JP4368595B2 - Hot melt adhesive - Google Patents
Hot melt adhesive Download PDFInfo
- Publication number
- JP4368595B2 JP4368595B2 JP2003048177A JP2003048177A JP4368595B2 JP 4368595 B2 JP4368595 B2 JP 4368595B2 JP 2003048177 A JP2003048177 A JP 2003048177A JP 2003048177 A JP2003048177 A JP 2003048177A JP 4368595 B2 JP4368595 B2 JP 4368595B2
- Authority
- JP
- Japan
- Prior art keywords
- hot melt
- melt adhesive
- heat
- polyvinyl alcohol
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000004831 Hot glue Substances 0.000 title claims description 69
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 70
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 70
- 229920005989 resin Polymers 0.000 claims description 65
- 239000011347 resin Substances 0.000 claims description 65
- -1 oxypropylene group Chemical group 0.000 claims description 48
- 238000006116 polymerization reaction Methods 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 29
- 239000004626 polylactic acid Substances 0.000 claims description 29
- 239000000853 adhesive Substances 0.000 claims description 27
- 230000001070 adhesive effect Effects 0.000 claims description 26
- 239000000178 monomer Substances 0.000 claims description 24
- 239000012943 hotmelt Substances 0.000 claims description 22
- 239000003945 anionic surfactant Substances 0.000 claims description 21
- 239000004014 plasticizer Substances 0.000 claims description 19
- 238000007127 saponification reaction Methods 0.000 claims description 19
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 13
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 12
- 239000000194 fatty acid Substances 0.000 claims description 12
- 229930195729 fatty acid Natural products 0.000 claims description 12
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 12
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 claims description 5
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 239000004711 α-olefin Substances 0.000 claims description 5
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 3
- 125000006353 oxyethylene group Chemical group 0.000 claims description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 19
- 238000000034 method Methods 0.000 description 19
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 12
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 229920001567 vinyl ester resin Polymers 0.000 description 10
- 239000000155 melt Substances 0.000 description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 7
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 239000004310 lactic acid Substances 0.000 description 6
- 235000014655 lactic acid Nutrition 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 6
- 229920001451 polypropylene glycol Polymers 0.000 description 6
- 239000011118 polyvinyl acetate Substances 0.000 description 6
- 229920002689 polyvinyl acetate Polymers 0.000 description 6
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 229920005601 base polymer Polymers 0.000 description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 239000000123 paper Substances 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011111 cardboard Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- LAYAKLSFVAPMEL-UHFFFAOYSA-N 1-ethenoxydodecane Chemical compound CCCCCCCCCCCCOC=C LAYAKLSFVAPMEL-UHFFFAOYSA-N 0.000 description 3
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 3
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000003093 cationic surfactant Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- QJJDJWUCRAPCOL-UHFFFAOYSA-N 1-ethenoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOC=C QJJDJWUCRAPCOL-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 206010040844 Skin exfoliation Diseases 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 2
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 description 2
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 2
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 1
- QLZJUIZVJLSNDD-UHFFFAOYSA-N 2-(2-methylidenebutanoyloxy)ethyl 2-methylidenebutanoate Chemical compound CCC(=C)C(=O)OCCOC(=O)C(=C)CC QLZJUIZVJLSNDD-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- VCYCUECVHJJFIQ-UHFFFAOYSA-N 2-[3-(benzotriazol-2-yl)-4-hydroxyphenyl]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 VCYCUECVHJJFIQ-UHFFFAOYSA-N 0.000 description 1
- SFTRWCBAYKQWCS-UHFFFAOYSA-N 2-butanoyloxyethyl butanoate Chemical compound CCCC(=O)OCCOC(=O)CCC SFTRWCBAYKQWCS-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- FKOZPUORKCHONH-UHFFFAOYSA-N 2-methylpropane-1-sulfonic acid Chemical compound CC(C)CS(O)(=O)=O FKOZPUORKCHONH-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
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 1
- WHNPOQXWAMXPTA-UHFFFAOYSA-N 3-methylbut-2-enamide Chemical compound CC(C)=CC(N)=O WHNPOQXWAMXPTA-UHFFFAOYSA-N 0.000 description 1
- AHHQDHCTHYTBSV-UHFFFAOYSA-N 3-methylpentane-1,3,5-triol Chemical compound OCCC(O)(C)CCO AHHQDHCTHYTBSV-UHFFFAOYSA-N 0.000 description 1
- OIYTYGOUZOARSH-UHFFFAOYSA-N 4-methoxy-2-methylidene-4-oxobutanoic acid Chemical compound COC(=O)CC(=C)C(O)=O OIYTYGOUZOARSH-UHFFFAOYSA-N 0.000 description 1
- MKXAREWNUVZNTJ-UHFFFAOYSA-N 5-acetyl-7-butyl-6-hydroxyundecane-4,5,6-tricarboxylic acid Chemical compound CCCCC(CCCC)(C(O)=O)C(O)(C(O)=O)C(CCCC)(C(C)=O)C(O)=O MKXAREWNUVZNTJ-UHFFFAOYSA-N 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- QMWATAZIUKHINA-UHFFFAOYSA-N C(CCCCCCCCC(=O)O)(=O)O.C(CCCCCCCCC(=O)O)(=O)O.C(COCCOCCO)O Chemical compound C(CCCCCCCCC(=O)O)(=O)O.C(CCCCCCCCC(=O)O)(=O)O.C(COCCOCCO)O QMWATAZIUKHINA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229930182843 D-Lactic acid Natural products 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 1
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 description 1
- VIZORQUEIQEFRT-UHFFFAOYSA-N Diethyl adipate Chemical compound CCOC(=O)CCCCC(=O)OCC VIZORQUEIQEFRT-UHFFFAOYSA-N 0.000 description 1
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- XXIKYCPRDXIMQM-UHFFFAOYSA-N Isopentenyl acetate Chemical compound CC(C)=CCOC(C)=O XXIKYCPRDXIMQM-UHFFFAOYSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- UYXTWWCETRIEDR-UHFFFAOYSA-N Tributyrin Chemical compound CCCC(=O)OCC(OC(=O)CCC)COC(=O)CCC UYXTWWCETRIEDR-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000006359 acetalization reaction Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 125000005600 alkyl phosphonate group Chemical group 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
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- 229940063953 ammonium lauryl sulfate Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- XRJBMOBWWDKSDQ-UHFFFAOYSA-N benzhydryl(ethenyl)silane Chemical compound C=1C=CC=CC=1C([SiH2]C=C)C1=CC=CC=C1 XRJBMOBWWDKSDQ-UHFFFAOYSA-N 0.000 description 1
- 229920006167 biodegradable resin Polymers 0.000 description 1
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 1
- 235000015895 biscuits Nutrition 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
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- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- BEWFIPLBFJGWSR-UHFFFAOYSA-N butyl 12-acetyloxyoctadec-9-enoate Chemical compound CCCCCCC(OC(C)=O)CC=CCCCCCCCC(=O)OCCCC BEWFIPLBFJGWSR-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
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- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 238000007334 copolymerization reaction Methods 0.000 description 1
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- UYAAVKFHBMJOJZ-UHFFFAOYSA-N diimidazo[1,3-b:1',3'-e]pyrazine-5,10-dione Chemical compound O=C1C2=CN=CN2C(=O)C2=CN=CN12 UYAAVKFHBMJOJZ-UHFFFAOYSA-N 0.000 description 1
- ZJVWGOLNVKJRDF-UHFFFAOYSA-N dimethylallyl acetate Natural products CC(=O)OC(C)(C)C=C ZJVWGOLNVKJRDF-UHFFFAOYSA-N 0.000 description 1
- 229960000878 docusate sodium Drugs 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
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- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
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- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 235000013773 glyceryl triacetate Nutrition 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 238000007757 hot melt coating Methods 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008268 mayonnaise Substances 0.000 description 1
- 235000010746 mayonnaise Nutrition 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical group 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
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- 229940096992 potassium oleate Drugs 0.000 description 1
- 229940114930 potassium stearate Drugs 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- BPJZKLBPJBMLQG-KWRJMZDGSA-N propanoyl (z,12r)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(=O)OC(=O)CC BPJZKLBPJBMLQG-KWRJMZDGSA-N 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 229940116423 propylene glycol diacetate Drugs 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229940066675 ricinoleate Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- FWFUWXVFYKCSQA-UHFFFAOYSA-M sodium;2-methyl-2-(prop-2-enoylamino)propane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(C)(C)NC(=O)C=C FWFUWXVFYKCSQA-UHFFFAOYSA-M 0.000 description 1
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
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- Adhesives Or Adhesive Processes (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、熱溶融性ポリビニルアルコール系樹脂とポリ乳酸からなる水溶性もしくは水分散性ホットメルト接着剤に関するものであり、より詳細には高温高湿下における接着力が低下し難い水溶性もしくは水分散性ホットメルト接着剤に関する。
【０００２】
【従来の技術】
ホットメルト接着剤は無溶剤でも瞬間接着又は高速接着が可能であるから工業上の利点を有している。そのため、製本、包装、木工、製鞄、織物などの分野を主体として大量に使用されている。ホットメルト接着剤は、接着性、溶融性、耐熱性、耐寒性、柔軟性などの性能を満たすことが要求され、一般的にはエチレン−酢酸ビニル共重合体（ＥＶＡ）、エチレン−アクリル酸エチルエステル共重合体（ＥＥＡ）、ポリエチレン、ポリプロピレン、ポリアミド、ポリエステル等がベースポリマーとして用いられており、特に、包装、製本、製袋の用途には、接着性、作業性、柔軟性に優れたＥＶＡをベースとしたホットメルト接着剤が広く利用されている。しかしながら、近年省資源化、無公害化の視点から接着製品のリサイクル適正が問われてきており、前記したような従来型ホットメルト接着剤では、ホットメルト接着剤が疎水性であるため、たとえば古紙を再生処理するときに、水に溶解ないし分散しない部分が残り、再生処理が困難となる。そこで、リサイクル適正に優れた水溶性もしくは水分散性に優れたホットメルト接着剤の検討が進められている。その中でも水溶性もしくは水分散性に優れ、かつ接着性、溶融性を有するポリビニルアルコール（ＰＶＡ）系樹脂をホットメルト接着剤のベースポリマーとして利用する検討が数多くなされている。
【０００３】
例えば、重合度が低い部分ケン化ＰＶＡ系樹脂をベースポリマーとして使用し、これに５価以上のアルコール、グリセリン、ポリエチレングリコールまたはエチレン尿素などのＰＶＡ用可塑剤、粘度低下剤およびその他の添加剤を混合してなる水溶性もしくは水分散性のホットメルト接着剤が提案されている（例えば特許文献１〜３）。これらの接着剤では、溶融粘度の低下により、塗工性を改善することができ、かつ接着剤皮膜の柔軟性を高めることができる。
【０００４】
また、カルボン酸、スルホン酸もしくはアミドなどの親水基を含むモノマーまたはビニルピロリドンと、酢酸ビニルとを共重合して得られた変性ポリ酢酸ビニルをケン化することにより得られた変性ＰＶＡ系樹脂をベースポリマーとして使用した水溶性もしくは水分散性のホットメルト接着剤が提案されている（例えば特許文献４〜６参照）。これらの先行技術に記載のホットメルト接着剤では、特定の変性ＰＶＡ系樹脂を用いることにより水溶性が高められるとされている。
【０００５】
また、酢酸アリルまたは飽和分岐脂肪酸ビニルなどのモノマーを酢酸ビニルモノマーと共重合することにより得られた変性ポリ酢酸ビニル樹脂をケン化して得られた変性ＰＶＡ系樹脂をベースポリマーとして使用したホットメルト接着剤が開示されている。（例えば特許文献７〜８参照）このホットメルト接着剤では、高温高湿下における接着力が高められ、かつ耐寒性も高められ、接着剤に含まれる他の樹脂との相溶性に優れているとされている。
【０００６】
しかしながら、これらのＰＶＡ系樹脂をベース樹脂として使用したホットメルト接着剤は、ホットメルト接着剤の性能として不可欠な▲１▼高温高湿下における接着力、▲２▼常温中性下における水溶性もしくは水分散性、▲３▼優れた加熱安定性および▲４▼容易に塗工され得る程度の溶融粘度といった４つの諸物性を全て満足し得るホットメルト接着剤とはいえなかった。
【０００７】
上記４つの諸物性を達成するべく本発明者らは、平均重合度５０〜１２００及びケン化度６０モル％以下のポリビニルアルコール系樹脂１００質量部と、アニオン界面活性剤０．０１〜３０質量部と、可塑剤０．１〜５０質量部とを含む水溶性もしくは水分散性ホットメルト接着剤を提案した（例えば特許文献９参照）。
このホットメルト接着剤は上記４つの諸物性をほぼ満足し得るものであったが、なお高温高湿下における接着力をさらに改善することが望まれている。
【０００８】
【特許文献１】
特開昭５１−７７６３２号公報（請求項１）
【特許文献２】
特開昭５１−９５４４０号公報（請求項１〜２）
【特許文献３】
特開昭５１−１４９３２８号公報（請求項１）
【特許文献４】
特開昭５３−５０２３９号公報（請求項１〜４）
【特許文献５】
特開昭５４−１３８０３３号公報（請求項（１〜４）
【特許文献６】
特開昭５４−１３９９４５号公報（請求項１〜３）
【特許文献７】
特開昭５４−７６６３４号公報（請求項１）
【特許文献８】
特開昭５５−９４９７８号公報（請求項１〜２）
【特許文献９】
特開２００３−３１４０号公報（請求項１〜７）
【０００９】
【発明が解決しようとする課題】
したがって、本発明は上記の如き実情に鑑みてなされたものであって、工業的に容易に製造され、高温高湿下での接着力が向上したホットメルト接着剤を提供する事にある。
【００１０】
【課題を解決するための手段】
本発明らは上記目的を達成すべく鋭意検討を重ねた結果、熱溶融性ポリビニルアルコール系樹脂とポリ乳酸とを含有し、熱溶融性ポリビニルアルコール系樹脂とポリ乳酸との配合割合が９９／１〜１０／９０（質量比）の範囲であることを特徴とするホットメルト接着剤を用いることが、上記課題を達成するのに有効であることを見出し、さらに検討を重ねて本発明を完成するに至った。
【００１１】
すなわち、本発明は、
（１） 熱溶融性ポリビニルアルコール系樹脂とポリ乳酸とを含有し、熱溶融性ポリビニルアルコール系樹脂とポリ乳酸との配合割合が９９／１〜１０／９０（質量比）の範囲であることを特徴とするホットメルト接着剤、
（２） さらに、可塑剤又は／及びアニオン界面活性剤を含有し、ホットメルト接着剤１００質量部に対して、可塑剤の含有量が０．１〜３０質量部、アニオン界面活性剤の含有量が０．０１〜１０質量部であることを特徴とする（１）記載のホットメルト接着剤、
（３） 熱溶融性ポリビニルアルコールの平均重合度が５０〜１２００であり、熱溶融性ポリビニルアルコールのケン化度が８４モル％以下であることを特徴とする（１）又は（２）に記載のホットメルト接着剤、
（４） 熱溶融性ポリビニルアルコール系樹脂が主鎖または側鎖にスルホン酸基またはスルホン酸塩基を有することを特徴とする（１）〜（３）のいずれかに記載のホットメルト接着剤、
（５） 熱溶融性ポリビニルアルコール系樹脂が主鎖または側鎖にオキシアルキレン基を有することを特徴とする（１）〜（４）のいずれかに記載のホットメルト接着剤、
（６） オキシアルキレン基が一般式
【化３】
で示されるオキシエチレン基または一般式
【化４】
で示されるオキシプロピレン基であり、かつ、熱溶融性ポリビニルアルコール系樹脂が全単量体単位に対してオキシアルキレン基を含む単量体単位を０．１〜５０モル％含有する熱溶融性ポリビニルアルコール系樹脂であることを特徴とする（１）〜（５）のいずれかに記載のホットメルト接着剤、
（７） 熱溶融性ポリビニルアルコール系樹脂が酢酸ビニルとα―オレフィンとの共重合体のケン化物であることを特徴とする（１）〜（６）のいずれかに記載のホットメルト接着剤、
（８） 熱溶融性ポリビニルアルコール系樹脂が側鎖にアルキル基を有することを特徴とする（１）〜（７）のいずれかに記載のホットメルト接着剤、
（９） アニオン界面活性剤が、アルキル硫酸塩、アルキルスルホン酸塩、アルキルベンゼンスルホン酸塩、ジアルキルスルホコハク酸塩および脂肪酸アルカリ塩からなる群から選ばれる少なくとも１種であることを特徴とする（１）〜（８）のいずれかに記載のホットメルト接着剤、
に関する。
【００１２】
【発明の実施の形態】
以下、本発明を詳細に説明する。本発明において用いられる熱溶融性ＰＶＡ系樹脂は、熱溶融するものであれば特に制限はなく、好ましくは平均重合度約５０〜１２００、ケン化度約８４モル％以下である。平均重合度が約５０未満の場合には接着力が低下し、約１２００を超えると、接着剤の溶融粘度が著しく高くなり、ホットメルト接着剤として使用することは好ましくない。また、ケン化度が８４モル％を超えると、ＰＶＡ系の融点が高くなり、低温塗工性が低下し、かつ高温高湿下における接着力が低下する。熱溶融性ＰＶＡ系樹脂の好ましい平均重合度の範囲は約１００〜７００、ケン化度の範囲は約２０〜７０モル％である。また、熱溶融性ＰＶＡ系樹脂とポリ乳酸の配合割合は約９９／１〜１０／９０（質量比）であり、約９９／１以上では高温高湿下での接着力不足が生じ、１０／９０以下では水への分散性が低下する。より好ましい配合割合は約９５／５〜３０／７０である。
【００１３】
熱溶融性ＰＶＡ樹脂は、通常、脂肪族ビニルエステル類を重合させることにより製造される。本発明の熱溶融性ＰＶＡ系樹脂を製造する際に用いられる脂肪族ビニルエステル類としては、ギ酸ビニル、酢酸ビニル、プロピオン酸ビニル、ピバリン酸ビニル、ステアリン酸ビニルなどがあげられるが、工業的には酢酸ビニルが望ましい。脂肪族ビニルエステル類の重合方法は公知のものでよく、塊状重合法、溶液重合法、懸濁重合法、乳化重合法等があげられるが、中でもメチルアルコール等の溶剤中でα，α'−アゾビスイソブチロニトリル、２，２'−アゾビス（２，４−ジメチルバレロニトリル）、過酢酸、ジ−ｎ−プロピルパーオキシジカーボネート等のアゾ系または過酸化物系の開始剤を用いて重合する方法が一般的である。重合の際には２−メルカプトエタノール等の重合度調整用の連鎖移動剤を用いたり、重合終了の際にハイドロキノン、ＴＥＭＰＯ、メタ−ジニトロベンゼン等の重合禁止剤・重合用抑制剤等を用いても良い。また、未反応の単量体の除去方法及びケン化、乾燥、粉砕方法等も公知の方法でよく、特に制限は無い。
【００１４】
また、本発明の効果を損なわない範囲で脂肪族ビニルエステルと共重合可能な不飽和単量体と脂肪族ビニルエステルとの共重合を行っても良い。脂肪族ビニルエステルと共重合可能な不飽和単量体としては、例えば、マレイン酸モノメチル、イタコン酸モノメチル等の不飽和二塩基酸モノアルキルエステル類、ダイアセトンアクリルアミド、アクリルアミド、ジメチルアクリルアミド、Ｎ−メチロールアクリルアミド、Ｎ−ビニル−２−ピロリドン等のアミド基含有単量体、ラウリルビニルエーテル、ステアリルビニルエーテル等のアルキルビニルエーテル類、アリルアルコール、ジメチルアリルアルコール、イソプロペニルアリルアルコール等の水酸基含有単量体、アリルアセテート、ジメチルアリルアセテート、イソプロペニルアリルアセテート等のアセチル基含有単量体、塩化ビニル、塩化ビニリデン、フッ化ビニル等のハロゲン化ビニル、トリメトキシビニルシラン、トリブチルビニルシラン、ジフェニルメチルビニルシラン等のビニルシラン類、エチレン、プロピレン等のアルファオレフィン類、アリルスルホン酸Ｎａ、メタリルスルホン酸Ｎａ、スチレンスルホン酸Ｎａ、２−アクリルアミド−２−メチルプロパンスルホン酸Ｎａ等のスルホン酸塩基含有単量体、アクリル酸、メタクリル酸、アクリル酸−２−エチルへキシル、アクリル酸−ｎ−ブチル、２−（２‘−ヒドロキシ−５’−メタクリロキシエチルフェニル）−２Ｈ−ベンゾトリアゾール等のアクリル酸系単量体、ポリオキシエチレン（メタ）アクリレート、ポリオキシプロピレン（メタ）アクリレート、ポリオキシエチレン（メタ）アクリル酸アミド、ポリオキシプロピレン（メタ）アクリル酸アミド、ポリオキシエチレン（メタ）アリルエーテル、ポリオキシプロピレン（メタ）アリルエーテル、ポリオキシエチレンビニルエーテル、ポリオキシプロピレンビニルエーテル等のオキシアルキレン基含有単量体等が挙げられるが、中でもスルホン酸塩基含有単量体、オキシアルキレン基含有単量体、α―オレフィン類、アルキルビニルエーテル類が特に好ましい。
【００１５】
この他、熱溶融性ＰＶＡ系樹脂は部分的にウレタン化、アセタール化、エーテル化、グラフト化、リン酸エステル化などの反応によって変性させた変性樹脂であってもよい。
【００１６】
熱溶融性ＰＶＡ系樹脂は、主鎖または側鎖にスルホン酸基またはスルホン酸塩基を有していてもよい。本発明に用いられる主鎖または側鎖にスルホン酸基またはスルホン酸塩基を有する熱溶融性ＰＶＡ系樹脂とは、主鎖または側鎖にスルホン酸基またはスルホン酸塩基が導入されているものであれば特に制限はなく、例えば脂肪酸ビニルエステルとスルホン酸基またはスルホン酸塩基含有不飽和単量体との共重合し、ケン化を行う方法、又は脂肪酸ビニルエステルの重合又は共重合後に、アルデヒド類などを反応させて後変性によりスルホン酸基（スルホ基）またはスルホン酸塩基（塩基で中和されたスルホ基）を導入する方法により得ることができる。これらは、公知方法によって行われる。前記スルホン酸基もしくはスルホン酸塩基含有不飽和単量体としては、ビニルスルホン酸またはその塩、アリルスルホン酸またはその塩、メタリルスルホン酸またはその塩、スチレンスルホン酸またはその塩、２−アクリルアミド−２−メチルプロパンスルホン酸またはその塩などが挙げられるがこれらに限らない。中でもスルホン酸Ｎａ塩含有不飽和単量体を用いると、接着剤の水溶性または水分散性の改良効果が高い。また、後変性に用いられるアルデヒド類としてはベンズアルデヒドスルホン酸またはその塩やベンズアルデヒドジスルホン酸またはその塩などが挙げられるがこれに限らない。スルホン酸Ｎａ塩が好適に用いられる。
【００１７】
本発明に用いられる主鎖または側鎖にオキシアルキレン基を有する熱溶融性ＰＶＡ系樹脂とは、主鎖または側鎖にオキシアルキレン基が導入されているものであれば特に制限はなく、その中でも脂肪酸ビニルエステルとオキシアルキレン基含有不飽和単量体との共重合体ケン化物が好適に用いられる。
【００１８】
本発明で言うオキシアルキレン基とは一般式
【化５】
で表される構造を有するものであり、なかでもｎが１〜５０、好ましくは３〜５０のオキシエチレン基もしくはオキシプロピレン基が好適である。
【００１９】
また、前記オキシアルキレン基不飽和単量体としては、ポリオキシエチレン（メタ）アクリレート、ポリオキプロピレン（メタ）アクリレート等のポリオキシアルキレン（メタ）アクリレート類、ポリオキシエチレン（メタ）アクリル酸アミド、ポリオキシプロピレン（メタ）アクリル酸アミド等のポリオキシアルキレン（メタ）アクリル酸アミド類、ポリオキシエチレン（メタ）アリルエーテル、ポリオキシプロピレン（メタ）アリルエーテル等のポリオキシアルキレン（メタ）アリルエーテル類、ポリオキシエチレンビニルエーテル、ポリオキシプロピレンビニルエーテル等のポリオキシアルキレンビニルエーテル類等があげられるがこれに限らない。
【００２０】
本発明で使用される酢酸ビニルと共重合されるα―オレフィンとは、例えばエチレン、プロピレン、ｎ−ブテン、イソブチレンなどが挙げられるが、中でもエチレンが工業的には好ましい。
【００２１】
本発明中の側鎖にアルキル基を有する熱溶融性ＰＶＡ系樹脂とは、側鎖にアルキル基を有するものであれば特に制限はなく、その中でも脂肪酸ビニルエステルとアルキル基含有不飽和単量体との共重合体ケン化物が好適に用いられる。
【００２２】
アルキル基含有不飽和単量体としては、ラウリルビニルエーテル、ステアリルビニルエーテルなどのアルキルビニルエーテル類などが挙げられるがこれに限らない。
【００２３】
本発明のポリ乳酸樹脂は、通常、糖類・でんぷんを主原料として得られる乳酸を重合したものである。この際、乳酸のみである必要はなく、乳酸の一部として例えばリンゴ酸、グルコール酸等の他のヒドロキシカルボン酸が用いられてもよい。乳酸は、Ｌ−乳酸、Ｄ−乳酸又はそれらの混合物であってよい。また、層状ケイ酸塩やカーボンブラック、シリカ等を添加したナノコンポジットポリ乳酸を用いてもかまわない。本発明のポリ乳酸樹脂は、乳酸と多価アルコールや多塩基酸との共重合物であってよい。乳酸を得るための発酵方法、ポリ乳酸を得るための重合方法等は公知のものでよく特に制限はない。例えば、ラクチド法、多価アルコールと多塩基酸との重縮合、または分子内に水酸基とカルボキシル基とを有するヒドロキシカルボン酸の分子間重縮合などが好都合に用いられる。
【００２４】
本発明のホットメルト接着剤には、熱溶融性ＰＶＡ系樹脂とポリ乳酸以外に可塑剤が含まれていてもよい。本発明に用いられる熱溶融性ＰＶＡ系樹脂とポリ乳酸に対して配合される可塑剤は、ホットメルト接着剤の溶融粘度を低下させたい場合や柔軟性を高めたい場合に用いられる。
なお、本発明のホットメルト接着剤の溶融粘度は、１０，０００ｍＰａ・ｓ未満が好ましい。
【００２５】
本発明で言う可塑剤とは、熱溶融性ＰＶＡ系樹脂、ポリ乳酸との相溶性が良く、溶融粘度低下効果があるものが用いられ、２種以上を併用して使用してもよい。このような可塑剤としてはグリセリン、ジグリセリン、ポリグリセリン、トリメチロールエタン、トリメチロールプロパン、ペンタエリスリトール、エチレングリコール、プロパンジオール、ブタンジオール、ヘキサンジオール、ポリエチレングリコール、３−メチルペンタン―１、３、５―トリオール、キシリット、キシロール、アラビット、アドニット、マンニット、ソルビット、ダルシットなどの多価アルコール類またはこれらの高級脂肪酸エステル、およびこれらにエチレンオキサイド、プロピレンオキサイドを付加した付加物、エチレン尿素などの尿素誘導体などのＰＶＡ系樹脂用可塑剤やジメチルアジペート、ジエチルアジペート、ジ−ブチルアジペート、ジ−２−エチルヘキシルアジペートなどの脂肪族多価カルボン酸エステル類、エチレングリコールジアセテート、エチレングリコールジブチレート、ポリエチレングリコールジアセテート、トリエチレングリコールジセバケート、プロピレングリコールジアセテート、ポリプロピレングリコールジアセテート、グリセリントリアセテート、グリセリントリブチレートなどの脂肪族多価アルコールエステル、アセチルリシノール酸メチル、アセチルリシノール酸プロピル、アセチルリシノール酸ブチル、アセチルトリブチルクエン酸などの脂肪族オキシ酸エステル類、ジメチルジグリコールサクシネート、ジエチルジグリコールサクシネート、ジプロピルジグリコールサクシネート、ジメチルジグリコールアジペート、ジエチルジグリコールアジペート、ジプロピルジグリコールアジペート、ジブチルジグリコールアジペートなどの脂肪族ポリエーテル多価カルボン酸エステル類などのポリ乳酸用可塑剤が挙げられるがこれに限らない。
【００２６】
可塑剤の使用量は、熱溶融性ＰＶＡ系樹脂とポリ乳酸とを合わせた１００質量部に対して、約０．１〜３０質量部である。可塑剤の添加量が約０．１質量部より少ないとホットメルト接着剤の柔軟性が不足し、また約３０質量部より多いと、ホットメルト接着剤の高温高湿下での接着性の低下やベタつき、可塑剤のブリードが生じる。可塑剤が配合される好適な範囲は約５〜２０質量部である。
【００２７】
本発明のホットメルト接着剤には、熱溶融性ＰＶＡ系樹脂とポリ乳酸以外にアニオン界面活性剤が含まれていてもよい。本発明で用いられ、熱溶融性ＰＶＡ系樹脂とポリ乳酸に対して配合されるアニオン界面活性剤は、ホットメルト接着剤の水分散性を向上させたい場合に用いられる。本発明に使用されるアニオン界面活性剤としては、ラウリル硫酸ソーダ、ラウリル硫酸アンモニウムなどのアルキル硫酸塩類、直鎖第二級アルキル（炭素数１２〜１６）スルホン酸ソーダなどのアルキルスルホン酸塩類、ドデシルベンゼンスルホン酸ソーダなどの長鎖アルキル基を有する水溶性のアルキルベンゼンスルホン酸塩類、ジオクチルスルホコハク酸ソーダなどのジアルキルベンゼンスルホコハク酸塩類、オレイン酸ソーダ、半硬化牛脂ナトリウム石ケン、オレイン酸カリウム、半硬化牛脂カリウム石ケン、ヒマシ油カリウム石ケン、ステアリン酸ソーダ、ステアリン酸カリウムなどの脂肪酸アルカリ塩類などが挙げられる。なお、ノニオン界面活性剤やカチオン界面活性剤を各種試みてはいるが充分な効果が得られるものは認められてはいない。
【００２８】
アニオン界面活性剤であればどのようなものでもホットメルト接着剤の水分散性に優れているが、ポリオキシエチレンアルキルエーテル硫酸塩、ポリオキシエチレンアルキルフェニルエーテル硫酸塩、アルキルホスフォネート塩、アルキルナフタレンスルホン酸塩等がホットメルト接着剤の水分散性を付与する効果が比較的小さい。また、高級脂肪酸アルキロールアミド硫酸エステル塩、高級脂肪酸アルキロールアミドスルホン酸塩などはホットメルト接着剤の水分散性を付与する効果が上記したアニオン界面活性剤よりも大きいが、それでもホットメルト接着剤の水分散性を付与する効果は最も大きくはない。
【００２９】
しかしながら、アニオン界面活性剤の中でも、アルキル硫酸塩、アルキルスルホン酸塩、アルキルベンゼンスルホン酸塩、ジアルキルスルホコハク酸塩、脂肪酸アルカリ塩などは、ホットメルト接着剤に水分散性を付与する効果が特に顕著であり、本発明のアニオン界面活性剤として特に好ましい。これらのアニオン界面活性剤は、いくつかの種類を混合して用いてもよい。
【００３０】
また、アニオン界面活性剤は、熱安定性を有することが好ましい。ホットメルト接着剤として使用するので接着剤は使用時に加熱され高温となる。したがって、加熱安定性の優れたアニオン界面活性剤であることが好ましく、中でもアルキルベンゼンスルホン酸塩が好適である。
【００３１】
アニオン界面活性剤の使用量は、熱溶融性ＰＶＡ系樹脂とポリ乳酸との合計量１００質量部に対して、約０．０１〜１０質量部である。アニオン界面活性剤添加量が約０．０１質量部より少ないとホットメルト接着剤の水分散性改良効果が少なく、約１０質量部より多く添加しても水分散性改良効果が頭打ちとなる。アニオン界面活性剤が好適に用いられる範囲は約０．１〜５．０質量部である。
【００３２】
この他ホットメルト接着剤には、本発明の効果を損なわない範囲で粘着剤、酸化防止剤、滑剤、充填剤、着色剤、香料、安定剤をはじめ種々の添加剤を配合することができる。
【００３３】
本発明のホットメルト接着剤は、熱溶融性ポリビニルアルコール系樹脂とポリ乳酸とさらに所望により上記したその他の成分を加熱し、溶融することによって製造できる。溶融温度は特に制限はないが原料であるＰＶＡ系樹脂およびポリ乳酸の熱分解を防止するためにも加熱温度は、ＰＶＡ系樹脂の融点以上でポリ乳酸樹脂の熱分解温度以下であるのが好ましく、具体的には、約２３０℃以下、好ましくは約２００℃以下、さらに好ましくは約１８０℃以下にした方が良く、混練時間も樹脂の分解を抑制するという意味で約１時間以内が好ましい。
【００３４】
また、ホットメルト接着剤は、溶融ブレンド後、任意の形状に成形して製品化される。例えば、従来よりホットメルト接着剤の製品化に用いられている任意の方法が実施でき、ブロック、短冊、ビスケット、ペレット、ロープ、粉末、フィルム状など適当な形状に加工できる。成形方法はかかる形状によって異なる。例えば、短冊状に成形する場合、前記のごとく溶融混合した溶融物をステンレス等のベルト板上にフィーダーから流出させ、ベルトの内側から冷却水をスプレーして間接的に吐出されたストランドを冷却固化し、固化後カッターで短冊状にカットして成形する方法が挙げられる。かくして得られた水溶性又は水分散性ホットメルト接着剤は、エチレン―酢酸ビニル系ホットメルト接着剤など一般的なホットメルト接着剤の製造装置や塗工機械をそのまま利用できるので工業的に非常に有利である。よって、本発明の接着剤を塗工する方法としては公知のロール、ダイ、ノズル、リップ等のホットメルト塗工機によって行うことが望ましい。
【００３５】
かかるホットメルト接着剤などが適用可能な物品は特に制限はなく、例えば、コピー用紙、包装紙、おもちゃ等を包装する包装容器、段ボール箱やカートン箱などの製函ないし封函容器、電話帳やカタログや伝票等の製本物品、段ボールパレット、ファイバー缶、紙管、紙おむつ等の衛生材料製品などに対して用いることが出来る。また、おもちゃ等を包装する包装容器や段ボール箱やカートン箱などを製函ないし封函する際に使用する接着剤、袋の上端、下端もしくは胴部が接着シールされた袋製品の接着シールに使用する接着剤として使用してもよく、さらに、本発明の接着剤をクラフト紙などの支持体に塗工した接着テープを製造し、これを加熱により貼り付け可能となる感熱接着テープや吸湿により貼り付け可能となる感湿接着テープやこれらを用いたラベルとして用いてもよい。なお、紙製品はリサイクル適性に優れるので本接着剤を適用する物品として好適である。
【００３６】
本発明において、ポリビニルアルコールの重合度（Ｐ）及びケン化度は、ＪＩＳ−Ｋ６７２６に従って測定される。
【００３７】
【実施例】
以下に本発明を実施例により具体的に説明するために、本発明の一例を示す実施例およびこれとの比較を示す比較例をいくつか挙げ、さらに得られた各接着剤について行った性能試験結果について示す。
【００３８】
＜熱溶融性ＰＶＡ系樹脂の合成例１＞
撹拌機、還流冷却管、窒素導入管、温度計、圧力計を備えた反応器を窒素置換した後、脱酸素した酢酸ビニルモノマー２０００質量部、エタノール１０００質量部を仕込み撹拌下で昇温を開始し、内温が６０℃となったところで、別途エタノール５０質量部に開始剤としてＡＩＢＮ２．５質量部を溶解した溶液を添加して重合を開始した。６０℃で４時間重合した後、冷却して重合を停止した。このときの重合溶液中の固形分濃度は５７．３％であった。得られた重合溶液を塔内に多孔板を多段数有する脱モノマー塔に供給して塔下部よりメタノール蒸気を吹き込んで重合溶液と接触させて未反応の酢酸ビニルモノマーを除去した。このときのポリ酢酸ビニル系樹脂−メタノール溶液の固形分濃度は６４％であった。このポリ酢酸ビニル系樹脂−メタノール溶液１０００質量部に２％水酸化ナトリウム−メタノール溶液を１０質量部添加後、よく混合して４０℃で１時間放置した。乾燥後粉砕を行い本発明の熱溶融性ＰＶＡ系樹脂を得た。重合度が３８０でケン化度が３８モル％であった。得られた熱溶融性ＰＶＡ系樹脂をＰＶＡ１とする。
【００３９】
＜熱溶融性ＰＶＡ系樹脂の合成例２＞
撹拌機、還流冷却管、窒素導入管、温度計、圧力計を備えた反応器を窒素置換した後、脱酸素した酢酸ビニルモノマー１５００質量部、ヒドロキシブチルビニルエーテル−ＥＯ付加物（ＥＯの付加数は１０単位）１０００質量部、メタノール１７００質量部を仕込み撹拌下で昇温を開始し、内温が６０℃となったところで、別途メタノール１００質量部に開始剤としてＡＩＢＮ４．０質量部を溶解した溶液を添加して重合を開始した。６０℃で６時間重合した後、冷却して重合を停止した。このときの重合溶液中の固形分濃度は５５．１％であった。得られた重合溶液を塔内に多孔板を多段数有する脱モノマー塔に供給して塔下部よりメタノール蒸気を吹き込んで重合溶液と接触させ未反応の酢酸ビニルモノマーを除去した。このときのポリ酢酸ビニル系樹脂−メタノール溶液の固形分濃度は４５％であった。このポリ酢酸ビニル系樹脂−メタノール溶液１０００質量部に２％水酸化ナトリウム−メタノール溶液を１２質量部添加後よく混合して４０℃で１時間放置した。ケン化後得られたゲルを粉砕機で粉砕した後、６０℃の送風乾燥機で乾燥した。乾燥後粉砕を行い本発明の熱溶融性ＰＶＡ系樹脂を得た。重合度が２６０でケン化度が４０モル％であった。また変性量は５．２モル％であった。得られた熱溶融性ＰＶＡ系樹脂をＰＶＡ５とする。
【００４０】
［使用した材料］
＜熱溶融性ＰＶＡ系樹脂＞
ＰＶＡ１；平均重合度３８０、ケン化度３８モル％のＰＶＡ
ＰＶＡ２；平均重合度１５０、ケン化度５９モル％のＰＶＡ
ＰＶＡ３；平均重合度５００、ケン化度３２モル％のＰＶＡ
ＰＶＡ４；平均重合度３００、ケン化度２５モル％、アリルスルホン酸Ｎａ３．１モル％変性のＰＶＡ
ＰＶＡ５；平均重合度２６０、ケン化度４０モル％、ポリオキシエチレングリコールブチルビニルエーテル（エチレンオキサイド１０付加）５．２モル％変性のＰＶＡ
ＰＶＡ６；平均重合度２４０、ケン化度５０モル％、エチレン８．５モル％変性のＰＶＡ
ＰＶＡ７；平均重合度１２０、ケン化度４５モル％、ラウリルビニルエーテル７．４モル％変性のＰＶＡ
ＰＶＡ８；平均重合度１５０、ケン化度８８モル％のＰＶＡ
上記熱溶融性ＰＶＡ系樹脂は熱溶融性ＰＶＡ系樹脂の合成例１もしくは合成例２と同様の方法を用いて得られる。
＜ポリ乳酸＞
ポリ乳酸１；重量平均分子量１３０，０００、ｄ体含有割合１２．０質量％でｌ体含有割合８８．０質量％のポリ乳酸
ポリ乳酸２；公開特許２００２−３６３３９３号公報の実施例１に従って作製したナノコンポジットポリ乳酸
＜可塑剤＞
可塑剤１；ジグリセリン誘導体（阪本薬品社製、商品名；ＳＣＥ−７５０）
可塑剤２；アセチルトリブチルクエン酸
＜界面活性剤＞
界面活性剤１；ドデシルベンゼンスルホン酸ソーダ（ハード型、アニオン界面活性剤）
界面活性剤２；ポリオキシエチレンノニルフェニルエーテル（ノニオン界面活性剤）
界面活性剤３；ラウリルトリメチルアンモニウムクロライド（カチオン界面活性剤）
【００４１】
（実施例１〜７）
表１に示すように、本発明のホットメルト接着剤に合致する成分および配合割合で各成分をミキサー試験機に投入し、配合物を１５０℃で溶融混合して均一な混合組成物とし、実施例のホットメルト接着剤を得た。
【００４２】
（比較例１）
表２に示すように、本発明のホットメルト接着剤に合致しない配合割合で各成分を配合し、以降は前記実施例と同じ操作を行ってホットメルト接着剤を得た。
【００４３】
【表１】
【表２】
［性能試験］
実施例および比較例で得られた接着剤について、下記の方法で性能試験を行った。
＜耐湿熱接着性＞
接着剤を２枚の汎用段ボール（サイズ５０ｍｍ×１００ｍｍ、「Ｋライナー」）に塗布温度１５０℃、塗布量０．０３ｇ／ｃｍ、塗布速度７．５ｍ／分にて塗布し、ホットメルトオープンタイムテスターを用いて、オープンタイム２秒、プレス荷重２ｋｇで貼り合わせて耐湿熱接着性試験片を作製した。次いで、上記で得られた耐湿熱接着性試験片を２５ｍｍ×１００ｍｍサイズに切断し、温度４０℃、湿度８０％の条件で放置し、手で強制的に剥離して材破率を測定した。３０時間放置後の材破率が８０％以上のものを耐湿熱接着性良好（○印）とした。
＜水分散性＞
２５ｍｍ×５０ｍｍ×１ｍｍの接着剤小片を準備し、これを試験片として温度２０℃の２００ｍＬ水中に浸漬し、ジューサーミキサーを用いて攪拌し、接着剤の分散状態を目視で観察した。こうして接着剤の水分散性の良否を調べた。
○：水中に完全に微分散する。
×：一部分散するが、不溶物が残る。
＜溶融粘度＞
（JIS-K-6862による）
○：１５０℃での溶融粘度が１０，０００ｍＰａ・ｓ未満となるもの
×：１５０℃での溶融粘度が１０，０００ｍＰａ・ｓ以上となるもの
＜加熱安定性＞
あらかじめ溶融された試料約３０ｍＬを入れ、アルミ箔で蓋をした試料容器（１４０ｍｌマヨネーズ瓶）を使用温度（溶融粘度が１０，０００ｍＰａ・ｓ未満となる温度）±２℃に保持した恒温槽に入れる。試料が使用温度に達してから２４時間毎に表面に皮が発生する時間を観察した。
○：２４時間以上表面に皮はりが発生しなかった
×：表面に皮はりが発生するまでの時間が２４時間未満であった
【００４６】
＜総合評価＞
上記の各評価を総合的に以下の基準で総合評価した。
○：すべての項目の性能が良好。（○印）
×：１つ以上の性能が劣っている。
【００４７】
【表３】
【発明の効果】
上記記載の通り、本発明のホットメルト接着剤は、▲１▼高温高湿下における接着力、▲２▼常温中性下における水溶性もしくは水分散性、▲３▼優れた加熱安定性および▲４▼容易に塗工され得る程度の溶融粘度の諸物性のバランスに優れている。また、本発明のホットメルト接着剤は、熱溶融性ＰＶＡ系樹脂、ポリ乳酸などの生分解性を有する樹脂が用いられており、ホットメルト接着剤を廃棄する際にも環境への負荷が少なく、リサイクル適性に優れている。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a water-soluble or water-dispersible hot melt adhesive composed of a heat-meltable polyvinyl alcohol resin and polylactic acid, and more specifically, water-soluble or water-resistant adhesive strength hardly decreases under high temperature and high humidity. The present invention relates to a dispersible hot melt adhesive.
[0002]
[Prior art]
Hot melt adhesives have an industrial advantage because they can be bonded instantaneously or at high speed without solvent. Therefore, it is used in large quantities mainly in fields such as bookbinding, packaging, woodworking, iron making, and textiles. Hot melt adhesives are required to satisfy performance such as adhesiveness, meltability, heat resistance, cold resistance and flexibility, and are generally ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate. Ester copolymer (EEA), polyethylene, polypropylene, polyamide, polyester, etc. are used as base polymers, especially for packaging, bookbinding and bag making, EVA with excellent adhesion, workability and flexibility. Hot melt adhesives based on these are widely used. However, in recent years, the appropriateness of recycling of adhesive products has been questioned from the viewpoint of resource saving and non-pollution. In the conventional hot melt adhesive as described above, the hot melt adhesive is hydrophobic. When the material is regenerated, a portion that does not dissolve or disperse in water remains, which makes the regeneration process difficult. Therefore, studies are being made on hot melt adhesives with excellent water solubility or water dispersibility, which are excellent in recycling. Among them, many studies have been made to use a polyvinyl alcohol (PVA) -based resin having excellent water solubility or water dispersibility and having adhesiveness and meltability as a base polymer of a hot melt adhesive.
[0003]
For example, a partially saponified PVA resin having a low polymerization degree is used as a base polymer, and a PVA plasticizer such as alcohol, glycerin, polyethylene glycol or ethylene urea having a valence of 5 or more, a viscosity reducing agent, and other additives are used. Water-soluble or water-dispersible hot melt adhesives prepared by mixing have been proposed (for example, Patent Documents 1 to 3). With these adhesives, the coating properties can be improved and the flexibility of the adhesive film can be increased by lowering the melt viscosity.
[0004]
Further, a modified PVA-based resin obtained by saponifying a modified polyvinyl acetate obtained by copolymerizing a monomer containing a hydrophilic group such as carboxylic acid, sulfonic acid or amide or vinyl pyrrolidone and vinyl acetate. A water-soluble or water-dispersible hot melt adhesive used as a base polymer has been proposed (see, for example, Patent Documents 4 to 6). In the hot melt adhesives described in these prior arts, it is said that the water solubility is enhanced by using a specific modified PVA resin.
[0005]
Also, hot-melt bonding using a modified PVA resin obtained by saponifying a modified polyvinyl acetate resin obtained by copolymerizing monomers such as allyl acetate or saturated branched fatty acid vinyl with a vinyl acetate monomer as a base polymer Agents are disclosed. (For example, refer to Patent Documents 7 to 8) In this hot melt adhesive, the adhesive strength under high temperature and high humidity is enhanced, and the cold resistance is enhanced, and the compatibility with other resins contained in the adhesive is excellent. It is said that.
[0006]
However, hot melt adhesives using these PVA-based resins as base resins are: (1) adhesive strength under high temperature and high humidity, (2) water-soluble or It was not a hot melt adhesive that could satisfy all four physical properties such as water dispersibility, (3) excellent heat stability, and (4) melt viscosity that can be easily applied.
[0007]
In order to achieve the above four physical properties, the inventors have 100 parts by weight of a polyvinyl alcohol resin having an average degree of polymerization of 50 to 1200 and a saponification degree of 60 mol% or less, and 0.01 to 30 parts by weight of an anionic surfactant. And a water-soluble or water-dispersible hot melt adhesive containing 0.1 to 50 parts by mass of a plasticizer was proposed (see, for example, Patent Document 9).
Although this hot melt adhesive can satisfy the above four physical properties, it is still desired to further improve the adhesive strength under high temperature and high humidity.
[0008]
[Patent Document 1]
JP 51-77632 A (Claim 1)
[Patent Document 2]
JP-A 51-95440 (Claims 1 and 2)
[Patent Document 3]
JP-A-51-149328 (Claim 1)
[Patent Document 4]
JP-A-53-50239 (Claims 1 to 4)
[Patent Document 5]
JP 54-138033 A (claims (1-4))
[Patent Document 6]
JP-A-54-139945 (Claims 1 to 3)
[Patent Document 7]
JP-A-54-76634 (Claim 1)
[Patent Document 8]
JP 55-94978 A (Claims 1 and 2)
[Patent Document 9]
Japanese Patent Laying-Open No. 2003-3140 (Claims 1 to 7)
[0009]
[Problems to be solved by the invention]
Accordingly, the present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a hot melt adhesive which is easily manufactured industrially and has improved adhesive strength under high temperature and high humidity.
[0010]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present invention contains a hot-melt polyvinyl alcohol resin and polylactic acid, and the blending ratio of the hot-melt polyvinyl alcohol resin and polylactic acid is 99/1. -10/90 (mass ratio) is used to find that it is effective to achieve the above-mentioned problems by using a hot-melt adhesive, and the present invention is completed through further studies. It came to.
[0011]
That is, the present invention
(1) It contains a heat-meltable polyvinyl alcohol resin and polylactic acid, and the blending ratio of the heat-meltable polyvinyl alcohol resin and polylactic acid is in the range of 99/1 to 10/90 (mass ratio). Hot melt adhesive,
(2) Furthermore, it contains a plasticizer and / or an anionic surfactant, and the content of the plasticizer is 0.1 to 30 parts by mass with respect to 100 parts by mass of the hot melt adhesive, and the content of the anionic surfactant 0.01 to 10 parts by mass of the hot melt adhesive according to (1),
(3) The average degree of polymerization of the hot-melt polyvinyl alcohol is 50 to 1200, and the saponification degree of the hot-melt polyvinyl alcohol is 84 mol% or less, as described in (1) or (2) Hot melt adhesive,
(4) The hot melt adhesive according to any one of (1) to (3), wherein the hot-melt polyvinyl alcohol-based resin has a sulfonic acid group or a sulfonic acid group in the main chain or side chain.
(5) The hot melt adhesive according to any one of (1) to (4), wherein the heat-meltable polyvinyl alcohol-based resin has an oxyalkylene group in the main chain or side chain,
(6) The oxyalkylene group has the general formula
[Chemical 3]
An oxyethylene group represented by or a general formula
[Formula 4]
A heat-meltable polyvinyl which is an oxypropylene group represented by the formula (1) and the heat-meltable polyvinyl alcohol-based resin contains 0.1 to 50 mol% of a monomer unit containing an oxyalkylene group with respect to all monomer units. The hot melt adhesive according to any one of (1) to (5), which is an alcohol-based resin,
(7) The hot melt adhesive according to any one of (1) to (6), wherein the heat-meltable polyvinyl alcohol resin is a saponified product of a copolymer of vinyl acetate and α-olefin,
(8) The hot melt adhesive according to any one of (1) to (7), wherein the heat-meltable polyvinyl alcohol-based resin has an alkyl group in a side chain,
(9) The anionic surfactant is at least one selected from the group consisting of alkyl sulfates, alkyl sulfonates, alkyl benzene sulfonates, dialkyl sulfosuccinates and fatty acid alkali salts (1) Hot melt adhesive according to any one of to (8),
About.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail. The heat-meltable PVA resin used in the present invention is not particularly limited as long as it can be melted by heat, and preferably has an average degree of polymerization of about 50 to 1200 and a degree of saponification of about 84 mol% or less. When the average degree of polymerization is less than about 50, the adhesive strength decreases. When it exceeds about 1200, the melt viscosity of the adhesive is remarkably increased, and it is not preferable to use it as a hot melt adhesive. On the other hand, when the degree of saponification exceeds 84 mol%, the melting point of the PVA system becomes high, the low-temperature coating property is lowered, and the adhesive force under high temperature and high humidity is lowered. The preferable range of the average degree of polymerization of the heat-meltable PVA resin is about 100 to 700, and the range of the saponification degree is about 20 to 70 mol%. Further, the blending ratio of the heat-meltable PVA resin and polylactic acid is about 99/1 to 10/90 (mass ratio), and if it is about 99/1 or more, insufficient adhesive strength under high temperature and high humidity occurs. If it is 90 or less, the dispersibility in water decreases. A more preferable blending ratio is about 95/5 to 30/70.
[0013]
The hot-melt PVA resin is usually produced by polymerizing aliphatic vinyl esters. Examples of the aliphatic vinyl esters used in producing the heat-meltable PVA resin of the present invention include vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl stearate, and the like. Is preferably vinyl acetate. The polymerization method of the aliphatic vinyl ester may be a known one, and examples thereof include a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method. Among them, α, α′- in a solvent such as methyl alcohol. Using an azo or peroxide initiator such as azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), peracetic acid, di-n-propylperoxydicarbonate, etc. A polymerization method is common. Use a chain transfer agent for adjusting the degree of polymerization such as 2-mercaptoethanol at the time of polymerization, or use a polymerization inhibitor / polymerization inhibitor such as hydroquinone, TEMPO, or meta-dinitrobenzene at the end of the polymerization. Also good. Also, a method for removing unreacted monomers and a saponification, drying, and pulverization method may be known methods, and there is no particular limitation.
[0014]
Moreover, you may copolymerize the unsaturated monomer and aliphatic vinyl ester which can be copolymerized with aliphatic vinyl ester in the range which does not impair the effect of this invention. Examples of unsaturated monomers copolymerizable with aliphatic vinyl esters include unsaturated dibasic acid monoalkyl esters such as monomethyl maleate and monomethyl itaconate, diacetone acrylamide, acrylamide, dimethyl acrylamide, and N-methylol. Amide group-containing monomers such as acrylamide and N-vinyl-2-pyrrolidone, alkyl vinyl ethers such as lauryl vinyl ether and stearyl vinyl ether, hydroxyl group-containing monomers such as allyl alcohol, dimethylallyl alcohol and isopropenyl allyl alcohol, allyl acetate Acetyl group-containing monomers such as dimethylallyl acetate, isopropenyl allyl acetate, vinyl halides such as vinyl chloride, vinylidene chloride, vinyl fluoride, trimethoxyvinylsilane, tributy Vinyl silanes such as vinyl silane and diphenylmethyl vinyl silane, alpha olefins such as ethylene and propylene, sulfonic acids such as sodium allyl sulfonate, sodium methallyl sulfonate, sodium styrene sulfonate, and sodium 2-acrylamido-2-methylpropane sulfonate Base-containing monomers, acrylic acid, methacrylic acid, 2-ethylhexyl acrylate, n-butyl acrylate, 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole, etc. Acrylic acid monomers, polyoxyethylene (meth) acrylate, polyoxypropylene (meth) acrylate, polyoxyethylene (meth) acrylic amide, polyoxypropylene (meth) acrylic amide, polyoxyethylene (meth) Allyl ether, poly Examples include oxyalkylene group-containing monomers such as reoxypropylene (meth) allyl ether, polyoxyethylene vinyl ether, and polyoxypropylene vinyl ether. Among them, sulfonate group-containing monomers, oxyalkylene group-containing monomers, α-olefins and alkyl vinyl ethers are particularly preferred.
[0015]
In addition, the heat-meltable PVA resin may be a modified resin partially modified by a reaction such as urethanization, acetalization, etherification, grafting, or phosphoric esterification.
[0016]
The hot-melt PVA resin may have a sulfonic acid group or a sulfonic acid group in the main chain or side chain. The heat-meltable PVA resin having a sulfonic acid group or sulfonate group in the main chain or side chain used in the present invention is one in which a sulfonic acid group or sulfonate group is introduced into the main chain or side chain. There is no particular limitation, for example, a method in which a fatty acid vinyl ester is copolymerized with a sulfonic acid group or a sulfonate group-containing unsaturated monomer and saponified, or after the polymerization or copolymerization of a fatty acid vinyl ester, aldehydes, etc. And a sulfonic acid group (sulfo group) or a sulfonic acid group (sulfo group neutralized with a base) is introduced by post-modification. These are performed by a known method. Examples of the sulfonic acid group or sulfonate group-containing unsaturated monomer include vinyl sulfonic acid or a salt thereof, allyl sulfonic acid or a salt thereof, methallyl sulfonic acid or a salt thereof, styrene sulfonic acid or a salt thereof, 2-acrylamide- Examples include, but are not limited to, 2-methylpropanesulfonic acid or a salt thereof. Among them, when an unsaturated monomer containing a sulfonic acid Na salt is used, the effect of improving the water solubility or water dispersibility of the adhesive is high. Examples of aldehydes used for post-modification include, but are not limited to, benzaldehyde sulfonic acid or a salt thereof, benzaldehyde disulfonic acid or a salt thereof, and the like. A sulfonic acid Na salt is preferably used.
[0017]
The heat-meltable PVA resin having an oxyalkylene group in the main chain or side chain used in the present invention is not particularly limited as long as the oxyalkylene group is introduced into the main chain or side chain, and among them, A saponified copolymer of a fatty acid vinyl ester and an oxyalkylene group-containing unsaturated monomer is preferably used.
[0018]
The oxyalkylene group referred to in the present invention is a general formula.
[Chemical formula 5]
Among them, an oxyethylene group or an oxypropylene group having n of 1 to 50, preferably 3 to 50 is suitable.
[0019]
The oxyalkylene group unsaturated monomer includes polyoxyethylene (meth) acrylates such as polyoxyethylene (meth) acrylate and polyoxypropylene (meth) acrylate, polyoxyethylene (meth) acrylic amide, Polyoxyalkylene (meth) allyl ethers such as polyoxyalkylene (meth) acrylic amides such as polyoxypropylene (meth) acrylic amide, polyoxyethylene (meth) allyl ether, polyoxypropylene (meth) allyl ether, etc. Examples thereof include polyoxyalkylene vinyl ethers such as polyoxyethylene vinyl ether and polyoxypropylene vinyl ether, but are not limited thereto.
[0020]
Examples of the α-olefin copolymerized with vinyl acetate used in the present invention include ethylene, propylene, n-butene, and isobutylene. Among them, ethylene is industrially preferable.
[0021]
The heat-meltable PVA resin having an alkyl group in the side chain in the present invention is not particularly limited as long as it has an alkyl group in the side chain, and among them, fatty acid vinyl ester and alkyl group-containing unsaturated monomer. A saponified product of the above is preferably used.
[0022]
Examples of the alkyl group-containing unsaturated monomer include, but are not limited to, alkyl vinyl ethers such as lauryl vinyl ether and stearyl vinyl ether.
[0023]
The polylactic acid resin of the present invention is usually obtained by polymerizing lactic acid obtained using saccharides and starch as a main raw material. At this time, it is not necessary to use only lactic acid, and other hydroxycarboxylic acids such as malic acid and glycolic acid may be used as a part of lactic acid. The lactic acid may be L-lactic acid, D-lactic acid or a mixture thereof. Alternatively, nanocomposite polylactic acid to which layered silicate, carbon black, silica, or the like is added may be used. The polylactic acid resin of the present invention may be a copolymer of lactic acid and a polyhydric alcohol or polybasic acid. The fermentation method for obtaining lactic acid and the polymerization method for obtaining polylactic acid may be known ones and are not particularly limited. For example, lactide method, polycondensation of polyhydric alcohol and polybasic acid, or intermolecular polycondensation of hydroxycarboxylic acid having a hydroxyl group and a carboxyl group in the molecule is advantageously used.
[0024]
The hot melt adhesive of the present invention may contain a plasticizer in addition to the hot-melt PVA resin and polylactic acid. The plasticizer blended with the heat-meltable PVA resin and polylactic acid used in the present invention is used when it is desired to reduce the melt viscosity of the hot melt adhesive or to increase the flexibility.
The melt viscosity of the hot melt adhesive of the present invention is preferably less than 10,000 mPa · s.
[0025]
As the plasticizer in the present invention, those having good compatibility with a hot-melt PVA resin and polylactic acid and having an effect of lowering melt viscosity are used, and two or more kinds may be used in combination. Such plasticizers include glycerin, diglycerin, polyglycerin, trimethylolethane, trimethylolpropane, pentaerythritol, ethylene glycol, propanediol, butanediol, hexanediol, polyethylene glycol, 3-methylpentane-1, 3, 5-triol, xylit, xylol, arabit, adnit, mannitol, sorbit, polyhydric alcohols such as dalbit, higher fatty acid esters thereof, adducts obtained by adding ethylene oxide or propylene oxide to these, urea such as ethylene urea PVA resin plasticizers such as derivatives and aliphatic polycarboxylic acid esters such as dimethyl adipate, diethyl adipate, di-butyl adipate, di-2-ethylhexyl adipate , Aliphatic polyhydric alcohol esters such as ethylene glycol diacetate, ethylene glycol dibutyrate, polyethylene glycol diacetate, triethylene glycol disebacate, propylene glycol diacetate, polypropylene glycol diacetate, glycerin triacetate, glycerin tributyrate, Aliphatic oxyacid esters such as methyl acetyl ricinoleate, propyl acetyl ricinoleate, butyl acetyl ricinoleate and acetyl tributyl citrate, dimethyl diglycol succinate, diethyl diglycol succinate, dipropyl diglycol succinate, dimethyl diglycol Adipate, diethyl diglycol adipate, dipropyl diglycol adipate, dibutyl diglycol Polylactic acid plasticizer such as aliphatic polyether polycarboxylic acid esters such as Jipeto including but not limited to.
[0026]
The usage-amount of a plasticizer is about 0.1-30 mass parts with respect to 100 mass parts which match | combined the heat-meltable PVA-type resin and polylactic acid. If the added amount of the plasticizer is less than about 0.1 parts by mass, the flexibility of the hot melt adhesive is insufficient, and if it is more than about 30 parts by mass, the adhesiveness of the hot melt adhesive under high temperature and high humidity decreases. Or stickiness and bleeding of plasticizer. The preferred range in which the plasticizer is blended is about 5-20 parts by weight.
[0027]
The hot melt adhesive of the present invention may contain an anionic surfactant in addition to the hot-melt PVA resin and polylactic acid. The anionic surfactant used in the present invention and blended with the hot-melt PVA resin and polylactic acid is used when it is desired to improve the water dispersibility of the hot melt adhesive. Examples of the anionic surfactant used in the present invention include alkyl sulfonates such as sodium lauryl sulfate and ammonium lauryl sulfate, alkyl sulfonates such as linear secondary alkyl (carbon number 12 to 16) sulfonic acid soda, and dodecylbenzene. Water-soluble alkylbenzene sulfonates with long-chain alkyl groups such as sodium sulfonate, dialkylbenzene sulfosuccinates such as dioctyl sulfosuccinate, sodium oleate, semi-cured tallow sodium soap, potassium oleate, semi-cured tallow potassium Examples include soaps, castor oil potassium soaps, fatty acid alkali salts such as sodium stearate and potassium stearate. Although various attempts have been made with nonionic surfactants and cationic surfactants, no non-ionic surfactant or cationic surfactant has been recognized.
[0028]
Any anionic surfactant is excellent in water dispersibility of the hot melt adhesive, but polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, alkyl phosphonate salt, alkyl Naphthalene sulfonate and the like have a relatively small effect of imparting water dispersibility of the hot melt adhesive. Further, higher fatty acid alkylolamide sulfate ester salts, higher fatty acid alkylolamide sulfonates, and the like have a greater effect of imparting water dispersibility to hot melt adhesives than the above-mentioned anionic surfactants. The effect of imparting water dispersibility is not the greatest.
[0029]
However, among the anionic surfactants, alkyl sulfates, alkyl sulfonates, alkyl benzene sulfonates, dialkyl sulfosuccinates, fatty acid alkali salts, and the like are particularly effective in imparting water dispersibility to hot melt adhesives. And is particularly preferred as the anionic surfactant of the present invention. These anionic surfactants may be used in combination of several kinds.
[0030]
Moreover, it is preferable that an anionic surfactant has heat stability. Since it is used as a hot melt adhesive, the adhesive is heated during use and becomes a high temperature. Accordingly, an anionic surfactant having excellent heat stability is preferable, and alkylbenzene sulfonate is particularly preferable.
[0031]
The usage-amount of an anionic surfactant is about 0.01-10 mass parts with respect to 100 mass parts of total amounts of a heat-meltable PVA-type resin and polylactic acid. When the amount of the anionic surfactant added is less than about 0.01 parts by mass, the effect of improving the water dispersibility of the hot melt adhesive is small, and even when added in an amount of more than about 10 parts by mass, the effect of improving the water dispersibility reaches a peak. The range in which the anionic surfactant is preferably used is about 0.1 to 5.0 parts by mass.
[0032]
In addition, various additives such as a pressure-sensitive adhesive, an antioxidant, a lubricant, a filler, a colorant, a fragrance, and a stabilizer can be blended with the hot melt adhesive as long as the effects of the present invention are not impaired.
[0033]
The hot melt adhesive of the present invention can be produced by heating and melting a heat-meltable polyvinyl alcohol-based resin, polylactic acid, and other components described above as desired. The melting temperature is not particularly limited, but the heating temperature is preferably not less than the melting point of the PVA resin and not more than the pyrolysis temperature of the polylactic acid resin in order to prevent thermal decomposition of the raw material PVA resin and polylactic acid. Specifically, the temperature should be about 230 ° C. or less, preferably about 200 ° C. or less, more preferably about 180 ° C. or less, and the kneading time is preferably about 1 hour or less in the sense of suppressing the decomposition of the resin.
[0034]
Further, the hot melt adhesive is formed into a product after being melt-blended and then molded into an arbitrary shape. For example, any method conventionally used for commercialization of hot melt adhesives can be carried out, and can be processed into an appropriate shape such as a block, strip, biscuit, pellet, rope, powder, or film. The molding method varies depending on the shape. For example, when forming into a strip shape, the melt melted and mixed as described above is discharged from a feeder onto a belt plate such as stainless steel, and cooling water is sprayed from the inside of the belt to indirectly cool and solidify the strands discharged. In addition, a method of forming by cutting into a strip shape with a cutter after solidification can be mentioned. The water-soluble or water-dispersible hot melt adhesive obtained in this way is very industrially available because it can be used as it is with general hot melt adhesive manufacturing equipment and coating machines such as ethylene-vinyl acetate hot melt adhesives. It is advantageous. Therefore, as a method for applying the adhesive of the present invention, it is desirable to use a known hot melt coating machine such as a roll, die, nozzle, lip or the like.
[0035]
Articles to which such hot melt adhesives can be applied are not particularly limited, for example, copy paper, wrapping paper, packaging containers for packaging toys, etc., box making or sealing containers such as cardboard boxes and carton boxes, telephone books, It can be used for bookbinding items such as catalogs and slips, sanitary material products such as cardboard pallets, fiber cans, paper tubes, and paper diapers. Also used for boxing or sealing of packaging containers for packaging toys, cardboard boxes, carton boxes, etc., used for adhesive sealing of bag products with the top, bottom, or body of the bag adhesively sealed It can also be used as an adhesive, and an adhesive tape in which the adhesive of the present invention is coated on a support such as kraft paper is manufactured, and this can be applied by heat-sensitive adhesive tape or moisture absorption. It may be used as a moisture-sensitive adhesive tape or a label using these. In addition, since paper products are excellent in recyclability, they are suitable as articles to which the present adhesive is applied.
[0036]
In the present invention, the polymerization degree (P) and saponification degree of polyvinyl alcohol are measured according to JIS-K6726.
[0037]
【Example】
In order to describe the present invention more specifically with reference to the following examples, examples showing the examples of the present invention and some comparative examples showing comparisons with the examples are given, and further performance tests performed on the obtained adhesives. It shows about a result.
[0038]
<Synthesis example 1 of hot-melt PVA resin>
A reactor equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and pressure gauge was replaced with nitrogen, and then 2000 parts by mass of deoxygenated vinyl acetate monomer and 1000 parts by mass of ethanol were charged, and heating was started under stirring. When the internal temperature reached 60 ° C., polymerization was started by separately adding a solution in which 2.5 parts by mass of AIBN was dissolved in 50 parts by mass of ethanol as an initiator. After polymerization at 60 ° C. for 4 hours, the polymerization was stopped by cooling. The solid content concentration in the polymerization solution at this time was 57.3%. The obtained polymerization solution was supplied to a demonomer tower having a multi-stage perforated plate in the tower, and methanol vapor was blown from the bottom of the tower to contact the polymerization solution to remove unreacted vinyl acetate monomer. The solid content concentration of the polyvinyl acetate resin-methanol solution at this time was 64%. 10 parts by weight of a 2% sodium hydroxide-methanol solution was added to 1000 parts by weight of this polyvinyl acetate resin-methanol solution, mixed well, and allowed to stand at 40 ° C. for 1 hour. After drying, pulverization was performed to obtain the hot-melt PVA resin of the present invention. The degree of polymerization was 380 and the saponification degree was 38 mol%. The obtained hot-melt PVA resin is designated as PVA1.
[0039]
<Synthesis example 2 of heat-meltable PVA resin>
The reactor equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, pressure gauge was replaced with nitrogen, and then deoxygenated 1500 parts by weight of vinyl acetate monomer, hydroxybutyl vinyl ether-EO adduct (addition number of EO was 10 units) 1000 parts by mass and 1700 parts by mass of methanol were charged and the temperature was raised under stirring. When the internal temperature reached 60 ° C., 4.0 parts by mass of AIBN was separately dissolved as an initiator in 100 parts by mass of methanol. Was added to initiate the polymerization. After polymerization at 60 ° C. for 6 hours, the polymerization was stopped by cooling. The solid concentration in the polymerization solution at this time was 55.1%. The obtained polymerization solution was supplied to a demonomer tower having a multi-stage perforated plate in the tower, and methanol vapor was blown from the bottom of the tower to come into contact with the polymerization solution to remove unreacted vinyl acetate monomer. The solid content concentration of the polyvinyl acetate resin-methanol solution at this time was 45%. After adding 12 parts by mass of 2% sodium hydroxide-methanol solution to 1000 parts by mass of this polyvinyl acetate resin-methanol solution, the mixture was thoroughly mixed and allowed to stand at 40 ° C. for 1 hour. The gel obtained after saponification was pulverized with a pulverizer and then dried with a blow dryer at 60 ° C. After drying, pulverization was performed to obtain the hot-melt PVA resin of the present invention. The polymerization degree was 260 and the saponification degree was 40 mol%. The amount of modification was 5.2 mol%. The obtained hot-melt PVA resin is designated as PVA5.
[0040]
[Materials used]
<Hot-melting PVA resin>
PVA1: average degree of polymerization 380 PVA having a saponification degree of 38 mol%
PVA2: PVA having an average polymerization degree of 150 and a saponification degree of 59 mol%
PVA3: PVA having an average polymerization degree of 500 and a saponification degree of 32 mol%
PVA4: PVA modified with an average polymerization degree of 300, a saponification degree of 25 mol%, and an allyl sulfonic acid Na of 3.1 mol%
PVA5: PVA having an average polymerization degree of 260, a saponification degree of 40 mol%, and a polyoxyethylene glycol butyl vinyl ether (addition of ethylene oxide 10) 5.2 mol% modified PVA
PVA6: PVA having an average polymerization degree of 240, a saponification degree of 50 mol%, and an ethylene of 8.5 mol%
PVA7: PVA having an average degree of polymerization of 120, a degree of saponification of 45 mol%, and 7.4 mol% of lauryl vinyl ether
PVA8: PVA having an average polymerization degree of 150 and a saponification degree of 88 mol%
The hot-melt PVA resin is obtained using the same method as in Synthesis Example 1 or Synthesis Example 2 of the hot-melt PVA resin.
<Polylactic acid>
Polylactic acid 1; polylactic acid having a weight average molecular weight of 130,000, a d-form content of 12.0% by mass, and an l-form content of 88.0% by mass
Polylactic acid 2; nanocomposite polylactic acid prepared according to Example 1 of JP 2002-363393 A
<Plasticizer>
Plasticizer 1: Diglycerin derivative (manufactured by Sakamoto Pharmaceutical Co., Ltd., trade name: SCE-750)
Plasticizer 2; Acetyltributylcitric acid
<Surfactant>
Surfactant 1; sodium dodecylbenzenesulfonate (hard type, anionic surfactant)
Surfactant 2; polyoxyethylene nonylphenyl ether (nonionic surfactant)
Surfactant 3; Lauryltrimethylammonium chloride (cationic surfactant)
[0041]
(Examples 1-7)
As shown in Table 1, each component was added to a mixer tester at a component and blending ratio that matched the hot melt adhesive of the present invention, and the blend was melted and mixed at 150 ° C. to obtain a uniform mixed composition. An example hot melt adhesive was obtained.
[0042]
(Comparative Example 1)
As shown in Table 2, each component was blended at a blending ratio that did not match the hot melt adhesive of the present invention, and thereafter the same operation as in the above example was performed to obtain a hot melt adhesive.
[0043]
[Table 1]
[Table 2]
[performance test]
About the adhesive agent obtained by the Example and the comparative example, the performance test was done by the following method.
<Moisture and heat resistance>
Adhesive was applied to two general-purpose cardboards (size 50 mm x 100 mm, "K liner") at an application temperature of 150 ° C, an application amount of 0.03 g / cm, and an application speed of 7.5 m / min. Were used for bonding with a press load of 2 kg and a wet heat resistant test piece. Next, the wet heat and heat resistance test piece obtained above was cut into a size of 25 mm × 100 mm, left under conditions of a temperature of 40 ° C. and a humidity of 80%, and forcibly peeled by hand to measure the material breakage rate. A material having a material breakage rate of 80% or more after being left for 30 hours was defined as having good moisture and heat resistance (circle mark).
<Water dispersibility>
A 25 mm × 50 mm × 1 mm adhesive piece was prepared, immersed in 200 mL water at a temperature of 20 ° C. as a test piece, stirred using a juicer mixer, and the dispersed state of the adhesive was visually observed. Thus, the water dispersibility of the adhesive was examined.
○: Completely finely dispersed in water.
X: Partially dispersed, but insoluble matter remains.
<Melt viscosity>
(According to JIS-K-6862)
○: The melt viscosity at 150 ° C. is less than 10,000 mPa · s.
X: The melt viscosity at 150 ° C. is 10,000 mPa · s or more.
<Heating stability>
About 30 mL of a pre-melted sample is put, and a sample container (140 ml mayonnaise bottle) covered with aluminum foil is put in a constant temperature bath maintained at a working temperature (temperature at which the melt viscosity is less than 10,000 mPa · s) ± 2 ° C. . The time for the skin to appear on the surface was observed every 24 hours after the sample reached the working temperature.
○: Skin peeling did not occur on the surface for 24 hours or more
X: The time until skin peeling occurred on the surface was less than 24 hours
[0046]
<Comprehensive evaluation>
Each of the above evaluations was comprehensively evaluated based on the following criteria.
○: The performance of all items is good. (○ mark)
X: One or more performances are inferior.
[0047]
[Table 3]
【The invention's effect】
As described above, the hot melt adhesive of the present invention has (1) adhesive strength under high temperature and high humidity, (2) water solubility or water dispersibility under normal temperature neutrality, (3) excellent heat stability and 4) Excellent balance of physical properties of melt viscosity that can be easily applied. In addition, the hot melt adhesive of the present invention uses a biodegradable resin such as a heat-meltable PVA resin or polylactic acid, and has a low environmental impact even when the hot melt adhesive is discarded. Excellent recyclability.
Claims (9)
で示されるオキシエチレン基または一般式
で示されるオキシプロピレン基であり、かつ、熱溶融性ポリビニルアルコール系樹脂が全単量体単位に対してオキシアルキレン基を含む単量体単位を０．１〜５０モル％含有する熱溶融性ポリビニルアルコール系樹脂であることを特徴とする請求項１〜５のいずれかに記載の水分散性ホットメルト接着剤。Oxyalkylene group is general formula
An oxyethylene group represented by or a general formula
A heat-meltable polyvinyl which is an oxypropylene group represented by the formula (1) and the heat-meltable polyvinyl alcohol-based resin contains 0.1 to 50 mol% of a monomer unit containing an oxyalkylene group with respect to all monomer units. The water-dispersible hot melt adhesive according to any one of claims 1 to 5, which is an alcohol resin.
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| JP2003048177A JP4368595B2 (en) | 2003-02-25 | 2003-02-25 | Hot melt adhesive |
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| JP2003048177A JP4368595B2 (en) | 2003-02-25 | 2003-02-25 | Hot melt adhesive |
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| JP4368595B2 true JP4368595B2 (en) | 2009-11-18 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101319507B1 (en) * | 2011-12-06 | 2013-10-17 | 주식회사 오공 | Natural based adhesive composition containing poly latic acid emulsion |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0708327D0 (en) * | 2006-12-11 | 2007-06-06 | Twist Cyril | Polymeric films |
| GB2464910B (en) * | 2008-10-29 | 2011-07-20 | Evap Environmentals Ltd | Polymeric multi-layer substrates |
| JP5883344B2 (en) | 2012-04-26 | 2016-03-15 | ヘンケルジャパン株式会社 | Hot melt adhesive |
| JP5921946B2 (en) | 2012-04-26 | 2016-05-24 | ヘンケルジャパン株式会社 | Hot melt adhesive |
| JP5925094B2 (en) | 2012-09-27 | 2016-05-25 | ヘンケルジャパン株式会社 | Hot melt adhesive for labels |
| JP6057837B2 (en) | 2013-05-30 | 2017-01-11 | ヘンケルジャパン株式会社 | Hot melt adhesive |
| JP2014234399A (en) | 2013-05-30 | 2014-12-15 | ヘンケルジャパン株式会社 | Hot melt adhesive |
| JP6154725B2 (en) * | 2013-10-24 | 2017-06-28 | ヘンケルジャパン株式会社 | Hot melt adhesive |
| WO2021132625A1 (en) * | 2019-12-27 | 2021-07-01 | 積水フーラー株式会社 | Hot melt composition and layered body for hygienic material |
| US20240392173A1 (en) * | 2021-09-22 | 2024-11-28 | Chukyo Yushi Co., Ltd. | Aqueous dispersion |
| CN115466586A (en) * | 2022-10-17 | 2022-12-13 | 浙江澳宇新材料科技有限公司 | Castor oil modified degradable hot melt adhesive and preparation method thereof |
| CN119161850A (en) * | 2024-11-25 | 2024-12-20 | 山东凯恩新材料科技有限公司 | A low-odor hot melt adhesive and preparation method thereof |
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2003
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101319507B1 (en) * | 2011-12-06 | 2013-10-17 | 주식회사 오공 | Natural based adhesive composition containing poly latic acid emulsion |
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