JP2017186552A - Aqueous adhesive - Google Patents
Aqueous adhesive Download PDFInfo
- Publication number
- JP2017186552A JP2017186552A JP2017066530A JP2017066530A JP2017186552A JP 2017186552 A JP2017186552 A JP 2017186552A JP 2017066530 A JP2017066530 A JP 2017066530A JP 2017066530 A JP2017066530 A JP 2017066530A JP 2017186552 A JP2017186552 A JP 2017186552A
- Authority
- JP
- Japan
- Prior art keywords
- adhesive
- aqueous
- polyolefin resin
- water
- mass
- 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 115
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 115
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 54
- 239000000758 substrate Substances 0.000 claims abstract description 40
- 239000006185 dispersion Substances 0.000 claims abstract description 32
- 239000003960 organic solvent Substances 0.000 claims abstract description 19
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012736 aqueous medium Substances 0.000 claims abstract description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 239000011248 coating agent Substances 0.000 claims description 39
- 238000000576 coating method Methods 0.000 claims description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 229920000098 polyolefin Polymers 0.000 claims description 7
- 229920000728 polyester Polymers 0.000 claims description 5
- 239000003513 alkali Substances 0.000 abstract description 19
- 230000008961 swelling Effects 0.000 abstract description 3
- -1 ethylene, propylene, isobutylene Chemical group 0.000 description 47
- 235000019645 odor Nutrition 0.000 description 23
- 239000000463 material Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 13
- 239000002585 base Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 239000010410 layer Substances 0.000 description 10
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 description 9
- 239000012972 dimethylethanolamine Substances 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 239000000123 paper Substances 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- 239000003995 emulsifying agent Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000001993 wax Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000007514 bases Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-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
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical class O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PRPINYUDVPFIRX-UHFFFAOYSA-N 1-naphthaleneacetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CC=CC2=C1 PRPINYUDVPFIRX-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-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
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 1
- SOYBEXQHNURCGE-UHFFFAOYSA-N 3-ethoxypropan-1-amine Chemical compound CCOCCCN SOYBEXQHNURCGE-UHFFFAOYSA-N 0.000 description 1
- XYUINKARGUCCQJ-UHFFFAOYSA-N 3-imino-n-propylpropan-1-amine Chemical compound CCCNCCC=N XYUINKARGUCCQJ-UHFFFAOYSA-N 0.000 description 1
- FAXDZWQIWUSWJH-UHFFFAOYSA-N 3-methoxypropan-1-amine Chemical compound COCCCN FAXDZWQIWUSWJH-UHFFFAOYSA-N 0.000 description 1
- QCDLYSWWNOMMMT-UHFFFAOYSA-N 4-ethenoxy-4-oxo-3-sulfobutanoic acid Chemical class OC(=O)CC(S(O)(=O)=O)C(=O)OC=C QCDLYSWWNOMMMT-UHFFFAOYSA-N 0.000 description 1
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229920005682 EO-PO block copolymer Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
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- 230000002411 adverse Effects 0.000 description 1
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- 238000007754 air knife coating Methods 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
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- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
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- 238000012661 block copolymerization Methods 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
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- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
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- 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
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- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
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- 238000003618 dip coating Methods 0.000 description 1
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- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- RPOCFUQMSVZQLH-UHFFFAOYSA-N furan-2,5-dione;2-methylprop-1-ene Chemical compound CC(C)=C.O=C1OC(=O)C=C1 RPOCFUQMSVZQLH-UHFFFAOYSA-N 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
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- 238000001879 gelation Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
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- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
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Landscapes
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、接着性、作業性、安全性に優れた水性接着剤に関する。 The present invention relates to an aqueous adhesive excellent in adhesiveness, workability, and safety.
近年、水などの液体中の不純物を取り除く液体浄化用フィルターや、悪臭や汚染物質、微粒子などを大気中から取り除く気体浄化用フィルターの需要が高まっている。このようなフィルターには、通気抵抗を小さくし、強度を付与するために形状をハニカム構造にしたり、活性炭を含有させて吸着能を高めるなど、形状や材料が工夫されてきた。
ハニカム構造は、紙や不織布、フィルム、金属をコルゲート（波形）加工し、積層、接着することにより、空隙が形成されている。例えば、コルゲートハニカム構造は、平面基材（ライナー）と波板基材（フルート）を交互に積層し、層間接着することにより形成されている。このような構造では層間の接触部分が「面」ではなく「線」であるため、層間の接着には、高粘度の接着剤が求められている。
ハニカム構造を形成するための接着剤としては、例えば、特許文献１に開示された水系接着剤や、炭化水素やアルコールを含有する溶剤系接着剤が知られている。
In recent years, there has been an increasing demand for liquid purification filters that remove impurities in liquids such as water, and gas purification filters that remove bad odors, pollutants, and fine particles from the atmosphere. For such a filter, the shape and material have been devised, for example, in order to reduce the airflow resistance and give strength, the shape is a honeycomb structure, or activated carbon is included to increase the adsorption capacity.
In the honeycomb structure, voids are formed by corrugating (corrugating) paper, nonwoven fabric, film, and metal, and laminating and bonding. For example, the corrugated honeycomb structure is formed by alternately laminating a planar base material (liner) and a corrugated base material (flute) and bonding the layers. In such a structure, the contact portion between the layers is not a “surface” but a “line”, and thus a high-viscosity adhesive is required for adhesion between the layers.
As an adhesive for forming a honeycomb structure, for example, an aqueous adhesive disclosed in Patent Document 1 and a solvent-based adhesive containing a hydrocarbon or alcohol are known.
しかしながら、特許文献１に開示された水系接着剤は、基材の種類によっては、接着性に問題があり、また主成分の組成によっては、悪臭等の問題が生じることもあった。溶剤系接着剤においても同様に悪臭等による作業環境への悪影響が大きいものであった。 However, the water-based adhesive disclosed in Patent Document 1 has a problem in adhesiveness depending on the type of base material, and may cause problems such as bad odor depending on the composition of the main component. Similarly, solvent-based adhesives have a great adverse effect on the working environment due to bad odors and the like.
また、活性炭を含有する高性能フィルターにおいては、活性炭の吸着性能を向上させるためにアルカリ処理をおこなう。しかしながら、従来の接着剤から形成された塗膜は、アルカリ処理をおこなった場合、塗膜が膨潤したり、臭気が発生することがあった。すなわち、活性炭を含有する浄化用フィルターに用いる接着剤には、アルカリ処理をおこなっても接着剤塗膜が膨潤せず、塗膜から臭気が発生しないことが求められている。 Moreover, in the high performance filter containing activated carbon, alkali treatment is performed in order to improve the adsorption performance of activated carbon. However, when a coating film formed from a conventional adhesive is subjected to an alkali treatment, the coating film may swell or an odor may be generated. That is, the adhesive used for the purification filter containing activated carbon is required not to swell and to generate no odor from the coating film even when subjected to alkali treatment.
本発明の目的は、基材との接着性に優れ、低臭気であり、アルカリ処理後においても塗膜が膨潤せず、臭気が発生しない耐アルカリ性に優れた水性接着剤を提供することにある。 An object of the present invention is to provide an aqueous adhesive excellent in alkali resistance that has excellent adhesion to a substrate, has low odor, does not swell after alkali treatment, and does not generate odor. .
本発明者らは上記課題を解決するために鋭意検討した結果、特定の成分を有するポリオレフィン樹脂および水性媒体を含有する水性分散体を水性接着剤として用いることで、上記課題が解決できることを見出し本発明に到達した。
すなわち、本発明の要旨は下記のとおりである。
（１）ポリオレフィン樹脂および水性媒体を含有する水性分散体であって、
水性分散体中の有機溶剤含有量が３質量％以下であり、
ポリオレフィン樹脂が（メタ）アクリル酸エステル成分と無水マレイン酸成分を含有することを特徴とする水性接着剤。
（２）２５℃における粘度が１０００〜５０００ｍＰａ・ｓであることを特徴とする（１）記載の水性接着剤。
（３）上記（１）または（２）記載の水性接着剤からなることを特徴とするハニカム構造形成用水性接着剤。
（４）上記（１）または（２）記載の水性接着剤からなることを特徴とするフィルター用水性接着剤。
（５）上記（１）または（２）記載の水性接着剤を用いて形成されたことを特徴とする塗膜。
（６）基材上に、（５）記載の塗膜が形成されたことを特徴とする積層体。
（７）基材が、ポリエステル、ポリオレフィンまたは紙であることを特徴とする（６）記載の積層体。
（８）活性炭を含有することを特徴とする（６）または（７）記載の積層体。
（９）上記（６）〜（８）のいずれかに記載の積層体が二層以上積層され、層間に空隙が形成されたことを特徴とする積層体。
As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using an aqueous dispersion containing a polyolefin resin having a specific component and an aqueous medium as an aqueous adhesive. The invention has been reached.
That is, the gist of the present invention is as follows.
(1) An aqueous dispersion containing a polyolefin resin and an aqueous medium,
The organic solvent content in the aqueous dispersion is 3% by mass or less,
A water-based adhesive, wherein the polyolefin resin contains a (meth) acrylic acid ester component and a maleic anhydride component.
(2) The aqueous adhesive according to (1), wherein the viscosity at 25 ° C. is 1000 to 5000 mPa · s.
(3) A water-based adhesive for forming a honeycomb structure, comprising the water-based adhesive according to (1) or (2).
(4) A water-based adhesive for a filter comprising the water-based adhesive according to the above (1) or (2).
(5) A coating film formed using the water-based adhesive described in (1) or (2) above.
(6) A laminate in which the coating film according to (5) is formed on a substrate.
(7) The laminate according to (6), wherein the substrate is polyester, polyolefin or paper.
(8) The laminate according to (6) or (7), which contains activated carbon.
(9) A laminate in which two or more of the laminates according to any one of (6) to (8) are laminated, and voids are formed between the layers.
本発明の水性接着剤は、（メタ）アクリル酸エステル成分と無水マレイン酸成分を含有するポリオレフィン樹脂を含み、有機溶剤含有量が特定の範囲以下であるため、基材への接着性に優れ、低臭気であり、また水性分散体であるため、作業環境への影響を低減することが可能となる。さらに、本発明の水性接着剤は、形成された塗膜が、アルカリ処理しても塗膜が膨潤しないため外観変化がなく、臭気を発生しないものであり、活性炭を含有するフィルターなどの積層体に用いる水性接着剤として特に好適である。 The aqueous adhesive of the present invention includes a polyolefin resin containing a (meth) acrylic acid ester component and a maleic anhydride component, and since the organic solvent content is below a specific range, it has excellent adhesion to a substrate. Since it has a low odor and is an aqueous dispersion, the influence on the working environment can be reduced. Furthermore, the water-based adhesive of the present invention is a laminate such as a filter containing activated carbon, in which the formed coating film does not swell even when alkali-treated, so that the coating film does not swell and does not change its appearance. It is particularly suitable as a water-based adhesive used in
以下、本発明を詳細に説明する。
本発明の水性接着剤は、ポリオレフィン樹脂および水性媒体を含有する水性分散体であって、ポリオレフィン樹脂は（メタ）アクリル酸エステル成分と無水マレイン酸成分を含有する。
Hereinafter, the present invention will be described in detail.
The aqueous adhesive of the present invention is an aqueous dispersion containing a polyolefin resin and an aqueous medium, and the polyolefin resin contains a (meth) acrylic acid ester component and a maleic anhydride component.
ポリオレフィン樹脂のオレフィン成分としては、エチレン、プロピレン、イソブチレン、１−ブテン、１−ペンテン、１−ヘキセン、１−オクテン等のアルケンや、ノルボルネン等のシクロアルケンが挙げられ、これらの混合物を用いることもできる。中でも、エチレン、プロピレン、イソブチレン、１−ブテン、１−ペンテン、１−ヘキセン等の炭素数２〜６のアルケンが好ましく、エチレン、プロピレン、イソブチレン、１−ブテン等の炭素数２〜４のアルケンがより好ましく、特にエチレンが好ましい。
オレフィン成分の含有量は、５０質量％以上であることが好ましく、７０質量％以上であることがより好ましい。オレフィン成分の含有量が５０質量％未満では、基材密着性等のポリオレフィン樹脂由来の特性が失われてしまう。
Examples of the olefin component of the polyolefin resin include alkenes such as ethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene and 1-octene, and cycloalkenes such as norbornene, and a mixture thereof may be used. it can. Among these, alkenes having 2 to 6 carbon atoms such as ethylene, propylene, isobutylene, 1-butene, 1-pentene and 1-hexene are preferable, and alkenes having 2 to 4 carbon atoms such as ethylene, propylene, isobutylene and 1-butene are preferable. More preferred is ethylene.
The content of the olefin component is preferably 50% by mass or more, and more preferably 70% by mass or more. When the content of the olefin component is less than 50% by mass, characteristics derived from the polyolefin resin such as adhesion to the substrate are lost.
ポリオレフィン樹脂は、無水マレイン酸成分により酸変性されていることが必要である。無水マレイン酸成分の量は、塗膜と基材との接着性の点から、ポリオレフィン樹脂の０．１〜２５質量％であることが好ましく、０．５〜１５質量％がより好ましく、１〜８質量％がさらに好ましく、１〜５質量％が特に好ましい。
無水マレイン酸成分は、ポリオレフィン樹脂中に共重合されていればよく、その形態は限定されず、例えば、ランダム共重合、ブロック共重合、グラフト共重合等が挙げられる。
The polyolefin resin needs to be acid-modified with a maleic anhydride component. The amount of the maleic anhydride component is preferably 0.1 to 25% by mass of the polyolefin resin, more preferably 0.5 to 15% by mass, from the viewpoint of adhesion between the coating film and the substrate. 8 mass% is further more preferable and 1-5 mass% is especially preferable.
The maleic anhydride component may be copolymerized in the polyolefin resin, and the form thereof is not limited, and examples thereof include random copolymerization, block copolymerization, and graft copolymerization.
ポリオレフィン樹脂は、基材を構成する熱可塑性樹脂基材、特にポリプロピレン等のポリオレフィン基材との接着性を向上させる理由から、（メタ）アクリル酸エステル成分を含有していることが必要である。（メタ）アクリル酸エステル成分の含有量は、ポリオレフィン樹脂の０．５〜４０質量％であることが好ましく、様々な熱可塑性樹脂基材との良好な接着性を持たせるために、この範囲は１〜３５質量％であることがより好ましく、３〜３０質量％であることがさらに好ましく、５〜２５質量％であることが特に好ましく、１０〜２５質量％であることが最も好ましい。ポリオレフィン樹脂は、（メタ）アクリル酸エステル成分の含有量が０．５質量％未満では、アクリル酸エステル成分を含有させた効果が得られず、基材との接着性が低下するおそれがあり、４０質量％を超えるとオレフィン由来の樹脂の性質が失われ、基材との密着性が低下するおそれがある。
（メタ）アクリル酸エステル成分としては、（メタ）アクリル酸と炭素数１〜３０のアルコールとのエステル化物が挙げられ、中でも入手のし易さの点から、（メタ）アクリル酸と炭素数１〜２０のアルコールとのエステル化物が好ましい。そのような化合物の具体例としては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸デシル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸オクチル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸ステアリル等が挙げられる。これらの混合物を用いてもよい。この中で、基材との接着性の点から、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、アクリル酸ヘキシル、アクリル酸オクチルがより好ましく、アクリル酸エチル、アクリル酸ブチルがより好ましく、アクリル酸エチルが特に好ましい。（なお、「（メタ）アクリル酸〜」とは、「アクリル酸〜またはメタクリル酸〜」を意味する。）
The polyolefin resin needs to contain a (meth) acrylic acid ester component for the reason of improving the adhesiveness with the thermoplastic resin base material which comprises a base material, especially polyolefin base materials, such as a polypropylene. The content of the (meth) acrylic acid ester component is preferably 0.5 to 40% by mass of the polyolefin resin, and in order to have good adhesion to various thermoplastic resin substrates, this range is It is more preferably 1 to 35% by mass, further preferably 3 to 30% by mass, particularly preferably 5 to 25% by mass, and most preferably 10 to 25% by mass. If the content of the (meth) acrylic acid ester component is less than 0.5% by mass, the polyolefin resin cannot obtain the effect of containing the acrylic acid ester component, and the adhesiveness to the substrate may be lowered. If it exceeds 40% by mass, the properties of the olefin-derived resin are lost, and the adhesion to the substrate may be reduced.
Examples of the (meth) acrylic acid ester component include an esterified product of (meth) acrylic acid and an alcohol having 1 to 30 carbon atoms, and (meth) acrylic acid and carbon number 1 from the viewpoint of easy availability. Esterified products with ˜20 alcohols are preferred. Specific examples of such compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic acid. Examples include decyl, lauryl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, and the like. Mixtures of these may be used. Among these, from the viewpoint of adhesion to the substrate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl acrylate, octyl acrylate are more preferable, ethyl acrylate, More preferred is butyl acrylate, and particularly preferred is ethyl acrylate. ("(Meth) acrylic acid" means "acrylic acid or methacrylic acid".)
また、上記成分以外に他の成分をポリオレフィン樹脂全体の１０質量％以下程度、含有していてもよい。他の成分としては、ジエン類、マレイン酸ジメチル、マレイン酸ジエチル、マレイン酸ジブチル等のマレイン酸エステル類、（メタ）アクリル酸アミド類、メチルビニルエーテル、エチルビニルエーテルなどのアルキルビニルエーテル類、ビニルエステル類を塩基性化合物等でケン化して得られるビニルアルコール、２−ヒドロキシエチルアクリレート、グリシジル（メタ）アクリレート、（メタ）アクリロニトリル、スチレン、置換スチレン、一酸化炭素、二酸化硫黄などが挙げられ、これらの混合物を用いることもできる。 Moreover, you may contain other components other than the said component about 10 mass% or less of the whole polyolefin resin. Other components include dienes, maleic esters such as dimethyl maleate, diethyl maleate and dibutyl maleate, alkyl vinyl ethers such as (meth) acrylic acid amides, methyl vinyl ether and ethyl vinyl ether, and vinyl esters. Examples include vinyl alcohol obtained by saponification with a basic compound, 2-hydroxyethyl acrylate, glycidyl (meth) acrylate, (meth) acrylonitrile, styrene, substituted styrene, carbon monoxide, sulfur dioxide, and the like. It can also be used.
ポリオレフィン樹脂は、分子量の目安となる１９０℃、２１６０ｇ荷重におけるメルトフローレートが、通常０．０１〜５０００ｇ／１０分、好ましくは０．１〜１０００ｇ／１０分、より好ましくは１〜５００ｇ／１０分、さらに好ましくは２〜３００ｇ／１０分、特に好ましくは２〜２００ｇ／１０分のものを用いることができる。ポリオレフィン樹脂のメルトフローレートが０．０１ｇ／１０分未満では、基材との密着性が低下する。一方、ポリオレフィン樹脂のメルトフローレートが５０００ｇ／１０分を超えると、塗膜は硬くてもろくなり、接着性や基材との密着性が低下してしまう。 The polyolefin resin has a melt flow rate at 190 ° C. and a load of 2160 g, which is a measure of molecular weight, usually from 0.01 to 5000 g / 10 minutes, preferably from 0.1 to 1000 g / 10 minutes, more preferably from 1 to 500 g / 10 minutes. More preferably, those having 2 to 300 g / 10 min, particularly preferably 2 to 200 g / 10 min can be used. When the melt flow rate of the polyolefin resin is less than 0.01 g / 10 minutes, the adhesion to the substrate is lowered. On the other hand, when the melt flow rate of the polyolefin resin exceeds 5000 g / 10 minutes, the coating film becomes hard and brittle, and the adhesiveness and the adhesion to the substrate are lowered.
本発明の水性接着剤は、ポリオレフィン樹脂および水性媒体を含有する水性分散体であり、水性媒体は、後述するポリオレフィン樹脂を分散化する際に使用する有機溶剤やアミン化合物を含有してもよい。しかしながら、低臭気な接着剤とするために、水性接着剤における有機溶剤の含有量は、３質量％以下であることが必要であり、１質量％以下であることが好ましく、０．５質量％以下であることがより好ましく、０．１質量％以下であることがさらに好ましい。また、アミン化合物の含有量は、５質量％未満であることが好ましく、４質量％未満であることがより好ましく、２質量％未満であることがさらに好ましく、１．５質量％未満であることが特に好ましい。水性接着剤が含有する有機溶剤やアミン化合物は、後述するストリッピングによって、減少させることができる。 The aqueous adhesive of the present invention is an aqueous dispersion containing a polyolefin resin and an aqueous medium, and the aqueous medium may contain an organic solvent or an amine compound used when dispersing the polyolefin resin described later. However, in order to obtain a low odor adhesive, the content of the organic solvent in the aqueous adhesive is required to be 3% by mass or less, preferably 1% by mass or less, and 0.5% by mass. More preferably, it is more preferably 0.1% by mass or less. Further, the content of the amine compound is preferably less than 5% by mass, more preferably less than 4% by mass, further preferably less than 2% by mass, and less than 1.5% by mass. Is particularly preferred. The organic solvent and amine compound contained in the aqueous adhesive can be reduced by stripping described later.
本発明の水性接着剤は、不揮発性の水性分散化助剤を実質的に含有しないことが好ましい。本発明は、水性分散化助剤を用いずとも、酸変性されたポリオレフィン樹脂を水性媒体中に安定的に分散することができる。本発明の水性接着剤は、不揮発性の水性分散化助剤を実質的に含有しないため、基材との接着性、耐アルカリ性が優れており、これらの性能は長期的にもほとんど変化しない。 The aqueous adhesive of the present invention preferably contains substantially no nonvolatile aqueous dispersion aid. The present invention can stably disperse an acid-modified polyolefin resin in an aqueous medium without using an aqueous dispersion aid. Since the aqueous adhesive of the present invention does not substantially contain a non-volatile aqueous dispersion aid, it has excellent adhesion to the substrate and alkali resistance, and these performances hardly change even in the long term.
ここで、「水性分散化助剤」とは、水性接着剤の製造において、水性分散化促進や水性接着剤の安定化の目的で添加される薬剤や化合物のことであり、「不揮発性」とは、常圧での沸点を有さないか、もしくは常圧で高沸点（例えば３００℃以上）であることを指す。 Here, the “aqueous dispersion aid” is a drug or compound added for the purpose of promoting aqueous dispersion or stabilizing the aqueous adhesive in the production of an aqueous adhesive. Means that it does not have a boiling point at normal pressure or has a high boiling point (for example, 300 ° C. or higher) at normal pressure.
本発明において、「不揮発性水性分散化助剤を実質的に含有しない」とは、こうした助剤を製造時（酸変性ポリオレフィン樹脂の水性分散化時）に用いる必要がなく、得られる水性接着剤が結果的にこの助剤を含有しないことを意味する。したがって、こうした水性分散化助剤は、含有量がゼロであることが特に好ましいが、水性接着剤の使用目的において、水性分散化助剤を必要とした場合は、本発明の効果を損ねない範囲で、酸変性ポリオレフィン樹脂成分に対して５質量％以下、好ましくは２質量％以下、さらに好ましくは０．５質量％未満を添加することで含有していても構わない。 In the present invention, “substantially no non-volatile aqueous dispersion aid” means that it is not necessary to use such an aid during production (when the acid-modified polyolefin resin is dispersed in water), and the resulting aqueous adhesive is obtained. Means that it does not contain this auxiliary as a result. Therefore, it is particularly preferable that the content of such an aqueous dispersion aid is zero. However, when the aqueous dispersion aid is required for the purpose of using the aqueous adhesive, the effect of the present invention is not impaired. In the acid-modified polyolefin resin component, it may be contained by adding 5% by mass or less, preferably 2% by mass or less, more preferably less than 0.5% by mass.
本発明でいう不揮発性水性分散化助剤としては、例えば、後述する乳化剤、保護コロイド作用を有する化合物、変性ワックス類、高酸価の酸変性化合物、水溶性高分子などが挙げられる。 Examples of the non-volatile aqueous dispersion aid used in the present invention include an emulsifier described later, a compound having a protective colloid effect, a modified wax, a high acid value acid-modified compound, a water-soluble polymer, and the like.
乳化剤としては、カチオン性乳化剤、アニオン性乳化剤、ノニオン性乳化剤、あるいは両性乳化剤が挙げられ、一般に乳化重合に用いられるもののほか、界面活性剤類も含まれる。例えば、アニオン性乳化剤としては、高級アルコールの硫酸エステル塩、高級アルキルスルホン酸塩、高級カルボン酸塩、アルキルベンゼンスルホン酸塩、ポリオキシエチレンアルキルサルフェート塩、ポリオキシエチレンアルキルフェニルエーテルサルフェート塩、ビニルスルホサクシネート等が挙げられ、ノニオン性乳化剤としては、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリエチレングリコール脂肪酸エステル、エチレンオキサイドプロピレンオキサイドブロック共重合体、ポリオキシエチレン脂肪酸アミド、エチレンオキサイド−プロピレンオキサイド共重合体などのポリオキシエチレン構造を有する化合物やポリオキシエチレンソルビタン脂肪酸エステルなどのソルビタン誘導体等が挙げられ、両性乳化剤としては、ラウリルベタイン、ラウリルジメチルアミンオキサイド等が挙げられる。 Examples of the emulsifier include a cationic emulsifier, an anionic emulsifier, a nonionic emulsifier, and an amphoteric emulsifier. In addition to those generally used for emulsion polymerization, surfactants are also included. For example, anionic emulsifiers include higher alcohol sulfates, higher alkyl sulfonates, higher carboxylates, alkyl benzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, vinyl sulfosuccinates. Nonionic emulsifiers include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, ethylene oxide propylene oxide block copolymer, polyoxyethylene fatty acid amide, ethylene oxide-propylene oxide. Compounds having a polyoxyethylene structure such as copolymers and sorbitan derivatives such as polyoxyethylene sorbitan fatty acid esters And examples of the amphoteric emulsifiers, lauryl betaine, lauryl dimethyl amine oxide, and the like.
保護コロイド作用を有する化合物、変性ワックス類、高酸価の酸変性化合物、水溶性高分子としては、ポリビニルアルコール、カルボキシル基変性ポリビニルアルコール、カルボキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、変性デンプン、ポリビニルピロリドン、ポリアクリル酸およびその塩、カルボキシル基含有ポリエチレンワックス、カルボキシル基含有ポリプロピレンワックス、カルボキシル基含有ポリエチレン−プロピレンワックスなどの数平均分子量が通常５０００以下の酸変性ポリオレフィンワックス類およびその塩、アクリル酸−無水マレイン酸共重合体およびその塩、スチレン−（メタ）アクリル酸共重合体、エチレン−（メタ）アクリル酸共重合体、イソブチレン−無水マレイン酸交互共重合体、（メタ）アクリル酸−（メタ）アクリル酸エステル共重合体等の不飽和カルボン酸含有量が１０質量％以上のカルボキシル基含有ポリマーおよびその塩、ポリイタコン酸およびその塩、アミノ基を有する水溶性アクリル系共重合体、ゼラチン、アラビアゴム、カゼイン等、一般に微粒子の分散安定剤として用いられている化合物等が挙げられる。 Compounds having protective colloid action, modified waxes, acid-modified compounds with high acid value, water-soluble polymers include polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, modified starch, polyvinylpyrrolidone Polyacrylic acid and salts thereof, carboxyl group-containing polyethylene wax, carboxyl group-containing polypropylene wax, carboxyl group-containing polyethylene-propylene wax, and other acid-modified polyolefin waxes having a number average molecular weight of usually 5000 or less and salts thereof, acrylic acid-anhydride Maleic acid copolymer and salt thereof, styrene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid copolymer, isobutylene-maleic anhydride A carboxyl group-containing polymer having an unsaturated carboxylic acid content of 10% by mass or more, such as an acid alternating copolymer, a (meth) acrylic acid- (meth) acrylic acid ester copolymer, and a salt thereof, polyitaconic acid and a salt thereof, amino Examples thereof include water-soluble acrylic copolymers having a group, gelatin, gum arabic, and casein, and compounds generally used as fine particle dispersion stabilizers.
本発明の水性接着剤は、２５℃における粘度が１０００〜５０００ｍＰａ・ｓであることが好ましく、２０００〜４０００ｍＰａ・ｓであることがより好ましく、接着剤に高粘度が求められる基材や用途に用いることができる。水性接着剤は、２５℃における粘度が１０００ｍＰａ・ｓ未満であると、たとえば、ハニカム構造を形成する目的で基材に塗布した際に、水性接着剤が基材に浸透してしまい、基材どうしが充分に接着しないことがあり、粘度が５０００ｍＰａ・ｓを超えると、接着強度が低下することがある。上記の好ましい水性接着剤粘度は、ポリオレフィン樹脂の体積平均粒子径と樹脂含有率を後述する好ましい範囲にすることで達成できる。 The water-based adhesive of the present invention preferably has a viscosity at 25 ° C. of 1000 to 5000 mPa · s, more preferably 2000 to 4000 mPa · s, and is used for a base material or application in which a high viscosity is required for the adhesive. be able to. For example, when the water-based adhesive has a viscosity of less than 1000 mPa · s at 25 ° C., the water-based adhesive permeates into the base material when applied to the base material for the purpose of forming a honeycomb structure. May not adhere sufficiently, and if the viscosity exceeds 5000 mPa · s, the adhesive strength may decrease. Said preferable water-based adhesive viscosity can be achieved by setting the volume average particle diameter and resin content of the polyolefin resin to the preferred ranges described below.
本発明の水性接着剤におけるポリオレフィン樹脂の体積平均粒子径は、水性接着剤の粘度を好ましい範囲にし、かつ良好な接着層形成能を発現させる点で、７０〜１３０ｎｍであることが好ましく、８０〜１２０ｎｍであることがより好ましく、９０〜１１０ｎｍであることがさらに好ましい。ポリオレフィン樹脂の体積平均粒子径が１３０ｎｍを超えると、接着剤は、粘度が上がりにくく、粘度を所定の範囲の粘度に調整することが難しく、本用途での効果が十分に発揮できないおそれがある。また、ポリオレフィン樹脂の体積平均粒子径が７０ｎｍ未満であると、接着剤は、粘度が上がり過ぎ、接着剤の粘度を所定の範囲の粘度に調整することが難しくなる。
本発明の水性接着剤におけるポリオレフィン樹脂の体積平均粒子径を好ましい範囲にするためには、水酸基を有するアミン化合物を含有させることが好ましく、Ｎ，Ｎ−ジメチルエタノールアミンを含有させることがより好ましい。また、アミン化合物の含有量は上述した範囲であることが好ましい。
The volume average particle diameter of the polyolefin resin in the water-based adhesive of the present invention is preferably 70 to 130 nm from the viewpoint that the viscosity of the water-based adhesive is in a preferable range and good adhesive layer forming ability is expressed, and 80 to More preferably, it is 120 nm, and it is further more preferable that it is 90-110 nm. When the volume average particle diameter of the polyolefin resin exceeds 130 nm, the adhesive is difficult to increase in viscosity, it is difficult to adjust the viscosity to a predetermined range, and the effects in this application may not be sufficiently exhibited. Further, when the volume average particle diameter of the polyolefin resin is less than 70 nm, the viscosity of the adhesive is excessively increased, and it becomes difficult to adjust the viscosity of the adhesive to a predetermined range.
In order to make the volume average particle diameter of the polyolefin resin in the aqueous adhesive of the present invention into a preferable range, it is preferable to contain an amine compound having a hydroxyl group, and it is more preferable to contain N, N-dimethylethanolamine. Moreover, it is preferable that content of an amine compound is the range mentioned above.
次に、本発明の水性接着剤の製造方法を説明する。
本発明の水性接着剤の製造方法としては、ポリオレフィン樹脂が水性媒体中に均一に混合・分散される方法であれば、限定されるものではないが、たとえば、ポリオレフィン樹脂の原料樹脂を、水や溶媒と共に攪拌・加熱を行って水性分散体を得る方法が挙げられる。
Next, the manufacturing method of the aqueous adhesive of this invention is demonstrated.
The method for producing the water-based adhesive of the present invention is not limited as long as the polyolefin resin is uniformly mixed and dispersed in an aqueous medium. The method of stirring and heating with a solvent and obtaining an aqueous dispersion is mentioned.
ポリオレフィン樹脂の分散化を容易にするために、水性媒体は、２０℃における水の溶解性が５質量％以上である有機溶剤を含有してもよい。
有機溶剤の具体例としては、メタノール、エタノール、ｎ−プロパノール、イソプロパノール等のアルコール類、テトラヒドロフラン、１，４−ジオキサン等のエーテル類、アセトン、メチルエチルケトン等のケトン類、酢酸メチル、酢酸−ｎ−プロピル、酢酸イソプロピル、プロピオン酸メチル、プロピオン酸エチル、炭酸ジメチル等のエステル類、エチレングリコール−ｎ−ブチルエーテル等のエチレングリコール誘導体類が挙げられる。
ポリオレフィン樹脂の分散化のために添加する有機溶剤の量は、水性接着剤全量の、２０質量％以下が好ましく、１６質量％以下がより好ましい。ポリオレフィン樹脂の分散化において２０質量％を超えて有機溶剤を添加すると、得られる接着剤は、脱溶剤に長時間を要して生産性が低下したり、ゲル化するおそれがある。
In order to facilitate the dispersion of the polyolefin resin, the aqueous medium may contain an organic solvent having a water solubility at 20 ° C. of 5% by mass or more.
Specific examples of the organic solvent include alcohols such as methanol, ethanol, n-propanol and isopropanol, ethers such as tetrahydrofuran and 1,4-dioxane, ketones such as acetone and methyl ethyl ketone, methyl acetate, and acetic acid-n-propyl. And esters such as isopropyl acetate, methyl propionate, ethyl propionate and dimethyl carbonate, and ethylene glycol derivatives such as ethylene glycol-n-butyl ether.
The amount of the organic solvent added for dispersing the polyolefin resin is preferably 20% by mass or less, more preferably 16% by mass or less, based on the total amount of the aqueous adhesive. If the organic solvent is added in an amount exceeding 20% by mass in the dispersion of the polyolefin resin, the resulting adhesive may take a long time to remove the solvent, resulting in a decrease in productivity or gelation.
ポリオレフィン樹脂の分散化において、ポリオレフィン樹脂中のカルボキシル基は、塩基性化合物によってその一部を中和することが好ましい。塩基性化合物によってカルボキシル基または酸無水物基をアニオン化し、アニオンの静電気的反発力によって水性媒体中における樹脂微粒子間の凝集が防がれ、良好な分散化が達成される。
このような塩基性化合物として、塗膜形成時に揮発するアンモニア又は有機アミン化合物が塗膜の耐水性、耐ボイル性の面から好ましく、中でも沸点が３０〜２５０℃、さらには５０〜２００℃の有機アミン化合物が好ましい。沸点が３０℃未満の場合は、後述する樹脂の水性化時に揮発する割合が多くなり、水性化が完全に進行しない場合がある。沸点が２５０℃を超えると樹脂塗膜から乾燥によって有機アミン化合物を飛散させることが困難になり、塗膜の耐水性が低下する場合がある。
有機アミン化合物の具体例としては、トリエチルアミン、Ｎ，Ｎ−ジメチルエタノールアミン、Ｎ−メチル−Ｎ，Ｎ−ジエタノールアミン、イソプロピルアミン、イミノビスプロピルアミン、エチルアミン、ジエチルアミン、３−エトキシプロピルアミン、３−ジエチルアミノプロピルアミン、ｓｅｃ−ブチルアミン、プロピルアミン、メチルアミノプロピルアミン、３−メトキシプロピルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モルホリン、Ｎ−メチルモルホリン、Ｎ−エチルモルホリン等を挙げることができる。このなかでも、トリエタノールアミンやＮ，Ｎ−ジメチルエタノールアミンは、水酸基を有していることによりポリオレフィン樹脂の粒子径を前記好ましい範囲とすることができ、分散性が向上し、また沸点が高いことにより脱溶剤、濾過後の分散安定性が向上して好ましく、なかでも、臭気、水性化後のろ過性、接着剤の粘度、保存安定性の観点から、Ｎ，Ｎ−ジメチルエタノールアミンがより好ましい。
In dispersing the polyolefin resin, it is preferable to neutralize a part of the carboxyl group in the polyolefin resin with a basic compound. The carboxyl group or acid anhydride group is anionized with the basic compound, and the electrostatic repulsion of the anion prevents aggregation between the resin fine particles in the aqueous medium, thereby achieving good dispersion.
As such a basic compound, ammonia or an organic amine compound which volatilizes during the formation of the coating film is preferable from the viewpoint of water resistance and boil resistance of the coating film, and an organic solvent having a boiling point of 30 to 250 ° C, more preferably 50 to 200 ° C. Amine compounds are preferred. When the boiling point is less than 30 ° C., the rate of volatilization when the resin described later becomes aqueous may increase, and the aqueous formation may not proceed completely. When the boiling point exceeds 250 ° C., it becomes difficult to disperse the organic amine compound from the resin coating film by drying, and the water resistance of the coating film may decrease.
Specific examples of the organic amine compound include triethylamine, N, N-dimethylethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, 3-ethoxypropylamine, and 3-diethylamino. Examples include propylamine, sec-butylamine, propylamine, methylaminopropylamine, 3-methoxypropylamine, monoethanolamine, diethanolamine, triethanolamine, morpholine, N-methylmorpholine, and N-ethylmorpholine. Among these, triethanolamine and N, N-dimethylethanolamine have a hydroxyl group, so that the particle diameter of the polyolefin resin can be within the above preferred range, dispersibility is improved, and the boiling point is high. Therefore, it is preferable to improve the dispersion stability after solvent removal and filtration. Among them, N, N-dimethylethanolamine is more preferable from the viewpoints of odor, filterability after aqueous formation, adhesive viscosity, and storage stability. preferable.
水性分散体の製造時に上記の有機溶剤や有機アミン化合物を用いた場合には、樹脂の水性化の後に、その一部を、一般に「ストリッピング」と呼ばれる脱溶剤処理によって系外へ留去させ、有機溶剤や有機アミン化合物の含有量を低減させることができる。本発明では、低臭気な接着剤とするため、水性接着剤における有機溶剤の含有量を３質量％以下とする必要がある。
ストリッピングの方法としては、常圧または減圧下で水性分散体を攪拌しながら加熱し、有機溶剤や有機アミン化合物を留去する方法が挙げられる。また、水性媒体が留去されることにより、固形分濃度が高くなるので、例えば、粘度が上昇して作業性が低下するような場合には、予め水性分散体に水を添加しておいてもよい。
When the above organic solvent or organic amine compound is used in the production of the aqueous dispersion, a part of the resin is distilled out of the system by a solvent removal process generally called “stripping” after the resin is made aqueous. The content of organic solvents and organic amine compounds can be reduced. In the present invention, in order to obtain a low-odor adhesive, the content of the organic solvent in the aqueous adhesive needs to be 3% by mass or less.
Examples of the stripping method include a method in which the aqueous dispersion is heated with stirring under normal pressure or reduced pressure to distill off the organic solvent or the organic amine compound. In addition, since the solid content concentration is increased by distilling off the aqueous medium, for example, when the viscosity increases and the workability decreases, water is added to the aqueous dispersion in advance. Also good.
水性接着剤における樹脂含有率は、成膜条件、目的とする接着層の厚さや性能等により適宜調整され、特に限定されるものではないが、接着剤の粘度を好ましい範囲とし、かつ良好な接着層形成能を発現させる点で、１〜５０質量％が好ましく、３〜５０質量％がより好ましく、５〜４５質量％がさらに好ましく、５〜４０質量％が特に好ましい。 The resin content in the water-based adhesive is appropriately adjusted depending on the film forming conditions, the desired thickness and performance of the adhesive layer, and is not particularly limited. 1-50 mass% is preferable at the point which expresses layer forming ability, 3-50 mass% is more preferable, 5-45 mass% is further more preferable, and 5-40 mass% is especially preferable.
本発明の水性接着剤には、耐薬品性などの各種の塗膜性能をさらに向上させるために、架橋剤を水性分散体中のポリオレフィン樹脂１００質量部に対して０．１〜５０質量部、好ましくは０．５〜３０質量部含有させることができる。架橋剤の添加量が０．１質量部未満の場合は、塗膜性能の向上の程度が小さく、５０質量部を超える場合は、水性接着剤の液安定性や加工性等の塗膜性能が低下する傾向がある。架橋剤としては、自己架橋性を有する架橋剤、カルボキシル基と反応する官能基を分子内に複数個有する化合物、多価の配位座を有する金属錯体等を用いることができ、このうちイソシアネート化合物、メラミン化合物、尿素化合物、エポキシ化合物、カルボジイミド化合物、オキサゾリン基含有化合物、アジリジン化合物、ジルコニウム塩化合物、シランカップリング剤等が好ましい。 In the aqueous adhesive of the present invention, in order to further improve various coating film performances such as chemical resistance, the crosslinking agent is added in an amount of 0.1 to 50 parts by mass with respect to 100 parts by mass of the polyolefin resin in the aqueous dispersion. Preferably 0.5-30 mass parts can be contained. When the addition amount of the crosslinking agent is less than 0.1 parts by mass, the degree of improvement in the coating film performance is small, and when it exceeds 50 parts by mass, the coating film performance such as liquid stability and workability of the aqueous adhesive is low. There is a tendency to decrease. As the crosslinking agent, a crosslinking agent having self-crosslinking property, a compound having a plurality of functional groups that react with a carboxyl group in the molecule, a metal complex having a polyvalent coordination site, etc. can be used. Of these, isocyanate compounds , A melamine compound, a urea compound, an epoxy compound, a carbodiimide compound, an oxazoline group-containing compound, an aziridine compound, a zirconium salt compound, a silane coupling agent, and the like are preferable.
本発明の水性接着剤は、基材に塗膜を形成して積層体を作製することができ、この積層体を二層以上積層してもよい。基材としては、ハニカム構造が形成できる基材（以下、ハニカム構造形成用基材と称する）が好ましい。本発明でいうハニカム構造とは、正六角柱に限らず立体図形をすきまなく並べた構造（三次元空間充填構造）のことである。
ハニカム構造形成用基材としては、通常ハニカム構造に使用されている基材が挙げられ、本発明の水性接着剤がポリオレフィン樹脂を含有することから、好ましい基材としては、例えば、ポリエステル、ポリオレフィンまたは紙などが挙げられる。ポリエステルとしては、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリ乳酸、ポリブチレンテレフタレートなどが挙げられ、ポリオレフィンとしては、ポリプロピレン、ポリエチレンなどが挙げられ、フィルム形状や不織布形状などが挙げられ、紙としては、濾紙や化繊紙などが挙げられる。
ハニカム構造形成用基材は、特定の物質を選択的に分離する目的で、活性炭を含有してもよく、基材における活性炭の含有量は、１０〜８０質量％であることが好ましい。基材に活性炭を含有させる方法としては、活性炭を基材に練り込む方法でもよく、基材に活性炭を含むコート液を塗布して付着させる方法でもよく、これらの方法に限定されるものではない。
The water-based adhesive of the present invention can form a laminate by forming a coating film on a base material, and two or more layers of this laminate may be laminated. As the substrate, a substrate capable of forming a honeycomb structure (hereinafter referred to as a honeycomb structure forming substrate) is preferable. The honeycomb structure referred to in the present invention is not limited to a regular hexagonal column but a structure in which three-dimensional figures are arranged without gaps (three-dimensional space filling structure).
Examples of the substrate for forming a honeycomb structure include a substrate usually used in a honeycomb structure. Since the aqueous adhesive of the present invention contains a polyolefin resin, examples of preferable substrates include polyester, polyolefin or For example, paper. Examples of the polyester include polyethylene terephthalate, polyethylene naphthalate, polylactic acid, polybutylene terephthalate, and the like. Examples of the polyolefin include polypropylene and polyethylene. Examples of the paper include a film shape and a nonwoven fabric shape. Examples of the paper include filter paper and Examples include synthetic paper.
The substrate for forming a honeycomb structure may contain activated carbon for the purpose of selectively separating a specific substance, and the content of activated carbon in the substrate is preferably 10 to 80% by mass. The method for containing activated carbon in the substrate may be a method in which activated carbon is kneaded into the substrate, or a method in which a coating liquid containing activated carbon is applied to the substrate and adhered thereto, and is not limited to these methods. .
本発明の水性接着剤を、基材に塗布する方法としては、公知の方法、例えばグラビアロールコーティング、リバースロールコーティング、ワイヤーバーコーティング、リップコーティング、エアナイフコーティング、カーテンフローコーティング、スプレーコーティング、浸漬コーティング、はけ塗り法などが挙げられる。水性接着剤を基材の必要な箇所に塗布したのち、６０〜１５０℃で６０秒程度乾燥することにより、基材上に塗膜が形成された積層体が得られる。 As a method for applying the aqueous adhesive of the present invention to a substrate, known methods such as gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dip coating, Examples include brushing. After apply | coating an aqueous adhesive to the required location of a base material, the laminated body in which the coating film was formed on the base material is obtained by drying at 60-150 degreeC for about 60 seconds.
本発明において、ハニカム構造の作製方法は特に限定されるものではないが、たとえばハニカム構造形成用基材上に本発明の水性接着剤から得られる塗膜が形成された積層体を、波状に賦形するコルゲート処理して、これらを二層以上積層することにより層間に空隙を形成させる方法や、あらかじめコルゲート処理されたハニカム構造形成用基材の凸部に、本発明の水性接着剤を塗布して、塗布部分が接するようにハニカム構造形成用基材を二層以上積層することで、層間に空隙を形成させる方法が挙げられる。 In the present invention, the manufacturing method of the honeycomb structure is not particularly limited. For example, a laminate in which a coating film obtained from the aqueous adhesive of the present invention is formed on a substrate for forming a honeycomb structure is applied in a wave shape. A method of forming a void between the layers by laminating two or more layers by corrugating, or applying the aqueous adhesive of the present invention to the convex portions of a honeycomb structure forming substrate that has been corrugated in advance. Then, a method of forming a void between the layers by laminating two or more layers of the honeycomb structure forming substrate so that the coated portion is in contact therewith can be mentioned.
本発明の水性接着剤は、上記したようにハニカム構造を形成するための接着剤として好適である。また、耐アルカリ性に優れていることから、活性炭が用いられている用途にも適しており、特にフィルターの接着剤として好適である。 The aqueous adhesive of the present invention is suitable as an adhesive for forming a honeycomb structure as described above. Moreover, since it is excellent in alkali resistance, it is suitable also for the use in which activated carbon is used, and is especially suitable as a filter adhesive.
以下に実施例によって本発明を具体的に説明する。ただし、本発明はこれらによって限定されるものではない。 The present invention will be specifically described below with reference to examples. However, the present invention is not limited by these.
水性接着剤の特性は下記の方法で測定した。
（１）ポリオレフィン樹脂の構成
１Ｈ−ＮＭＲ分析装置（日本電子社製 ＥＣＡ５００、５００ＭＨｚ）より求めた。テトラクロロエタン（ｄ２）を溶媒とし、１２０℃で測定した
The characteristics of the water-based adhesive were measured by the following method.
(1) Composition of polyolefin resin
It calculated | required from <1> H-NMR analyzer (JEOL ECA500, 500MHz). Tetrachloroethane (d 2 ) was used as a solvent and measured at 120 ° C.
（２）固形分濃度
水性接着剤を適宜秤量し、これを１５０℃で残存物（固形分）の質量が恒量に達するまで加熱し、固形分濃度を求めた。
(2) Solid Content Concentration The aqueous adhesive was weighed appropriately and heated at 150 ° C. until the mass of the residue (solid content) reached a constant weight to determine the solid content concentration.
（３）有機溶剤の含有量
ガスクロマトグラフグラフ（島津製作所社製 ＧＣ−８Ａ、検出器：ＦＩＤ、キャリアーガス:窒素、カラム充填物質：ジーエルサイエンス社製 ＰＥＧ−ＨＴ（５％）−ＵｎｉｐｏｒｔＨＰ（６０／８０メッシュ）、カラムサイズ：直径３ｍｍ×３ｍ、試料投入温度(インジェクション温度)：１５０℃、カラム温度：６０℃、内部標準物質：ｎ−ブタノール）を用い、水性分散体または水性分散体を水で希釈したものを直接装置内に投入して、有機溶剤の含有率を求めた。検出限界は０．０１質量％であった。
(3) Content of organic solvent Gas chromatograph (GC-8A manufactured by Shimadzu Corporation, detector: FID, carrier gas: nitrogen, column packing material: PEG-HT (5%)-Uniport HP (60 / 80 mesh), column size: diameter 3 mm × 3 m, sample charging temperature (injection temperature): 150 ° C., column temperature: 60 ° C., internal standard substance: n-butanol), and the aqueous dispersion or aqueous dispersion is made of water. The diluted product was directly charged into the apparatus, and the organic solvent content was determined. The detection limit was 0.01% by mass.
（４）アミン化合物の含有量
ガスクロマトグラフグラフ（島津製作所社製 ＧＣ−８Ａ、検出器：ＦＩＤ、キャリアーガス:窒素、カラム充填物質：ジーエルサイエンス社製 ＰＥＧ−ＨＴ＋ＫＯＨ（５＋１）％−ＵｎｉｐｏｒｔＨＰ（６０／８０メッシュ）、カラムサイズ：直径３ｍｍ×３ｍ、試料投入温度(インジェクション温度)：１５０℃、カラム温度：7０℃、内部標準物質：ｎ−ブタノール）を用い、水性分散体または水性分散体を水で希釈したものを直接装置内に投入して、アミン化合物の含有率を求めた。検出限界は０．０１質量％であった。
(4) Content of amine compound Gas chromatograph (GC-8A manufactured by Shimadzu Corporation, detector: FID, carrier gas: nitrogen, column packing material: PEG-HT + KOH (5 + 1)%-uniportHP (60 / 80 mesh), column size: diameter 3 mm × 3 m, sample charging temperature (injection temperature): 150 ° C., column temperature: 70 ° C., internal standard substance: n-butanol), and the aqueous dispersion or aqueous dispersion is made of water. The diluted product was directly charged into the apparatus to determine the amine compound content. The detection limit was 0.01% by mass.
（５）体積平均粒子径
粒子径分布測定装置（日機装社製Ｎａｎｏｔａｃ ｗａｖｅ）を使用して求めた。
(5) Volume average particle diameter It calculated | required using the particle size distribution measuring apparatus (Nikkiso Co., Ltd. Nanotac wave).
（６）粘度
Ｂ型粘度計（東機産業社製）を用いてＪＩＳ Ｚ ８８０３に準拠して温度２５℃で測定し粘度を求めた。
(6) Viscosity Using a B-type viscometer (manufactured by Toki Sangyo Co., Ltd.), the viscosity was measured at a temperature of 25 ° C. in accordance with JIS Z 8803.
（７）ろ過性
４００メッシュのステンレスフィルター（線径０．０２５ｍｍ、平織）を使用し、加圧ろ過(空気圧０．２ＭＰａ)を行った。下記の指標でろ過性を評価した。
○：詰まり無く、ろ過が完了する。
△：詰まりは生じるが、都度フィルター交換実施することでろ過が可能である。
×：詰まりがひどく、ろ過が困難である。
(7) Filterability Using a 400 mesh stainless steel filter (wire diameter 0.025 mm, plain weave), pressure filtration (air pressure 0.2 MPa) was performed. Filterability was evaluated by the following index.
○: Filtration is completed without clogging.
Δ: Clogging occurs, but filtration is possible by exchanging the filter each time.
X: Clogging is severe and filtration is difficult.
（８）保存安定性
水性接着剤を２５℃の乾燥機中に保管し、３か月後のゲル発生の有無、粘度により、保存安定性を評価した。
○：ゲルが生じない。
△：水性接着剤のゲルは生じないが、粘度が２００ｍＰａ・ｓ以上上昇する、または初期の２倍以上に粘度が上昇する。
×：ゲルが生じる。
(8) Storage stability The aqueous adhesive was stored in a dryer at 25 ° C., and the storage stability was evaluated by the presence or absence of gel generation and the viscosity after 3 months.
○: No gel is formed.
Δ: A gel of the water-based adhesive does not occur, but the viscosity increases by 200 mPa · s or more, or the viscosity increases to twice or more of the initial value.
X: A gel is formed.
（９）接触角（塗工性）
接触角計（協和界面科学社製、ＣＡ−Ａ型）より求めた。基材（ユニチカ社製エンブレット）上に水性接着剤を滴下し、接触角を測定し、浸透性により、塗工性を評価した。接触角が低いと基材へ浸透してしまい、基材表面に接着層を形成するのに支障が出る。
◎：７０度以上。基材に殆ど浸透しない。
○：５０度以上、７０度未満。基材へあまり浸透しない。
△：３０度以上、５０度未満。基材への浸透が見られる。
×：０度以上、３０度未満。基材へ浸透しやすい。
(9) Contact angle (coatability)
It calculated | required from the contact angle meter (the Kyowa Interface Science company make, CA-A type | mold). A water-based adhesive was dropped on a substrate (Embret made by Unitika Ltd.), the contact angle was measured, and the coating property was evaluated by the permeability. When the contact angle is low, it penetrates into the base material, which hinders the formation of an adhesive layer on the base material surface.
A: 70 degrees or more. It hardly penetrates into the substrate.
○: 50 degrees or more and less than 70 degrees. It does not penetrate much into the substrate.
Δ: 30 degrees or more and less than 50 degrees. Penetration into the substrate is observed.
X: 0 degree or more and less than 30 degree | times. Easy to penetrate into the substrate.
（１０）臭気
官能試験にて評価した。水性接着剤を塗布する工程における臭気を以下の指標で評価した
◎：全く臭いがない。
○：殆ど臭いがない。
△：臭いがある。
×：かなり臭いがあり、作業に支障が出る場合がある。
(10) Odor Evaluated by sensory test. The odor in the step of applying the water-based adhesive was evaluated by the following index: A: No odor at all.
○: Almost no odor.
Δ: There is a smell.
×: There is a considerable odor, which may hinder the work.
（１１）接着強度
平面基材（ライナー）として、ポリエステル（ユニチカ社製エンブレット）、ポリエチレン（タマポリ社製ＬＤＰＥ）、紙（安積濾紙社製化繊紙）を使用して、それぞれに水性接着剤をバーコーター♯１０で塗布し、未乾燥の塗膜上に、コルゲート加工した同種の材料からなる波板基材（フルート）をそれぞれ重ねて、９０℃、６０秒間の条件で乾燥して、コルゲートハニカム構造の積層体を作製した。
引張・圧縮万能試験機（ＩＮＴＥＳＣＯ社製）を使用し、重ね合わせた平面基材と波板基材とが剥離する際の強度を測定し、接着強度を求めた。コルゲートハニカム構造の接着強度は０．５Ｎ／２５ｍｍ以上であれば実用的であり、１．０Ｎ／２５ｍｍ以上であることが好ましく、１．５Ｎ／２５ｍｍ以上であることがより好ましい。
(11) Adhesive strength Polyester (Embret made by Unitika Co., Ltd.), polyethylene (LDPE made by Tamapoly Co., Ltd.) and paper (Asei Filter Paper Co., Ltd.) are used as the planar substrate (liner). A corrugated honeycomb coated with a bar coater # 10 and overlaid with a corrugated base material (flute) made of the same type of corrugated material and dried under conditions of 90 ° C. for 60 seconds. A laminate of structure was produced.
Using a tensile / compression universal testing machine (manufactured by INTESCO), the strength when the flat substrate and the corrugated plate substrate were separated was measured, and the adhesive strength was determined. The adhesive strength of the corrugated honeycomb structure is practical if it is 0.5 N / 25 mm or more, preferably 1.0 N / 25 mm or more, and more preferably 1.5 N / 25 mm or more.
（１２）アルカリ処理後の外観評価
２５μｍ厚みのポリエチレンフィルム（タマポリ社製ＬＤＰＥ）に水性接着剤をバーコーターで乾燥厚み３μｍとなるように塗布し、１００℃、６０秒間の条件で乾燥して塗膜を形成した。塗膜に対して２０％ＫＯＨ水溶液を滴下し、常温で１週間経過した際の状態を観察し、以下の指標でアルカリ処理後の外観を評価した。
○：塗膜の膨潤なし。
×：塗膜の膨潤がある。
(12) Appearance evaluation after alkali treatment An aqueous adhesive was applied to a 25 μm thick polyethylene film (LDPE manufactured by Tamapoly Co., Ltd.) with a bar coater to a dry thickness of 3 μm, and dried and coated at 100 ° C. for 60 seconds. A film was formed. A 20% KOH aqueous solution was dropped onto the coating film, and the state when 1 week had passed at room temperature was observed. The appearance after alkali treatment was evaluated using the following indices.
○: No swelling of the coating film.
X: There exists swelling of a coating film.
（１３）アルカリ処理後の臭気評価
ポリオレフィン不織布（ユニチカ社製エルベスＴ０３０３ＷＤＯ、目付３０ｇ／ｍ２）に水性接着剤を塗布量２０ｇ／ｍ２でディッピングにより塗布し、１００℃、５分の条件で乾燥して塗膜を形成した。得られた積層体を２０％ＫＯＨ水溶液に浸漬し、浸漬後に４０℃で密封容器に２４時間保管し、取り出し後の臭気を以下の指標で評価した。
○：殆ど臭いがない。
△：臭いがある。
×：かなり臭いがある。
−：塗膜がアルカリ処理により膨潤したため、評価しなかった。
(13) Odor evaluation after alkali treatment A polyolefin adhesive (Elves T0303WDO manufactured by Unitika Ltd., 30 g / m 2 basis weight) is coated with a water-based adhesive by dipping at a coating amount of 20 g / m 2 and dried at 100 ° C. for 5 minutes. Thus, a coating film was formed. The obtained laminate was immersed in a 20% aqueous KOH solution, stored in a sealed container for 24 hours at 40 ° C. after immersion, and the odor after removal was evaluated by the following index.
○: Almost no odor.
Δ: There is a smell.
X: There is a considerable smell.
-: Since the coating film was swollen by alkali treatment, it was not evaluated.
実施例１
ヒーター付きの密閉できる耐圧１リットル容ガラス容器を備えた攪拌機を用いて７５ｇのポリオレフィン樹脂〔アルケマ社製、ボンダインＨＸ−８２９０（以下ＨＸ−８２９０と示す）〕、４８．０ｇのイソプロパノール、３．０ｇのＮ，Ｎ−ジメチルエタノールアミン（ＤＭＥＡ）、および１７４．０ｇの蒸留水をガラス容器内に仕込み、撹拌翼の回転速度を３００ｒｐｍとして撹拌したところ、容器底部には樹脂粒状物の沈殿は認められず、浮遊状態となっていることが確認された。そこでこの状態を保ちつつ、１０分後にヒーターの電源を入れ加熱した。そして系内温度を１４０〜１４５℃に保ちさらに３０分間撹拌した。
イソプロパノール４８ｇを脱溶剤し、固形分を水で希釈し、回転速度３００ｒｐｍのまま撹拌しつつ２５℃まで冷却した後、３００メッシュのステンレス製フィルター（線径０．０３５ｍｍ、平織）で加圧ろ過（空気圧０．２ＭＰａ）し、乳白色の均一な水性接着剤Ｅ−１を得た。
Example 1
75 g of polyolefin resin [manufactured by Arkema, Bondine HX-8290 (hereinafter referred to as HX-8290)], 48.0 g of isopropanol, 3.0 g N, N-dimethylethanolamine (DMEA) and 174.0 g of distilled water were charged in a glass container and stirred at a stirring blade rotation speed of 300 rpm. Precipitation of resin particles was observed at the bottom of the container. It was confirmed that it was in a floating state. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. And the system temperature was kept at 140-145 degreeC, and also it stirred for 30 minutes.
48 g of isopropanol was removed, the solid content was diluted with water, cooled to 25 ° C. while stirring at a rotational speed of 300 rpm, and then pressure filtered through a 300-mesh stainless steel filter (wire diameter 0.035 mm, plain weave) ( The air pressure was 0.2 MPa, and a milky white uniform aqueous adhesive E-1 was obtained.
実施例２
ポリオレフィン樹脂ＨＸ−８２９０の仕込み量を１０５ｇに変更し、ＤＭＥＡの仕込み量を２．１ｇに変更した以外は実施例１と同様の操作を行い、水性接着剤Ｅ−２を得た。
Example 2
The same operation as in Example 1 was carried out except that the amount of the polyolefin resin HX-8290 was changed to 105 g and the amount of DMEA was changed to 2.1 g, to obtain an aqueous adhesive E-2.
実施例３
ポリオレフィン樹脂ＨＸ−８２９０の仕込み量を８０ｇに変更し、ＤＭＥＡの仕込み量を６ｇに変更した以外は実施例１と同様の操作を行い、水性接着剤Ｅ−３を得た。
Example 3
An aqueous adhesive E-3 was obtained in the same manner as in Example 1 except that the amount of the polyolefin resin HX-8290 was changed to 80 g and the amount of DMEA was changed to 6 g.
実施例４〜６
ポリオレフィン樹脂ＨＸ−８２９０の仕込み量を、実施例４では１０５ｇに、実施例５では１１１ｇに、実施例６では１１７ｇに変更した以外は実施例１と同様の操作を行い、水性接着剤Ｅ−４〜Ｅ−６を得た。
Examples 4-6
The same procedure as in Example 1 was carried out, except that the amount of polyolefin resin HX-8290 was changed to 105 g in Example 4, 111 g in Example 5, and 117 g in Example 6, and aqueous adhesive E-4 ~ E-6 was obtained.
実施例７
ポリオレフィン樹脂ＨＸ−８２９０の仕込み量を１０５ｇに変更し、ＤＭＥＡの仕込み量を６ｇに変更した以外は実施例１と同様の操作を行い、水性接着剤Ｅ−７を得た。
Example 7
An aqueous adhesive E-7 was obtained by performing the same operation as in Example 1 except that the amount of the polyolefin resin HX-8290 was changed to 105 g and the amount of DMEA was changed to 6 g.
実施例８〜９
ポリオレフィン樹脂ＨＸ−８２９０の仕込み量を、実施例８では１０５ｇに、実施例９では１１７ｇに変更し、いずれも、ＤＭＥＡ３ｇに代えて、アンモニア水（２８％）１０．７ｇを仕込み、水の仕込み量を１６６．３ｇに変更した以外は実施例１と同様の操作を行い、水性接着剤Ｅ−８〜Ｅ−９を得た。
Examples 8-9
The amount of polyolefin resin HX-8290 charged was changed to 105 g in Example 8 and 117 g in Example 9, and in each case, 10.7 g of ammonia water (28%) was charged instead of 3 g of DMEA, and the amount of water charged Except having changed into 166.3g, operation similar to Example 1 was performed and the water-based adhesives E-8-E-9 were obtained.
実施例１０
ポリオレフィン樹脂ＨＸ−８２９０の仕込み量を１０５ｇに変更し、ＤＭＥＡ３ｇに代えて、トリエタノールアミン（ＴＥＡ）３ｇを仕込んだ以外は実施例１と同様の操作を行い、水性接着剤Ｅ−１０を得た。
Example 10
The amount of the polyolefin resin HX-8290 was changed to 105 g, and the same operation as in Example 1 was carried out except that 3 g of triethanolamine (TEA) was used instead of 3 g of DMEA to obtain an aqueous adhesive E-10. .
比較例１
ヒーター付きの密閉できる耐圧１リットル容ガラス容器を備えた攪拌機を用いて７５．０ｇのポリオレフィン樹脂ＨＸ−８２９０、９０．０ｇのイソプロパノール、３．０ｇのＤＭＥＡ、および１３２．０ｇの蒸留水をガラス容器内に仕込み、撹拌翼の回転速度を３００ｒｐｍとして撹拌したところ、容器底部には樹脂粒状物の沈殿は認められず、浮遊状態となっていることが確認された。そこでこの状態を保ちつつ、１０分後にヒーターの電源を入れ加熱した。そして系内温度を１４０〜１４５℃に保ちさらに３０分間撹拌した。回転速度３００ｒｐｍのまま撹拌しつつ２５℃まで冷却した後、３００メッシュのステンレス製フィルター（線径０．０３５ｍｍ、平織）で加圧ろ過(空気圧０．２ＭＰａ)し、乳白色の均一な水性接着剤Ｅ−１１を得た。
Comparative Example 1
75.0 g polyolefin resin HX-8290, 90.0 g isopropanol, 3.0 g DMEA, and 132.0 g distilled water were added to a glass container using a stirrer equipped with a heater and a pressure-resistant 1-liter glass container. When the stirring speed was set to 300 rpm and the stirring blade was stirred at a rotational speed of 300 rpm, no precipitation of resin particles was observed at the bottom of the container, and it was confirmed that the container was in a floating state. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. And the system temperature was kept at 140-145 degreeC, and also it stirred for 30 minutes. After cooling to 25 ° C. while stirring at a rotational speed of 300 rpm, pressure filtration (air pressure 0.2 MPa) with a 300-mesh stainless steel filter (wire diameter 0.035 mm, plain weave) is used to produce a milky white uniform aqueous adhesive E. -11 was obtained.
比較例２
ポリオレフィン樹脂をＨＸ−８２９０からプリマコール５９８０Ｉ（ダウ・ケミカル社製）に変更した以外は実施例１と同様の操作を行い、乳白色の水性接着剤Ｅ−１２を得た。
Comparative Example 2
A milky white aqueous adhesive E-12 was obtained in the same manner as in Example 1 except that the polyolefin resin was changed from HX-8290 to Primacol 5980I (manufactured by Dow Chemical Co.).
比較例３
水性接着剤Ｊ−１として、コニシ社製、ＳＰ−２００（主成分：ビニル共重合樹脂）を原液で使用した。
Comparative Example 3
As the aqueous adhesive J-1, SP-200 (main component: vinyl copolymer resin) manufactured by Konishi Co., Ltd. was used as a stock solution.
比較例４
水性接着剤Ｊ−２として、アイカ工業社製、ウルトラゾール（主成分：アクリル酸エステル）を原液で使用した。
Comparative Example 4
As the aqueous adhesive J-2, Ultrazol (main component: acrylic ester) manufactured by Aika Kogyo Co., Ltd. was used as a stock solution.
比較例５
水性接着剤Ｊ−３として、住友精化社製、ザイクセンＡＣ（主成分：エチレン−アクリル酸共重合樹脂）を原液で使用した。
Comparative Example 5
As aqueous adhesive J-3, Sumix Seika Co., Ltd., and Syxen AC (main component: ethylene-acrylic acid copolymer resin) were used as a stock solution.
使用したポリオレフィン樹脂の組成を表１に示し、実施例、比較例の水性接着剤の特性、評価結果を表２に示す。 The composition of the polyolefin resin used is shown in Table 1, and the characteristics and evaluation results of the aqueous adhesives of Examples and Comparative Examples are shown in Table 2.
実施例の水性接着剤は、接着剤そのものの臭気はないか低減され、得られた塗膜は、アルカリ処理した後でも膨潤はなく、外観に優れ、臭気はほとんどなかった。また、積層体は、ハニカム構造であっても基材を選ばず良好な接着強度を有していた。アミン化合物としてＤＭＥＡを使用した水性接着剤は、アンモニアやＴＥＡを使用したものに比較して、ポリオレフィン樹脂の分散性が良好となって粒子径が小さくなり、保存安定性に優れたものであった。実施例２、４、７の水性接着剤において、ＤＭＥＡの含有量が増加すると、分散粒子の体積平均粒子径を小さくすることができ、粘度を上げることができ、特に実施例４の水性接着剤は、粘度がより好ましい範囲であったため、形成された積層体は、塗工性、接着強度に優れていた。 The aqueous adhesives of the examples were free from or reduced the odor of the adhesive itself, and the resulting coating film did not swell even after alkali treatment, was excellent in appearance, and had almost no odor. Further, even if the laminate had a honeycomb structure, it had good adhesive strength regardless of the substrate. The water-based adhesive using DMEA as the amine compound has a good dispersibility of the polyolefin resin and a smaller particle size and excellent storage stability compared to those using ammonia or TEA. . In the aqueous adhesives of Examples 2, 4, and 7, when the content of DMEA increases, the volume average particle diameter of the dispersed particles can be reduced, and the viscosity can be increased. In particular, the aqueous adhesive of Example 4 Since the viscosity was in a more preferable range, the formed laminate was excellent in coatability and adhesive strength.
一方、比較例１の水性接着剤は、本発明の規定量を超えた有機溶剤を含有するため、接着剤の臭気評価で劣っており、積層体の接着強度も不十分であった。
比較例２〜５の水性接着剤は、本発明で規定したポリオレフィン樹脂を用いた水性接着剤ではなかったため、比較例２では、得られた塗膜はアルカリ処理した後の外観評価が劣り、積層体の接着強度も劣っており、比較例３では、得られた塗膜はアルカリ処理した後にかなりの臭気があり、積層体の接着強度も劣っていた。また比較例４では、接着剤の臭気があり、得られた塗膜はアルカリ処理した後の外観評価が劣り、積層体の接着強度も劣っており、比較例５では、得られた塗膜はアルカリ処理した後の外観評価が劣っていた。
On the other hand, since the water-based adhesive of Comparative Example 1 contained an organic solvent exceeding the specified amount of the present invention, the odor evaluation of the adhesive was inferior, and the adhesive strength of the laminate was also insufficient.
Since the water-based adhesives of Comparative Examples 2 to 5 were not water-based adhesives using the polyolefin resin defined in the present invention, in Comparative Example 2, the obtained coating film was inferior in appearance evaluation after alkali treatment, and was laminated. The adhesive strength of the body was also inferior. In Comparative Example 3, the obtained coating film had a considerable odor after alkali treatment, and the adhesive strength of the laminate was also inferior. In Comparative Example 4, there was an odor of the adhesive, and the obtained coating film was inferior in appearance evaluation after alkali treatment, and the adhesive strength of the laminate was also inferior. In Comparative Example 5, the obtained coating film was The appearance evaluation after the alkali treatment was inferior.
Claims (9)
水性分散体中の有機溶剤含有量が３質量％以下であり、
ポリオレフィン樹脂が（メタ）アクリル酸エステル成分と無水マレイン酸成分を含有することを特徴とする水性接着剤。 An aqueous dispersion containing a polyolefin resin and an aqueous medium,
The organic solvent content in the aqueous dispersion is 3% by mass or less,
A water-based adhesive, wherein the polyolefin resin contains a (meth) acrylic acid ester component and a maleic anhydride component.
A laminate comprising the laminate according to any one of claims 6 to 8, wherein two or more layers are laminated, and voids are formed between the layers.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2003119328A (en) * | 2001-01-15 | 2003-04-23 | Unitika Ltd | Aqueous dispersion of polyolefin resin and method for producing the same |
| JP2003213233A (en) * | 2002-01-18 | 2003-07-30 | Unitika Ltd | Aqueous adhesive for paper and laminate |
| JP2004026909A (en) * | 2002-06-21 | 2004-01-29 | Nippon Shokubai Co Ltd | Acrylic emulsion-type pressure-sensitive adhesive |
| JP2006255562A (en) * | 2005-03-16 | 2006-09-28 | Toyobo Co Ltd | Honeycomb filter |
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| JP2003119328A (en) * | 2001-01-15 | 2003-04-23 | Unitika Ltd | Aqueous dispersion of polyolefin resin and method for producing the same |
| JP2003213233A (en) * | 2002-01-18 | 2003-07-30 | Unitika Ltd | Aqueous adhesive for paper and laminate |
| JP2004026909A (en) * | 2002-06-21 | 2004-01-29 | Nippon Shokubai Co Ltd | Acrylic emulsion-type pressure-sensitive adhesive |
| JP2006255562A (en) * | 2005-03-16 | 2006-09-28 | Toyobo Co Ltd | Honeycomb filter |
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