JP2005213373A - Copolymer latex for aqueous vinylurethane adhesive - Google Patents
Copolymer latex for aqueous vinylurethane adhesive Download PDFInfo
- Publication number
- JP2005213373A JP2005213373A JP2004022009A JP2004022009A JP2005213373A JP 2005213373 A JP2005213373 A JP 2005213373A JP 2004022009 A JP2004022009 A JP 2004022009A JP 2004022009 A JP2004022009 A JP 2004022009A JP 2005213373 A JP2005213373 A JP 2005213373A
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- JP
- Japan
- Prior art keywords
- adhesive
- weight
- meth
- copolymer
- copolymer latex
- 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.)
- Pending
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- 239000000853 adhesive Substances 0.000 title claims abstract description 113
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 111
- 229920001577 copolymer Polymers 0.000 title claims abstract description 68
- 229920000126 latex Polymers 0.000 title claims abstract description 58
- 239000004816 latex Substances 0.000 title claims abstract description 58
- HNPDNOZNULJJDL-UHFFFAOYSA-N ethyl n-ethenylcarbamate Chemical compound CCOC(=O)NC=C HNPDNOZNULJJDL-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 59
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 42
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 150000001993 dienes Chemical class 0.000 claims abstract description 6
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 6
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 30
- 239000000203 mixture Substances 0.000 abstract description 22
- 239000002023 wood Substances 0.000 abstract description 18
- 239000012948 isocyanate Substances 0.000 abstract description 14
- 238000009472 formulation Methods 0.000 abstract description 8
- 150000002513 isocyanates Chemical class 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 description 42
- 239000002585 base Substances 0.000 description 35
- -1 isocyanate compound Chemical class 0.000 description 26
- 238000006116 polymerization reaction Methods 0.000 description 23
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 229920002451 polyvinyl alcohol Polymers 0.000 description 15
- 239000003513 alkali Substances 0.000 description 14
- 239000002245 particle Substances 0.000 description 14
- 238000009835 boiling Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000003995 emulsifying agent Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920002472 Starch Polymers 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000012986 chain transfer agent Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 238000007127 saponification reaction Methods 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 229920006174 synthetic rubber latex Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920003169 water-soluble polymer Polymers 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical class [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 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
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 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
- 238000012545 processing Methods 0.000 description 2
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- 229920001187 thermosetting polymer Polymers 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
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- HDTRYLNUVZCQOY-UHFFFAOYSA-N α-D-glucopyranosyl-α-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(O)C(O)C(CO)O1 HDTRYLNUVZCQOY-UHFFFAOYSA-N 0.000 description 1
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N 1,5-Pentadiol Natural products OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- SLBOQBILGNEPEB-UHFFFAOYSA-N 1-chloroprop-2-enylbenzene Chemical compound C=CC(Cl)C1=CC=CC=C1 SLBOQBILGNEPEB-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- 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 1
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-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
- 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
- GYHZLNKMZPYTFB-UHFFFAOYSA-N 2-(oxiran-2-yl)acetamide Chemical compound NC(=O)CC1CO1 GYHZLNKMZPYTFB-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 1
- OWHSTLLOZWTNTQ-UHFFFAOYSA-N 2-ethylhexyl 2-sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS OWHSTLLOZWTNTQ-UHFFFAOYSA-N 0.000 description 1
- UYXQLQUXXCIFQM-UHFFFAOYSA-N 2-hydroxy-1,3,2$l^{5}-dioxaphospholane 2-oxide Chemical compound OP1(=O)OCCO1 UYXQLQUXXCIFQM-UHFFFAOYSA-N 0.000 description 1
- RYRDKOIZZRUCMC-UHFFFAOYSA-N 2-hydroxy-4-methyl-1,3,2$l^{5}-dioxaphospholane 2-oxide Chemical compound CC1COP(O)(=O)O1 RYRDKOIZZRUCMC-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- GQTFHSAAODFMHB-UHFFFAOYSA-N 2-prop-2-enoyloxyethanesulfonic acid Chemical compound OS(=O)(=O)CCOC(=O)C=C GQTFHSAAODFMHB-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical group C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- IGLWCQMNTGCUBB-UHFFFAOYSA-N 3-methylidenepent-1-ene Chemical compound CCC(=C)C=C IGLWCQMNTGCUBB-UHFFFAOYSA-N 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
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は特に木材の接着に好適に使用でき、接着剤の可使時間（いわゆる、接着剤のポットライフ）が長いとともに、低温環境での初期接着強さ及び高いアルカリ性の配合における接着剤の安定性に優れる水性高分子イソシアネ−ト系接着剤（いわゆる、水性ビニルウレタン接着剤）用共重合体ラテックスに関する。 The present invention can be suitably used particularly for bonding wood, has a long adhesive use time (so-called adhesive pot life), and has an initial adhesive strength in a low temperature environment and stability of the adhesive in a high alkaline formulation. The present invention relates to a copolymer latex for an aqueous polymer isocyanate adhesive (so-called aqueous vinyl urethane adhesive) having excellent properties.
従来、木材の接着剤には尿素系樹脂、メラミン系樹脂、フェノ−ル系樹脂及びレゾルシノ−ル系樹脂などのホルムアルデヒト縮合型の熱硬化樹脂が主に使用されてきた。一方、約２５年程前にホルムアルデヒトをほとんど含まなく、常温で比較的短時間の圧締で高い常態接着強さと耐水接着強さを有する合成ゴムラテックス，無機充填材、ポリビニルアルコ−ル及びイソシアネ−ト系化合物からなる水性ビニルウレタン接着剤が集成材用に使用され始めた（例えば、特許文献１〜４および非特許文献１参照。）。現在では、この水性ビニルウレタン接着剤は特に集成材分野においてホルムアルデヒド縮合型樹脂に代わって大量に使用されている。また、最近では家屋、特に屋内に用いられるホルムアルデヒド縮合型樹脂から放散されるホルムアルデヒドが、いわゆるシックハウスの原因物質として挙げられており、この意味でもホルムアルデヒドを含まない水性ビニルウレタン接着剤が改めて注目されている。 Conventionally, formaldehyde condensation type thermosetting resins such as urea resins, melamine resins, phenol resins, and resorcinol resins have been mainly used for wood adhesives. On the other hand, synthetic rubber latex, inorganic filler, polyvinyl alcohol, and isocyanate, which contain almost no formaldehyde about 25 years ago and have high normal adhesion strength and water-resistant adhesion strength with a relatively short pressing time at room temperature. Aqueous vinyl urethane adhesives made of a To-based compound have begun to be used for laminated materials (see, for example, Patent Documents 1 to 4 and Non-Patent Document 1). At present, this water-based vinyl urethane adhesive is used in large quantities in place of formaldehyde condensation type resin, particularly in the field of laminated wood. Recently, formaldehyde released from formaldehyde condensation resins used in houses, especially indoors, has been cited as a causative substance for so-called sick houses. In this sense, water-based vinyl urethane adhesives that do not contain formaldehyde have attracted attention again. Yes.
水性ビニルウレタン接着剤に用いられる共重合体ラテックス（いわゆる、合成樹脂ラテックス）としては合成ゴムラテックスの他、アクリル酸エステル系共重合体ラテックス、エチレン−酢酸ビニル系共重合体ラテックスなども使用されている。ここで、水性ビニルウレタン接着剤に用いられる合成ゴムラテックスとしては種々報告されている。例えば、スチレン−ブタジエン共重合体（以下、ＳＢ共重合体）ラテックスにカルボキシル基、水酸基、アミド基、アミノ基、スルホン酸基などの官能基を付与することで、接着強度の経時変化の安定性に優れるものなどが開示されている（例えば、特許文献３参照。）。
ここで、水性ビニルウレタン接着剤とは、官能基を有する共重合体ラテックス、炭酸カルシウムなどの無機充填材、ポリビニルアルコール等からなる水溶性高分子からなる主剤水溶液（ベースコンパウンド）に、各種官能基含有化合物と極めて反応し易いイソシアネ−ト系化合物を硬化剤として配合された接着剤である。
As copolymer latex (so-called synthetic resin latex) used for aqueous vinyl urethane adhesives, in addition to synthetic rubber latex, acrylic ester copolymer latex, ethylene-vinyl acetate copolymer latex, etc. are also used. Yes. Here, various types of synthetic rubber latex used in the aqueous vinyl urethane adhesive have been reported. For example, by adding functional groups such as carboxyl group, hydroxyl group, amide group, amino group, and sulfonic acid group to styrene-butadiene copolymer (hereinafter referred to as SB copolymer) latex, the stability of adhesive strength over time is improved. (For example, refer to Patent Document 3).
Here, the aqueous vinyl urethane adhesive refers to a copolymer latex having a functional group, an inorganic filler such as calcium carbonate, and an aqueous main agent solution (base compound) composed of a water-soluble polymer composed of polyvinyl alcohol or the like. An adhesive compounded with an isocyanate compound that is extremely reactive with the contained compound as a curing agent.
接着剤を使用する木材加工業者では、使用直前にこのベースコンパウンドに硬化剤を配合し、硬化反応の終了する接着剤の可使時間（いわゆる、接着剤のポットライフ）の間に加工を行うのが通例である。
硬化剤の配合の後、このイソシアネ−ト基の硬化反応が急激に進むことによって、接着剤塗布後の未乾燥状態での接着強さ（いわゆる、常温初期接着強さ）や接着剤塗布乾燥後の加工木材の耐水性（いわゆる、煮沸繰り返し強さ）がえられる。その反面、接着剤を配合した後、保存中の接着剤系内で複雑な硬化反応が常温で進行する。この結果、接着剤の粘度が急激に増加するため、接着剤のポットライフが短いといった操業上の不便さも有している。この接着剤のポットライフは共重合体ラテックスの性質や硬化剤の量によってある程度調整が可能である。
A wood processor that uses an adhesive mixes the base compound with a hardener just before use and processes it during the pot life (so-called adhesive pot life) when the curing reaction ends. Is customary.
After the curing agent is blended, the curing reaction of this isocyanate group proceeds rapidly, so that the adhesive strength in an undried state after applying the adhesive (so-called normal temperature initial adhesive strength) and after the adhesive coating is dried The water resistance of the processed wood (so-called boiling repeated strength) can be obtained. On the other hand, after blending the adhesive, a complex curing reaction proceeds at room temperature in the adhesive system being stored. As a result, since the viscosity of the adhesive increases rapidly, there is an inconvenience in operation such that the pot life of the adhesive is short. The pot life of this adhesive can be adjusted to some extent by the nature of the copolymer latex and the amount of curing agent.
この点に関しては、例えば、共重合体ラテックスの粒子径を大きくすることで、硬化剤の添加後における可使時間を改良したＳＢ共重合体ラテックスなどが開示されている（例えば、特許文献４参照。）。
しかし、このような手法では、接着剤の基本的な性能である、常温初期接着強さや煮沸繰り返し強さは逆に低下するといった欠点については解決していない。このことは、硬化反応の進行を遅らせることでポットライフの改良を行っていることに起因すると考えられている。
With regard to this point, for example, SB copolymer latex and the like in which the usable time after addition of the curing agent is improved by increasing the particle size of the copolymer latex has been disclosed (see, for example, Patent Document 4). .)
However, such a technique does not solve the disadvantage that the basic performance of the adhesive, that is, the normal-temperature initial adhesive strength and the repeated boiling strength are decreased. This is considered to be caused by improving the pot life by delaying the progress of the curing reaction.
さらに、最近になり、木材加工製品の生産効率化の要望が高まりから、生産スピ−ドのアップが強く求められている。このため、木材加工場の接着工程における接着剤の常温初期接着強さの向上必要とされている。常温初期接着強さの向上により、木材加工品の圧締保持の時間が短縮されるためである。特に、寒冷地における冬場の接着工程においては、硬化反応が室温に大きく左右されるため、低温時の初期接着強さ（低温初期接着強さ）が充分得らず、操業時間の短縮が図れないという問題があった。接着剤に使用される共重合体ラテックスはこれらの性質に深く係わっている。よって、非常に困難ではあるが、接着剤のポットライフ、塗料安定性に優れると同時に高度の煮沸繰り返し強さ及び初期接着強さを与える共重合体ラテックスの開発が当業界にとって必要となっている。 Furthermore, recently, a demand for increasing the production efficiency of processed wood products has been increasing, and thus an increase in production speed has been strongly demanded. For this reason, it is necessary to improve the normal temperature initial adhesive strength of the adhesive in the bonding process of the wood processing plant. This is because the time required for pressing and holding the processed wood product is shortened due to the improvement in the initial strength at normal temperature. In particular, in the winter bonding process in cold regions, the curing reaction depends greatly on the room temperature, so the initial bonding strength at low temperatures (low temperature initial bonding strength) cannot be obtained sufficiently, and the operation time cannot be shortened. There was a problem. The copolymer latex used in the adhesive is closely related to these properties. Therefore, it is very difficult to develop a copolymer latex that has excellent pot life and coating stability of the adhesive, and at the same time provides a high boiling repetition strength and initial adhesive strength. .
一方、硬化剤配合前の主剤（いわゆるベースコンパウンド）は、主に、接着剤業者によって加工、生産され、ベースコンパウンドの形態で木材加工業者などへ流通する。このため、ベースコンパウンドには、流通と保存に耐えられる長期の安定性が求められる。安定性の不足するベースコンパウンドを用いた場合、ベースコンパウンドのゲル化や充填材の沈降が発生する。特に無機充填材の使用の多い場合はベースコンパウンドが高いアルカリ性（例えばｐＨ９以上）を有する場合が多い。この高いアルカリ性におけるベースコンパウンドの安定性は、木材加工業における操業上、接着剤の重要な性能である。しかし、共重合体ラテックスは金属塩溶液に対する安定性が乏しいことから、これまで充分な高いアルカリ性での接着剤の安定性を有するベースコンパウンドは得られていなかった。このことは共重合体ラテックスの機械的、化学的な安定性がその表面の電気二重層によって構成される点に起因する。 On the other hand, a main agent (so-called base compound) before blending a curing agent is mainly processed and produced by an adhesive agent and distributed to a wood processor or the like in the form of a base compound. For this reason, the base compound is required to have long-term stability that can withstand distribution and storage. When a base compound with insufficient stability is used, gelation of the base compound or sedimentation of the filler occurs. In particular, when the inorganic filler is frequently used, the base compound often has high alkalinity (for example, pH 9 or more). The stability of the base compound at this high alkalinity is an important performance of the adhesive for operation in the wood processing industry. However, since the copolymer latex has poor stability with respect to the metal salt solution, a base compound having a sufficiently high alkaline adhesive stability has not been obtained so far. This is due to the fact that the mechanical and chemical stability of the copolymer latex is constituted by the electric double layer on the surface.
これまで、上記の課題を解決するために種々の共重合体ラテックスが開示されている。例えば、新規なポリビニルアルコールを用いた共重合体ラテックスを用いる水性ビニルウレタン接着剤（例えば、特許文献５参照。）、新規な乳化剤を用いて乳化重合した共重合体ラテックスを用いる水性ビニルウレタン接着剤（例えば、特許文献６参照。）、あるいは、水酸基含有エチレン系不飽和単量体を用いて乳化重合した水性ビニルウレタン接着剤用共重合体ラテックス（例えば、特許文献７参照。）が公開されている。しかしながら、上記の公知の発明では、業界の要望に充分答えるほど、優れた接着剤のポットライフ、煮沸繰り返し強さ及び初期接着強さを併せもつ性能が接着剤に付与されていない。 So far, various copolymer latexes have been disclosed in order to solve the above problems. For example, an aqueous vinyl urethane adhesive using a copolymer latex using a novel polyvinyl alcohol (for example, see Patent Document 5), and an aqueous vinyl urethane adhesive using a copolymer latex emulsion-polymerized using a novel emulsifier. (For example, refer patent document 6.) Or copolymer latex for water-based vinyl urethane adhesives (for example, refer patent document 7) which carried out the emulsion polymerization using the hydroxyl-containing ethylenically unsaturated monomer was published. Yes. However, in the above-mentioned known invention, the performance having the pot life, the boiling repeated strength and the initial adhesive strength of the adhesive is not given to the adhesive enough to meet the demands of the industry.
特に低温環境での初期接着強さ及び高いアルカリ性の配合におけるベースコンパウンドの安定性にかかる課題に関しては十分な解決策は開示されていないのが現状である。
本発明は特に木材の接着に好適に使用でき、接着剤の可使時間が長いとともに、低温環境での初期接着強さ及び高いアルカリ性の配合における接着剤の安定性に優れる水性高分子イソシアネ−ト系接着剤用共重合体ラテックス提供することを目的とする。 INDUSTRIAL APPLICABILITY The present invention is an aqueous polymer isocyanate that can be suitably used particularly for bonding wood, has a long usable life of the adhesive, and has excellent initial adhesive strength in a low temperature environment and adhesive stability in a high alkaline formulation. It is an object of the present invention to provide a copolymer latex for a base adhesive.
本発明者は、前記課題を解決するため、接着剤の可使時間が長いとともに、低温環境での初期接着強さ及び高いアルカリ性の配合における接着剤の安定性に優れる水性高分子イソシアネ−ト系接着剤用共重合体ラテックスを得るべく、これらの性能に及ぼすラテックスの共重合体組成、粒子径などの因子について鋭意検討した。この結果、特定の官能基をもつ単量体で変性された、特定組成の共重合体ラテックスで、かつ共重合体のゲル含有率が特定の高い範囲にあるものが意外にも接着剤の可使時間が長いとともに、低温環境での初期接着強さ及び高いアルカリ性の配合における接着剤の安定性に優れ、同時に接着剤のポットライフに優れるとともに高い初期接着強さ及び煮沸繰り返し強さを有することを見出し本発明をなすに至った。 In order to solve the above problems, the present inventor has an aqueous polymer isocyanate system in which the usable time of the adhesive is long and the initial adhesive strength in a low-temperature environment and the stability of the adhesive in a high alkaline composition are excellent. In order to obtain a copolymer latex for adhesives, factors such as the copolymer composition and particle size of the latex that affect these performances were studied earnestly. As a result, a copolymer latex modified with a monomer having a specific functional group and having a gel content of the copolymer in a specific high range is unexpectedly usable as an adhesive. Long working time, excellent initial adhesive strength in low temperature environment and excellent adhesive stability in high alkaline formulation, at the same time excellent in pot life of adhesive and high initial adhesive strength and repeated boiling strength And have led to the present invention.
すなわち、本発明は、下記の水性ビニルウレタン接着剤用共重合体ラテックスである。
Ａ：脂肪族共役ジエン系単量体（ａ）２０〜６０重量％、（メタ）アクリル酸アルキル単量体（ｂ）１５〜７０重量％、水酸基含有エチレン系不飽和単量体（ｃ）２〜１５重量％及びこれらと共重合可能な他の単量体（ｄ）５〜４０重量％（但し（ａ）から（ｄ）の合計１００重量％）を乳化重合させて得られる共重合体であって、Ｂ：共重合体のトルエン不溶分が８５重量％以上であることを特徴とする水性ビニルウレタン接着剤用共重合体ラテックス。
That is, this invention is the following copolymer latex for aqueous vinyl urethane adhesives.
A: Aliphatic conjugated diene monomer (a) 20 to 60% by weight, alkyl (meth) acrylate monomer (b) 15 to 70% by weight, hydroxyl group-containing ethylenically unsaturated monomer (c) 2 A copolymer obtained by emulsion polymerization of -15 wt% and other monomers (d) 5-40 wt% (total 100 wt% of (a) to (d)) copolymerizable therewith B: A copolymer latex for an aqueous vinyl urethane adhesive, wherein the toluene-insoluble content of the copolymer is 85% by weight or more.
本発明は特に木材の接着に好適に使用でき、接着剤の可使時間が長いとともに、低温環境での初期接着強さ及び高いアルカリ性の配合における接着剤の安定性に優れる水性高分子イソシアネ−ト系接着剤用共重合体ラテックス提供する。 INDUSTRIAL APPLICABILITY The present invention is an aqueous polymer isocyanate that can be suitably used particularly for bonding wood, has a long usable life of the adhesive, and has excellent initial adhesive strength in a low temperature environment and adhesive stability in a high alkaline formulation. Copolymer latex for adhesives is provided.
本発明について、以下具体的に説明する。
水性ビニルウレタン接着剤に用いる本発明の共重合体ラテックスは、脂肪族共役ジエン系単量体、（メタ）アクリル酸アルキル単量体、水酸基含有エチレン系不飽和単量体及びこれらと共重合可能な他の単量体を合成することによって得られる。
共役ジエン系単量体（ａ）としては、例えば１、３−ブタジエン、イソプレン、２，３−ジメチル−１，３−ブタジエン、２−エチル−１、３−ブタジエン、２−メチル−１，３−ブタジエン、１，３−ペンタジエン、クロロプレン、２−クロロ−１，３−ブタジエン、シクロブタジエンなどを挙げることができ、これらを単独で、又は２種以上組み合わせて使用できる。これらの中でも１、３−ブタジエンが好適に使用できる。共役ジエン系単量体の使用割合は２０〜６０重量％である。２０重量％以上では高アルカリでのベースコンパウンドの安定性が良好であり、６０重量％を以下においては低温初期接着強さが良好である。また３０〜４０重量％の範囲では低温初期接着強度が強く特に良好である。
The present invention will be specifically described below.
The copolymer latex of the present invention used for an aqueous vinyl urethane adhesive can be copolymerized with an aliphatic conjugated diene monomer, an alkyl (meth) acrylate monomer, a hydroxyl group-containing ethylenically unsaturated monomer, and these. It is obtained by synthesizing other monomers.
Examples of the conjugated diene monomer (a) include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, and 2-methyl-1,3. -Butadiene, 1,3-pentadiene, chloroprene, 2-chloro-1,3-butadiene, cyclobutadiene and the like can be mentioned, and these can be used alone or in combination of two or more. Among these, 1,3-butadiene can be preferably used. The proportion of the conjugated diene monomer used is 20 to 60% by weight. If it is 20% by weight or more, the stability of the base compound at high alkali is good, and if it is 60% by weight or less, the low-temperature initial adhesive strength is good. In the range of 30 to 40% by weight, the low-temperature initial adhesive strength is strong and particularly good.
本発明で用いられる（メタ）アクリル酸アルキル単量体（ｂ）は（メタ）アクリル酸の一級アルコールエステルの構造からなる単量体である。（メタ）アクリル酸アルキル単量体（ｂ）としては、例えばメチル（メタ）アクリレ−ト、エチル（メタ）アクリレ−ト、プロピル（メタ）アクリレ−ト、ｎ−ブチル（メタ）アクリレ−ト、ｔ−ブチル（メタ）アクリレ−ト、イソブチル（メタ）アクリレ−ト、ｎ−アミル（メタ）アクリレ−ト、イソアミルヘキシル（メタ）アクリレ−ト、オクチル（メタ）アクリレ−ト、ノニル（メタ）アクリレ−ト、デシル（メタ）アクリレ−ト、ドデシル（メタ）アクリレ−ト、オクタデシル（メタ）アクリレ−ト、シクロヘキシル（メタ）アクリレ−ト、フェニル（メタ）アクリレ−ト、ベンジル（メタ）アクリレ−ト、２−エルヘキシル（メタ）アクリレ−ト、アリル（メタ）アクリレ−などを挙げることができ、これらを単独に、又は２種以上を組み合わせて用いることができる。 The alkyl (meth) acrylate monomer (b) used in the present invention is a monomer having a primary alcohol ester structure of (meth) acrylic acid. Examples of the (meth) acrylic acid alkyl monomer (b) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, n-amyl (meth) acrylate, isoamylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate -Decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate , 2-erhexyl (meth) acrylate, allyl (meth) acrylate, etc., and these may be used alone or in combination of two or more. It can be used in combination.
これらの中でもメチルメタアクリレ−トが好適に使用できる。（メタ）アクリル酸アルキル単量体の使用割合は１５〜７０重量％である。１５重量％以上では高アルカリでのベースコンパウンドの安定性が良好であり、７０重量％を以下においては低温初期接着強さが良好である。また４０〜６０重量％の範囲では低温初期接着強度が強く特に良好である。 Among these, methyl methacrylate is preferably used. The proportion of the alkyl (meth) acrylate monomer used is 15 to 70% by weight. If it is 15% by weight or more, the stability of the base compound at high alkali is good, and if it is 70% by weight or less, the low-temperature initial adhesive strength is good. In the range of 40 to 60% by weight, the low-temperature initial adhesive strength is strong and particularly good.
本発明で用いられる水酸基含有エチレン系不飽和単量体（ｃ）は水酸基と不飽和単量体を有する単量体である。水酸基含有エチレン系不飽和単量体（ｃ）としては例えば、（メタ）アクリル酸の多価アルコールエステル、アリルアルコ−ル、多価アルコ−ルのモノアリルエ−テルなどを挙げることができる。（メタ）アクリル酸の多価アルコールエステルとしては、例えばヒドロキシエチルアクリレ−ト、ヒドロキシメチルアクリレ−ト、ヒドロキシエチルメタクリレ−ト、ヒドロキシプロピルアクリレ−ト、ヒドロキシプロピルメタクリレ−ト、エチレングリコ−ルジ（メタ）アクリレ−ト、１、３−ブチレングリコ−ルジ（メタ）アクリレ−ト、１，４−ブチレングリコ−ルジ（メタ）アクリレ−ト、プロピレングリコ−ルジ（メタ）アクリレ−ト、１，５−ペンタジオ−ルジ（メタ）アクリレ−ト、ネオペンチルグリコ−ルジ（メタ）アクリレ−ト、１，６−ヘキサンジオ−ルジ（メタ）アクリレ−ト、ジエチレングリコ−ルジ（メタ）アクリレ−ト、ポリエチレングリコ−ルジ（メタ）アクリレ−ト、ポリプロピレングリコ−ルジ（メタ）アクリレ−トなどを挙げることができる。その使用量は２〜１５重量％である。２重量％以上では高アルカリでのベースコンパウンドの安定性が良好であり、１５重量％を以下においては低温初期接着強さが良好である。また５〜１０重量％の範囲では低温初期接着強度が強く特に良好である。 The hydroxyl group-containing ethylenically unsaturated monomer (c) used in the present invention is a monomer having a hydroxyl group and an unsaturated monomer. Examples of the hydroxyl group-containing ethylenically unsaturated monomer (c) include (meth) acrylic acid polyhydric alcohol ester, allyl alcohol, polyhydric alcohol monoallyl ether, and the like. Examples of polyhydric alcohol esters of (meth) acrylic acid include hydroxyethyl acrylate, hydroxymethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, ethylene Glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate 1,5-pentadiol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate , Polyethylene glycol (meth) acrylate, polypropylene glycol (meth) Kurire - door, and the like. The amount used is 2 to 15% by weight. If it is 2% by weight or more, the stability of the base compound at high alkali is good, and if it is 15% by weight or less, the low-temperature initial adhesive strength is good. In the range of 5 to 10% by weight, the low-temperature initial adhesive strength is strong and particularly good.
これらと共重合可能な他の単量体（ｄ）としては、芳香族ビニル化合物、シアン化ビニル系単量体、エチレン系不飽和カルボン酸、（メタ）アクリルアミド系単量体、その他の単量体などを挙げることができる。
芳香族ビニル化合物としては、単量体としては、例えばスチレン、α−メチルスチレン、ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、エチルスチレン、ビニルキシレン、ブロモスチレン、ビニルベンジルクロリド、ｐ−ｔ−ブチルスチレン、クロロスチレン、アルキルスチレン、ジビニルベンゼン、トリビニルベンゼンなどを挙げることができ、これらを単独に、又は２種以上を組み合わせて用いることができる。
Other monomers (d) copolymerizable with these include aromatic vinyl compounds, vinyl cyanide monomers, ethylenically unsaturated carboxylic acids, (meth) acrylamide monomers, and other single monomers. The body can be mentioned.
Examples of the aromatic vinyl compound include monomers such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, ethylstyrene, vinylxylene, bromostyrene, vinylbenzyl chloride, p. -T-butyl styrene, chlorostyrene, alkyl styrene, divinylbenzene, trivinylbenzene, etc. can be mentioned, These can be used individually or in combination of 2 or more types.
シアン化ビニル系単量体としては、例えばアクリロニトリル、メタクリロニトリル、α−クロルアクリロニトリルなどを挙げることができ、これらを単独に、又は２種以上組み合わせて用いることができる。
エチレン系不飽和カルボン酸単量体としてはアクリル酸、メタクリル酸、イタコン酸、フマル酸、マレイン酸などを挙げることができ、これらを単独に、又は２種以上組み合わせて用いることができる。
Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and the like, and these can be used alone or in combination of two or more.
Examples of the ethylenically unsaturated carboxylic acid monomer include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid and the like, and these can be used alone or in combination of two or more.
（メタ）アクリルアミド系単量体としては、例えば（メタ）アクリルアミド、Ｎ−メチロ−ル（メタ）アクリルアミドやＮ−メチル（メタ）アクリルアミドなどのＮ−モノアルキル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミドなどのＮ，Ｎジアルキル（メタ）アクリルアミド、グリシジルメタアクリルアミド、Ｎ−アルコキシ（メタ）アクリルアミド、２−アクリルアミド−２−メチルプロパンスルホン酸などをあげることができ、これらを単独に、又は２種以上組み合わせて用いることができる。 Examples of the (meth) acrylamide monomer include N-monoalkyl (meth) acrylamide such as (meth) acrylamide, N-methylol (meth) acrylamide and N-methyl (meth) acrylamide, and N, N-dimethyl. N, N dialkyl (meth) acrylamide such as (meth) acrylamide, glycidylmethacrylamide, N-alkoxy (meth) acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and the like can be mentioned, and these can be used alone or Two or more types can be used in combination.
その他の単量体としては、例えばトグリシジル（メタ）アクリレ−ト、ペンタエリスリト−ルトリ（メタ）アクリレ−ト、トリメチロ−ルプロパントリ（メタ）アクリレ−ト、テトラメチロ−ルメタンテトラ（メタ）アクリレ−ト、ビス（４−アクリロキシポリエトキシフェニル）プロパン、フェノキシエチル（メタ）アクリレ−ト、２，２−ビス［４−（（メタ）アクリロキシエトキシ）フェニル］プロパン、２，２−ビス［４−（（メタ）アクリロキシ・ジエトキシ）フェニル］プロパン、２，２−ビス［４−（（メタ）アクリロキシ・ポリエトキシ）フェニル］プロパン、イソボルニル（メタ）アクリレ−トアミノエチル（メタ）アクリレ−トやジメチルアミノエチル（メタ）アクリレ−ト及び２−ビニルピリジンなどのアミノ基含有エチレン性単量体、酢酸ビニルなどのカルボン酸ビニルエステル類、塩化ビニルや塩化ビニリデンなどのハロゲン化ビニル、スチレンスルホン酸塩や２−（メタ）アクリロイルオキシエチルスルホン酸及び（メタ）アリルスルホン酸塩などのスルホン酸基含有単量体、燐酸エチレン（メタ）アクリレ−トや燐酸プロピレン（メタ）アクリレ−ト及び２−（メタ）アクリロイルオキシエチルアシッドホスフェ−トなどの燐酸基含有単量体などを挙げることができ、これらを単独に、又は２種以上を組み合わせて用いることができる。 Examples of other monomers include toglycidyl (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, Bis (4-acryloxypolyethoxyphenyl) propane, phenoxyethyl (meth) acrylate, 2,2-bis [4-((meth) acryloxyethoxy) phenyl] propane, 2,2-bis [4- ( (Meth) acryloxy-diethoxy) phenyl] propane, 2,2-bis [4-((meth) acryloxy-polyethoxy) phenyl] propane, isobornyl (meth) acrylate aminoethyl (meth) acrylate and dimethylaminoethyl (meth) ) Contains amino groups such as acrylate and 2-vinylpyridine Tylene monomers, vinyl esters such as vinyl acetate, vinyl halides such as vinyl chloride and vinylidene chloride, styrene sulfonate, 2- (meth) acryloyloxyethyl sulfonate, and (meth) allyl sulfonate Sulfonic acid group-containing monomers such as phosphoric acid group-containing monomers such as ethylene phosphate (meth) acrylate, propylene phosphate (meth) acrylate, and 2- (meth) acryloyloxyethyl acid phosphate These can be used alone or in combination of two or more.
その他の単量体の使用量は５〜４０重量％である。４０重量％以下では高アルカリでのベースコンパウンドの安定性が良好である。また５〜１５重量％の範囲では低温初期接着強度が強く特に良好である。
本願発明の共重合体ラテックスは水性媒体中で単量体、連鎖移動剤などを乳化剤、ラジカル重合開始剤，及び必要に応じてその他の添加剤成分を用いて重合する従来公知の乳化重合方法によって得られる。
The amount of other monomers used is 5 to 40% by weight. If it is 40% by weight or less, the stability of the base compound at high alkali is good. In the range of 5 to 15% by weight, the low-temperature initial adhesive strength is strong and particularly good.
The copolymer latex of the present invention is obtained by a conventionally known emulsion polymerization method in which a monomer, a chain transfer agent and the like are polymerized using an emulsifier, a radical polymerization initiator, and other additive components as necessary in an aqueous medium. can get.
連鎖移動剤としては、例えばα−メチルスチレンダイマ−などの核置換α−メチルスチレンの二量体、ｎ−ブチルメルカプタン、ｎ−オクチルメルカプタン， ｎ−ラウリルメルカプタン、ｎ−ドデシルメルカプタン及びｔ−ドデシルメルカプタンなどのメルカプタン類、テトラメチルチウラムジスルフィド及びテトラエチルチウラムジスルフィドなどのジスルフィド類、２−エチルヘキシルチオグリコレ−ト、タ−ピノ−レン、シクロペンテン、シクロヘキセンなどの公知の全てのものを単独、又は２種以上組み合わせて用いることができる。 Examples of chain transfer agents include dimers of nucleus-substituted α-methylstyrene such as α-methylstyrene dimer, n-butyl mercaptan, n-octyl mercaptan, n-lauryl mercaptan, n-dodecyl mercaptan and t-dodecyl mercaptan. All known ones such as mercaptans such as disulfides such as tetramethylthiuram disulfide and tetraethylthiuram disulfide, 2-ethylhexylthioglycolate, terpinolene, cyclopentene, cyclohexene, or two or more They can be used in combination.
乳化剤としては、例えば脂肪族石鹸、ロジン酸石鹸、アルキルスルホン酸塩、ジアルキルアリ−ルスルホン酸塩、アルキルスルホコハク酸塩、ポリオキシエチレンアルキル硫酸塩及びポリオキシエチレンアルキルアリ−ル硫酸塩などのアニオン性乳化剤、ポリオキシエチレンアルキルエ−テル、ポリオキシエチレンアルキルアリ−ルエ−テル及びポリオキシエチレンオキシプロピレンブロックコポリマ−などのノニオン性乳化剤など公知のものを単独、あるいは２種以上組み合わせて用いることができる。又これらの他に親水基と親油基を有する界面活性剤の化学構造式の中にエチレン性二重結合を導入した反応性乳化剤も好適に使用でき、更に、ベタイン型などの両性乳化剤及びポリビニルアルコ−ル、変性ポリビニルアルコ−ル（末端にメルカプト基を有するものなど）、カルボキシメチルセルロ−ス、メチルセルロ−ス、ポリビニルピロリドンなどの水溶性高分子の保護コロイド乳化剤なども必要に応じて用いることができる。 Examples of the emulsifier include anionic properties such as aliphatic soap, rosin acid soap, alkyl sulfonate, dialkyl aryl sulfonate, alkyl sulfosuccinate, polyoxyethylene alkyl sulfate and polyoxyethylene alkyl aryl sulfate. Known nonionic emulsifiers such as emulsifiers, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers and polyoxyethylene oxypropylene block copolymers can be used alone or in combination of two or more. . In addition to these, reactive emulsifiers in which an ethylenic double bond is introduced into the chemical structural formula of a surfactant having a hydrophilic group and a lipophilic group can also be suitably used. Further, amphoteric emulsifiers such as betaine type and polyvinyl Protective colloid emulsifiers for water-soluble polymers such as alcohol, modified polyvinyl alcohol (such as those having a mercapto group at the end), carboxymethyl cellulose, methyl cellulose, polyvinyl pyrrolidone, etc. should be used as necessary. Can do.
ラジカル重合開始剤は、熱又は還元性物質の存在下ラジカル分解して単量体の付加重合を開始させるものであり、無機系開始剤及び有機系開始剤のいずれも使用できる。このようなものとしては、例えば水溶性及び油溶性のペルオキソ二硫酸塩、過酸化物、アゾビス化合物などで、具体的にはペルオキソ二硫酸カリウム、ペルオキソ二硫酸ナトリウム、ペルオキソ二硫酸アンモニウム、過酸化水素、ｔ−ブチルヒドロペルオキシド、過酸化ベンゾイル、２，２−アゾビスブチロニトリル、クメンハイドロパ−オキサイドを挙げることができ、又他に、ＰＯＬＹＭＥＲ ＨＡＮＤＢＯＯＫ（３ｒｄ．ｅｄｉｔｉｏｎ）、Ｊ．Ｂｒａｎｄｒｕｐ及びＥ．Ｈ．Ｉｍｍｅｒｇｕｔ著、Ｊｏｈｎ Ｗｉｌｌｙ＆Ｓｏｎｓ刊（１９８９）に記載されている化合物も用いることができる。又、酸性亜硫酸ナトリウム、アスコルビン酸やその塩、エリソルビン酸やその塩、ロンガリットなどの還元剤を重合開始剤に組み合わせて用いる、いわゆるレドックス重合法を採用することもできる。この重合開始剤の使用量は全単量体の重量に基づき、通常０．１〜５．０重量％、好ましくは０．２〜３．０重量％使用する。 The radical polymerization initiator is one that initiates addition polymerization of a monomer by radical decomposition in the presence of heat or a reducing substance, and both inorganic and organic initiators can be used. Examples of such compounds include water-soluble and oil-soluble peroxodisulfates, peroxides, azobis compounds, specifically potassium peroxodisulfate, sodium peroxodisulfate, ammonium peroxodisulfate, hydrogen peroxide, Mention may be made of t-butyl hydroperoxide, benzoyl peroxide, 2,2-azobisbutyronitrile, cumene hydroperoxide, and in addition, POLYMER HANDBOOK (3rd. edition), J. Org. Brandrup and E.I. H. The compounds described by Immersutt, published by John Willy & Sons (1989) can also be used. In addition, a so-called redox polymerization method in which a reducing agent such as acidic sodium sulfite, ascorbic acid or a salt thereof, erythorbic acid or a salt thereof or Rongalite is used in combination with a polymerization initiator may be employed. The amount of the polymerization initiator used is usually 0.1 to 5.0% by weight, preferably 0.2 to 3.0% by weight, based on the weight of all monomers.
本発明の共重合体ラテックスを重合する際、重合中及び重合後に、必要に応じて各種調整剤を添加することができる。例えば、ｐＨ調整剤として水酸化カリウム、水酸化ナトリウム、水酸化アンモニウム、炭酸水素ナトリウム、炭酸ナトリウム、リン酸水素二ナトリウムなどを添加することができる。又、エチレンジアミン四酢酸ナトリウムなどの各種キレ−ト剤なども重合調整剤として添加することができる。
本発明の共重合体ラテックスを乳化重合で得る際の重合温度は通常５〜１２０℃であり、工業的な生産効率等から４０〜１００℃が好適である。
本発明の共重合体ラテックスは一段重合以外に多段重合でも製造することができ、単量体混合物の重合系への添加は一括添加法、連続的にあるいは断続的に添加する方法、これらの方法を組み合わせた方法（例えば、単量体混合物の一部添加した後に重合の進行に従って連続的もしくは断続的に添加する方法）などいずれでも良い。
When the copolymer latex of the present invention is polymerized, various regulators can be added as necessary during and after the polymerization. For example, potassium hydroxide, sodium hydroxide, ammonium hydroxide, sodium hydrogen carbonate, sodium carbonate, disodium hydrogen phosphate and the like can be added as a pH adjuster. In addition, various chelating agents such as sodium ethylenediaminetetraacetate can also be added as a polymerization regulator.
The polymerization temperature for obtaining the copolymer latex of the present invention by emulsion polymerization is usually 5 to 120 ° C., and 40 to 100 ° C. is preferable from the viewpoint of industrial production efficiency.
The copolymer latex of the present invention can be produced by multistage polymerization in addition to single-stage polymerization, and the addition of the monomer mixture to the polymerization system is a batch addition method, a method of adding continuously or intermittently, these methods (For example, a method in which a monomer mixture is partially added and then added continuously or intermittently as the polymerization progresses).
また、重合にあたってシ−ド重合方法もとることができる。シ−ド用ラテックスの組成は特に限定されず、共重合体ラテックスの組成と同じであっても異なってもよく、シ−ド用ラテックスも同一反応容器で製造したもの、異なる他の反応容器で製造したものを用いてもよい。
乳化重合における単量体の重合転化率工業的生産性から、通常６０％以上、好ましくは８０％以上であることが好ましい。
本発明の共重合体は、その共重合組成が極めて特定であることに加えて共重合体の架橋割合の目安となるトルエン不溶分が８５重量％以上有することが必要である。トルエン不溶分が８５重量％以上の場合、高アルカリでのベースコンパウンドの安定性が良好であり、低温初期接着強さが良好である。この場合、初期接着強度、煮沸繰り返し強度も良好であり好ましい。また９０〜９９重量％の範囲では低温初期接着強度が強く特に良好である。
In addition, a seed polymerization method can be used for the polymerization. The composition of the seed latex is not particularly limited, and may be the same as or different from the composition of the copolymer latex. The seed latex may be produced in the same reaction vessel or in another different reaction vessel. You may use what was manufactured.
The polymerization conversion rate of the monomer in the emulsion polymerization is preferably 60% or more, preferably 80% or more, from the industrial productivity.
The copolymer of the present invention needs to have a toluene insoluble content of 85% by weight or more, which is a measure of the crosslinking ratio of the copolymer, in addition to the very specific copolymer composition. When the toluene insoluble content is 85% by weight or more, the stability of the base compound at high alkali is good and the low-temperature initial adhesive strength is good. In this case, the initial adhesive strength and the repeated boiling strength are also preferable. In the range of 90 to 99% by weight, the low-temperature initial adhesive strength is strong and particularly good.
共重合体のトルエン不溶分は用いる単量体組成、重合処方、重合条件などによってコントロ−ルすることもできるが、連鎖移動剤量によってより容易にコントロ−ルすることができ、連鎖移動剤を増量することによりトルエン不溶分は減少する。
本発明の共重合体ラテックスの平均粒子径は、約１００〜６００ｎｍが好ましい。粒子径が大きいとポットライフが長く、操業性が良好となる。しかし、粒子の沈降に対する安定性から粒子径は６００ｎｍ以下が好ましい。
本発明の共重合体は、重合後にスチームストリッピング法による水蒸気蒸留によって未反応単量体の除去を行って調整される。ラテックス中のスチレン残留量が０．０５重量％（５０ｐｐｍ）以下の場合、木材加工品等での臭気発生の面で好ましい。
The toluene-insoluble content of the copolymer can be controlled depending on the monomer composition used, polymerization formulation, polymerization conditions, etc., but can be controlled more easily depending on the amount of chain transfer agent. Increasing the amount reduces the insoluble content of toluene.
The average particle diameter of the copolymer latex of the present invention is preferably about 100 to 600 nm. When the particle size is large, the pot life is long and the operability is good. However, the particle diameter is preferably 600 nm or less from the viewpoint of the stability against particle sedimentation.
The copolymer of the present invention is prepared by removing unreacted monomers by steam distillation by a steam stripping method after polymerization. When the residual amount of styrene in the latex is 0.05% by weight (50 ppm) or less, it is preferable in terms of odor generation in processed wood products.
ラテックスの固形分及びｐＨについては、４０〜６５重量％の範囲の固形分、４．０〜１２．０の範囲のｐＨが好ましい。
水性ビニルウレタン接着剤は、本発明の共重合体ラテックスにビニルアルコ−ル系重合体及び充填剤などを配合してベ−スコンパウンドを作成し、これに架橋剤としてイソシアネ−ト化合物を加えることによって得られる。
ビニルアルコ−ル系重合体は、部分ケン化ポリビニルアルコ−ル、完全ケン化ポリビニルアルコ−ル、ポリビニルアルコ−ルの誘導体、酢酸ビニルなどのビニルエステル系単量体とエチレン系不飽和単量体を共重合し、それをケン化したもの（スルホン酸変性、カルボキシ変性、シラノ−ル基変性、アセトアセチル化変性ポリビニルアルコ−ルなど）やチオ−ル酢酸などのチオ−ル化合物の存在下でビニルエステル系単量体を共重合し、それをケン化したものなどの変性ポリビニルアルコ−ルなどを用いることができる。これらのビニルアルコ−ル系重合体の重合度、ケン化度は特に限定されるものではないが、３００〜３０００の重合度、７５モル％以上のケン化度のものが好ましい。
Regarding the solid content and pH of the latex, a solid content in the range of 40 to 65% by weight and a pH in the range of 4.0 to 12.0 are preferred.
An aqueous vinyl urethane adhesive is prepared by adding a base compound by blending a vinyl alcohol polymer and a filler with the copolymer latex of the present invention, and adding an isocyanate compound as a crosslinking agent thereto. can get.
The vinyl alcohol polymer comprises a partially saponified polyvinyl alcohol, a fully saponified polyvinyl alcohol, a derivative of polyvinyl alcohol, a vinyl ester monomer such as vinyl acetate, and an ethylenically unsaturated monomer. Vinyl in the presence of thiol compounds such as saponification (such as sulfonic acid modification, carboxy modification, silanol group modification, acetoacetylation modified polyvinyl alcohol) and saponified saponification Modified polyvinyl alcohols such as those obtained by copolymerizing ester monomers and saponifying them can be used. The polymerization degree and saponification degree of these vinyl alcohol polymers are not particularly limited, but those having a polymerization degree of 300 to 3000 and a saponification degree of 75 mol% or more are preferred.
ビニルアルコ−ル系重合体の使用割合は、本発明の共重合体ラテックス１００重量部（固形分）に対して５〜２００重量部が好ましい。５重量部以上では接着強度が良好であり、また、２００重量部以下の場合は接着剤作成直後の粘度が良好であり、ポットライフも長くなるため好ましい。
イソシアネ−ト化合物は、イソシアネ−ト基を分子中に２個以上有する化合物又は重合物であれば良く、例えばトリレンジイソシアネ−ト及びその水素化物、トリフェニルメタントリイソシアネ−ト、トリメチロ−ルプロパン−トリレンジイソシアネ−トアダクト、ジフェニルメタンジイソシアネ−ト（ＭＤＩ、クル−ドＭＤＩ含む）及びその水素化物、ヘキサメチレンジイソシアネ−ト、キシレンジイソシアネ−ト、イソホロンジイソシアネ−ト、４、４’−ジシクロヘキシルメタンジイソシアネ−トなどを挙げることができ、これらに高沸点溶剤などを配合したものも使用できる。また、ポリエステルなどのポリオ−ルに上記イソシアネ−ト系化合物を過剰に混合したもの、ポリオ−ルと過剰のポリイソシアネ−トで予めポリマ−化したＯＨ基末端プレポリマ−、過剰のポリオ−ルで予めポリマ−化したＯＨ基末端プレポリマ−にポリイソシアネ−ト化合物を過剰に加えたもの、ノニオン界面活性剤を含有するポリイソシアネ−トなども使用できる。
The use ratio of the vinyl alcohol polymer is preferably 5 to 200 parts by weight with respect to 100 parts by weight (solid content) of the copolymer latex of the present invention. If it is 5 parts by weight or more, the adhesive strength is good, and if it is 200 parts by weight or less, the viscosity immediately after the preparation of the adhesive is good, and the pot life is also long.
The isocyanate compound may be a compound or polymer having two or more isocyanate groups in the molecule. For example, tolylene diisocyanate and its hydride, triphenylmethane triisocyanate, trimethylo- Rupropane-tolylene diisocyanate adduct, diphenylmethane diisocyanate (including MDI and crushed MDI) and hydrides thereof, hexamethylene diisocyanate, xylene diisocyanate, isophorone diisocyanate 4,4'-dicyclohexylmethane diisocyanate and the like, and those containing a high boiling point solvent or the like can also be used. In addition, the above isocyanate compound is excessively mixed with a polyol such as polyester, an OH group-terminated prepolymer previously polymerized with a polyol and an excess polyisocyanate, and an excess polyol in advance. A polymerized OH group-terminated prepolymer obtained by adding an excessive amount of a polyisocyanate compound, a polyisocyanate containing a nonionic surfactant, or the like can also be used.
イソシアネ−ト化合物の使用割合は、本発明の共重合体ラテックス１００重量部（固形分）に対して１０〜５００重量部の範囲が好ましい。１０重量部以上では煮沸接着強さや初期接着力が良好であり好ましい、５００重量部以下ではポットライフが良好であり好ましい。
充填剤としては炭酸カルシウム、クレ−、カオリン、タルク、水酸化アルミニウム、やし殻紛、木紛などの無機及び有機の充填剤を挙げることができる。
充填剤は、接着剤製造と常態接着強さの点から、本発明の共重合体ラテックス１００重量部（固形分）に対して１０〜５００重量部の範囲で使用することが好ましい。
The use ratio of the isocyanate compound is preferably in the range of 10 to 500 parts by weight with respect to 100 parts by weight (solid content) of the copolymer latex of the present invention. When it is 10 parts by weight or more, boiling adhesive strength and initial adhesive force are good and preferable, and when it is 500 parts by weight or less, pot life is good and preferable.
Examples of the filler include inorganic and organic fillers such as calcium carbonate, clay, kaolin, talc, aluminum hydroxide, coconut powder and wood powder.
The filler is preferably used in the range of 10 to 500 parts by weight with respect to 100 parts by weight (solid content) of the copolymer latex of the present invention from the viewpoint of adhesive production and normal adhesive strength.
本発明の共重合体ラテックスを用いた水性ビニルウレタン接着剤には、ビニルアルコ−ル系重合体、イソシアネート化合物、充填剤以外に小麦粉、澱粉類（小麦、馬鈴薯、米、タピオカなどの澱粉及びエステル化澱粉、エ−テル化澱粉、カチオン澱粉などの澱粉誘導体並びに酸化澱粉、デキストリンなど）、脱脂大豆紛、血紛などの増量剤、塩化カルシウムや塩化マグネシウムなどの潮解性化合物、ホウ酸、ホウ酸塩、硫酸アルミニウム、明礬、ホウ酸クロムなどの反応促進剤、エチレングリコ−ルやプロピレングリコ−ルなどの凍結防止剤、ポリエチレンオキサイド・プロピレンオキサイドの共重合体やポリエチレンオキサイド・アルキルフェノ−ルエ−テル及びポリエチレンオキサイド・アルキルエ−テルなどのノニオン界面活性剤、各種アニオン性界面活性剤、グルコ−ス、トレハロ−スなどの糖類、多糖類及びカルボキシメチルセルロ−ス、メチルセルロ−ス、ヒドロキシエチルセルロ−スなどのセルロ−ス誘導体並びに無水マレイン酸−イソブテン共重合体、無水マレイン酸−スチレン共重合体、無水マレイン酸−メチルビニルエ−テル共重合体、アルギン酸ソ−ダ、ポリアクリル酸ソ−ダなどの水溶性高分子保水剤、尿素−ホルマリン樹脂、尿素−メラミン樹脂、フェノ−ル−ホルマリン樹脂などの熱硬化性樹脂、ロジン及びロジンエステル系、テルペンフェノ−ル樹脂やテルペン重合体などの粘着付与剤、各種防腐剤などを必要に応じて添加することができる。 The aqueous vinyl urethane adhesive using the copolymer latex of the present invention includes, in addition to vinyl alcohol polymers, isocyanate compounds and fillers, flours and starches (starches such as wheat, potato, rice, tapioca, and esterification). Starch, etherified starch, starch derivatives such as cationic starch, oxidized starch, dextrin, etc.), defatted soybean powder, blood powder, etc., deliquescent compounds such as calcium chloride and magnesium chloride, boric acid, borate , Reaction accelerators such as aluminum sulfate, alum and chromium borate, antifreezing agents such as ethylene glycol and propylene glycol, polyethylene oxide / propylene oxide copolymers and polyethylene oxide / alkylphenol ether and Nonionic surfactants such as polyethylene oxide and alkyl ether, each Anionic surfactants, sugars such as glucose and trehalose, polysaccharides and cellulose derivatives such as carboxymethyl cellulose, methyl cellulose and hydroxyethyl cellulose, and maleic anhydride-isobutene copolymer , Maleic anhydride-styrene copolymer, maleic anhydride-methyl vinyl ether copolymer, water-soluble polymer water retention agent such as sodium alginate, polyacrylic acid soda, urea-formalin resin, urea-melamine resin Thermosetting resins such as phenol-formalin resin, rosin and rosin ester series, tackifiers such as terpene phenol resin and terpene polymer, various preservatives and the like can be added as necessary.
本発明の共重合体ラテックスを用いた水性ビニルウレタン接着剤は、集成材、合板、ＬＶＬ、パ−ティクルボ−ド、家具など木材の接着に好適に使用できるが、木質材と紙、繊維製品類、無機質板、フィルムなどとの接着にも使用できる。接着剤の濃度、塗布量は用途によって適宜調整する必要があるが、通常３５〜７０重量％の濃度（固形分）、５０〜５００ｇ／m２の塗布量である。
本発明の共重合体ラテックスを用いた水性ビニルウレタン接着剤は、ハケ、ロ−ルコ−タ−、スプレ−、カ−テンコ−タ−などで被着材に塗布し、堆積、圧締、乾燥（熱プレスなど）することによって接着製品を得ることができる。圧締及び乾燥の温度は常温から高温（約２００℃）まで任意に選択できるが、通常常温で、60分以内の圧締でも十分接着する。
次に実施例および比較例によって本発明を説明する。
The water-based vinyl urethane adhesive using the copolymer latex of the present invention can be suitably used for bonding wood such as laminated wood, plywood, LVL, particle board, furniture, etc. It can also be used for bonding to inorganic plates and films. Although it is necessary to adjust the density | concentration of an adhesive agent and an application quantity suitably by a use, it is a 35-70 weight% density | concentration (solid content), and the application quantity of 50-500 g / m < 2 > normally.
The aqueous vinyl urethane adhesive using the copolymer latex of the present invention is applied to an adherend with a brush, a roll coater, a spray, a curtain coater, etc., and deposited, pressed, and dried. An adhesive product can be obtained by (such as hot pressing). The temperature of pressing and drying can be arbitrarily selected from room temperature to high temperature (about 200 ° C.), but it usually adheres well even at pressing at room temperature within 60 minutes.
Next, the present invention will be described with reference to examples and comparative examples.
ラテックスの粒子径及びトルエン不溶分の測定、残留スチレン量、水性ビニルウレタン接着剤の調整並びにポットライフ、ベースコンパウンドの安定性、高アルカリでのベースコンパウンドの安定性、常温初期接着強さ、低温初期接着強さ、常態接着強さ、煮沸繰り返し接着強さの測定は以下の方法に従った。
（１）粒子径
ブラウン運動している微粒子に光を当て、粒子から戻ってくる光（後方散乱光）の振動数（光の周波数）の変化量から、微粒子の粒子径を求める方法で体積平均粒子径（ｎｍ）を測定した。測定装置はマイクロトラックＵＰＡ１５０（日機装株式会社）を用いた。
Measurement of latex particle size and toluene insoluble content, adjustment of residual styrene content, aqueous vinyl urethane adhesive, pot life, stability of base compound, stability of base compound at high alkali, normal temperature initial adhesive strength, low temperature initial The following methods were used to measure the bond strength, normal bond strength, and boiling repeated bond strength.
(1) Particle size Volume average by applying the light to the Brownian moving fine particles and determining the particle size of the fine particles from the amount of change in the frequency (light frequency) of the light returning from the particles (backscattered light). The particle diameter (nm) was measured. Microtrack UPA150 (Nikkiso Co., Ltd.) was used as a measuring device.
（２）トルエン不溶分（重量％）
テフロン（登録商標）シ−ト上で５０％に調整したラテックスサンプル約１ｇを１３０℃で３０分乾燥する。乾燥したサンプルを約０．５ｇ精秤し、３０ｍｌのトルエンが入った容器に入れ、振とう器で３時間振とうする。振とう後のトルエン分散液を３２５メッシュのステンレス金網で濾過し、濾過残さ量を１３０℃で１時間乾燥して測定する。トルエン不溶分は乾燥サンプル重量に対する濾過残さ乾燥重量の割合（重量％）から求めた。
(2) Toluene insoluble matter (wt%)
About 1 g of a latex sample adjusted to 50% on a Teflon sheet is dried at 130 ° C. for 30 minutes. About 0.5 g of the dried sample is precisely weighed, placed in a container containing 30 ml of toluene, and shaken with a shaker for 3 hours. The toluene dispersion after shaking is filtered through a 325 mesh stainless steel wire mesh, and the amount of filtration residue is measured by drying at 130 ° C. for 1 hour. The toluene insoluble content was determined from the ratio (% by weight) of the dry weight of the filtration residue to the dry sample weight.
（３）スチレン量の測定
ラテックス１０ｇをイソオクタン２０ｇ、メタノール５ｇ中に混ぜ、６０分しんとう後、上澄み液をとりガスクロマトグラフィー（島津GC14A、ガラスカラム）で測定し、ラテックス実液（固形分５０％水分散体）中のスチレン量（ｐｐｍ）を測定した。
測定値（重量標準）の校正はスチレンの１ｐｐｍ、５０ｐｐｍ、２００ｐｐｍ、４００ｐｐｍ、１０００ｐｐｍの標準液（イソオクタン８０重量％、メタノール２０重量％混合溶媒使用）の測定値から求めた。
(3) Measurement of styrene content 10 g of latex was mixed in 20 g of isooctane and 5 g of methanol. After 60 minutes of stirring, the supernatant was taken and measured by gas chromatography (Shimadzu GC14A, glass column), and the actual latex (solid content 50%). The amount of styrene (ppm) in the aqueous dispersion was measured.
Calibration of the measured value (weight standard) was determined from the measured value of a standard solution of styrene of 1 ppm, 50 ppm, 200 ppm, 400 ppm, and 1000 ppm (using a mixed solvent of 80% by weight of isooctane and 20% by weight of methanol).
（４）水性ビニルウレタン接着剤の調整
１５重量％濃度に調整したポリビニルアルコ−ル（株式会社クラレ製、ポバ−ル２１７）水溶液４０重量部、分散剤（ヘキサメタリン酸ソ−ダ）０．１重量部、水６重量部、炭酸カルシウム（日東紛化株式会社製、ＮＳ１００）２１重量部及び共重合体ラテックス（固形分濃度５０重量％）３３重量部を混合撹拌し、ベ−スコンパウンドを作成した。次いで、このベ−スコンパウンドに架橋剤としてジフェニルメタン−４、４’−ジイソシアネ−ト系化合物を１５重量部配合し、撹拌して、水性ビニルウレタン接着剤を作成した。
(4) Preparation of aqueous vinyl urethane adhesive 40 parts by weight of aqueous solution of polyvinyl alcohol (Kuraray Co., Ltd., Poval 217) adjusted to a concentration of 15% by weight, dispersant (hexametaphosphate soda) 0.1 A base compound is prepared by mixing and stirring parts by weight, 6 parts by weight of water, 21 parts by weight of calcium carbonate (manufactured by NS did. Next, 15 parts by weight of diphenylmethane-4,4′-diisocyanate compound as a crosslinking agent was blended with this base compound and stirred to prepare an aqueous vinyl urethane adhesive.
（５）ポットライフ
上記（４）で作成した水性ビニルウレタン接着剤の作成直後の粘度及び２５℃で６０分放置後の粘度をＢＨ型粘度計で測定し、作成直後の粘度に対して６０分放置後の粘度の比が低い程ポットライフが良好と判定した。
なお判定基準は×（３倍以上）、△（２倍以上〜３倍未満）、○（２倍未満）で判定した。
(5) Pot life Viscosity immediately after preparation of the aqueous vinyl urethane adhesive prepared in the above (4) and viscosity after standing at 25 ° C. for 60 minutes were measured with a BH viscometer, and 60 minutes with respect to the viscosity immediately after preparation. The pot life was judged to be better as the viscosity ratio after standing was lower.
Judgment criteria were x (3 times or more), Δ (2 times to less than 3 times), and ○ (less than 2 times).
（６）ベースコンパウンドの安定性
上記（４）で作成したベースコンパウンドを２５％苛性ソーダ水溶液を用いてｐＨ７に調整し作成直後の粘度及び２５℃で７日間放置後の粘度をＢＨ型粘度計で測定し、作成直後の粘度に対して７日間放置後の粘度の比が低い程塗料安定性が良好と判定した。
なお判定基準は×（３倍以上）、△（２倍以上〜３倍未満）、○（２倍未満）で判定した。
(6) Stability of base compound The base compound prepared in (4) above was adjusted to pH 7 using a 25% aqueous solution of caustic soda, and the viscosity immediately after preparation and after standing for 7 days at 25 ° C was measured with a BH viscometer. The lower the ratio of the viscosity after standing for 7 days to the viscosity immediately after preparation, the better the paint stability.
Judgment criteria were x (3 times or more), Δ (2 times to less than 3 times), and ○ (less than 2 times).
（７）高アルカリでのベースコンパウンドの安定性
上記（４）で作成したベースコンパウンドを２５％苛性ソーダ水溶液を用いてｐＨ１０に調整し、高アルカリ性のベースコンパウンドを作成した。作成直後の粘度及び２５℃で７日間放置後の粘度をＢＨ型粘度計で測定し、作成直後の粘度に対して７日間放置後の粘度の比が低い程、塗料アルカリ安定性が良好と判定した。
なお判定基準は×（３倍以上）、△（２倍以上〜３倍未満）、○（２倍未満）で判定した。
(7) Stability of base compound in high alkali The base compound prepared in (4) above was adjusted to pH 10 using a 25% aqueous sodium hydroxide solution to prepare a highly alkaline base compound. The viscosity immediately after preparation and the viscosity after standing for 7 days at 25 ° C. are measured with a BH viscometer, and the lower the ratio of the viscosity after standing for 7 days to the viscosity immediately after creation, the better the coating alkali stability is determined. did.
Judgment criteria were x (3 times or more), Δ (2 times to less than 3 times), and ○ (less than 2 times).
（８）常温初期接着強度
厚さ１１ｍｍ、縦２５ｍｍ、横３０ｍｍの大きさのカバ材サンプルの表面（２５ｍｍ×２５ｍｍ）に水性ビニルウレタン接着剤を塗布し、その上に同一のカバ材サンプルを重ね、圧締した。初期接着強さは２０℃で３０分圧締した後直ちにＪＩＳ Ｋ ６８５２に基づいて圧縮せん断強さを測定した。
塗布量：２５０ｇ／ｍ２
圧締条件：圧力０．１５ＭＰａ、時間３０分、温度２０℃
(8) Normal temperature initial adhesive strength A water-based vinyl urethane adhesive is applied to the surface (25 mm × 25 mm) of a cover material sample having a thickness of 11 mm, a length of 25 mm, and a width of 30 mm, and the same cover material sample is stacked thereon. Squeezed. The initial adhesive strength was measured by compressing shear strength according to JIS K 6852 immediately after pressing at 20 ° C. for 30 minutes.
Application amount: 250 g / m 2
Clamping conditions: pressure 0.15 MPa, time 30 minutes, temperature 20 ° C.
（９）低温初期接着強度
常温初期接着強さ測定試験（８）と同様に圧締したサンプルを５℃で３０分圧締した後直ちにＪＩＳ Ｋ ６８５２に基づいて圧縮せん断強さを測定した。
塗布量：２５０ｇ／ｍ２
圧締条件：圧力０．１５ＭＰａ、時間３０分、温度５℃
(9) Low-temperature initial adhesive strength A sample pressed in the same manner as the normal temperature initial adhesive strength measurement test (8) was pressed at 5 ° C. for 30 minutes, and immediately after that, compressive shear strength was measured based on JIS K 6852.
Application amount: 250 g / m 2
Clamping conditions: pressure 0.15 MPa, time 30 minutes, temperature 5 ° C.
（１０）常態接着強度
初期接着強さ測定試験（８）と同様に圧締したサンプルを２０℃、７日間養生した後ＪＩＳ Ｋ ６８５２に基づき圧縮せん断強さを測定した。
（１１）煮沸繰り返し接着強度
常態接着強さ（１０）の測定用に作成した接着したサンプルについてＪＩＳ Ｋ ６８５２の煮沸繰り返し試験に基づいて測定した。
(10) Normal bond strength After compressing the sample pressed in the same manner as in the initial bond strength measurement test (8) at 20 ° C. for 7 days, the compression shear strength was measured based on JIS K 6852.
(11) Repeated boiling adhesive strength The bonded sample prepared for measurement of normal state adhesive strength (10) was measured based on the repeated boiling test of JIS K 6852.
［実施例１］
撹拌装置と温度調節用ジャケットを備えた耐圧反応容器に、窒素置換後真空脱気した後イオン交換水７０部、平均粒子径約８６ｎｍを有するシ−ドラテックスの水分散体（固形分）２．０重量部、ラウリル硫酸ナトリウム０．１重量部、イタコン酸１．５重量部を入れ、内温を８５℃に昇温する。その後、１，３−ブタジエン３６重量部、メチルメタアクリレート５６重量部、ヒドロキシエチルメタクリレ−ト８重量部、αメチルスチレンダイマー０．０５、ｔ−ドデシルメルカプタン０．２重量部からなる単量体混合物を７時間かけてし込んだ。単量体混合物を添加し始めるとほぼ同時に、水１５重量部、ラウリル硫酸ナトリウム０．１重量部、水酸化ナトリウム０．２５重量部、ペルオキソ二硫酸カリウム１．０重量部からなる水溶液を８時間かけて添加した。添加終了後、反応系の温度を８５℃で約２時間維持し重合を終了した。単量体の重合添加率は９８重量％であった。次いで、水酸化ナトリウムを加えて反応系のｐＨを約６．０に調整し、スチ−ムストリッピングで残留単量体を除去し、加熱減圧濃縮し、冷却後、８０メッシュの濾布で濾過し、固形分濃度を５０重量％に調整して、実施例１の共重合体ラテックスを得た。この共重合ラテックスについて、平均粒子径を測定したところ、３２０ｎｍであった。又、この共重合体のトルエン不溶分は９０重量％であった。またスチレン量は０ｐｐｍであった。
[Example 1]
1. Water dispersion (solid content) of seed latex having 70 parts of ion-exchanged water and an average particle size of about 86 nm after vacuum deaeration after nitrogen substitution in a pressure-resistant reaction vessel equipped with a stirrer and a temperature control jacket 0 parts by weight, 0.1 parts by weight of sodium lauryl sulfate and 1.5 parts by weight of itaconic acid are added, and the internal temperature is raised to 85 ° C. Thereafter, a monomer comprising 36 parts by weight of 1,3-butadiene, 56 parts by weight of methyl methacrylate, 8 parts by weight of hydroxyethyl methacrylate, 0.05 of α-methylstyrene dimer, and 0.2 parts by weight of t-dodecyl mercaptan. The mixture was charged over 7 hours. Almost simultaneously with the start of addition of the monomer mixture, an aqueous solution comprising 15 parts by weight of water, 0.1 parts by weight of sodium lauryl sulfate, 0.25 parts by weight of sodium hydroxide, and 1.0 part by weight of potassium peroxodisulfate was added for 8 hours. Added over time. After completion of the addition, the temperature of the reaction system was maintained at 85 ° C. for about 2 hours to complete the polymerization. The polymerization addition rate of the monomer was 98% by weight. Next, sodium hydroxide is added to adjust the pH of the reaction system to about 6.0, residual monomer is removed by steam stripping, heating and concentration under reduced pressure, cooling, and filtration through an 80 mesh filter cloth. The copolymer latex of Example 1 was obtained by adjusting the solid content concentration to 50% by weight. The average particle diameter of this copolymer latex was measured and found to be 320 nm. Further, the toluene insoluble content of this copolymer was 90% by weight. The amount of styrene was 0 ppm.
この共重合体ラテックスを前述した配合処方で混合し、ベ−スコンパウンドを作成し、次いでイソシアネ−ト系化合物を前述の配合処方に基づいて加えて水性ビニルウレタン接着剤を得た。
得られた水性ビニルウレタン接着剤についてポットライフ、ベースコンパウンドの安定性、高アルカリでのベースコンパウンドの安定性、常温初期接着強さ、低温初期接着強さ、常態接着強さ、煮沸繰り返し接着強さを測定した。これらの結果を表１に示す。
This copolymer latex was mixed with the above-mentioned blending recipe to make a base compound, and then an isocyanate compound was added based on the above-mentioned blending recipe to obtain an aqueous vinyl urethane adhesive.
Pot life, stability of base compound, stability of base compound in high alkali, normal temperature initial bond strength, low temperature initial bond strength, normal bond strength, boiling repeated bond strength Was measured. These results are shown in Table 1.
［実施例２〜９］
表１の実施例２〜９に該当する単量体配合組成及び連鎖移動剤量を用いて実施例１と同様の重合処方及び重合条件で重合し、実施例２〜９の共重合体ラテックスを得た。得られたこれらの共重合体ラテックスについて実施例１と同様に行った測定結果を表１に示す。
[Examples 2 to 9]
Polymerization was performed under the same polymerization prescription and polymerization conditions as in Example 1 using the monomer composition and chain transfer agent amount corresponding to Examples 2 to 9 in Table 1, and the copolymer latex of Examples 2 to 9 was obtained. Obtained. Table 1 shows the measurement results of these copolymer latexes obtained in the same manner as in Example 1.
［比較例１〜１０］
表２の比較例１〜１０に該当する単量体配合組成及び連鎖移動剤量を用いて実施例１と同様の重合処方及び重合条件で重合し、比較例１〜１０の共重合体ラテックスを得た。得られたこれらの共重合体ラテックスについて実施例１と同様に行った測定結果を表２に示す。
以上の実施例及び比較例の結果（表１、表２）から、特定の単量体組成からなり、特定の高ゲル含有率を有する本発明の共重合体ラテックスを用いて作成した水性ビニルウレタン接着剤はポットライフに優れることに加えて高度の初期接着強さ及び煮沸繰り返し強さを有することがわかる。
[Comparative Examples 1 to 10]
Polymerization was performed under the same polymerization prescription and polymerization conditions as in Example 1 using the monomer blend composition and chain transfer agent amount corresponding to Comparative Examples 1 to 10 in Table 2, and the copolymer latex of Comparative Examples 1 to 10 was used. Obtained. Table 2 shows the measurement results of these copolymer latexes obtained in the same manner as in Example 1.
From the results of the above Examples and Comparative Examples (Tables 1 and 2), an aqueous vinyl urethane made of the copolymer latex of the present invention having a specific monomer composition and having a specific high gel content. It can be seen that the adhesive has a high initial adhesive strength and repeated boiling strength in addition to excellent pot life.
実施例１〜３および比較例１〜３の結果から１，３−ブタジエンが１８重量％を超えると高アルカリでのベースコンパウンドの安定性が良好であり、１，３−ブタジエンが６２重量％未満で低温初期接着強さが良好である。
実施例１、４〜５および比較例４〜５の結果からメチルメタアクリレートが１３重量％を超えると高アルカリでのベースコンパウンドの安定性が良好であり、メチルメタアクリレートが７２重量％未満で低温初期接着強さが良好である。
From the results of Examples 1 to 3 and Comparative Examples 1 to 3, when 1,3-butadiene exceeds 18% by weight, the stability of the base compound at high alkali is good, and 1,3-butadiene is less than 62% by weight. And low temperature initial adhesive strength is good.
From the results of Examples 1, 4 to 5 and Comparative Examples 4 to 5, when methyl methacrylate exceeds 13% by weight, the stability of the base compound at high alkali is good, and methyl methacrylate is less than 72% by weight and low temperature. Good initial bond strength.
実施例１、６〜７および比較例６〜７の結果から２−ヒドロキシエチルアクリレートが１重量％を超えると高アルカリでのベースコンパウンドの安定性が良好であり、２−ヒドロキシエチルアクリレートが１８重量％未満で低温初期接着強さが良好である。
実施例１、３〜４および比較例８〜９の結果からその他の共重合体が３重量％を超えると、低温初期接着強さが良好であり。４０重量％以下では高アルカリでのベースコンパウンドの安定性が良好であり、
実施例１、８〜９および比較例１０の結果からトルエン不溶分が８０重量％を超えると、高アルカリでのベースコンパウンドの安定性が良好であり、低温初期接着強さが良好である。
From the results of Examples 1 and 6 to 7 and Comparative Examples 6 to 7, when the amount of 2-hydroxyethyl acrylate exceeds 1% by weight, the stability of the base compound at high alkali is good, and the amount of 2-hydroxyethyl acrylate is 18%. Less than%, the low temperature initial adhesive strength is good.
From the results of Examples 1, 3 to 4 and Comparative Examples 8 to 9, when the other copolymer exceeds 3% by weight, the low-temperature initial adhesive strength is good. Below 40% by weight, the stability of the base compound at high alkali is good,
From the results of Examples 1, 8 to 9 and Comparative Example 10, when the toluene-insoluble content exceeds 80% by weight, the stability of the base compound at high alkali is good and the low-temperature initial adhesive strength is good.
本発明は特に木材の接着に好適に使用でき、接着剤の可使時間が長いとともに、低温環境での初期接着強さ及び高いアルカリ性の配合における接着剤の安定性に優れる水性高分子イソシアネ−ト系接着剤用共重合体ラテックスに関する。 INDUSTRIAL APPLICABILITY The present invention is an aqueous polymer isocyanate that can be suitably used particularly for bonding wood, has a long usable life of the adhesive, and has excellent initial adhesive strength in a low temperature environment and adhesive stability in a high alkaline formulation. The present invention relates to a copolymer latex for a system adhesive.
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Cited By (4)
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|---|---|---|---|---|
| JP2003082309A (en) * | 2001-09-10 | 2003-03-19 | Asahi Kasei Corp | Latex for aqueous vinylurethane adhesive |
| JP2015166429A (en) * | 2014-03-04 | 2015-09-24 | アイカ工業株式会社 | aqueous adhesive |
| JP2019077734A (en) * | 2017-10-19 | 2019-05-23 | 旭化成株式会社 | Copolymer latex and manufacturing method thereof |
| JP2020139055A (en) * | 2019-02-28 | 2020-09-03 | 旭化成株式会社 | Aqueous composition, coating film, and method for producing aqueous composition |
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| JP7280061B2 (en) | 2019-02-28 | 2023-05-23 | 旭化成株式会社 | Water-based composition, coating film, and method for producing water-based composition |
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