JPWO2012070311A1 - Adhesive composition and method for producing the same - Google Patents
Adhesive composition and method for producing the same Download PDFInfo
- Publication number
- JPWO2012070311A1 JPWO2012070311A1 JP2012545645A JP2012545645A JPWO2012070311A1 JP WO2012070311 A1 JPWO2012070311 A1 JP WO2012070311A1 JP 2012545645 A JP2012545645 A JP 2012545645A JP 2012545645 A JP2012545645 A JP 2012545645A JP WO2012070311 A1 JPWO2012070311 A1 JP WO2012070311A1
- Authority
- JP
- Japan
- Prior art keywords
- adhesive composition
- vinyl acetate
- monomer
- containing copolymerizable
- emulsion
- 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.)
- Granted
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 21
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 21
- 239000000203 mixture Substances 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- -1 acetoacetoxy group Chemical group 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 25
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 20
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000002148 esters Chemical class 0.000 claims abstract description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000000839 emulsion Substances 0.000 claims description 33
- 229920005989 resin Polymers 0.000 claims description 28
- 239000011347 resin Substances 0.000 claims description 28
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 claims description 12
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 11
- 239000000084 colloidal system Substances 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- ZGLJYJVYUYQOHR-UHFFFAOYSA-N 3-oxobutanoyl 4-hydroxy-2-methylidenebutanoate Chemical group CC(=O)CC(=O)OC(=O)C(=C)CCO ZGLJYJVYUYQOHR-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 26
- 238000006116 polymerization reaction Methods 0.000 abstract description 16
- 238000003860 storage Methods 0.000 abstract description 6
- 239000007787 solid Substances 0.000 description 16
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 238000009835 boiling Methods 0.000 description 6
- 239000011120 plywood Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- 238000007127 saponification reaction Methods 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229920001567 vinyl ester resin Polymers 0.000 description 3
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 2
- 101100425389 Arabidopsis thaliana TIFY9 gene Proteins 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- AUIWZRLALNEDGC-UHFFFAOYSA-N (2-methylprop-2-enoylamino)methyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCNC(=O)C(C)=C AUIWZRLALNEDGC-UHFFFAOYSA-N 0.000 description 1
- AOAGVPIEEAAAOL-RXSVEWSESA-N (2r)-2-[(1s)-1,2-dihydroxyethyl]-3,4-dihydroxy-2h-furan-5-one;hydrogen peroxide Chemical compound OO.OC[C@H](O)[C@H]1OC(=O)C(O)=C1O AOAGVPIEEAAAOL-RXSVEWSESA-N 0.000 description 1
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- AMWBYPRXSHDWCG-ZPYUXNTASA-N (e)-but-2-enoic acid;3-oxobutanoic acid Chemical compound C\C=C\C(O)=O.CC(=O)CC(O)=O AMWBYPRXSHDWCG-ZPYUXNTASA-N 0.000 description 1
- NFXPFTUEEYYFFS-UHFFFAOYSA-N (prop-2-enoylamino)methyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCNC(=O)C=C NFXPFTUEEYYFFS-UHFFFAOYSA-N 0.000 description 1
- NGZDFOYYIXAAPC-UHFFFAOYSA-N 1-prop-2-enoyloxypropan-2-yl 3-oxobutanoate Chemical compound C=CC(=O)OCC(C)OC(=O)CC(C)=O NGZDFOYYIXAAPC-UHFFFAOYSA-N 0.000 description 1
- LRRBNLHPFPHVCW-UHFFFAOYSA-N 2,3-dihydroxybutanedioic acid;hydrogen peroxide Chemical compound OO.OC(=O)C(O)C(O)C(O)=O LRRBNLHPFPHVCW-UHFFFAOYSA-N 0.000 description 1
- CRRYHGFIJXAGHN-UHFFFAOYSA-N 2-(2-methylprop-2-enoylamino)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCNC(=O)C(C)=C CRRYHGFIJXAGHN-UHFFFAOYSA-N 0.000 description 1
- CZVMDPUTEUXCPK-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 2-cyano-3-oxobutanoate Chemical compound CC(=O)C(C#N)C(=O)OCCOC(=O)C(C)=C CZVMDPUTEUXCPK-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical compound OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-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
- FHPDNLOSEWLERE-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCCOC(=O)C(C)=C FHPDNLOSEWLERE-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
- YKXAYLPDMSGWEV-UHFFFAOYSA-N 4-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCO YKXAYLPDMSGWEV-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- RRGHDTRMTBHQIX-UHFFFAOYSA-N C(C=C)(=O)N.C(CC(=O)C)(=O)O Chemical compound C(C=C)(=O)N.C(CC(=O)C)(=O)O RRGHDTRMTBHQIX-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229920002472 Starch Polymers 0.000 description 1
- 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 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 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
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 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
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 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
- 239000004927 clay Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- ZEYMDLYHRCTNEE-UHFFFAOYSA-N ethenyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OC=C ZEYMDLYHRCTNEE-UHFFFAOYSA-N 0.000 description 1
- CYKDLUMZOVATFT-UHFFFAOYSA-N ethenyl acetate;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(=O)OC=C CYKDLUMZOVATFT-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- AXLMPTNTPOWPLT-UHFFFAOYSA-N prop-2-enyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCC=C AXLMPTNTPOWPLT-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
-
- 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
- C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
- C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
- C08F261/04—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols on to polymers of vinyl alcohol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
- C09J131/00—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 acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
- C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C09J131/04—Homopolymers or copolymers of vinyl acetate
-
- 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
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- 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
- C09J2431/00—Presence of polyvinyl acetate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polymerisation Methods In General (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Graft Or Block Polymers (AREA)
Abstract
本発明の接着剤組成物は、エチレン変性ポリビニルアルコールの存在下で酢酸ビニル単量体を乳化重合して種粒子を形成した後、この種粒子にアセトアセトキシ基含有共重合性単量体を乳化重合して得られる。アセトアセトキシ基含有共重合性単量体としては、アルキレングリコールの(メタ)アクリル酸アセト酢酸エステルを使用することが好ましい。本発明の接着剤組成物は、優れた耐水性及び耐熱水性を有し、経時で着色することがなく、高温下における貯蔵安定性に優れる環境対応型のものである。In the adhesive composition of the present invention, after vinyl acetate monomer is emulsion-polymerized in the presence of ethylene-modified polyvinyl alcohol to form seed particles, an acetoacetoxy group-containing copolymerizable monomer is emulsified in the seed particles. Obtained by polymerization. As the acetoacetoxy group-containing copolymerizable monomer, (meth) acrylic acid acetoacetate ester of alkylene glycol is preferably used. The adhesive composition of the present invention has excellent water resistance and hot water resistance, does not color with time, and is environmentally friendly with excellent storage stability at high temperatures.
Description
本発明は、接着剤組成物、特に耐水性が要求される合板・木材用接着剤として有用な接着剤組成物及びその製造方法に関する。 The present invention relates to an adhesive composition, particularly an adhesive composition useful as an adhesive for plywood and wood, which requires water resistance, and a method for producing the same.
従来、ポリビニルアルコールを保護コロイドとする酢酸ビニル樹脂系エマルジョンは、その優れた接着力とロール適正等の良好な作業性やマイルドな臭気等、取り扱いの容易さなどにより、主として紙管や紙工用接着剤、木材用接着剤等に幅広く使用されている。しかしながら、酢酸ビニル樹脂系エマルジョンは樹脂自体が親水性である上に、その保護コロイドも水溶性であるため、耐水性が低いという欠点があった。そのため、酢酸ビニル樹脂系エマルジョンの耐水性を改良する目的で、種々の方法が検討されてきた。 Conventionally, a vinyl acetate resin emulsion using polyvinyl alcohol as a protective colloid is mainly used for paper tube and paper industry bonding due to its excellent adhesive strength and good workability such as roll suitability and mild odor. Widely used in adhesives and adhesives for wood. However, the vinyl acetate resin emulsion has the disadvantage that the water resistance is low because the resin itself is hydrophilic and the protective colloid is water-soluble. Therefore, various methods have been studied for the purpose of improving the water resistance of the vinyl acetate resin emulsion.
そこで、例えば、特許文献1には、炭素数4以下のα−オレフィンで変性されたポリビニルアルコールの存在下で酢酸ビニルとアクリル酸とを乳化重合して得られる酢酸ビニル−アクリル酸樹脂エマルジョンを主成分とする樹脂組成物が提案されている。また、特許文献2には、炭素数4以下のα−オレフィンで変性されたポリビニルアルコールの存在下で酢酸ビニル等の炭素数4以下の脂肪酸のビニルエステル系単量体とアクリル酸等のカルボキシル基含有エチレン性不飽和単量体とバーサチック酸ビニル等の炭素数5以上の脂肪酸のビニルエステル系単量体とを乳化重合して得られる水性エマルジョンに、アルミニウム化合物を添加した水性エマルジョン組成物が提案されている。
Thus, for example,
しかしながら、特許文献1の樹脂組成物は、耐水性及び耐熱水性が不十分であるという問題があった。また、特許文献2の水性エマルジョン組成物は、アルミニウム化合物の添加により耐水性は良好となるものの、高温下における貯蔵安定性が不十分であり、経時で着色するという問題があった。
However, the resin composition of
従って、本発明は、上記従来技術の課題を解決し、優れた耐水性及び耐熱水性を有し、経時で着色することがなく、高温下における貯蔵安定性に優れる環境対応型の接着剤組成物を提供することを目的とする。 Accordingly, the present invention solves the above-mentioned problems of the prior art, has an excellent water resistance and hot water resistance, does not color with time, and is excellent in storage stability at high temperatures. The purpose is to provide.
本発明者らは、上記課題を解決すべく検討を行った結果、次の樹脂組成物が上記課題を解決できることを見出し、本発明を完成させるに至った。
即ち、本発明は、保護コロイドとしてエチレン変性ポリビニルアルコールを用い、酢酸ビニル単量体とアセトアセトキシ基含有共重合性単量体とを乳化重合して得られた接着剤組成物である。As a result of investigations to solve the above problems, the present inventors have found that the following resin composition can solve the above problems, and have completed the present invention.
That is, the present invention is an adhesive composition obtained by emulsion polymerization of a vinyl acetate monomer and an acetoacetoxy group-containing copolymerizable monomer using ethylene-modified polyvinyl alcohol as a protective colloid.
本発明によれば、優れた耐水性及び耐熱水性を有し、経時で着色することがなく、高温下における貯蔵安定性に優れる環境対応型の接着剤組成物を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, it can provide the environment-friendly adhesive composition which has the outstanding water resistance and hot water resistance, does not color with time, and is excellent in the storage stability under high temperature.
本発明による接着剤組成物は、エチレン変性ポリビニルアルコールを保護コロイドとする酢酸ビニル単量体とアセトアセトキシ基含有共重合性単量体との共重合体エマルジョンを主成分とするものである。
本発明において使用されるアセトアセトキシ基含有共重合性単量体としては、アリルアセトアセテート、ビニルアセトアセテート、2−アセトアセトキシエチルアクリレート、2−アセトアセトキシエチルメタクリレート、2−アセトアセトキシプロピルアクリレート、2−アセトアセトキシプロピルメタクリレート、2−シアノアセトアセトキシエチルメタクリレート等のアルキレングリコールの(メタ)アクリル酸アセト酢酸エステル、2−アセトアセトキシエチルクロトネート、2−アセトアセトキシプロピルクロトネート等のアルキレングリコールのクロトン酸アセト酢酸エステル、N−(アセトアセトキシメチル)アクリルアミド、N−(アセトアセトキシメチル)メタクリルアミド、N−(アセトアセトキシエチル)アクリルアミド、N−(アセトアセトキシエチル)メタクリルアミド等のN−アルキロール(メタ)アクリルアミドのアセト酢酸エステル及び2−ヒドロキシエチルアクリレート、2−ヒドロキシエチルメタクリレート、ヒドロキシプロピルアクリレート、2−ヒドロキシ−3−クロロプロピルメタクリレート、1,4−ブチレングリコールモノアクリレート、1,4−ブチレングリコールモノメタクリレート、N−メチロールアクリルアミド、N−メチロールメタクリルアミド、ヒドロキシスチレン等の水酸基を有するエチレン性不飽和単量体のアセトアセチル化物等が例示される。これらのアセトアセトキシ基含有共重合性単量体は、単独で用いてもよいし、2種以上を組み合わせて用いてもよい。これらの中でも、安価で入手が容易であるという点から、2−アセトアセトキシエチルアクリレート及び2−アセトアセトキシエチルメタクリレートが好ましい。The adhesive composition according to the present invention is mainly composed of a copolymer emulsion of a vinyl acetate monomer having ethylene-modified polyvinyl alcohol as a protective colloid and an acetoacetoxy group-containing copolymerizable monomer.
Examples of the acetoacetoxy group-containing copolymerizable monomer used in the present invention include allyl acetoacetate, vinyl acetoacetate, 2-acetoacetoxyethyl acrylate, 2-acetoacetoxyethyl methacrylate, 2-acetoacetoxypropyl acrylate, 2- (Meth) acrylic acid acetoacetate ester of alkylene glycol such as acetoacetoxypropyl methacrylate, 2-cyanoacetoacetoxyethyl methacrylate, etc. Crotonic acid acetoacetate of alkylene glycol such as 2-acetoacetoxyethyl crotonate, 2-acetoacetoxypropyl crotonate Esters, N- (acetoacetoxymethyl) acrylamide, N- (acetoacetoxymethyl) methacrylamide, N- (acetoacetoxyethyl) acrylic , N-alkylol (meth) acrylamide acetoacetate such as N- (acetoacetoxyethyl) methacrylamide and 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, 2-hydroxy-3-chloropropyl Acetacetylates of ethylenically unsaturated monomers having hydroxyl groups such as methacrylate, 1,4-butylene glycol monoacrylate, 1,4-butylene glycol monomethacrylate, N-methylol acrylamide, N-methylol methacrylamide, hydroxystyrene, etc. Is exemplified. These acetoacetoxy group-containing copolymerizable monomers may be used alone or in combination of two or more. Among these, 2-acetoacetoxyethyl acrylate and 2-acetoacetoxyethyl methacrylate are preferable because they are inexpensive and easily available.
酢酸ビニル単量体及びアセトアセトキシ基含有共重合性単量体の使用割合は、酢酸ビニル単量体が好ましくは90重量%〜99.5重量%、より好ましくは95重量%〜99重量%、及びアセトアセトキシ基含有共重合性単量体が好ましくは0.5重量%〜10重量%、より好ましくは1重量%〜5重量%である。アセトアセトキシ基含有共重合性単量体の使用割合が0.5重量%より少ない場合には、耐水性及び耐熱水性に優れた樹脂エマルジョンが得られにくくなり、一方、10重量%より多い場合には、乳化重合が進行しにくくなり、得られる樹脂エマルジョンの安定性が低下する傾向となるので好ましくない。 The use ratio of the vinyl acetate monomer and the acetoacetoxy group-containing copolymerizable monomer is preferably 90% to 99.5% by weight of the vinyl acetate monomer, more preferably 95% to 99% by weight, And the acetoacetoxy group-containing copolymerizable monomer is preferably 0.5 wt% to 10 wt%, more preferably 1 wt% to 5 wt%. When the proportion of the acetoacetoxy group-containing copolymerizable monomer is less than 0.5% by weight, it becomes difficult to obtain a resin emulsion excellent in water resistance and hot water resistance. Is not preferred because emulsion polymerization is less likely to proceed and the stability of the resulting resin emulsion tends to decrease.
本発明による接着剤組成物は、エチレン変性ポリビニルアルコールを保護コロイドとして、公知の乳化重合法により製造することができる。ただし、酢酸ビニル単量体とアセトアセトキシ基含有共重合性単量体との共重合反応性は低いため、重合反応開始直後から酢酸ビニル単量体及びアセトアセトキシ基含有共重合性単量体を同時に滴下するとゲル化し易い。そこで、安定した重合の場を提供し、ゲル化を引き起こすことなく乳化重合を進めるために、エチレン変性ポリビニルアルコールの存在下で酢酸ビニル単量体を乳化重合(プレ反応)して種粒子を形成し、その種粒子にアセトアセトキシ基含有共重合性単量体を乳化重合することが好ましい。
重合反応は、公知の重合開始剤により開始される。代表的な重合開始剤としては、過硫酸カリウム、過硫酸アンモニウムや過酸化水素−酒石酸、過酸化水素−アスコルビン酸等のレドックス系重合開始剤、ベンゾイルパーオキサイド、クメンハイドロパーオキサイド等の有機過酸化物、アゾビスイソブチルニトリル等のアゾ化合物が挙げられる。
重合時の温度は、使用する重合開始剤等によって変わるが、通常、60℃〜90℃である。反応時間は、特に制限されることはなく、各成分の配合量及び反応温度等に応じて適宜調整すればよい。The adhesive composition according to the present invention can be produced by a known emulsion polymerization method using ethylene-modified polyvinyl alcohol as a protective colloid. However, since the copolymerization reactivity between the vinyl acetate monomer and the acetoacetoxy group-containing copolymerizable monomer is low, the vinyl acetate monomer and the acetoacetoxy group-containing copolymerizable monomer are added immediately after the start of the polymerization reaction. If dripped simultaneously, it is easy to gel. Therefore, in order to provide a stable polymerization field and advance emulsion polymerization without causing gelation, emulsion particles (pre-reaction) of vinyl acetate monomer in the presence of ethylene-modified polyvinyl alcohol form seed particles. The seed particles are preferably emulsion-polymerized with an acetoacetoxy group-containing copolymerizable monomer.
The polymerization reaction is initiated by a known polymerization initiator. Typical polymerization initiators include red peroxide polymerization initiators such as potassium persulfate, ammonium persulfate, hydrogen peroxide-tartaric acid, hydrogen peroxide-ascorbic acid, and organic peroxides such as benzoyl peroxide and cumene hydroperoxide. And azo compounds such as azobisisobutylnitrile.
The temperature at the time of polymerization varies depending on the polymerization initiator used, but is usually 60 ° C to 90 ° C. The reaction time is not particularly limited and may be appropriately adjusted according to the blending amount of each component, the reaction temperature, and the like.
乳化重合の際に用いるエチレン変性ポリビニルアルコールとしては、エチレンと酢酸ビニル、蟻酸ビニル、プロピオン酸ビニル等のビニルエステルとの共重合体を鹸化したものであればよく、例えば、株式会社クラレ製エクセバール(登録商標)シリーズ等が挙げられる。また、エチレン変性度、鹸化度、重合度等の異なるエチレン変性ポリビニルアルコールを組み合わせることで、粘度、グラフト率、基材への密着性及び凝集力等の調整が可能となる。
保護コロイドとしてのエチレン変性ポリビニルアルコールは、酢酸ビニル単量体とアセトアセトキシ基含有共重合性単量体との合計100重量部に対して、好ましくは5重量部〜20重量部、より好ましくは10重量部〜15重量部の割合で使用される。The ethylene-modified polyvinyl alcohol used in the emulsion polymerization may be a saponified copolymer of ethylene and a vinyl ester such as vinyl acetate, vinyl formate, or vinyl propionate. Registered trademark) series and the like. In addition, by combining ethylene-modified polyvinyl alcohols having different degrees of ethylene modification, saponification, polymerization, etc., it is possible to adjust the viscosity, graft ratio, adhesion to the substrate, cohesion and the like.
The ethylene-modified polyvinyl alcohol as the protective colloid is preferably 5 parts by weight to 20 parts by weight, more preferably 10 parts by weight with respect to a total of 100 parts by weight of the vinyl acetate monomer and the acetoacetoxy group-containing copolymerizable monomer. Used in a ratio of 15 to 15 parts by weight.
また、本発明の効果を損なわない範囲で、界面活性剤(重合安定助剤)を適宜使用してもよい。更に、必要に応じて各種の添加剤を配合することができる。添加剤としては、ポリビニルアルコールやヒドロキシエチルセルロース、カルボキシメチルセルロース、デンプン等のセルロース誘導体、カゼイン、ポリアクリルアミド等の天然及び合成の水溶性高分子、ジブチルフタレート、ジオクチフタレート、テキサノール、DBE(ダイベーシックエステル)等の可塑剤及び造膜助剤、ロジン、テルペン樹脂等の粘着付与剤、酸化チタン等の顔料、炭酸カルシウムやクレー等の無機物、各種消泡剤、防腐剤などが適宜用いられる。 In addition, a surfactant (polymerization stabilization aid) may be appropriately used within a range not impairing the effects of the present invention. Furthermore, various additives can be mix | blended as needed. Additives include cellulose derivatives such as polyvinyl alcohol, hydroxyethyl cellulose, carboxymethyl cellulose and starch, natural and synthetic water-soluble polymers such as casein and polyacrylamide, dibutyl phthalate, dioctiphthalate, texanol, DBE (Dibasic ester) Plasticizers and film forming aids such as rosin, terpene resin and other tackifiers, pigments such as titanium oxide, inorganic substances such as calcium carbonate and clay, various antifoaming agents, preservatives and the like are appropriately used.
以下、実施例及び比較例によって本発明をより具体的に説明するが、本発明はこれら実施例に制限されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention more concretely, this invention is not restrict | limited to these Examples.
<実施例1>
攪拌機、温度計、還流冷却機及び滴下ロートを備えた1リットルセパラブルフラスコに、エチレン変性ポリビニルアルコールとしてエクセバール(登録商標)HR−3010(株式会社クラレ製、鹸化度99.3モル%、重合度1000)25g、エクセバール(登録商標)RS−1717(株式会社クラレ製、鹸化度93.0モル%、重合度1700)25g及び水420gを仕込み、90℃以上に昇温し、エチレン変性ポリビニルアルコールを溶解させた。その後、70℃に設定し、30%過酸化水素水0.35g及び酒石酸1.0gを加えた後、酢酸ビニル450g及び30%過酸化水素水1.0gに水49gを加えて希釈した過酸化水素水溶液を5時間かけて滴下した。酢酸ビニル及び過酸化水素水溶液の滴下を開始してから1時間後に、酢酸ビニルが入っている滴下ロートに2−アセトアセトキシエチルメタクリレート(以下、AAEMと略記する)4.5gを入れて混和し、その混和物を滴下して乳化重合を行った。
なお、乳化共重合時のセパラブルフラスコ内温が75℃〜85℃になるように、外温をコントロールした。滴下終了後、75℃〜85℃で1時間保った後、30℃以下に冷却し、テキサノール25gを添加し、実施例1の樹脂エマルジョンを得た。得られた樹脂エマルジョンの固形分濃度(105℃で1時間乾燥させた時の固形分量)は、49.0重量%であり、粘度(BH型粘度計、10回転、23℃)は、13960mPa・sであった。<Example 1>
Into a 1 liter separable flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel, Exebar (registered trademark) HR-3010 (manufactured by Kuraray Co., Ltd., saponification degree 99.3 mol%, polymerization degree) 1000) 25 g, Exebar (registered trademark) RS-1717 (manufactured by Kuraray Co., Ltd., saponification degree 93.0 mol%, polymerization degree 1700) 25 g and water 420 g were charged, the temperature was raised to 90 ° C. or higher, and ethylene-modified polyvinyl alcohol was added. Dissolved. Thereafter, the temperature was set at 70 ° C., 0.35 g of 30% hydrogen peroxide water and 1.0 g of tartaric acid were added, and then the peroxide was diluted by adding 49 g of water to 450 g of vinyl acetate and 1.0 g of 30% hydrogen peroxide water. An aqueous hydrogen solution was added dropwise over 5 hours. One hour after the start of dropping of vinyl acetate and hydrogen peroxide aqueous solution, 4.5 g of 2-acetoacetoxyethyl methacrylate (hereinafter abbreviated as AAEM) was added to and mixed with a dropping funnel containing vinyl acetate, The mixture was added dropwise to conduct emulsion polymerization.
The external temperature was controlled so that the temperature inside the separable flask during emulsion copolymerization was 75 ° C to 85 ° C. After completion of dropping, the mixture was kept at 75 ° C. to 85 ° C. for 1 hour, then cooled to 30 ° C. or less, and 25 g of texanol was added to obtain a resin emulsion of Example 1. The obtained resin emulsion has a solid content concentration (solid content when dried at 105 ° C. for 1 hour) of 49.0% by weight, and a viscosity (BH viscometer, 10 revolutions, 23 ° C.) of 13960 mPa · s.
<実施例2>
AAEMの添加量を22.5gに変更したこと以外は、実施例1と同様の操作を行い、実施例2の樹脂エマルジョンを得た。得られた樹脂エマルジョンの固形分濃度(105℃で1時間乾燥させた時の固形分量)は49.9重量%であり、粘度(BH型粘度計、10回転、23℃)は、13800mPa・sであった。<Example 2>
A resin emulsion of Example 2 was obtained by performing the same operation as in Example 1 except that the amount of AAEM added was changed to 22.5 g. The resulting resin emulsion has a solid content concentration (solid content when dried at 105 ° C. for 1 hour) of 49.9% by weight, and a viscosity (BH viscometer, 10 revolutions, 23 ° C.) of 13800 mPa · s. Met.
<実施例3>
2−アセトアセトキシエチルメタクリレート(AAEM)を2−アセトアセトキシエチルアクリレートに変更した以外は、実施例1と同様の操作を行い、実施例3の樹脂エマルジョンを得た。得られた樹脂エマルジョンの固形分濃度(105℃で1時間乾燥させた時の固形分量)は49.0重量%であり、粘度(BH型粘度計、10回転、23℃)は、13500mPa・sであった。<Example 3>
A resin emulsion of Example 3 was obtained in the same manner as in Example 1 except that 2-acetoacetoxyethyl methacrylate (AAEM) was changed to 2-acetoacetoxyethyl acrylate. The obtained resin emulsion has a solid content concentration (solid content when dried at 105 ° C. for 1 hour) of 49.0% by weight, and a viscosity (BH viscometer, 10 revolutions, 23 ° C.) of 13500 mPa · s. Met.
<実施例4>
2−アセトアセトキシエチルメタクリレート(AAEM)を2−アセトアセトキシエチルアクリレートに変更し、添加量を22.5gに変更したこと以外は、実施例1と同様の操作を行い、実施例4の樹脂エマルジョンを得た。得られた樹脂エマルジョンの固形分濃度(105℃で1時間乾燥させた時の固形分量)は49.7重量%であり、粘度(BH型粘度計、10回転、23℃)は、13900mPa・sであった。<Example 4>
The same procedure as in Example 1 was performed except that 2-acetoacetoxyethyl methacrylate (AAEM) was changed to 2-acetoacetoxyethyl acrylate and the addition amount was changed to 22.5 g. Obtained. The resulting resin emulsion had a solid content concentration (solid content when dried at 105 ° C. for 1 hour) of 49.7 wt%, and a viscosity (BH viscometer, 10 revolutions, 23 ° C.) of 13900 mPa · s. Met.
<比較例1>
AAEMを添加しないこと以外は、実施例1と同様の操作を行い、比較例1の樹脂エマルジョンを得た。得られた樹脂エマルジョンの固形分濃度(105℃で1時間乾燥させた時の固形分量)は49.0重量%であり、粘度(BH型粘度計、10回転、23℃)は、13000mPa・sであった。<Comparative Example 1>
Except not adding AAEM, operation similar to Example 1 was performed and the resin emulsion of the comparative example 1 was obtained. The obtained resin emulsion has a solid content concentration (solid content when dried at 105 ° C. for 1 hour) of 49.0% by weight, and a viscosity (BH viscometer, 10 rotations, 23 ° C.) of 13000 mPa · s. Met.
<比較例2>
エチレン変性ポリビニルアルコールの代わりに、完全鹸化ポリビニルアルコールであるクラレポバールPVA 117(株式会社クラレ製、鹸化度98.5モル%、重合度1700)50gを使用したこと以外は、実施例1と同様の操作を行い、比較例2の樹脂エマルジョンを得た。得られた樹脂エマルジョンの固形分濃度(105℃で1時間乾燥させた時の固形分量)は48.7重量%であり、粘度(BH型粘度計、10回転、23℃)は、14000mPa・sであった。<Comparative example 2>
Except for using 50 g of Kuraray Poval PVA 117 (manufactured by Kuraray Co., Ltd., degree of saponification of 98.5 mol%, degree of polymerization of 1700) instead of ethylene-modified polyvinyl alcohol, the same as in Example 1 The operation was carried out to obtain a resin emulsion of Comparative Example 2. The obtained resin emulsion has a solid content concentration (solid content when dried at 105 ° C. for 1 hour) of 48.7% by weight, and a viscosity (BH viscometer, 10 revolutions, 23 ° C.) of 14000 mPa · s. Met.
<比較例3>
AAEMの代わりに、アクリル酸12gを使用したこと以外は、実施例1と同様の操作を行い、比較例3の樹脂エマルジョンを得た。得られた樹脂エマルジョンの固形分濃度(105℃で1時間乾燥させた時の固形分量)は50.0重量%であり、粘度(BH型粘度計、10回転、23℃)は、13000mPa・sであった。<Comparative Example 3>
A resin emulsion of Comparative Example 3 was obtained in the same manner as in Example 1 except that 12 g of acrylic acid was used instead of AAEM. The resulting resin emulsion has a solid content concentration (the solid content when dried at 105 ° C. for 1 hour) of 50.0% by weight, and a viscosity (BH viscometer, 10 revolutions, 23 ° C.) of 13000 mPa · s. Met.
<比較例4>
比較例3で得られた樹脂エマルジョンに50%硝酸アルミニウム水溶液40gを添加し、比較例4の樹脂エマルジョンを得た。得られた樹脂エマルジョンの固形分濃度(105℃で1時間乾燥させた時の固形分量)は48.5重量%であり、粘度(BH型粘度計、10回転、23℃)は、13500mPa・sであった。<Comparative Example 4>
40 g of a 50% aluminum nitrate aqueous solution was added to the resin emulsion obtained in Comparative Example 3 to obtain a resin emulsion of Comparative Example 4. The resulting resin emulsion has a solid content concentration (solid content when dried at 105 ° C. for 1 hour) of 48.5% by weight, and a viscosity (BH viscometer, 10 revolutions, 23 ° C.) of 13500 mPa · s. Met.
実施例及び比較例で得られた樹脂エマルジョンの物性を以下の方法に従って評価した。 The physical properties of the resin emulsions obtained in the examples and comparative examples were evaluated according to the following methods.
<JAS1類浸漬剥離試験>
(1)接着条件
基材:市販品 9.0mm合板/9.0mm合板JASタイプ1合格品
塗布量:Wet 20g/尺2
圧締条件:室温×10kg/cm2×30分
養生:23℃×50%RH×3日
(2)試験方法
JAS特殊加工化粧合板規格に準拠して実施した。
Wet時の評価として、75mm×75mmの試験片を沸騰水中に4時間浸漬した後、60℃で20時間乾燥させ、更に、沸騰水中に4時間浸漬した後、試験片を観察し、試験片側面の剥離しない部分の長さが50mm以上であるか否かを判定した(n=4)。
また、Dry時の評価として、75mm×75mmの試験片を沸騰水中に4時間浸漬した後、60℃で20時間乾燥させ、更に、沸騰水中に4時間浸漬した後、60℃で3時間乾燥させ、試験片を観察し、試験片側面の剥離しない部分の長さが50mm以上であるか否かを判定した(n=4)。
4サンプルの全てで、側面の剥離しない部分の長さが50mm以上である場合を○と評価し、4サンプルのうち1サンプルでも、側面の剥離しない部分の長さが50mm未満である場合を×と評価した。<JAS1 immersion peeling test>
(1) Adhesion conditions Substrate: Commercially available product 9.0 mm plywood / 9.0 mm
Crushing condition: room temperature × 10 kg / cm 2 × 30 minutes Curing: 23 ° C. × 50% RH × 3 days (2) Test method The test was carried out according to JAS specially processed decorative plywood standards.
As a wet evaluation, a test piece of 75 mm × 75 mm was immersed in boiling water for 4 hours, then dried at 60 ° C. for 20 hours, and further immersed in boiling water for 4 hours. It was determined whether the length of the non-peeling portion was 50 mm or more (n = 4).
In addition, as an evaluation at the time of Dry, a test piece of 75 mm × 75 mm was immersed in boiling water for 4 hours, then dried at 60 ° C. for 20 hours, further immersed in boiling water for 4 hours, and then dried at 60 ° C. for 3 hours. The test piece was observed, and it was determined whether the length of the non-peeled portion on the side surface of the test piece was 50 mm or more (n = 4).
In all four samples, the case where the length of the part where the side surface does not peel is 50 mm or more is evaluated as ◯, and even when one of the four samples is the length of the part where the side surface does not peel is less than 50 mm It was evaluated.
<圧縮剪断試験>
(1)接着条件
基材:赤カバ
温度:23℃
塗布量:片面100g/m2(両面塗布)
圧締条件:室温×10kg/cm2×24時間
養生:23℃×50%RH×3日
(2)試験方法
JIS K 6852に準拠して実施した。常態における圧縮剪断強度は、23℃及び50%RH雰囲気下で測定した。熱水の圧縮剪断強度は、試験片を沸騰水に4時間浸漬した後、60℃で20時間乾燥させ、更に、沸騰水中に4時間浸漬した後、水に浸漬して測定した。結果を表1に示す。<Compression shear test>
(1) Adhesion conditions Substrate: Red hip Temperature: 23 ° C
Application amount: 100g / m 2 on one side (double-sided application)
Clamping conditions: room temperature × 10 kg / cm 2 × 24 hours Curing: 23 ° C. × 50% RH × 3 days (2) Test method The test was performed according to JIS K 6852. The compressive shear strength in a normal state was measured at 23 ° C. and 50% RH atmosphere. The compressive shear strength of hot water was measured by immersing the test piece in boiling water for 4 hours, drying at 60 ° C. for 20 hours, further immersing in boiling water for 4 hours, and then immersing in water. The results are shown in Table 1.
<高温下における貯蔵安定性の評価>
各樹脂エマルジョンを60℃の乾燥機に1日間及び7日間放置し、その後、23℃で粘度を測定した。結果を図1に示す。また、初期粘度を1.0としたときの1日後及び7日後の粘度の相対値を表1に示す。1日後及び7日後の粘度の相対値の両方が、±0.2以内のものを○と評価し、1日後及び7日後の粘度の相対値のいずれかが、±0.2以内とならないものを×と評価した。<Evaluation of storage stability at high temperature>
Each resin emulsion was left in a dryer at 60 ° C. for 1 day and 7 days, and then the viscosity was measured at 23 ° C. The results are shown in FIG. Table 1 shows the relative values of the viscosity after 1 day and after 7 days when the initial viscosity is 1.0. Those whose relative values of viscosity after 1 day and after 7 days are within ± 0.2 are evaluated as ○, and either of the relative values of viscosity after 1 day and after 7 days is not within ± 0.2 Was evaluated as x.
<重合安定性の評価>
重合中のセパラブルフラスコ内を観察し、下記基準に従って評価した。結果を表1に示す。
○:単量体が滞留することなく、重合が進行する。
×:重合が進行し難いため、単量体が滞留及びゲル化する。<Evaluation of polymerization stability>
The inside of the separable flask during the polymerization was observed and evaluated according to the following criteria. The results are shown in Table 1.
○: Polymerization proceeds without retention of monomers.
X: Since polymerization does not proceed easily, the monomer stays and gels.
上記の結果から分かるように、実施例1〜4の樹脂エマルジョンは、JAS1類浸漬剥離試験に合格し、常態及び熱水繰返し浸漬後の圧縮剪断強度も優れており、高温下における貯蔵安定性も極めて良好であった。また、重合時にゲル化が起こることもなく、重合安定性も良好であった。以上のことから、本発明の接着剤組成物は、合板・木工用接着剤として有用であると言うことができる。 As can be seen from the above results, the resin emulsions of Examples 1 to 4 passed the JAS1 class immersion peel test, excellent in compressive shear strength after repeated immersion in normal and hot water, and storage stability at high temperatures. It was very good. Further, gelation did not occur during the polymerization, and the polymerization stability was good. From the above, it can be said that the adhesive composition of the present invention is useful as an adhesive for plywood / woodwork.
本発明者らは、上記課題を解決すべく検討を行った結果、次の樹脂組成物が上記課題を解決できることを見出し、本発明を完成させるに至った。
即ち、本発明は、保護コロイドとしてエチレン変性ポリビニルアルコールを用い、酢酸ビニル単量体90重量%〜99.5重量%とアセトアセトキシ基含有共重合性単量体0.5重量%〜10重量%とを乳化重合して得られた接着剤組成物である。
As a result of investigations to solve the above problems, the present inventors have found that the following resin composition can solve the above problems, and have completed the present invention.
That is, the present invention uses ethylene-modified polyvinyl alcohol as a protective colloid, 90 wt% to 99.5 wt% of vinyl acetate monomer and 0.5 wt% to 10 wt% of acetoacetoxy group-containing copolymerizable monomer. Is an adhesive composition obtained by emulsion polymerization.
Claims (5)
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH05287248A (en) * | 1992-04-10 | 1993-11-02 | Sumitomo Chem Co Ltd | Adhesive |
JPH11172216A (en) * | 1997-12-12 | 1999-06-29 | Shoei Kagaku Kogyo Kk | Aqueous adhesive composition |
JP2000282004A (en) * | 1999-03-29 | 2000-10-10 | Aica Kogyo Co Ltd | Adhesive |
JP2001123138A (en) * | 1999-10-26 | 2001-05-08 | Konishi Co Ltd | Synthetic resin emulsion adhesive |
JP2002256161A (en) * | 2001-02-27 | 2002-09-11 | Unitika Chem Co Ltd | Synthetic resin emulsion composition |
JP2002285119A (en) * | 2001-03-22 | 2002-10-03 | Chuo Rika Kogyo Corp | Adhesive composed of emulsion of vinyl acetate polymer |
JP2003160764A (en) * | 2001-11-26 | 2003-06-06 | Oji Paper Co Ltd | Pressure-sensitive adhesive sheet |
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Publication number | Priority date | Publication date | Assignee | Title |
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JPH05287248A (en) * | 1992-04-10 | 1993-11-02 | Sumitomo Chem Co Ltd | Adhesive |
JPH11172216A (en) * | 1997-12-12 | 1999-06-29 | Shoei Kagaku Kogyo Kk | Aqueous adhesive composition |
JP2000282004A (en) * | 1999-03-29 | 2000-10-10 | Aica Kogyo Co Ltd | Adhesive |
JP2001123138A (en) * | 1999-10-26 | 2001-05-08 | Konishi Co Ltd | Synthetic resin emulsion adhesive |
JP2002256161A (en) * | 2001-02-27 | 2002-09-11 | Unitika Chem Co Ltd | Synthetic resin emulsion composition |
JP2002285119A (en) * | 2001-03-22 | 2002-10-03 | Chuo Rika Kogyo Corp | Adhesive composed of emulsion of vinyl acetate polymer |
JP2003160764A (en) * | 2001-11-26 | 2003-06-06 | Oji Paper Co Ltd | Pressure-sensitive adhesive sheet |
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