 100: 100). Using this, storage stability and initial adhesiveness were evaluated according to the method described above. The results are shown in Table 4.
実施例１４
実施例１で得られた１３％のＰＶＡ１水溶液１００部に対しクレー（Ｈｕｂｅｒ−９００：カオリナイト系クレー、平均粒径０．６μｍ、Ｈｕｂｅｒ社製）２６部を添加・攪拌し、クレーを十分分散させて接着剤を調製した（固形分３１．０％：ＰＶＡ１とクレーの固形分重量比は１００：２００）。これを用い、前記の方法に従い、保存安定性および初期接着性を評価した。結果を表４に示す。Example 14
To 100 parts of the 13% PVA1 aqueous solution obtained in Example 1, 26 parts of clay (Huber-900: Kaolinite clay, average particle size 0.6 μm, manufactured by Huber) was added and stirred, and the clay was sufficiently dispersed. Thus, an adhesive was prepared (solid content 31.0%: solid content weight ratio of PVA1 and clay was 100: 200). Using this, storage stability and initial adhesiveness were evaluated according to the method described above. The results are shown in Table 4.
比較例１６
実施例１４においてＰＶＡ１水溶液に代えて比較例１１で得られたＰＶＡ２３水溶液を用いる以外は実施例１４と同様にクレーを添加し接着剤を調製した（固形分３１．０％：ＰＶＡ２３とクレーの固形分重量比は１００：２００）。これを用い、前記の方法に従い、保存安定性および初期接着性を評価した。結果を表４に示す。Comparative Example 16
In Example 14, an adhesive was prepared by adding clay in the same manner as in Example 14 except that the PVA23 aqueous solution obtained in Comparative Example 11 was used instead of the PVA1 aqueous solution (solid content: 31.0%: solid of PVA23 and clay The weight ratio is 100: 200). Using this, storage stability and initial adhesiveness were evaluated according to the method described above. The results are shown in Table 4.
実施例１５
実施例１で得られたＰＶＡ１水溶液１００部にクレー（Ｈｕｂｅｒ−９００：カオリナイト系クレー、平均粒径０．６μｍ、Ｈｕｂｅｒ社製）２６部を添加・攪拌し、クレーを十分分散させ、それに実施例１３で得られたＰＶＡｃエマルジョン２７．７部を添加混合し接着剤を調製した（固形分３３．８％：ＰＶＡ１とＰＶＡｃとクレーの固形分重量比は１００：１００：２００）。これを用い、前記の方法に従い、保存安定性および初期接着性を評価した。結果を表４に示す。Example 15
To 100 parts of the PVA1 aqueous solution obtained in Example 1, 26 parts of clay (Huber-900: kaolinite-based clay, average particle size 0.6 μm, manufactured by Huber) was added and stirred to sufficiently disperse the clay. An adhesive was prepared by adding and mixing 27.7 parts of the PVAc emulsion obtained in Example 13 (solid content 33.8%: solid content weight ratio of PVA1, PVAc, and clay was 100: 100: 200). Using this, storage stability and initial adhesiveness were evaluated according to the method described above. The results are shown in Table 4.
比較例１７
実施例１５において、ＰＶＡ１水溶液に代えて比較例１１で得られたＰＶＡ２３水溶液を用いる以外は実施例１５と同様にクレーとＰＶＡｃエマルジョンを混合し接着剤を調製した（固形分３３．８％：ＰＶＡ２３とＰＶＡｃとクレーの固形分重量比は１００：１００：２００）。これを用い、前記の方法に従い、保存安定性および初期接着性を評価した。結果を表４に示す。Comparative Example 17
In Example 15, an adhesive was prepared by mixing clay and PVAc emulsion in the same manner as in Example 15 except that the PVA23 aqueous solution obtained in Comparative Example 11 was used instead of the PVA1 aqueous solution (solid content 33.8%: PVA23). The weight ratio of PVAc and clay is 100: 100: 200). Using this, storage stability and initial adhesiveness were evaluated according to the method described above. The results are shown in Table 4.
実施例１６、１７
実施例１５のクレーに代えて炭酸カルシウム（実施例１６、ホワイトンＰ−３０、重質炭酸カルシウム、平均粒径１．７５μｍ、白石工業社製）および酸化澱粉（実施例１７、ＭＳ−３８００、日本食品加工製）をそれぞれ用いる以外は実施例１５と同様にして接着剤を得た。これらを用い、前記の方法に従い、保存安定性および初期接着性を評価した。結果を表４に示す。Examples 16, 17
In place of the clay of Example 15, calcium carbonate (Example 16, Whiten P-30, heavy calcium carbonate, average particle size 1.75 μm, manufactured by Shiroishi Kogyo Co., Ltd.) and oxidized starch (Example 17, MS-3800, An adhesive was obtained in the same manner as in Example 15 except that Nippon Food Processing Co., Ltd. was used. Using these, the storage stability and the initial adhesiveness were evaluated according to the above-described method. The results are shown in Table 4.
実施例１８
還流冷却器、滴下ロート、温度計、窒素吹込口を備えたガラス製重合容器に、イオン交換水５００部、末端にメルカプト基を有するポリビニルアルコール（Ｍ−２０５：重合度５５０、けん化度８８．２モル％、（株）クラレ製）２８部を仕込み、９５℃で溶解した。次に、メタクリル酸メチル２０ｇとアクリル酸ｎ−ブチル２０ｇを添加し、窒素置換後６５℃まで昇温し、１％過硫酸カリウム水溶液１２ｇを添加して重合を開始し、さらに２時間かけてメタクリル酸メチル１８０ｇ、アクリル酸ｎ−ブチル１８０ｇを連続的に添加した。重合は４時間で完結し、固形分濃度４５．１％、粘度２８００ｍＰａ．ｓのメタクリル酸メチル／アクリル酸ｎ−ブチル共重合体（ＡＣＲ）エマルジョンを得た。実施例１で得られたＰＶＡ１水溶液１００部にクレー（Ｈｕｂｅｒ−９００：カオリナイト系クレー、平均粒径０．６μｍ、Ｈｕｂｅｒ社製）２６部を添加・攪拌し、クレーを十分分散させ、それにＡＣＲエマルジョン２８．２部を添加混合し接着剤を調製した（固形分３３．７％：ＰＶＡ１とＡＣＲとクレーの固形分重量比は１００：１００：２００）。これを用い、前記の方法に従い、保存安定性および初期接着性を評価した。結果を表４に示す。Example 18
In a glass polymerization vessel equipped with a reflux condenser, a dropping funnel, a thermometer, and a nitrogen inlet, 500 parts of ion-exchanged water and polyvinyl alcohol having a mercapto group at the terminal (M-205: polymerization degree 550, saponification degree 88.2) 28 parts by mol% (manufactured by Kuraray Co., Ltd.) was charged and dissolved at 95 ° C. Next, 20 g of methyl methacrylate and 20 g of n-butyl acrylate were added, the temperature was raised to 65 ° C. after nitrogen substitution, and 12 g of 1% potassium persulfate aqueous solution was added to initiate polymerization. 180 g of methyl acid and 180 g of n-butyl acrylate were continuously added. The polymerization was completed in 4 hours, the solid content concentration was 45.1%, and the viscosity was 2800 mPa.s. A methyl methacrylate / n-butyl acrylate copolymer (ACR) emulsion was obtained. To 100 parts of the PVA1 aqueous solution obtained in Example 1, 26 parts of clay (Huber-900: kaolinite-based clay, average particle size 0.6 μm, manufactured by Huber) was added and stirred to sufficiently disperse the clay, and ACR was added thereto. An adhesive was prepared by adding and mixing 28.2 parts of the emulsion (solid content 33.7%: solid content weight ratio of PVA1, ACR and clay is 100: 100: 200). Using this, storage stability and initial adhesiveness were evaluated according to the method described above. The results are shown in Table 4.
実施例１９
実施例１８のメタクリル酸メチル／アクリル酸ｎ−ブチル共重合体（ＡＣＲ）エマルジョンに代えて、エチレン−酢酸ビニル共重合体（ＶＡＥ）エマルジョン（ＯＭ−４２００ＮＴ、固形分濃度５５．０％、（株）クラレ製）を２３．６部用いる以外は実施例１８と同様にして接着剤を調製した（固形分３４．８％：ＰＶＡ１とＶＡＥとクレーの固形分重量比は１００：１００：２００）。これを用い、前記の方法に従い、保存安定性および初期接着性を評価した。結果を表４に示す。Example 19
Instead of the methyl methacrylate / n-butyl acrylate copolymer (ACR) emulsion of Example 18, an ethylene-vinyl acetate copolymer (VAE) emulsion (OM-4200NT, solid content concentration 55.0%, (stock) The adhesive was prepared in the same manner as in Example 18 except that 23.6 parts of Kuraray) were used (solid content 34.8%: solid content weight ratio of PVA1, VAE and clay was 100: 100: 200). Using this, storage stability and initial adhesiveness were evaluated according to the method described above. The results are shown in Table 4.
実施例２０
実施例１８のメタクリル酸メチル／アクリル酸ｎ−ブチル共重合体（ＡＣＲ）エマルジョンに代えて、スチレン−ブタジエン共重合体（ＳＢＲ）エマルジョン（ナルスターＳＲ−１０７、固形分濃度４８．０％、日本エイアンドエル（株）製）を２７．１部用いる以外は実施例１９と同様にして接着剤を調製した（固形分３４．０％：ＰＶＡ１とＳＢＲとクレーの固形分重量比は１００：１００：２００）。これを用い、前記の方法に従い、保存安定性および初期接着性を評価した。結果を表４に示す。Example 20
Instead of the methyl methacrylate / n-butyl acrylate copolymer (ACR) emulsion of Example 18, a styrene-butadiene copolymer (SBR) emulsion (Nalstar SR-107, solid concentration 48.0%, Nippon A & L Co., Ltd.) An adhesive was prepared in the same manner as in Example 19 except that 27.1 parts (made by Co., Ltd.) were used (solid content 34.0%: solid content weight ratio of PVA1, SBR, and clay was 100: 100: 200). . Using this, storage stability and initial adhesiveness were evaluated according to the method described above. The results are shown in Table 4.
実施例において示されているように、本発明の水性接着剤は、初期接着性が高く、高速生産が可能であり、しかも保存安定性（粘度安定性、沈降安定性）に優れるため、段ボール、紙袋、紙箱、紙管、壁紙等の製造時又は使用時などに用いる紙用接着剤、木材同士、木材と繊維、木材と紙、木材とプラスチックスを接着する木工用接着剤として好適に使用される。また、布や不職布などの繊維、コンクリートなどのセメント成形物、各種プラスチックス、アルミ箔等を被着材とする用途にも使用でき、工業的な利用価値が極めて高い。 As shown in the examples, the water-based adhesive of the present invention has high initial adhesiveness, enables high-speed production, and is excellent in storage stability (viscosity stability, sedimentation stability). It is suitably used as an adhesive for paper used in the manufacture or use of paper bags, paper boxes, paper tubes, wallpaper, etc., as an adhesive for woodwork that bonds wood to each other, wood and fiber, wood and paper, wood and plastics. The In addition, it can be used for applications where fibers such as cloth and unemployed cloth, cement moldings such as concrete, various plastics, aluminum foil, and the like are used as the adherend, and the industrial utility value is extremely high.
Claims (6)
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| JP2011507055A JP5501345B2 (en) | 2009-03-31 | 2010-02-23 | Water-based adhesive |
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| PCT/JP2010/052783 WO2010113565A1 (en) | 2009-03-31 | 2010-02-23 | Aqueous adhesive |
| JP2011507055A JP5501345B2 (en) | 2009-03-31 | 2010-02-23 | Water-based adhesive |
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| JPWO2010113565A1 JPWO2010113565A1 (en) | 2012-10-04 |
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| CN111500223A (en) * | 2020-06-03 | 2020-08-07 | 浙江金科胶粘制品有限公司 | Glue and preparation process thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59155408A (en) * | 1983-02-22 | 1984-09-04 | Nippon Synthetic Chem Ind Co Ltd:The | Production of modified polyvinyl alcohol |
| JP2001019720A (en) * | 1999-07-09 | 2001-01-23 | Kuraray Co Ltd | Vinyl alcohol based polymer |
| JP2002173655A (en) * | 2000-12-05 | 2002-06-21 | Nippon Synthetic Chem Ind Co Ltd:The | Water-soluble or water-dispersible hot-melt adhesive, adhesive sheet by using the same and method for producing the sheet |
| JP4514836B2 (en) * | 2008-08-27 | 2010-07-28 | 株式会社クラレ | Vinyl alcohol polymer and film containing the same |
-
2010
- 2010-02-23 WO PCT/JP2010/052783 patent/WO2010113565A1/en active Application Filing
- 2010-02-23 JP JP2011507055A patent/JP5501345B2/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59155408A (en) * | 1983-02-22 | 1984-09-04 | Nippon Synthetic Chem Ind Co Ltd:The | Production of modified polyvinyl alcohol |
| JP2001019720A (en) * | 1999-07-09 | 2001-01-23 | Kuraray Co Ltd | Vinyl alcohol based polymer |
| JP2002173655A (en) * | 2000-12-05 | 2002-06-21 | Nippon Synthetic Chem Ind Co Ltd:The | Water-soluble or water-dispersible hot-melt adhesive, adhesive sheet by using the same and method for producing the sheet |
| JP4514836B2 (en) * | 2008-08-27 | 2010-07-28 | 株式会社クラレ | Vinyl alcohol polymer and film containing the same |
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| WO2010113565A1 (en) | 2010-10-07 |
| JPWO2010113565A1 (en) | 2012-10-04 |
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