JP2016204592A - Polyhydroxyurethane water dispersion composition, gas barrier aqueous coating agent using the water dispersion composition and gas barrier film - Google Patents
Polyhydroxyurethane water dispersion composition, gas barrier aqueous coating agent using the water dispersion composition and gas barrier film Download PDFInfo
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- JP2016204592A JP2016204592A JP2015091350A JP2015091350A JP2016204592A JP 2016204592 A JP2016204592 A JP 2016204592A JP 2015091350 A JP2015091350 A JP 2015091350A JP 2015091350 A JP2015091350 A JP 2015091350A JP 2016204592 A JP2016204592 A JP 2016204592A
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- Prior art keywords
- resin
- polyhydroxyurethane
- dispersion composition
- aqueous dispersion
- general formula
- 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
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- 239000006185 dispersion Substances 0.000 title claims abstract description 162
- 239000000203 mixture Substances 0.000 title claims abstract description 86
- 239000011248 coating agent Substances 0.000 title claims abstract description 42
- 230000004888 barrier function Effects 0.000 title claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title abstract description 75
- 229920005989 resin Polymers 0.000 claims abstract description 238
- 239000011347 resin Substances 0.000 claims abstract description 238
- 239000002734 clay mineral Substances 0.000 claims abstract description 78
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 39
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 39
- 125000000129 anionic group Chemical group 0.000 claims abstract description 32
- 239000002131 composite material Substances 0.000 claims abstract description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 66
- 238000006243 chemical reaction Methods 0.000 claims description 61
- 239000000126 substance Substances 0.000 claims description 39
- 239000007789 gas Substances 0.000 claims description 35
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 33
- 239000001569 carbon dioxide Substances 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 20
- 150000005676 cyclic carbonates Chemical group 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- 239000001301 oxygen Substances 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 19
- 230000035699 permeability Effects 0.000 claims description 18
- 239000011247 coating layer Substances 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 16
- 239000004215 Carbon black (E152) Substances 0.000 claims description 10
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 9
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 5
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 5
- 239000010445 mica Substances 0.000 claims description 5
- 229910052618 mica group Inorganic materials 0.000 claims description 5
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 229910000275 saponite Inorganic materials 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 3
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims description 3
- 229910000271 hectorite Inorganic materials 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 claims description 3
- 229910052622 kaolinite Inorganic materials 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 229910052902 vermiculite Inorganic materials 0.000 claims description 3
- 239000010455 vermiculite Substances 0.000 claims description 3
- 235000019354 vermiculite Nutrition 0.000 claims description 3
- 238000000576 coating method Methods 0.000 abstract description 33
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 52
- 238000003786 synthesis reaction Methods 0.000 description 49
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 48
- 238000004519 manufacturing process Methods 0.000 description 31
- -1 isocyanate compounds Chemical class 0.000 description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 28
- 238000000034 method Methods 0.000 description 26
- 239000002245 particle Substances 0.000 description 24
- 238000004945 emulsification Methods 0.000 description 23
- 239000002904 solvent Substances 0.000 description 21
- 238000011156 evaluation Methods 0.000 description 17
- 229920005749 polyurethane resin Polymers 0.000 description 17
- 239000000463 material Substances 0.000 description 16
- 239000003973 paint Substances 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 12
- 239000002585 base Substances 0.000 description 11
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 11
- 239000010410 layer Substances 0.000 description 11
- 239000004593 Epoxy Substances 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 7
- 229940125890 compound Ia Drugs 0.000 description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 235000010755 mineral Nutrition 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 0 *C(CO1)OC1=O Chemical compound *C(CO1)OC1=O 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000012790 confirmation Methods 0.000 description 4
- VGEWEGHHYWGXGG-UHFFFAOYSA-N ethyl n-hydroxycarbamate Chemical compound CCOC(=O)NO VGEWEGHHYWGXGG-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000007514 bases Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 3
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 2
- XYUINKARGUCCQJ-UHFFFAOYSA-N 3-imino-n-propylpropan-1-amine Chemical compound CCCNCCC=N XYUINKARGUCCQJ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000005587 carbonate group Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 125000003010 ionic group Chemical group 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 125000003156 secondary amide group Chemical group 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229940014800 succinic anhydride Drugs 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PIYNUZCGMLCXKJ-UHFFFAOYSA-N 1,4-dioxane-2,6-dione Chemical compound O=C1COCC(=O)O1 PIYNUZCGMLCXKJ-UHFFFAOYSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- FSYPIGPPWAJCJG-UHFFFAOYSA-N 2-[[4-(oxiran-2-ylmethoxy)phenoxy]methyl]oxirane Chemical compound C1OC1COC(C=C1)=CC=C1OCC1CO1 FSYPIGPPWAJCJG-UHFFFAOYSA-N 0.000 description 1
- OJPDDQSCZGTACX-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)anilino]ethanol Chemical compound OCCN(CCO)C1=CC=CC=C1 OJPDDQSCZGTACX-UHFFFAOYSA-N 0.000 description 1
- QHKGDMNPQAZMKD-UHFFFAOYSA-N 2-amino-2-methylbutan-1-ol Chemical compound CCC(C)(N)CO QHKGDMNPQAZMKD-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- ZAXCZCOUDLENMH-UHFFFAOYSA-N 3,3,3-tetramine Chemical compound NCCCNCCCNCCCN ZAXCZCOUDLENMH-UHFFFAOYSA-N 0.000 description 1
- OLQWMCSSZKNOLQ-UHFFFAOYSA-N 3-(2,5-dioxooxolan-3-yl)oxolane-2,5-dione Chemical compound O=C1OC(=O)CC1C1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- XNDSIASQMRYFSW-UHFFFAOYSA-N 3-oxaspiro[5.5]undecane-2,4-dione Chemical compound C1C(=O)OC(=O)CC11CCCCC1 XNDSIASQMRYFSW-UHFFFAOYSA-N 0.000 description 1
- HMMBJOWWRLZEMI-UHFFFAOYSA-N 4,5,6,7-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CCCC2=C1C(=O)OC2=O HMMBJOWWRLZEMI-UHFFFAOYSA-N 0.000 description 1
- QKAHKEDLPBJLFD-UHFFFAOYSA-N 6,6-dimethyl-3-oxabicyclo[3.1.0]hexane-2,4-dione Chemical compound O=C1OC(=O)C2C1C2(C)C QKAHKEDLPBJLFD-UHFFFAOYSA-N 0.000 description 1
- GFWLMILMVMCJDI-UHFFFAOYSA-N 8-oxaspiro[4.5]decane-7,9-dione Chemical compound C1C(=O)OC(=O)CC11CCCC1 GFWLMILMVMCJDI-UHFFFAOYSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UHFFFAOYSA-N 826-62-0 Chemical compound C1C2C3C(=O)OC(=O)C3C1C=C2 KNDQHSIWLOJIGP-UHFFFAOYSA-N 0.000 description 1
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Images
Abstract
Description
本発明は、塗料、コーティング剤用のバインダー樹脂として利用できる、ポリヒドロキシウレタン樹脂と、粘土鉱物との複合化を可能にした、水分散体組成物の技術に関する。特に、水分散塗料材料として使用でき、しかもポリヒドロキシウレタン樹脂の化学構造中に二酸化炭素を組み込むことが可能であることから、高度な環境対応製品の提供が可能であり、また、被膜の機能性の観点からも、従来の溶剤系塗料と遜色のない、耐熱性塗料、ガスバリア性塗料としての性能を示すポリヒドロキシウレタン樹脂の水分散体組成物を提供できる技術に関する。 The present invention relates to a technique for an aqueous dispersion composition that can be combined with a polyhydroxyurethane resin and a clay mineral, which can be used as a binder resin for paints and coating agents. In particular, it can be used as a water-dispersed paint material, and since carbon dioxide can be incorporated into the chemical structure of polyhydroxyurethane resin, it is possible to provide advanced environmentally friendly products, and the functionality of the coating. From this point of view, the present invention also relates to a technique capable of providing an aqueous dispersion composition of a polyhydroxyurethane resin that exhibits performance as a heat-resistant paint and a gas barrier paint that is comparable to conventional solvent-based paints.
ポリウレタン樹脂は、強度、柔軟性、耐摩耗性、耐油性に優れた樹脂であり、塗料や接着剤用の樹脂として広く使用されている。近年、新規なポリウレタン系の樹脂として化学構造中にウレタン結合と水酸基を併せ持つヒドロキシポリウレタン樹脂が開発され、その工業的な応用が期待されている（特許文献１参照）。既存のポリウレタン樹脂が、イソシアネート化合物とポリオールとを原料として得られるのに対して、ヒドロキシポリウレタン樹脂は、エポキシ化合物、二酸化炭素及びアミン化合物を原料に用い、これらの原料の組み合わせにより製造される。原料として使用された二酸化炭素は、ヒドロキシポリウレタン樹脂の化学構造中に−ＣＯ−Ｏ−結合として組み込まれることから、温室効果ガスである二酸化炭素の有効利用の観点からも注目されるべき樹脂材料である。 Polyurethane resins are resins having excellent strength, flexibility, wear resistance, and oil resistance, and are widely used as resins for paints and adhesives. In recent years, a hydroxy polyurethane resin having both a urethane bond and a hydroxyl group in its chemical structure has been developed as a novel polyurethane resin, and its industrial application is expected (see Patent Document 1). Whereas existing polyurethane resins are obtained using isocyanate compounds and polyols as raw materials, hydroxypolyurethane resins are produced by using a combination of these raw materials using epoxy compounds, carbon dioxide and amine compounds as raw materials. Since carbon dioxide used as a raw material is incorporated as a —CO—O— bond in the chemical structure of the hydroxy polyurethane resin, it is a resin material that should be noted from the viewpoint of effective use of carbon dioxide, which is a greenhouse gas. is there.
ヒドロキシポリウレタン樹脂は、既存のポリウレタン樹脂と同様に機械強度に優れた樹脂とできるが、さらに、既存ポリウレタン樹脂の構造中にはない水酸基に由来した機能性を生かした応用が検討されている。例えば、水酸基の架橋反応を利用した耐熱性塗料としての応用（特許文献２参照）や、水酸基由来のガスバリア性を利用したガスバリア性フィルムへの応用が検討されている（特許文献３参照）。 The hydroxy polyurethane resin can be made a resin having excellent mechanical strength like the existing polyurethane resin, but further, an application utilizing the functionality derived from the hydroxyl group not present in the structure of the existing polyurethane resin is being studied. For example, application as a heat-resistant coating using a hydroxyl group crosslinking reaction (see Patent Document 2) and application to a gas barrier film utilizing hydroxyl-derived gas barrier properties are being studied (see Patent Document 3).
これらの従来技術にもあるように、ヒドロキシポリウレタンの応用用途として、塗料、コーティング分野が有望である。しかし、これまでに開発されているヒドロキシポリウレタン樹脂は、ウレタン結合と共に水酸基を有する化学構造をもつため、有機溶剤に対する溶解性が低く、各用途で使用される基材や加工装置に応じて異なることも多く、多様な溶剤組成への対応が困難である点が応用上の問題となっている。これに対し、ヒドロキシポリウレタン樹脂を水分散体とすることで、この問題を解消すると同時に、近年、溶剤系塗料からの置き換えが進んでいる水系の塗料として応用することが検討され、提案されている（特許文献４参照）。 As in these prior arts, the paint and coating fields are promising as applications of hydroxypolyurethane. However, the hydroxy polyurethane resins that have been developed so far have a chemical structure with hydroxyl groups as well as urethane bonds, so they have low solubility in organic solvents and differ depending on the substrate and processing equipment used in each application. In many cases, it is difficult to cope with various solvent compositions. On the other hand, by using hydroxypolyurethane resin as an aqueous dispersion, this problem has been solved and, at the same time, application as a water-based paint that is being replaced by a solvent-based paint has been studied and proposed. (See Patent Document 4).
しかし、本発明者らの検討によれば、この技術は、水分散体を得るためにヒドロキシポリウレタンの水酸基をハーフエステル法によってカルボキシル基化したものであることから、ハーフエステル部分の加水分解に起因して、水分散体の保存安定性が悪い点で課題が残っており、問題を完全に解決したものではなかった。また、ヒドロキシポリウレタンの水酸基を反応に利用し減少させる点は、耐水性の向上に寄与するといった利点を有する反面、水酸基の機能性を利用する用途においては、欠点を有するものとなる。別の手法として、原料としてカルボン酸を含有するアミン化合物を使用し、カルボキシル基を有するポリヒドロキシウレタンを得る方法が考案されている（特許文献５参照）。しかしながら、本発明者らの検討によれば、この方法は、合成反応系内でカルボキシル基とアミノ基がイオン結合を形成して、環状カーボネートとの反応が進行しにくく、また、ＤＭＦ（ジメチルホルムアミド）などの高沸点溶剤中での反応が必要であり、高分子量化も困難であるといった欠点を有する。更に、使用した高沸点溶剤は、転相乳化後に減圧留去ができないという問題もあり、水分散体（エマルジョン）の製造方法としては完全なものではなかった。 However, according to the study by the present inventors, this technique results from hydrolysis of the half ester portion because the hydroxyl group of hydroxy polyurethane is carboxylated by the half ester method in order to obtain an aqueous dispersion. However, a problem remains in that the storage stability of the aqueous dispersion is poor, and the problem has not been completely solved. Moreover, the point of utilizing and reducing the hydroxyl group of hydroxypolyurethane has the advantage of contributing to the improvement of water resistance, but has a drawback in applications utilizing the functionality of the hydroxyl group. As another technique, a method of using an amine compound containing a carboxylic acid as a raw material to obtain a polyhydroxyurethane having a carboxyl group has been devised (see Patent Document 5). However, according to the study by the present inventors, this method is such that the carboxyl group and the amino group form an ionic bond in the synthesis reaction system so that the reaction with the cyclic carbonate does not proceed easily, and DMF (dimethylformamide) ) And the like in a high boiling point solvent, and it is difficult to increase the molecular weight. Furthermore, the high boiling point solvent used has a problem that it cannot be distilled off under reduced pressure after phase inversion emulsification, and is not a perfect method for producing an aqueous dispersion (emulsion).
上記したようにヒドロキシポリウレタン樹脂被膜は、ガスバリア性被膜としての機能を有している。一方で、ヒドロキシポリウレタン樹脂のガスバリア性を向上させる手法として、粘土鉱物と複合化させる方法が提案されている（特許文献６）。一般に、粘土鉱物を樹脂中に分散させるためには、層間の金属カチオンイオンを有機オニウム塩に置換する等の疎水化処理が必要であり、上記した方法でも、粘土鉱物を疎水化処理した後、複合化させている。 As described above, the hydroxy polyurethane resin film has a function as a gas barrier film. On the other hand, as a technique for improving the gas barrier property of hydroxypolyurethane resin, a method of compounding with clay mineral has been proposed (Patent Document 6). In general, in order to disperse the clay mineral in the resin, it is necessary to perform a hydrophobic treatment such as substitution of the metal cation ion between layers with an organic onium salt. It is compounded.
しかしながら、粘土鉱物の疎水化処理は複雑な工程を必要とし、また、本発明者らの検討によれば、有機オニウム塩の一部が樹脂の結晶化を阻害し、ガスバリア性を低下する要因ともなり得ることから、未変性の粘土鉱物が分散可能な水溶媒中にて樹脂との複合化を行うことができれば、ガスバリア性の発揮には好ましいと考えられる。これに対し、本発明者らの検討によれば、水中での複合化において粘土鉱物は未変性状態で使用可能であるが、水系樹脂の分散にアニオン性基を有する樹脂を使用した場合、アニオン性基と粘土鉱物層表面のアニオン性イオンが反発作用を有し、分散状態が不安定となる。これに対し、例えば、特開２００５−１３９４３６号公報に、カルボキシル基を有するポリウレタン樹脂の水分散体を得る場合に、第３成分として、カチオン性を有する成分を添加することが提案されている。しかし、このような第３成分の添加は、前記有機オニウム塩と同様に、樹脂の結晶化を阻害することから、有効な方法とはいえない。 However, the hydrophobization treatment of clay mineral requires a complicated process, and according to the study by the present inventors, a part of the organic onium salt inhibits crystallization of the resin and may cause a decrease in gas barrier properties. Therefore, it is considered preferable for exhibiting gas barrier properties if it can be combined with the resin in an aqueous solvent in which the unmodified clay mineral can be dispersed. On the other hand, according to the study by the present inventors, the clay mineral can be used in an unmodified state in complexing in water, but when a resin having an anionic group is used for dispersion of an aqueous resin, The anionic ions on the surface of the functional group and the clay mineral layer have a repulsive action, and the dispersion state becomes unstable. On the other hand, for example, JP-A-2005-139436 proposes to add a cationic component as the third component when obtaining an aqueous dispersion of a polyurethane resin having a carboxyl group. However, such addition of the third component is not an effective method because it inhibits crystallization of the resin as in the case of the organic onium salt.
従って、本発明の目的は、水系塗料やコーティング剤の被膜形成用樹脂として使用可能であり、ヒドロキシポリウレタン樹脂を利用した場合の従来技術の課題を克服し、粘土鉱物との良好な複合化によってガスバリア性を向上させた、実用化が可能な良好な安定性を有するポリヒドロキシウレタン水分散体組成物を提供すること、及び、該水分散体組成物を使用し、ガスバリア性水性コーティング剤や、ガスバリア性に優れたフィルムを提供することにある。また、この水性コーティング剤によって形成される塗膜（被膜層）が、粘土鉱物を利用したものでありながら、凝集物のない、粘度鉱物が微分散していることによってもたらされる光沢度を示す外観に優れたものにできる技術を提供することにある。 Accordingly, the object of the present invention is to be used as a resin for forming a film of water-based paints or coating agents, and overcomes the problems of the prior art when using a hydroxypolyurethane resin, and has a gas barrier through good complexation with clay minerals. The present invention provides a polyhydroxyurethane aqueous dispersion composition having improved stability and good practical use, and a gas barrier aqueous coating agent and gas barrier using the aqueous dispersion composition. The object is to provide a film having excellent properties. In addition, the coating film (coating layer) formed by this aqueous coating agent uses clay minerals, but has no agglomerates and has an appearance showing glossiness caused by fine dispersion of viscosity minerals. It is to provide a technology that can be made excellent.
上記課題は本発明によって解決される、すなわち、本発明は、（Ａ）カルボキシル基と水酸基とを有するアニオン性ポリヒドロキシウレタン樹脂と、（Ｂ）層状粘土鉱物とを含有してなる水分散体組成物であって、（Ａ）成分１００質量部に対して（Ｂ）成分が１〜５０質量部であり、水分散体組成物中の（Ａ）成分と（Ｂ）成分との合計含有量が１０〜５０質量％であることを特徴とするポリヒドロキシウレタン水分散体組成物を提供する。 The above-mentioned problem is solved by the present invention, that is, the present invention is an aqueous dispersion composition comprising (A) an anionic polyhydroxyurethane resin having a carboxyl group and a hydroxyl group, and (B) a layered clay mineral. The component (B) is 1 to 50 parts by mass with respect to 100 parts by mass of the component (A), and the total content of the component (A) and the component (B) in the aqueous dispersion composition is Provided is a polyhydroxyurethane aqueous dispersion composition having a content of 10 to 50% by mass.
上記した本発明のポリヒドロキシウレタン樹脂の水分散体組成物の好ましい形態としては、前記（Ａ）のアニオン性ポリヒドロキシウレタン樹脂の化学構造が、下記一般式（１）で示される繰り返し単位を有するものであることが挙げられる。
また、上記した本発明のポリヒドロキシウレタン樹脂の水分散体組成物の好ましい形態としては、前記一般式（１）で示される繰り返し単位の部分と、更に、前記一般式（１）中の−Ｚ−が、前記一般式（１１）に替えて、その構造中に、酸素原子、窒素原子を含んでいてもよい、炭素数１〜１００の炭化水素又は炭素数６〜１００の芳香族炭化水素である化学構造を有する前記一般式（１）で示される繰り返し単位の部分とが混在していることが挙げられる。 Moreover, as a preferable form of the aqueous dispersion composition of the polyhydroxyurethane resin of the present invention described above, a portion of the repeating unit represented by the general formula (1), and -Z in the general formula (1) are further included. -Is a hydrocarbon having 1 to 100 carbon atoms or an aromatic hydrocarbon having 6 to 100 carbon atoms which may contain an oxygen atom or a nitrogen atom in the structure instead of the general formula (11). It is mentioned that the repeating unit portion represented by the general formula (1) having a certain chemical structure is mixed.
更に、上記した本発明のポリヒドロキシウレタン樹脂の水分散体組成物の好ましい形態としては、下記のものが挙げられる。前記（Ａ）のアニオン性ポリヒドロキシウレタン樹脂は、その重量平均分子量が１００００〜１０００００の範囲であり、且つ、カルボキシル基の含有量が酸価１０ｍｇＫＯＨ／ｇ〜１００ｍｇＫＯＨ／ｇとなる範囲であり、且つ、水酸基価が１５０ｍｇＫＯＨ／ｇ〜３００ｍｇＫＯＨ／ｇの範囲であること；前記（Ａ）のアニオン性ポリヒドロキシウレタン樹脂は、少なくともその一部に二酸化炭素を原料として用いて合成された五員環環状カーボネート構造を有する、少なくとも２つの五員環環状カーボネート構造を有する化合物と、少なくとも２つのアミノ基を有する化合物の重付加反応により得られたものであり、全質量のうち１〜３０質量％を、前記二酸化炭素由来の−Ｏ−ＣＯ−結合が占めること；前記（Ｂ）の層状粘土鉱物が、モンモリロナイト、サポナイト、ヘクトライト、バーミキュライト、カオリナイト及びマイカからなる群から選択される少なくともいずれかであることである。 Furthermore, the following are mentioned as a preferable form of the aqueous dispersion composition of the above-mentioned polyhydroxy urethane resin of this invention. The anionic polyhydroxyurethane resin (A) has a weight average molecular weight in the range of 10,000 to 100,000, and a carboxyl group content in the range of 10 mgKOH / g to 100 mgKOH / g, and The hydroxyl value is in the range of 150 mgKOH / g to 300 mgKOH / g; the anionic polyhydroxyurethane resin (A) is a five-membered cyclic carbonate synthesized using carbon dioxide as a raw material at least in part. It is obtained by a polyaddition reaction of a compound having a structure and having at least two 5-membered cyclic carbonate structures and a compound having at least two amino groups. That the carbon dioxide-derived -O-CO- bond occupies; Montmorillonite, saponite, is that hectorite, vermiculite, at least one selected from the group consisting of kaolinite and mica.
また、本発明は別の実施の形態として、上記したポリヒドロキシウレタン水分散体組成物を必須成分とすることを特徴とするガスバリア性水性コーティング剤を提供する。 Moreover, this invention provides the gas-barrier aqueous coating agent characterized by using the above-mentioned polyhydroxyurethane aqueous dispersion composition as an essential component as another embodiment.
さらに、本発明は別の実施の形態として、上記したポリヒドロキシウレタン水分散体組成物によるポリヒドロキシウレタン樹脂−粘土鉱物複合被膜層が形成され、且つ、該複合被膜層の厚みが０．１〜１００μｍであり、フィルムの酸素透過率が、２３℃で、６５％の恒温恒湿度下において５０ｍＬ／ｍ2・ｄａｙ・ａｔｍ以下であるガスバリア性フィルムを提供する。 Furthermore, as another embodiment of the present invention, a polyhydroxyurethane resin-clay mineral composite coating layer is formed from the above-described polyhydroxyurethane aqueous dispersion composition, and the thickness of the composite coating layer is 0.1 to 0.1. A gas barrier film having a thickness of 100 μm and an oxygen permeability of 50 mL / m 2 · day · atm or less at 23 ° C. and a constant temperature and humidity of 65% is provided.
本発明によれば、水系塗料やコーティング剤の被膜形成用樹脂として使用可能な水中にポリヒドロキシウレタン樹脂を分散してなる水分散体が提供される。本発明によって提供されるポリヒドロキシウレタン樹脂の水分散体は、従来技術で提供される樹脂の水分散体と比較して、安定性に優れ、長期間の保存が可能であり、且つ、ヒドロキシポリウレタン樹脂の水酸基を一定量にコントロールできることから、本発明のポリヒドロキシウレタン樹脂の水分散体から得られる塗膜（被膜層）の性能も、従来の溶剤型ポリヒドロキシウレタン樹脂から得られる塗膜と同等の性能を得ることができる。加えて、本発明の水分散体組成物は、ガスバリア性を向上させることが知られている粘土鉱物を良好な状態で分散したものとなるので、ガスバリア性により優れた被膜を容易に作製することができる。また、粘土鉱物を良好な状態で微分散できたことで、粘土鉱物を分散したものでありながら、形成される塗膜（被膜層）は、凝集物のない、光沢のある外観に優れたのものになるので、高い実用性が期待される。本発明のポリヒドロキシウレタン水分散体組成物は、水系の塗料の被膜形成用樹脂として利用ができるので、これを用いることで、溶剤系の塗料で問題となっている使用時における有機溶剤の環境中への放出がなくなり、塗膜（被膜層）の性能を満足し得、且つ、環境負荷を低減した水系塗料等の提供ができる。また、本発明を構成するポリヒドロキシウレタン樹脂は、二酸化炭素を原材料（形成材料）として使用して製造することが可能な樹脂であり、水系材料であることによる環境負荷の低減に加えて、更なる環境負荷の低減にも貢献することができるので、この点でも有用である。 ADVANTAGE OF THE INVENTION According to this invention, the water dispersion formed by disperse | distributing a polyhydroxyurethane resin in the water which can be used as resin for film formation of a water-based coating material or a coating agent is provided. The aqueous dispersion of polyhydroxyurethane resin provided by the present invention is superior in stability and can be stored for a long period of time as compared with the aqueous dispersion of resin provided in the prior art. Since the hydroxyl group of the resin can be controlled to a certain amount, the performance of the coating film (coating layer) obtained from the aqueous dispersion of the polyhydroxyurethane resin of the present invention is equivalent to the coating film obtained from the conventional solvent-type polyhydroxyurethane resin. Performance can be obtained. In addition, since the water dispersion composition of the present invention is a dispersion of clay minerals known to improve gas barrier properties in a good state, a film excellent in gas barrier properties can be easily produced. Can do. In addition, because the clay mineral was finely dispersed in a good state, the formed coating film (coating layer) has excellent glossy appearance without agglomerates, although the clay mineral is dispersed. Therefore, high practicality is expected. Since the polyhydroxyurethane aqueous dispersion composition of the present invention can be used as a resin for forming a film of an aqueous paint, the use of this makes it possible to use the environment of the organic solvent at the time of use, which is a problem with solvent-based paints There is no release to the inside, the performance of the coating film (coating layer) can be satisfied, and a water-based paint or the like with reduced environmental load can be provided. In addition, the polyhydroxyurethane resin constituting the present invention is a resin that can be produced using carbon dioxide as a raw material (formation material). It is also useful in this respect because it can contribute to the reduction of environmental load.
次に、発明を実施するための好ましい形態を挙げて本発明を詳細に説明する。本発明のポリヒドロキシウレタン水分散体組成物は、（Ａ）カルボキシル基と水酸基を有するアニオン性ヒドロキシポリウレタン樹脂、（Ｂ）層状粘土鉱物、を含有する水分散体組成物であって、（Ａ）成分１００質量部に対して（Ｂ）成分が１〜５０質量部であり、該組成物中の（Ａ）成分と（Ｂ）成分との合計含有量が１０〜５０質量％であることを特徴とする。特に、前記（Ａ）のアニオン性ポリヒドロキシウレタン樹脂の化学構造が、下記一般式（１）で示される繰り返し単位を有するものであることが好ましい。 Next, the present invention will be described in detail with reference to preferred embodiments for carrying out the invention. The polyhydroxyurethane aqueous dispersion composition of the present invention is an aqueous dispersion composition containing (A) an anionic hydroxypolyurethane resin having a carboxyl group and a hydroxyl group, and (B) a layered clay mineral, The component (B) is 1 to 50 parts by mass with respect to 100 parts by mass of the component, and the total content of the component (A) and the component (B) in the composition is 10 to 50% by mass. And In particular, the chemical structure of the anionic polyhydroxyurethane resin (A) preferably has a repeating unit represented by the following general formula (1).
本発明を構成する（Ａ）のカルボキシル基と水酸基とを有するアニオン性ポリヒドロキシウレタン樹脂が、その構造中に有する繰り返し単位である上記一般式（１）で示される構造は、樹脂中のすべての繰り返し単位が同一の構造であってもよいが、上記で規定した構造が複数混在するものであってもよい。例えば、ポリヒドロキシウレタン樹脂の構造中に有する繰り返し単位が、一般式（１）中のＹ1とＹ2がいずれも式（２）の化学構造のものであってもよいし、これと、例えば、一般式（１）中のＹ1が式（３）で、Ｙ2が式（６）の化学構造のものとが混在したポリヒドロキシウレタン樹脂であってもよい。 The structure represented by the general formula (1), which is a repeating unit contained in the structure of the anionic polyhydroxyurethane resin having a carboxyl group and a hydroxyl group (A) constituting the present invention, The repeating unit may have the same structure, but a plurality of the structures defined above may be mixed. For example, the repeating unit possessed in the structure of the polyhydroxyurethane resin may be such that both Y 1 and Y 2 in the general formula (1) have the chemical structure of the formula (2), for example, The polyhydroxyurethane resin in which Y 1 in the general formula (1) is the formula (3) and Y 2 is mixed with the chemical structure of the formula (6) may be used.
上記したように、本発明を構成する（Ａ）の、カルボキシル基と水酸基とを有するアニオン性ポリヒドロキシウレタン樹脂は、繰り返し単位中に、少なくとも、前記一般式（１１）で表される水を加えて転相乳化を可能にするための「ＣＯＯＲ7」部分を含む構造を有するものであるが、本発明においては、全ての樹脂が上記構成を満足するものでもよいが、これに限定されず、下記の構造を有する樹脂が混在する構成のものも好ましく使用できる。具体的には、前記一般式（１）中の−Ｚ−が、前記一般式（１１）に替えて、その構造中に、酸素原子、窒素原子を含んでいてもよい、炭素数１〜１００の炭化水素又は炭素数６〜１００の芳香族炭化水素である化学構造を有するものである前記一般式（１）で示される繰り返し単位を有する樹脂が、混在している構成のものであってもよい。 As described above, the anionic polyhydroxyurethane resin having a carboxyl group and a hydroxyl group of (A) constituting the present invention adds at least water represented by the general formula (11) to the repeating unit. Although those having a structure comprising a "COOR 7" portion for allowing phase inversion emulsification Te, in the present invention, all of the resin may be achieved, thereby satisfying the above-described configuration, the present invention is not limited thereto, The thing of the structure where resin which has the following structure is mixed can also be used preferably. Specifically, -Z- in the general formula (1) may contain an oxygen atom or a nitrogen atom in the structure instead of the general formula (11). Even if the resin which has a repeating unit shown by the said General formula (1) which has a chemical structure which is a hydrocarbon of C6-100 or a C6-C100 aromatic hydrocarbon is mixed, Good.
一般的なポリマーエマルジョンの製造方法として、界面活性剤を乳化剤として使用する強制乳化法と、ポリマー鎖中に親水性基を導入しポリマー鎖自らに乳化粒子を形成させる自己乳化法がある。本発明の水分散体組成物は、上記した自己乳化型に属するものであり、前記一般式（１１）の構造に示されているように、使用する樹脂の構造中に、乳化に必要な親水性基としてアニオン性基であるカルボキシル基を導入したことで、自己乳化を可能にしたことを特徴としている。このため、一般式（１）中の−Ｚ−が、炭化水素又は芳香族炭化水素である構造のものを混在させる程度は、樹脂全体で、その酸価が１０ｍｇＫＯＨ／ｇ〜１００ｍｇＫＯＨ／ｇの範囲内となるようにすることが好ましい。 As a general method for producing a polymer emulsion, there are a forced emulsification method using a surfactant as an emulsifier and a self-emulsification method in which a hydrophilic group is introduced into a polymer chain to form emulsion particles in the polymer chain itself. The aqueous dispersion composition of the present invention belongs to the self-emulsifying type described above, and as shown in the structure of the general formula (11), the hydrophilic structure necessary for emulsification is included in the structure of the resin used. It is characterized in that self-emulsification is made possible by introducing a carboxyl group which is an anionic group as a functional group. For this reason, the degree to which -Z- in the general formula (1) is mixed with a hydrocarbon or aromatic hydrocarbon is such that the acid value is in the range of 10 mgKOH / g to 100 mgKOH / g for the entire resin. It is preferable to be within.
前記一般式（１）で示される構造の（Ａ）のアニオン性ポリヒドロキシウレタン樹脂は、以下の工程により製造できる。１分子中に少なくとも２つの五員環環状カーボネート（以下、単に環状カーボネートと略す）を有する化合物Ａと、１分子中に少なくとも２つのアミノ基を有する化合物Ｂの重付加反応より得られる。 The anionic polyhydroxyurethane resin (A) having the structure represented by the general formula (1) can be produced by the following steps. It can be obtained by a polyaddition reaction of compound A having at least two 5-membered cyclic carbonates (hereinafter simply referred to as cyclic carbonates) in one molecule and compound B having at least two amino groups in one molecule.
ポリヒドロキシウレタン樹脂の高分子鎖を形成する環状カーボネートとアミンとの反応においては、環状カーボネートの開裂は２種類であり、以下のモデル反応が示す２種類の構造が発生することが知られている。
本発明を特徴づける（Ａ）アニオン性ポリヒドロキシウレタン樹脂の製造に使用する環状カーボネートとしては、エポキシ化合物と二酸化炭素との反応によって得られたものであることが好ましい。具体的には、例えば、原材料であるエポキシ化合物を、触媒の存在下で、０℃〜１６０℃の温度にて、大気圧〜１ＭＰａ程度に加圧した二酸化炭素雰囲気下で４〜２４時間反応させることで、二酸化炭素を、エステル部位に固定化した環状カーボネート化合物を得ることができる。 The cyclic carbonate used for the production of the (A) anionic polyhydroxyurethane resin characterizing the present invention is preferably obtained by a reaction between an epoxy compound and carbon dioxide. Specifically, for example, an epoxy compound as a raw material is reacted in the presence of a catalyst at a temperature of 0 ° C. to 160 ° C. in a carbon dioxide atmosphere pressurized to about atmospheric pressure to 1 MPa for 4 to 24 hours. Thereby, the cyclic carbonate compound which fix | immobilized the carbon dioxide to the ester site | part can be obtained.
上記のようにして二酸化炭素を原料として合成された環状カーボネート化合物を、重付加反応に使用することで、得られるポリウレタン樹脂は、その構造中に二酸化炭素が固定化された−Ｏ−ＣＯ−結合を有したものとなる。二酸化炭素由来の−Ｏ−ＣＯ−結合（二酸化炭素の固定化量）のポリウレタン樹脂中における含有量は、二酸化炭素を原材料として有効利用する立場からはできるだけ多くなる方がよいが、例えば、上記した合成方法によって得られる（Ａ）アニオン性ポリヒドロキシウレタン樹脂は、その構造中に二酸化炭素を１〜２０質量％の範囲で含有させることができる。 By using the cyclic carbonate compound synthesized from carbon dioxide as a raw material in the polyaddition reaction as described above, the resulting polyurethane resin has an —O—CO— bond in which carbon dioxide is immobilized in its structure. It will have. The content of carbon dioxide-derived —O—CO— bonds (carbon dioxide immobilization amount) in the polyurethane resin should be as large as possible from the standpoint of effectively using carbon dioxide as a raw material. The (A) anionic polyhydroxyurethane resin obtained by the synthesis method can contain carbon dioxide in the range of 1 to 20% by mass in its structure.
上記したエポキシ化合物と二酸化炭素との反応に使用される触媒としては、例えば、塩化リチウム、臭化リチウム、ヨウ化リチウム、塩化ナトリウム、臭化ナトリウム、ヨウ化ナトリウムなどの塩類や、４級アンモニウム塩が好ましいものとして挙げられる。その使用量は、エポキシ化合物１００質量部当たり１〜５０質量部、好ましくは１〜２０質量部である。また、これら触媒となる塩類の溶解性を向上させるためにトリフェニルホスフィンなどを併用してもよい。 Examples of the catalyst used in the reaction of the epoxy compound with carbon dioxide include salts such as lithium chloride, lithium bromide, lithium iodide, sodium chloride, sodium bromide, sodium iodide, and quaternary ammonium salts. Is preferable. The usage-amount is 1-50 mass parts per 100 mass parts of epoxy compounds, Preferably it is 1-20 mass parts. Further, triphenylphosphine or the like may be used in combination in order to improve the solubility of the salts serving as the catalyst.
上記したエポキシ化合物と二酸化炭素との反応は、有機溶剤の存在下で行うこともできる。有機溶剤としては、前述の触媒を溶解するものであればいずれのものも使用可能である。具体的には、例えば、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシド、ジメチルアセトアミド、Ｎ−メチル−２−ピロリドンなどのアミド系溶剤、メタノール、エタノール、プロパノール、エチレングリコール、プロピレングリコールなどのアルコール系溶剤、エチレングリコールモノメチルエーテル、エチレングリコールジメチルエーテル、プロピレングリコールメチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールジメチルエーテル、テトラヒドロフランなどのエーテル系溶剤、が好ましいものとして挙げられる。 The reaction between the epoxy compound and carbon dioxide can also be performed in the presence of an organic solvent. Any organic solvent can be used as long as it dissolves the aforementioned catalyst. Specifically, for example, amide solvents such as N, N-dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methyl-2-pyrrolidone, alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, propylene glycol, Preferable examples include ether solvents such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, propylene glycol methyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, and tetrahydrofuran.
本発明を特徴づける（Ａ）アニオン性ポリヒドロキシウレタン樹脂の製造に使用可能な環状カーボネート化合物の構造には特に制限がなく、一分子中に２つ以上の環状カーボネート構造を有するものであれば使用可能である。例えば、ベンゼン骨格、芳香族多環骨格、縮合多環芳香族骨格を持つものや、脂肪族系や脂環式系のいずれも環状カーボネートも使用可能である。以下に使用可能な化合物について、構造式を挙げて例示する。なお、以下に列挙した構造式中にあるＲは、水素原子、ＣＨ3、のいずれかである。 The structure of the cyclic carbonate compound that can be used in the production of the (A) anionic polyhydroxyurethane resin characterizing the present invention is not particularly limited, and any structure having two or more cyclic carbonate structures in one molecule may be used. Is possible. For example, any of those having a benzene skeleton, an aromatic polycyclic skeleton, a condensed polycyclic aromatic skeleton, an aliphatic type, and an alicyclic type can use a cyclic carbonate. The compounds that can be used in the following are exemplified with structural formulas. Note that R in the structural formulas listed below is either a hydrogen atom or CH 3 .
ベンゼン骨格、芳香族多環骨格、縮合多環芳香族骨格を持つものとして以下の化合物が例示される。 The following compounds are exemplified as those having a benzene skeleton, an aromatic polycyclic skeleton, or a condensed polycyclic aromatic skeleton.
脂肪族系や脂環式系の環状カーボネートとして以下の化合物が例示される。
本発明を構成する（Ａ）の、アニオン性ポリヒドロキシウレタン樹脂は、上記に列挙したような、少なくともその一部に二酸化炭素を原料として用いて合成されてなる五員環環状カーボネート構造を有する、少なくとも２つの五員環環状カーボネート構造を有する化合物と、少なくとも２つのアミノ基を有するアミノ化合物との重付加反応によって製造されたものであることが好ましい。この際に使用される好ましいアミノ化合物としては、下記一般式（１２）で示される、分子内に少なくとも２つの１級アミノ基と、少なくとも１つの２級アミノ基のどちらも有する化合物が挙げられる。下記一般式（１２）で示されるアミノ化合物は、従来公知の多官能アミンを併用することができる。
上記一般式（１２）で示される化合物としては、例えば、ジエチレントリアミン、トリエチレンテトラミン、イミノビスプロピルアミン、テトラエチレンペンタミン、Ｎ，Ｎ’−ビス（３−アミノプロピル）−１，３−プロピレンジアミン、Ｎ，Ｎ’−ビス（３−アミノプロピル）−１，４−ブチレンジアミンなどが挙げられ、これら化合物の１種又は２種類以上を使用することが可能である。 Examples of the compound represented by the general formula (12) include diethylenetriamine, triethylenetetramine, iminobispropylamine, tetraethylenepentamine, N, N′-bis (3-aminopropyl) -1,3-propylenediamine. N, N′-bis (3-aminopropyl) -1,4-butylenediamine and the like, and one or more of these compounds can be used.
上記アミン化合物と併用できる多官能アミン化合物としては、従来公知のいずれのものも使用できる。好ましいものとしては、例えば、エチレンジアミン、１，３−ジアミノプロパン、１，４−ジアミノブタン、１，６−ジアミノへキサン（別名：ヘキサメチレンジアミン）、１，８−ジアミノオクタン、１，１０−ジアミノデカン、１，１２−ジアミノドデカンなどの鎖状脂肪族ポリアミン、イソホロンジアミン、ノルボルナンジアミン、１，６−シクロヘキサンジアミン、ピペラジン、２，５−ジアミノピリジンなどの環状脂肪族ポリアミン、キシリレンジアミン（別名：メタキシレンジアミン）などの芳香環を持つ脂肪族ポリアミン、メタフェニレンジアミン、ジアミノジフェニルメタンなどの芳香族ポリアミンが挙げられる。 Any conventionally known polyfunctional amine compound that can be used in combination with the above amine compound can be used. Preferred examples include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane (also known as hexamethylenediamine), 1,8-diaminooctane, and 1,10-diamino. Cyclic aliphatic polyamines such as decane, 1,12-diaminododecane, cycloaliphatic polyamines such as isophoronediamine, norbornanediamine, 1,6-cyclohexanediamine, piperazine, 2,5-diaminopyridine, and xylylenediamine (also known as: Aliphatic polyamines having an aromatic ring such as metaxylenediamine, and aromatic polyamines such as metaphenylenediamine and diaminodiphenylmethane.
一般式（１２）で示されるアミノ化合物の構造中の２級アミノ基は、環状カーボネートとの反応が起こらず、主鎖中に２級アミノ基を主鎖に含んだポリヒドロキシウレタンの合成ができることは、既に「Ｊ．Ｐｏｌｙｍ．Ｓｃｉ．，Ｐａｒｔ Ａ：Ｐｏｌｙｍ．Ｃｈｅｍ．２００５，４３，５８９９−５９０５」に報告されている。本発明においても、反応形態は、上記文献に記載されている通りであるので、２級アミノ基を含むポリヒドロキシウレタンを次反応の中間体として利用することとなる。ここで、環状カーボネート化合物と一般式（１０）で示される化合物を含むアミン化合物との反応条件は、例えば、両者を混合し、４０〜２００℃の温度で４〜２４時間反応させればよく、このようにすることで、２級アミノ基を含むポリヒドロキシウレタンを得ることができる。 The secondary amino group in the structure of the amino compound represented by the general formula (12) does not react with a cyclic carbonate, and can synthesize a polyhydroxyurethane containing a secondary amino group in the main chain. Has already been reported in "J. Polym. Sci., Part A: Polym. Chem. 2005, 43, 5899-5905". Also in the present invention, since the reaction form is as described in the above-mentioned document, polyhydroxyurethane containing a secondary amino group is used as an intermediate for the next reaction. Here, the reaction conditions of the cyclic carbonate compound and the amine compound containing the compound represented by the general formula (10) may be, for example, mixing both and reacting at a temperature of 40 to 200 ° C. for 4 to 24 hours. By doing in this way, the polyhydroxy urethane containing a secondary amino group can be obtained.
上記反応は、無溶剤で行うことも可能であるが、本発明においては次工程の反応及び乳化工程を考慮して、親水性溶剤中で行うことが好ましい。この際に使用し得る親水性溶剤の好ましいものを例示すると、例えば、テトラヒドロフラン、ジオキサン、ジメチルホルムアミド、Ｎ−メチルピロリドン、ジメチルスルホキシド、メタノール、エタノール、プロパノール、エチレングリコール、プロピレングリコール、エチレングリコールモノメチルエーテル、エチレングリコールジメチルエーテル、プロピレングリコールメチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールジメチルエーテルなどが挙げられる。上記に列挙した溶剤の中でも、特に好ましい溶剤としては、転相乳化後の蒸発留去が容易な沸点を有するものであるテトラヒドロフランが挙げられる。 The above reaction can be carried out in the absence of a solvent, but in the present invention, it is preferably carried out in a hydrophilic solvent in consideration of the next step reaction and emulsification step. Examples of preferred hydrophilic solvents that can be used in this case include, for example, tetrahydrofuran, dioxane, dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, methanol, ethanol, propanol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, Examples include ethylene glycol dimethyl ether, propylene glycol methyl ether, diethylene glycol monomethyl ether, and diethylene glycol dimethyl ether. Among the solvents listed above, a particularly preferable solvent is tetrahydrofuran that has a boiling point that allows easy evaporation and evaporation after phase inversion emulsification.
本発明を構成する（Ａ）アニオン性ポリヒドロキシウレタン樹脂の製造は、上記したように、特に触媒を使用せずに製造を行うことができるが、反応を促進させるためには、下記に挙げるような触媒の存在下で行うことも可能である。例えば、トリエチルアミン、トリブチルアミン、ジアザビシクロウンデセン（ＤＢＵ）、トリエチレンジアミン（ＤＡＢＣＯ）、ピリジン及びヒドロキシピリジンなどの塩基性触媒、テトラブチル錫、ジブチル錫ジラウリレートなどのルイス酸触媒などが使用できる。これらの触媒の好ましい使用量としては、反応に使用するカーボネート化合物とアミン化合物の総量（１００質量部）に対して、０．０１〜１０質量部の範囲内で使用する。 As described above, the production of the (A) anionic polyhydroxyurethane resin constituting the present invention can be carried out without using a catalyst, but in order to promote the reaction, the following may be mentioned. It is also possible to carry out in the presence of a simple catalyst. For example, basic catalysts such as triethylamine, tributylamine, diazabicycloundecene (DBU), triethylenediamine (DABCO), pyridine and hydroxypyridine, and Lewis acid catalysts such as tetrabutyltin and dibutyltin dilaurate can be used. As a preferable usage-amount of these catalysts, it uses within the range of 0.01-10 mass parts with respect to the total amount (100 mass parts) of the carbonate compound and amine compound which are used for reaction.
次に、（Ａ）アニオン性ヒドロキシポリウレタン樹脂へのカルボキシル基導入反応について説明する。本発明では、例えば、前記した方法により得られた２級アミノ基を主鎖に含むポリヒドロキシウレタンの２級アミノ基と、環状酸無水物の反応によって（Ａ）アニオン性ヒドロキシポリウレタン樹脂にカルボキシル基を導入する。 Next, (A) the carboxyl group introduction reaction to the anionic hydroxypolyurethane resin will be described. In the present invention, for example, a carboxyl group is added to (A) an anionic hydroxypolyurethane resin by a reaction between a secondary amino group of a polyhydroxyurethane containing a secondary amino group in the main chain obtained by the above-described method and a cyclic acid anhydride. Is introduced.
上記の反応に使用可能な環状酸無水物は、特に限定されるものではなく、複数のカルボキシル基を有する化合物のカルボキシル基が分子内で脱水縮合したものであれば使用可能である。具体的には、例えば、コハク酸無水物、イタコン酸無水物、マレイン酸無水物、カロン酸無水物、シトラコン酸無水物、グルタル酸無水物、ジグリコール酸無水物１，２，３，４−ブタンテトラカルボン酸二無水物などの脂肪族酸無水物や、その誘導体、フタル酸、トリメリット酸無水物、１，２−ナフタル酸無水物、ピロメリット酸無水物などの芳香族酸無水物、１，１−シクロヘキサン二酢酸無水物、１−シクロヘキセン−１，２−ジカルボン酸無水物、１，１−シクロペンタン二酢酸無水物、５−ノルボルネン−２，３−ジカルボン酸無水物、などの脂環族酸無水物などがいずれも使用可能である。これらの中でも特に好ましい化合物としては、分子量の低い化合物が、少量の使用で乳化安定性を示すことから、例えば、コハク酸無水物やマレイン酸無水物などが挙げられる。 The cyclic acid anhydride that can be used in the above reaction is not particularly limited, and any cyclic acid anhydride can be used as long as the carboxyl groups of a compound having a plurality of carboxyl groups are dehydrated and condensed in the molecule. Specifically, for example, succinic anhydride, itaconic anhydride, maleic anhydride, caronic anhydride, citraconic anhydride, glutaric anhydride, diglycolic anhydride 1,2,3,4- Aliphatic acid anhydrides such as butanetetracarboxylic dianhydride and its derivatives, aromatic acid anhydrides such as phthalic acid, trimellitic acid anhydride, 1,2-naphthalic acid anhydride, pyromellitic acid anhydride, Fats such as 1,1-cyclohexanediacetic anhydride, 1-cyclohexene-1,2-dicarboxylic anhydride, 1,1-cyclopentanediacetic anhydride, 5-norbornene-2,3-dicarboxylic anhydride Any of cyclic acid anhydrides can be used. Among these, particularly preferred compounds include, for example, succinic anhydride and maleic anhydride since a low molecular weight compound exhibits emulsion stability when used in a small amount.
本発明者らの検討によれば、上記した反応で使用する環状酸無水物の使用量や、環状酸無水物の種類、環状カーボネートの種類によって、得られる（Ａ）アニオン性ポリヒドロキシウレタン樹脂中のカルボキシル基量を制御することができる。また、本発明者らの検討によれば、カルボキシル基量と乳化粒子径はほぼ比例関係にあり、カルボキシル基量が多くなるほど乳化粒子径は小さくなる。逆に、カルボキシル基が少なくなると乳化粒子径が大きくなり、ある程度の大きさからは乳化状態が不安定となる。このような理由から、本発明の水分散体組成物を構成する水中に分散した（Ａ）アニオン性ポリヒドロキシウレタン樹脂の乳化粒子径は、０．０１μｍ〜１００μｍの範囲内であることが好ましい。その用途にもよるが、より好ましくは０．０１μｍ〜２μｍの範囲内のものになるように調整されたものであることが好ましい。また、カルボキシル基の導入量は、（Ａ）アニオン性ポリヒドロキシウレタン樹脂における酸価が、１０ｍｇＫＯＨ／ｇ〜１００ｍｇＫＯＨ／ｇとなるように配合比を調整するのが好ましい。また、乳化粒子の安定度は、樹脂の分子量にも影響を受けるため、重量平均分子量が１００００〜１０００００の範囲内にあることが好ましい。 According to the study by the present inventors, the amount of the cyclic acid anhydride used in the above reaction, the type of the cyclic acid anhydride, and the type of the cyclic carbonate can be obtained (A) in the anionic polyhydroxyurethane resin. It is possible to control the amount of carboxyl groups. Further, according to the study by the present inventors, the amount of carboxyl groups and the emulsified particle diameter are substantially proportional, and the larger the amount of carboxyl groups, the smaller the emulsified particle diameter. On the contrary, when the number of carboxyl groups decreases, the emulsified particle diameter increases, and the emulsified state becomes unstable from a certain size. For these reasons, the emulsified particle diameter of the (A) anionic polyhydroxyurethane resin dispersed in water constituting the aqueous dispersion composition of the present invention is preferably in the range of 0.01 μm to 100 μm. Although it depends on the use, it is more preferable that the thickness is adjusted so as to be within a range of 0.01 μm to 2 μm. The amount of carboxyl group introduced is preferably adjusted so that the acid value in the (A) anionic polyhydroxyurethane resin is 10 mgKOH / g to 100 mgKOH / g. Moreover, since the stability of emulsified particles is also affected by the molecular weight of the resin, the weight average molecular weight is preferably in the range of 10,000 to 100,000.
上記したようにして製造される本発明の水分散体組成物を利用することで、被膜層やフィルムを形成することができるが、これらが、ガスバリア性を有するものとなることも、本発明の特徴の一つである。ガスバリア性は、樹脂の構造中の水酸基の存在により発揮されるものであり、形成したフィルムのガスバリア性の程度は、使用する被膜形成樹脂の構造中の水酸基量に依存する。本発明者らの検討によれば、このような目的を達成するために必要となる樹脂の構造中における水酸基量の好ましい範囲は、水酸基価が１５０ｍｇＫＯＨ／ｇ〜３００ｍｇＫＯＨ／ｇの範囲である。更に、本発明の水分散体組成物は、上記した樹脂の特性に加え、ガスバリア性を向上させる機能を有する粘土鉱物が、良好な状態に分散されているため、これを利用することで、樹脂のみで構成した水分散体を利用した場合よりも高いガスバリア性を有するものとできる。 By using the aqueous dispersion composition of the present invention produced as described above, a coating layer or a film can be formed. However, these may have gas barrier properties. One of the features. The gas barrier properties are exhibited by the presence of hydroxyl groups in the resin structure, and the degree of gas barrier properties of the formed film depends on the amount of hydroxyl groups in the structure of the film-forming resin used. According to the study by the present inventors, a preferable range of the amount of hydroxyl group in the structure of the resin necessary for achieving such an object is a range of a hydroxyl value of 150 mgKOH / g to 300 mgKOH / g. Furthermore, since the water dispersion composition of the present invention has a clay mineral having a function of improving gas barrier properties in addition to the above-mentioned properties of the resin, it is dispersed in a good state. It is possible to have a higher gas barrier property than in the case of using an aqueous dispersion composed only of the above.
本発明の水分散体組成物を構成する樹脂の構造中に存在しているカルボキシル基は、水分散体とする際に、そのままの状態であってもよいが、水中でのイオン化を促進するために、カルボキシル基の一部、好ましくは全部を中和して、中和塩としておくことが好ましい。カルボキシル基を架橋や修飾反応に使用するために中和せずに残すことも可能であるが、乳化のためのイオン性基としてのみ利用する場合は、中和剤をカルボキシル基の当モル量か１〜１０％程度の過剰量使用することで、全てを中和塩とすることが好ましい。 In order to promote ionization in water, the carboxyl group present in the structure of the resin constituting the aqueous dispersion composition of the present invention may be left as it is when the aqueous dispersion is used. In addition, it is preferable to neutralize a part of the carboxyl group, preferably the whole, to obtain a neutralized salt. It is possible to leave the carboxyl group unneutralized for use in cross-linking and modification reactions, but when using it only as an ionic group for emulsification, the neutralizing agent should be equimolar to the carboxyl group. By using an excess amount of about 1 to 10%, it is preferable to use all as neutralized salts.
上記において、中和に使用する塩基性化合物としては、例えば、エチルアミン、トリメチルアミン、トリエチルアミン、トリイソプロピルアミン、トリブチルアミン、トリエタノールアミン、Ｎ−メチルジエタノールアミン、Ｎ−フェニルジエタノールアミン、モノエタノールアミン、ジメチルエタノールアミン、ジエチルエタノールアミン、モルホリン、Ｎ−メチルモルホリン、２−アミノ−２−エチル−１−プロパノール、トリメチルアミン、トリエチルアミン、トリプロピルアミン、トリブチルアミン、Ｎ−メチルジエタノールアミン、トリエタノールアミンなどの有機アミン、リチウム、カリウム、ナトリウムなどのアルカリ金属、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム、水酸化カリウム、アンモニアなどの無機塩基などが挙げられ、これらは併用できる。これら塩基性化合物の中でも特に好ましい化合物は、塗膜形成時に揮発可能なものであり、トリエチルアミンを用いることが好ましい。トリエチルアミンなどを用いて中和塩とした場合は、塗膜形成時に塩基性化合物が揮発するので、塗膜（被覆膜）の耐水性が向上する。 In the above, examples of the basic compound used for neutralization include ethylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, monoethanolamine, dimethylethanolamine. , Diethylethanolamine, morpholine, N-methylmorpholine, 2-amino-2-ethyl-1-propanol, trimethylamine, triethylamine, tripropylamine, tributylamine, N-methyldiethanolamine, organic amines such as triethanolamine, lithium, Inorganic salts such as alkali metals such as potassium and sodium, sodium hydroxide, potassium hydroxide, calcium hydroxide, potassium hydroxide and ammonia And the like, which can be used in combination. Among these basic compounds, particularly preferable compounds are those that can volatilize during the formation of the coating film, and it is preferable to use triethylamine. When the neutralized salt is formed using triethylamine or the like, the basic compound volatilizes during the formation of the coating film, so that the water resistance of the coating film (coating film) is improved.
前記で説明した方法によって得られた、水中でイオン性基となるカルボキシル基又はその塩を含有する（Ａ）アニオン性ポリヒドロキシウレタン樹脂は、その溶剤溶液に水を徐々に添加することで転相させ、Ｏ／Ｗ型のエマルジョンを得ることができる。転相させる際に添加する水の使用量は、ポリヒドロキシウレタンの樹脂の化学構造、樹脂の合成の際に使用した溶剤の種類、樹脂濃度、粘度、といったファクターに依存するが、概ね５０部〜２００部程度である。転相を行う際に使用する装置は、合成反応に使用する装置と同様の装置でよいが、連続式の乳化機や分散機を使用することもできる。通常、転相工程は、特に加熱する必要はなく、転相前の樹脂溶液に対する水の溶解性を低くするために、１０℃〜３０℃程度の温度で行うことが効率的であり、好ましい。 The (A) anionic polyhydroxyurethane resin containing a carboxyl group that becomes an ionic group in water or a salt thereof obtained by the method described above is phase-inverted by gradually adding water to the solvent solution. Thus, an O / W type emulsion can be obtained. The amount of water used for phase inversion depends on factors such as the chemical structure of the polyhydroxyurethane resin, the type of solvent used in the resin synthesis, the resin concentration, and the viscosity. About 200 parts. The apparatus used for phase inversion may be the same apparatus as that used for the synthesis reaction, but a continuous emulsifier or disperser can also be used. Usually, the phase inversion step is not particularly required to be heated, and it is efficient and preferable to carry out at a temperature of about 10 ° C. to 30 ° C. in order to reduce the solubility of water in the resin solution before phase inversion.
更に、転相乳化して作製したＯ／Ｗ型エマルジョンを減圧条件下で加熱することで、ポリヒドロキシウレタン樹脂の製造に使用した溶剤を揮発させ、樹脂分のみが水中に分散してなる本発明で使用する樹脂の水分散体を得ることができる。この際の加熱条件及び減圧条件は、揮発させる溶剤の沸点により異なるが、水が先に蒸発しないことが好ましい条件であり、概ね、３００Ｔｏｒｒ〜５０Ｔｏｒｒ、２０℃〜７０℃の範囲で調整する。なお、本発明で使用する樹脂の水分散体は、水中に（Ａ）アニオン性ポリヒドロキシウレタン樹脂を分散させてなるものであるが、最終的な溶媒が必ずしも水単独である必要はなく、転相前の溶剤が残存していても使用可能であり、用途に合わせて調節すればよい。 Furthermore, the O / W emulsion prepared by phase inversion emulsification is heated under reduced pressure conditions to volatilize the solvent used for the production of the polyhydroxyurethane resin, and only the resin content is dispersed in water. An aqueous dispersion of the resin used in the above can be obtained. The heating conditions and the reduced pressure conditions at this time differ depending on the boiling point of the solvent to be volatilized, but it is preferable that water does not evaporate first, and is generally adjusted in the range of 300 Torr to 50 Torr and 20 ° C to 70 ° C. The aqueous dispersion of the resin used in the present invention is obtained by dispersing the (A) anionic polyhydroxyurethane resin in water, but the final solvent does not necessarily need to be water alone. Even if the previous solvent remains, it can be used, and may be adjusted according to the application.
本発明のポリヒドロキシウレタン水分散体組成物は、前記のようにして得られたポリヒドロキシウレタンの水分散体に対して、粘土鉱物を分散させることで、容易に本発明の水分散体を製造することができる。この際、予め水に膨潤・分散させた粘土鉱物を用いることも好ましい形態である。 The polyhydroxyurethane aqueous dispersion composition of the present invention easily produces the aqueous dispersion of the present invention by dispersing clay minerals in the polyhydroxyurethane aqueous dispersion obtained as described above. can do. At this time, it is also a preferable form to use a clay mineral that has been previously swollen and dispersed in water.
粘土鉱物は、層状構造を有する珪酸塩鉱物等で多数のシートが積層することで構成された、層状構造を有する物質である。本発明では、この（Ｂ）層状粘土鉱物を使用する。具体的には、例えば、モンモリロナイト、サポナイト、ヘクトライト、バーミキュライト、カオリナイト、マイカなどが挙げられ、特に好ましいものは、モンモリロナイト、サポナイト、マイカ（雲母）である。これら粘土鉱物は天然物でも合成物でも使用可能である。 The clay mineral is a substance having a layered structure formed by laminating a large number of sheets with a silicate mineral having a layered structure. In the present invention, this (B) layered clay mineral is used. Specific examples include montmorillonite, saponite, hectorite, vermiculite, kaolinite, mica, and the like, and particularly preferred are montmorillonite, saponite, and mica (mica). These clay minerals can be used as natural products or synthetic products.
上記特性を有する粘土鉱物は、通常、水により膨潤し、層間の距離が広くなる。本発明の水分散体組成物では、膨潤した粘土鉱物の層間に樹脂が侵入することで、分散状態が安定すると共に、被膜形成時に粘土鉱物が均一に分散された被膜の形成が可能となる。粘土鉱物の層間には、通常、ナトリウムイオンなどのカチオン物質が挿入されており、通常は本発明で使用するヒドロキシポリウレタン樹脂のようにアニオン性のカルボキシル基を導入したポリマーは、層間への侵入が起こりにくいと考えられる。しかし、本発明で使用する（Ａ）アニオン性ポリヒドロキシウレタン樹脂を適用した場合は、均一な分散がなされることを見出した。本発明者らは、その理由を、下記のように考えている。すなわち、本発明で使用する樹脂は、その構造中の、カルボキシル基に近接した部位に２級アミド基を有しており、この２級アミド基のカチオン性が寄与することで、樹脂が、粘土鉱物の層間に侵入しやすくできたものと考えている。 Clay minerals having the above properties are usually swollen by water, and the distance between the layers is increased. In the aqueous dispersion composition of the present invention, the resin penetrates between the layers of the swollen clay mineral, so that the dispersion state is stabilized and the formation of a film in which the clay mineral is uniformly dispersed at the time of film formation is possible. In general, a cationic substance such as sodium ion is inserted between the clay mineral layers, and a polymer having an anionic carboxyl group introduced, such as the hydroxy polyurethane resin usually used in the present invention, does not penetrate into the interlayer. It seems unlikely to occur. However, it has been found that when the (A) anionic polyhydroxyurethane resin used in the present invention is applied, uniform dispersion is achieved. The present inventors consider the reason as follows. That is, the resin used in the present invention has a secondary amide group in the structure in the vicinity of the carboxyl group, and the contribution of the cationic property of the secondary amide group contributes to the resin being a clay. It is thought that it was easy to penetrate between the layers of minerals.
粘土鉱物が均一に分散されてなる樹脂被膜は、ガスバリア性が高くなることは広く知られており、本発明の分散体組成物を用いて形成した被膜においても、同様の効果が発揮される。本発明のポリヒドロキシウレタン水分散体組成物を構成する粘土鉱物の使用量は、ポリヒドロキシウレタン樹脂（Ａ）成分１００質量部に対して、粘土鉱物（Ｂ）成分が１〜５０質量部であることを要する。（Ｂ）成分である層状粘土鉱物の量が、上記範囲よりも多くなると塗膜が固く割れやすくなったり透明性が悪くなったりし、一方、（Ｂ）成分の量が上記範囲よりも少ないと、ガスバリア性の向上効果が弱くなる。好ましい範囲としては、（Ａ）成分１００質量部に対して（Ｂ）成分が３〜２０質量部である。 It is widely known that a resin film in which clay minerals are uniformly dispersed has high gas barrier properties, and the same effect is exhibited in a film formed using the dispersion composition of the present invention. The amount of the clay mineral used in the polyhydroxyurethane aqueous dispersion composition of the present invention is 1 to 50 parts by mass of the clay mineral (B) component with respect to 100 parts by mass of the polyhydroxyurethane resin (A) component. It takes a thing. When the amount of the layered clay mineral as the component (B) is larger than the above range, the coating film is hard and easily broken or the transparency is deteriorated. On the other hand, when the amount of the component (B) is less than the above range. , The effect of improving gas barrier properties is weakened. As a preferable range, (B) component is 3-20 mass parts with respect to 100 mass parts of (A) component.
また、本発明のポリヒドロキシウレタン水分散体組成物の濃度は、（Ａ）アニオン性ポリヒドロキシウレタン樹脂成分と、（Ｂ）層状粘土鉱物成分の合計含有量が、水分散体中の濃度として１０〜５０質量％であることを要す。好ましくは、２０〜４０質量％である。塗膜を得る際の各種加工方法に合わせて最適な濃度に調整することができる。 Further, the concentration of the polyhydroxyurethane aqueous dispersion composition of the present invention is such that the total content of (A) the anionic polyhydroxyurethane resin component and (B) the layered clay mineral component is 10 as the concentration in the aqueous dispersion. It needs to be -50 mass%. Preferably, it is 20-40 mass%. It can be adjusted to an optimum concentration according to various processing methods when obtaining a coating film.
本発明のポリヒドロキシウレタン水分散体組成物を製造する際の、ポリヒドロキシウレタン樹脂の水分散体中への粘度鉱物の分散方法は特に限定されない。例えば、樹脂の水分散体中へ、粘土鉱物をそのまま添加し分散させる方法であっても、予め、水に分散させた粘土鉱物を添加する方法であってもよく、いずれも適用が可能である。水膨潤性粘土鉱物の分散は、樹脂の水分散体と比べて水単独の方が効率的であるため、生産効率の点では、後者の方が好ましい。 The method for dispersing the viscosity mineral in the aqueous dispersion of the polyhydroxyurethane resin when producing the polyhydroxyurethane aqueous dispersion composition of the present invention is not particularly limited. For example, it may be a method of adding and dispersing a clay mineral as it is in an aqueous dispersion of a resin, or a method of adding a clay mineral previously dispersed in water, both of which are applicable. . As for the dispersion of the water-swellable clay mineral, water alone is more efficient than the water dispersion of the resin. Therefore, the latter is preferable in terms of production efficiency.
水中、或いは、ポリヒドロキシウレタン樹脂水分散体中に粘土鉱物を分散する場合、通常の撹拌のみで行うこともできるが、特に高濃度で分散させる場合には、時間が長くかかる場合がある。したがって、生産工程の短縮のため、７０℃以上に加熱して撹拌することが好ましく、また分散液は高チキソトロピー性を示すため、撹拌装置や超音波分散機などの分散機を使用する方が、より効果的である。 When the clay mineral is dispersed in water or in the polyhydroxyurethane resin aqueous dispersion, it can be carried out only by ordinary stirring, but it may take a long time especially when it is dispersed at a high concentration. Therefore, for shortening the production process, it is preferable to stir by heating to 70 ° C. or higher, and since the dispersion exhibits high thixotropy, it is better to use a disperser such as an agitator or an ultrasonic disperser. More effective.
本発明の水分散体組成物は、加工時（使用時）の必要特性に合わせて各種レオロジー調整剤を添加することができる。また、本発明の水分散体組成物には、必要に応じて各種添加剤を加えてもよく、例えば、酸化防止剤、光安定剤、紫外線吸収剤などを添加することができる。 Various rheology modifiers can be added to the aqueous dispersion composition of the present invention in accordance with the required characteristics during processing (during use). In addition, various additives may be added to the aqueous dispersion composition of the present invention as necessary, and for example, an antioxidant, a light stabilizer, an ultraviolet absorber and the like can be added.
また、本発明の水分散体組成物は、水に溶解・分散可能な硬化剤を配合して使用することで、架橋塗膜を作成できるものになる。この際に使用できる硬化剤としては、特に制限はないが、例えば、水酸基と反応可能な水分散性成分、ポリイソシアネート類、ブロックイソシアネート類、エポキシ化合物、アルミニウムやチタニウムなどの金属キレート化合物、メラミン樹脂、アルデヒド化合物、などが挙げられる。また、カルボキシル基と反応可能は架橋剤も使用可能であり、前記化合物に加えて水分散性カルボジイミドなども使用可能である。 Moreover, the water dispersion composition of this invention can create a crosslinked coating film by mix | blending and using the hardening | curing agent which can be melt | dissolved and disperse | distributed in water. The curing agent that can be used in this case is not particularly limited. For example, water-dispersible components capable of reacting with hydroxyl groups, polyisocyanates, blocked isocyanates, epoxy compounds, metal chelate compounds such as aluminum and titanium, and melamine resins. Aldehyde compounds, and the like. In addition, a crosslinking agent can be used as long as it can react with a carboxyl group, and water dispersible carbodiimide or the like can be used in addition to the above compound.
本発明の水分散体組成物を使用して塗膜（被覆膜）を得る方法としては、本発明の水分散体を基材となるフィルムに、例えば、グラビアコーター、ナイフコーター、リバースコーター、バーコーター、スプレーコーター、スリットコーターなどによって塗布し、水及び残存している溶剤を揮発させることが挙げられる。このようにすることで、基材と、該基材の少なくとも一方に、本発明の水分散体組成物によって形成したポリヒドロキシウレタン被膜層とを有してなる本発明のフィルムを得ることができる。 As a method for obtaining a coating film (coating film) using the aqueous dispersion composition of the present invention, for example, a gravure coater, knife coater, reverse coater, It may be applied by a bar coater, spray coater, slit coater or the like to volatilize water and remaining solvent. By doing in this way, the film of this invention which has a base material and the polyhydroxy urethane coating layer formed with the water dispersion composition of this invention in at least one of this base material can be obtained. .
上記で基材として使用するフィルム材料は、特に限定されるものではなく、従来から包装材料として使用される高分子材料は全て使用可能である。例えば、ポリエチレン、ポリプロピレン、ポリスチレンなどのポリオレフィン系樹脂、ポリエチレンテレフタレート、ポリ乳酸などのポリエステル系樹脂、ナイロン６やナイロン６６などのポリアミド系樹脂、その他ポリイミド等とこれらの樹脂の共重合体等が挙げられる。また、これらの高分子材料には、必要に応じて、例えば、公知の帯電防止剤、紫外線吸収剤、可塑剤、滑剤、着色剤等の添加剤を適宜に含ませることができる。 The film material used as a base material in the above is not particularly limited, and any polymer material conventionally used as a packaging material can be used. Examples thereof include polyolefin resins such as polyethylene, polypropylene and polystyrene, polyester resins such as polyethylene terephthalate and polylactic acid, polyamide resins such as nylon 6 and nylon 66, other polyimides, and copolymers of these resins. . In addition, these polymer materials can appropriately contain, for example, known antistatic agents, ultraviolet absorbers, plasticizers, lubricants, colorants and the like as necessary.
次に、具体的な製造例、実施例及び比較例を挙げて本発明を更に具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、以下の例における「部」及び「％」は特に断りのない限り質量基準である。 Next, the present invention will be described more specifically with reference to specific production examples, examples and comparative examples, but the present invention is not limited to these examples. In the following examples, “part” and “%” are based on mass unless otherwise specified.
［製造例１：環状カーボネート含有化合物（Ｉ−Ａ）の合成］
エポキシ当量１９２のビスフェノールＡジグリシジルエーテル（商品名：ｊＥＲ８２８、ジャパンエポキシレジン（株）製）１００部と、ヨウ化ナトリウム（和光純薬製）２０部と、Ｎ−メチル−２−ピロリドン１００部とを、撹拌装置及び大気開放口のある還流器を備えた反応容器内に仕込んだ。次いで、撹拌しながら二酸化炭素を連続して吹き込み、１００℃にて１０時間反応を行った。そして、反応終了後の溶液にイソプロパノール１，４００部を加え、反応物を白色の沈殿として析出させ、濾別した。得られた沈殿物をトルエンにて再結晶を行い、白色の粉末５２部を得た（収率４２％）。
[Production Example 1: Synthesis of cyclic carbonate-containing compound (IA)]
100 parts of bisphenol A diglycidyl ether (trade name: jER828, manufactured by Japan Epoxy Resins Co., Ltd.) having an epoxy equivalent of 192, 20 parts of sodium iodide (manufactured by Wako Pure Chemical Industries), and 100 parts of N-methyl-2-pyrrolidone Was charged in a reaction vessel equipped with a stirrer and a reflux with an air opening. Subsequently, carbon dioxide was continuously blown in with stirring, and the reaction was performed at 100 ° C. for 10 hours. Then, 1,400 parts of isopropanol was added to the solution after completion of the reaction to precipitate the reaction product as a white precipitate, which was filtered off. The resulting precipitate was recrystallized from toluene to obtain 52 parts of white powder (yield 42%).
上記で得られた粉末を、ＦＴ−ＩＲ（堀場製作所製、ＦＴ−７２０ 以下の製造例でも同様の装置で測定）にて分析でしたところ、９１０ｃｍ-1付近の原材料のエポキシ基由来の吸収は消失しており、１８００ｃｍ-1付近に原材料には存在しないカーボネート基のカルボニル由来の吸収が確認された。また、ＨＰＬＣ（日本分光製、ＬＣ−２０００；カラムＦｉｎｅｐａｋＳＩＬ Ｃ１８−Ｔ５；移動相 アセトニトリル＋水）による分析の結果、原材料のピークは消失し、高極性側に新たなピークが出現し、その純度は９８％であった。また、ＤＳＣ測定（示差走査熱量測定）の結果、融点は１７８℃であり、融点範囲は±５℃であった。 When the powder obtained above was analyzed by FT-IR (manufactured by Horiba, Ltd., also measured by the same apparatus in the following FT-720 production example), the absorption derived from the epoxy group of the raw material in the vicinity of 910 cm −1 was It disappeared, and absorption from the carbonyl of the carbonate group that was not present in the raw material was confirmed near 1800 cm −1 . In addition, as a result of analysis by HPLC (manufactured by JASCO, LC-2000; column FinepakSIL C18-T5; mobile phase acetonitrile + water), the peak of the raw material disappeared, a new peak appeared on the high polarity side, and its purity was It was 98%. As a result of DSC measurement (differential scanning calorimetry), the melting point was 178 ° C., and the melting point range was ± 5 ° C.
以上のことから、この粉末は、エポキシ基と二酸化炭素の反応により環状カーボネート基が導入された下記式で表わされる構造の化合物であると確認された。これをＩ−Ａと略称した。Ｉ−Ａの化学構造中に二酸化炭素由来の成分が占める割合は、２０．５％であった（計算値）。
［製造例２：環状カーボネート含有化合物（Ｉ−Ｂ）の合成］
エポキシ化合物として、エポキシ当量１１５のハイドロキノンジグリシジルエーテル（商品名：デナコールＥＸ２０３、ナガセケムテックス（株）製）を用いた以外は、前記した製造例１と同様の方法で、下記式（Ｉ−Ｂ）で表わされる構造の環状カーボネート化合物を合成した（収率５５％）。得られたＩ−Ｂは、白色の結晶であり、融点は１４１℃であった。ＦＴ−ＩＲ分析の結果は、Ｉ−Ａと同様に９１０ｃｍ-1付近の原材料のエポキシ基由来の吸収は消失しており、１８００ｃｍ-1付近に原材料には存在しないカーボネート基のカルボニル由来の吸収が確認された。ＨＰＬＣ分析による純度は９７％であった。Ｉ−Ｂの化学構造中に二酸化炭素由来の成分が占める割合は、２８．０％であった（計算値）。
Except that hydroquinone diglycidyl ether having an epoxy equivalent of 115 (trade name: Denacol EX203, manufactured by Nagase ChemteX Corp.) was used as the epoxy compound, the same formula (IB) ) Was synthesized (55% yield). The obtained IB was white crystals and had a melting point of 141 ° C. As a result of FT-IR analysis, the absorption derived from the epoxy group of the raw material in the vicinity of 910 cm −1 disappeared as in IA, and the absorption derived from the carbonyl of the carbonate group not present in the raw material in the vicinity of 1800 cm −1. confirmed. The purity by HPLC analysis was 97%. The proportion of the component derived from carbon dioxide in the chemical structure of IB was 28.0% (calculated value).
＜水中に分散させる前の実施例で使用するカルボキシル基含有ヒドロキシポリウレタン樹脂の製造＞
［実施例用の樹脂合成例１］
撹拌装置及び大気開放口のある還流器を備えた反応容器内に、製造例１で得た化合物Ｉ−Ａを１００部、ヘキサメチレンジアミン（東京化成工業製）１６．３部、ジエチレントリアミン（東京化成工業製）９．６部、さらに反応溶媒としてテトラヒドロフラン（ＴＨＦ）１８９部を加え、６０℃の温度で撹拌しながら２４時間の反応を行った。反応後の樹脂溶液をＦＴ−ＩＲにて分析したところ、１８００ｃｍ-1付近に観察されていた環状カーボネートのカルボニル基由来の吸収が完全に消失しており、新たに１７６０ｃｍ-1付近にウレタン結合のカルボニル基由来の吸収が確認された。得られた樹脂溶液を用いて測定したアミン価は、樹脂分１００％の換算値として４２．１ｍｇＫＯＨ／ｇであった。アミン価の測定方法については、後述する。次いで、この樹脂溶液に、無水フタル酸（東京化成工業製）１３．８部を加え４０℃で反応を行い、ＦＴ−ＩＲにて酸無水物カルボニル由来の１８００ｃｍ-1のピークが消失したことを確認して反応を終了し、水を加えて転相乳化する前の本発明で好適に使用するカルボキシル基含有ヒドロキシポリウレタン樹脂を得た。
<Production of carboxyl group-containing hydroxypolyurethane resin used in Examples before being dispersed in water>
[Resin Synthesis Example 1 for Examples]
In a reaction vessel equipped with a stirrer and a reflux opening with an atmosphere opening port, 100 parts of Compound IA obtained in Production Example 1, 16.3 parts of hexamethylenediamine (manufactured by Tokyo Chemical Industry), diethylenetriamine (Tokyo Chemical Industry) 9.6 parts (manufactured by Kogyo) and 189 parts of tetrahydrofuran (THF) as a reaction solvent were added, and the reaction was carried out for 24 hours while stirring at a temperature of 60 ° C. When the resin solution after the reaction was analyzed by FT-IR, 1800 cm -1 absorption due carbonyl group of cyclic carbonates that have been observed in the vicinity has completely disappeared, the new urethane bonds in the vicinity of 1760 cm -1 Absorption derived from a carbonyl group was confirmed. The amine value measured using the obtained resin solution was 42.1 mgKOH / g as a converted value of 100% resin content. A method for measuring the amine value will be described later. Next, 13.8 parts of phthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to this resin solution and reacted at 40 ° C., and the peak at 1800 cm −1 derived from acid anhydride carbonyl disappeared by FT-IR. After confirming, the reaction was completed, and a carboxyl group-containing hydroxypolyurethane resin suitably used in the present invention before phase inversion emulsification by adding water was obtained.
得られた樹脂の物性を確認するために、上記の樹脂溶液を、乾燥時の膜厚が５０μｍになるように、バーコーターにて離型紙に塗布し、８０℃オーブンで溶剤を乾燥させた後、離型紙を剥がして、樹脂合成例１で得た樹脂製の樹脂フィルムを得た。この樹脂フィルムの外観、機械強度、酸素透過率（ガスバリア性）、樹脂の酸価、樹脂の水酸基価、及び分子量（ＧＰＣ）を測定した。それぞれの測定方法については後述する。その結果を表１に示した。 In order to confirm the physical properties of the obtained resin, the above resin solution was applied to release paper with a bar coater so that the film thickness at the time of drying was 50 μm, and the solvent was dried in an 80 ° C. oven. The release paper was peeled off to obtain a resin resin film obtained in Resin Synthesis Example 1. The appearance, mechanical strength, oxygen permeability (gas barrier property), resin acid value, resin hydroxyl value, and molecular weight (GPC) of this resin film were measured. Each measuring method will be described later. The results are shown in Table 1.
［実施例用の樹脂合成例２］
樹脂合成例１で用いたのと同様の反応容器内に、製造例１で得た化合物Ｉ−Ａを１００部、メタキシレンジアミン（三菱ガス化学製）を２５．４部、イミノビスプロピルアミン（東京化成製）を６．１部、テトラヒドロフランを２０６部加え、６０℃の温度で撹拌しながら、２４時間の反応を行った。反応後の樹脂溶液についてのＦＴ−ＩＲによる反応経過確認の結果は、樹脂合成例１と同様であった。得られた樹脂のアミン価は樹脂分１００％の換算値として２５．５ｍｇＫＯＨ／ｇであった。次いで、樹脂合成例１で用いた無水フタル酸に変えて、無水マレイン酸４．６部を使用した以外は、樹脂合成例１と同様に反応させて、水を加えて転相乳化する前の樹脂溶液を得た。そして、得られた樹脂の物性を確認するために、樹脂合成例１と同様にして、樹脂フィルムを作製し、フィルムの外観、機械強度、酸素透過率、樹脂の酸価、樹脂の水酸基価、及び分子量（ＧＰＣ）を測定した。結果を表１に示した。
[Resin Synthesis Example 2 for Examples]
In a reaction container similar to that used in Resin Synthesis Example 1, 100 parts of Compound IA obtained in Production Example 1, 25.4 parts of metaxylenediamine (manufactured by Mitsubishi Gas Chemical), iminobispropylamine ( 6.1 parts of Tokyo Kasei) and 206 parts of tetrahydrofuran were added, and the reaction was carried out for 24 hours while stirring at a temperature of 60 ° C. The result of the reaction progress confirmation by FT-IR about the resin solution after reaction was the same as that of Resin Synthesis Example 1. The amine value of the obtained resin was 25.5 mgKOH / g as a converted value of 100% resin content. Next, except that 4.6 parts of maleic anhydride was used in place of the phthalic anhydride used in Resin Synthesis Example 1, the reaction was conducted in the same manner as in Resin Synthesis Example 1, and water was added before phase inversion emulsification. A resin solution was obtained. Then, in order to confirm the physical properties of the obtained resin, a resin film was prepared in the same manner as in Resin Synthesis Example 1, and the film appearance, mechanical strength, oxygen permeability, resin acid value, resin hydroxyl value, And the molecular weight (GPC) was measured. The results are shown in Table 1.
［実施例用の樹脂合成例３］
樹脂合成例１で用いたのと同様の反応容器内に、製造例２で得た化合物Ｉ−Ｂを１００部、へキサメチレンジアミンを２９．９部、トリエチレンテトラミン（東京化成工業製）を９．４部、テトラヒドロフランを２３６部加え、６０℃の温度で撹拌しながら、２４時間の反応を行った。反応後の樹脂溶液についてのＦＴ−ＩＲによる反応経過確認の結果は、樹脂合成例１と同様であった。得られた樹脂のアミン価は樹脂分１００％の換算値として２６．２ｍｇＫＯＨ／ｇであった。次いで、樹脂合成例１で用いた無水フタル酸に変えて、無水マレイン酸１２．６部を使用した以外は、樹脂合成例１同様に反応させて、水を加えて転相乳化する前の樹脂溶液を得た。そして、得られた樹脂の物性を確認するために、樹脂合成例１と同様にして、樹脂フィルムを作製し、フィルムの外観、機械強度、酸素透過率、樹脂の酸価、樹脂の水酸基価、及び分子量（ＧＰＣ）を測定した。結果を表１に示した。
[Resin Synthesis Example 3 for Examples]
In a reaction container similar to that used in Resin Synthesis Example 1, 100 parts of Compound IB obtained in Production Example 2, 29.9 parts of hexamethylenediamine, and triethylenetetramine (manufactured by Tokyo Chemical Industry Co., Ltd.) 9.4 parts and 236 parts of tetrahydrofuran were added, and the reaction was performed for 24 hours while stirring at a temperature of 60 ° C. The result of the reaction progress confirmation by FT-IR about the resin solution after reaction was the same as that of Resin Synthesis Example 1. The amine value of the obtained resin was 26.2 mgKOH / g as a converted value of 100% resin content. Next, the resin before the phase inversion emulsification by adding water and reacting in the same manner as in the resin synthesis example 1 except that 12.6 parts of maleic anhydride was used instead of the phthalic anhydride used in the resin synthesis example 1. A solution was obtained. Then, in order to confirm the physical properties of the obtained resin, a resin film was prepared in the same manner as in Resin Synthesis Example 1, and the film appearance, mechanical strength, oxygen permeability, resin acid value, resin hydroxyl value, And the molecular weight (GPC) was measured. The results are shown in Table 1.
［実施例用の樹脂合成例４］
実施例１で用いたのと同様の反応容器内に、化合物Ｉ−Ａを１００部、ジエチレントリアミンを２４．１部、テトラヒドロフランを２２０部加え、６０℃の温度で撹拌しながら、２４時間の反応を行った。反応後の樹脂溶液についてのＦＴ−ＩＲによる反応経過確認の結果は、樹脂合成例１と同様であった。得られた樹脂のアミン価は樹脂分１００％の換算値として１０７．０ｍｇＫＯＨ／ｇであった。次いで、樹脂合成例１で用いた無水フタル酸に変えて、無水マレイン酸２２．９部を使用した以外は、樹脂合成例１と同様に反応させて、水を加えて転相乳化する前の樹脂溶液を得た。そして、得られた樹脂の物性を確認するために、樹脂合成例１と同様にして、樹脂フィルムを作製し、フィルムの外観、機械強度、酸素透過率、樹脂の酸価、樹脂の水酸基価、及び分子量（ＧＰＣ）を測定した。結果を表１に示した。
[Resin Synthesis Example 4 for Examples]
In a reaction vessel similar to that used in Example 1, 100 parts of Compound IA, 24.1 parts of diethylenetriamine and 220 parts of tetrahydrofuran were added, and the reaction was carried out for 24 hours while stirring at a temperature of 60 ° C. went. The result of the reaction progress confirmation by FT-IR about the resin solution after reaction was the same as that of Resin Synthesis Example 1. The amine value of the obtained resin was 107.0 mgKOH / g as a converted value of 100% resin content. Next, except that 22.9 parts of maleic anhydride was used in place of the phthalic anhydride used in Resin Synthesis Example 1, the reaction was performed in the same manner as in Resin Synthesis Example 1, and water was added before phase inversion emulsification. A resin solution was obtained. Then, in order to confirm the physical properties of the obtained resin, a resin film was prepared in the same manner as in Resin Synthesis Example 1, and the film appearance, mechanical strength, oxygen permeability, resin acid value, resin hydroxyl value, And the molecular weight (GPC) was measured. The results are shown in Table 1.
［比較例用の樹脂合成例ａ］
撹拌装置及び大気開放口のある還流器を備えた反応容器内に、製造例１で得た化合物Ｉ−Ａを１００部、ヘキサメチレンジアミン（東京化成工業製）を２７．１部、さらに、反応溶媒としてテトラヒドロフラン２０４部を加え、６０℃の温度で撹拌しながら、２４時間の反応を行った。反応後の樹脂溶液についてのＦＴ−ＩＲによる反応経過確認の結果は、樹脂合成例１と同様であった。得られた比較例用の樹脂は、２級アミノ基を含まないポリヒドロキシウレタン樹脂であった。次いで、反応溶液を６０℃に保ったまま、無水マレイン酸を９．２部、付加反応用触媒（兼中和剤）として、トリエチルアミンを９．４部加え、６０℃で２時間の反応を行い、反応を終了した。反応後の比較例用の樹脂溶液をＦＴ−ＩＲで分析したところ、酸無水物カルボニル由来の１８００ｃｍ-1のピークは完全に消失していた。得られた樹脂の物性を確認するために、樹脂合成例１と同様にして、樹脂フィルムを作製し、フィルムの外観、機械強度、酸素透過率、樹脂の酸価、樹脂の水酸基価、及び分子量（ＧＰＣ）を測定した。結果を表１に示した。
[Resin Synthesis Example a for Comparative Example a]
In a reaction vessel equipped with a stirrer and a reflux opening having an air opening, 100 parts of Compound IA obtained in Production Example 1, 27.1 parts of hexamethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.), and reaction 204 parts of tetrahydrofuran was added as a solvent, and the reaction was performed for 24 hours while stirring at a temperature of 60 ° C. The result of the reaction progress confirmation by FT-IR about the resin solution after reaction was the same as that of Resin Synthesis Example 1. The obtained resin for a comparative example was a polyhydroxyurethane resin containing no secondary amino group. Next, with the reaction solution kept at 60 ° C., 9.2 parts of maleic anhydride and 9.4 parts of triethylamine as an addition reaction catalyst (also a neutralizing agent) were added and reacted at 60 ° C. for 2 hours. Finished the reaction. When the resin solution for the comparative example after the reaction was analyzed by FT-IR, the peak at 1800 cm −1 derived from the acid anhydride carbonyl had completely disappeared. In order to confirm the physical properties of the obtained resin, a resin film was prepared in the same manner as in Resin Synthesis Example 1, and the film appearance, mechanical strength, oxygen permeability, resin acid value, resin hydroxyl value, and molecular weight were obtained. (GPC) was measured. The results are shown in Table 1.
［比較例用の樹脂合成例ｂ］
製造例１で得た化合物Ｉ−Ａを１００部、メタキシレンジアミンを３１．８部、テトラヒドロフランを２２５部とし、無水マレイン酸を１８．３部、トリエチルアミンを１８．９部とした以外は、樹脂合成例ａと同様に反応を行い、比較例用の樹脂溶液を得た。得られた樹脂の物性を確認するために、樹脂合成例１と同様にして、樹脂フィルムを作製し、フィルムの外観、機械強度、酸素透過率、樹脂の酸価、樹脂の水酸基価、及び分子量（ＧＰＣ）を測定した。結果を表１に示した。
[Resin Synthesis Example b for Comparative Example]
Resin except that compound IA obtained in Production Example 1 was 100 parts, metaxylenediamine was 31.8 parts, tetrahydrofuran was 225 parts, maleic anhydride was 18.3 parts, and triethylamine was 18.9 parts. Reaction was performed in the same manner as in Synthesis Example a to obtain a resin solution for Comparative Example. In order to confirm the physical properties of the obtained resin, a resin film was prepared in the same manner as in Resin Synthesis Example 1, and the film appearance, mechanical strength, oxygen permeability, resin acid value, resin hydroxyl value, and molecular weight were obtained. (GPC) was measured. The results are shown in Table 1.
［比較例用の樹脂合成例ｃ］
上記で使用したと同様の反応容器内に、製造例１で得た化合物Ｉ−Ａを１００部、ヘキサメチレンジアミンを２７．１部、テトラヒドロフランを１９８部加え、６０℃の温度で撹拌しながら、２４時間の反応を行い、比較例用の樹脂溶液を得た。得られた樹脂溶液は、カルボキシル基を含まない通常のポリヒドロキシウレタン樹脂である。得られた樹脂の物性を確認するために、樹脂合成例１と同様にして、樹脂フィルムを作製し、フィルムの外観、機械強度、酸素透過率、樹脂の酸価、樹脂の水酸基価、及び分子量（ＧＰＣ）を測定した。結果を表１に示した。
[Resin Synthesis Example c for Comparative Example]
In a reaction container similar to that used above, 100 parts of Compound IA obtained in Production Example 1, 27.1 parts of hexamethylenediamine, and 198 parts of tetrahydrofuran were added and stirred at a temperature of 60 ° C., Reaction for 24 hours was performed and the resin solution for a comparative example was obtained. The obtained resin solution is a normal polyhydroxyurethane resin containing no carboxyl group. In order to confirm the physical properties of the obtained resin, a resin film was prepared in the same manner as in Resin Synthesis Example 1, and the film appearance, mechanical strength, oxygen permeability, resin acid value, resin hydroxyl value, and molecular weight were obtained. (GPC) was measured. The results are shown in Table 1.
（評価）
以上で説明した実施例用の樹脂合成例１〜４及び比較例用の樹脂合成例ａ〜ｃでそれぞれ得た各樹脂、及び各樹脂で作製した各フィルムについて、以下の方法及び基準で評価した。各樹脂についての二酸化炭素含有量は、以下のようにして算出した。評価結果を表１にまとめて示した。
(Evaluation)
Each resin obtained in each of the resin synthesis examples 1 to 4 for the examples and the resin synthesis examples a to c for the comparative examples described above and each film made of each resin was evaluated by the following methods and criteria. . The carbon dioxide content for each resin was calculated as follows. The evaluation results are summarized in Table 1.
［二酸化炭素含有量］
二酸化炭素含有量は、各合成例で使用したヒドロキシポリウレタン樹脂の化学構造中における、原料の二酸化炭素由来のセグメントの質量％を算出して求めた。具体的には、ポリウレタン樹脂の合成反応に使用した、化合物Ｉ−Ａ、Ｉ−Ｂを合成する際に使用した、モノマーに対して含まれる二酸化炭素の理論量から算出した計算値で示した。例えば、実施例用の樹脂合成例１の場合には、使用した化合物Ｉ−Ａの二酸化炭素由来の成分量は２０．５％、であり、これより実施例用の樹脂合成例１のポリウレタン中の二酸化炭素濃度は（１００部×２０．５％）／１３９．７全量＝１４．７質量％となる。
[CO2 content]
The carbon dioxide content was determined by calculating the mass% of the carbon dioxide-derived segment of the raw material in the chemical structure of the hydroxy polyurethane resin used in each synthesis example. Specifically, it was shown by a calculated value calculated from the theoretical amount of carbon dioxide contained in the monomer used in synthesizing the compounds IA and IB used in the synthesis reaction of the polyurethane resin. For example, in the case of Resin Synthesis Example 1 for Examples, the amount of the component derived from carbon dioxide of the compound IA used is 20.5%, and from this, in the polyurethane of Resin Synthesis Example 1 for Examples The carbon dioxide concentration of (100 parts × 20.5%) / 139.7 total amount = 14.7% by mass.
［分子量］
ＤＭＦを移動相としたＧＰＣ測定（東ソー製、ＧＰＣ−８２２０；カラムＳｕｐｅｒ ＡＷ２５００＋ＡＷ３０００＋ＡＷ４０００＋ＡＷ５０００；以下の実施例も同様）により測定した。ポリスチレン換算値として重量平均分子量を表す。
[Molecular weight]
GPC measurement using DMF as a mobile phase (manufactured by Tosoh Corporation, GPC-8220; column Super AW2500 + AW3000 + AW4000 + AW5000; the following examples are also the same) was used. The weight average molecular weight is expressed as a polystyrene equivalent value.
［フィルム外観］
作製したそれぞれの樹脂フィルムについて、全光線透過率及びヘイズを測定し、以下の基準で評価した。全光線透過率及びヘイズは、ＪＩＳ Ｋ−７１０５に準拠して、いずれもヘイズメーター（スガ試験機（株）製 ＨＺ−１）により測定した。ヘイズメーターで測定される全ての光量が全光線透過率であり、全光線透過率に対する拡散透過光の割合がヘイズである。
＜評価基準＞
〇：全光線透過率９０％以上 ヘイズ０．５％以下
×：〇に該当しないもの
[Film appearance]
About each produced resin film, the total light transmittance and haze were measured, and the following references | standards evaluated. The total light transmittance and haze were measured with a haze meter (HZ-1 manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS K-7105. All the light quantities measured with the haze meter are the total light transmittance, and the ratio of the diffuse transmitted light to the total light transmittance is the haze.
<Evaluation criteria>
○: Total light transmittance 90% or more Haze 0.5% or less ×: Not applicable to ○
［酸価、水酸基価］
いずれも各樹脂について、ＪＩＳ Ｋ−１５５７に準拠した滴定法により測定し、樹脂１ｇあたりの各官能基の含有量を、ＫＯＨのｍｇ当量で表した。なお、単位はｍｇＫＯＨ／ｇである。
[Acid value, hydroxyl value]
In each case, each resin was measured by a titration method based on JIS K-1557, and the content of each functional group per 1 g of the resin was expressed in mg equivalents of KOH. The unit is mgKOH / g.
［機械強度］
作製した各樹脂フィルムの機械強度として、破断点強度及び破断点伸度を測定した。測定はＪＩＳ Ｋ−６２５１に準拠して、オートグラフ〔島津製作所（株）製、ＡＧＳ−Ｊ（商品名）〕を使用した測定法によって、室温（２５℃）で測定を実施した。
[Mechanical strength]
As the mechanical strength of each of the produced resin films, the strength at break and the elongation at break were measured. The measurement was performed at room temperature (25 ° C.) by a measurement method using an autograph [manufactured by Shimadzu Corporation, AGS-J (trade name)] in accordance with JIS K-6251.
［ガスバリア性（酸素透過率）］
作製した各樹脂フィルムについて、ＪＩＳ Ｋ−７１２６に準拠して酸素の透過率を測定し、これをガスバリア性の評価値とした。すなわち、この値が低いほどガスバリア性に優れると判断できる。具体的には、酸素透過率測定装置（ＭＯＣＯＮ社製 ＯＸ−ＴＲＡＮ ２／２１ＭＬ）を使用して、温度２３℃で、湿度６５％の恒温恒湿条件下にて酸素透過率を測定した。なお、使用したフィルムは乾燥後の膜厚が５０μｍであるため、膜厚２０μｍに換算した値を表１に記載した。
[Gas barrier properties (oxygen permeability)]
About each produced resin film, the transmittance | permeability of oxygen was measured based on JISK-7126, and this was made into the evaluation value of gas barrier property. That is, it can be judged that the lower the value, the better the gas barrier property. Specifically, the oxygen transmission rate was measured under a constant temperature and humidity condition of a temperature of 23 ° C. and a humidity of 65% using an oxygen transmission rate measuring device (OX-TRAN 2 / 21ML manufactured by MOCON). In addition, since the film thickness after drying was 50 micrometers, the value converted into the film thickness of 20 micrometers was described in Table 1.
＜粘土鉱物の調製＞
［製造例３：粘土鉱物分散液Ａの調製］
ホモディスパーを用いて、水９５部と、粘土鉱物としてモンモリロナイト（クニミネ工業製 クニピアＦ）５部を予備混合した後、超音波分散機（株式会社ソニックテクノロジー製）を用いて、粘土鉱物層間の膨潤と分散を行った。粘土鉱物が均一に分散したことを確認し、これを粘土鉱物分散液Ａとした。
<Preparation of clay mineral>
[Production Example 3: Preparation of clay mineral dispersion A]
Using a homodisper, 95 parts of water and 5 parts of montmorillonite (Kunimine Industries Co., Ltd. Kunipia F) as a clay mineral are premixed and then swollen between clay mineral layers using an ultrasonic disperser (manufactured by Sonic Technology Co., Ltd.). And dispersed. After confirming that the clay mineral was uniformly dispersed, this was designated as clay mineral dispersion A.
［製造例４：粘土鉱物分散液Ｂの調製］
ホモディスパーを用いて、水９５部と、粘土鉱物として合成マイカ（コープケミカル製 ソマシフ ＭＥ−１００）５部を予備混合した後、超音波分散機を用いて、粘土鉱物の分散液を得た。これを粘土鉱物分散液Ｂとした。
[Production Example 4: Preparation of clay mineral dispersion B]
Using a homodisper, 95 parts of water and 5 parts of synthetic mica (Somacif ME-100 manufactured by Co-op Chemical) as a clay mineral were premixed, and then a clay mineral dispersion was obtained using an ultrasonic disperser. This was designated as clay mineral dispersion B.
［実施例１］
（樹脂の水分散体の製造）
撹拌及び減圧蒸留が可能な反応容器内に、実施例用の樹脂合成例１で得られた樹脂溶液（ＴＨＦ溶液）１００部及びトリエチルアミン２．９部を仕込んだ。そして、室温にて撹拌しながらイオン交換水１００部を徐々に添加し、転相乳化を行った。次に、反応容器を５０℃に加温、減圧し、ＴＨＦを留去した。減圧は、ＴＨＦの留出が無くなり、水が留出するまで行い、冷却後に、水を加え固形分を２３質量％に調整（以下の実施例も同様に調整）することにより、ポリヒドロキシウレタン樹脂の水分散体を得た。得られた水分散体の外観は、半透明状で均一であり、水分散体中のポリマー分散粒子の粒度分布（日機装製 ＵＰＡ−ＥＸ１５０にて測定）は、ｄ５０＝０．０７９０μｍであった。図１に、測定した水分散体の粒度分布を示した。また、得られた水分散体の安定性を、５０℃の恒温槽中で保存し評価したところ、良好な安定を示した。
[Example 1]
(Production of aqueous dispersion of resin)
In a reaction vessel capable of stirring and distillation under reduced pressure, 100 parts of the resin solution (THF solution) obtained in Resin Synthesis Example 1 for Examples and 2.9 parts of triethylamine were charged. Then, 100 parts of ion-exchanged water was gradually added while stirring at room temperature to carry out phase inversion emulsification. Next, the reaction vessel was heated to 50 ° C. and decompressed, and THF was distilled off. Depressurization is performed until THF is not distilled and water is distilled, and after cooling, water is added to adjust the solid content to 23% by mass (the following examples are also adjusted in the same manner). An aqueous dispersion was obtained. The appearance of the obtained water dispersion was translucent and uniform, and the particle size distribution (measured with UPA-EX150 manufactured by Nikkiso) of the polymer dispersion particles in the water dispersion was d50 = 0.0790 μm. FIG. 1 shows the measured particle size distribution of the aqueous dispersion. Moreover, when the stability of the obtained water dispersion was preserve | saved and evaluated in a 50 degreeC thermostat, favorable stability was shown.
（ポリヒドロキシウレタン水分散体組成物の製造）
上記で得られたポリヒドロキシウレタン樹脂の水分散体５部と、製造例３で調製した粘土鉱物分散液Ａの１０部を混合し、ホモディスパーで均一に撹拌して、本実施例の、水中に、ポリヒドロキシウレタン樹脂と粘土鉱物が分散してなる水分散体組成物を得た。得られた水分散体組成物の安定性を、５０℃の恒温槽中で保存し、後述する方法にて評価したところ、良好な安定を示した。
(Production of polyhydroxyurethane aqueous dispersion composition)
5 parts of the polyhydroxyurethane resin aqueous dispersion obtained above and 10 parts of the clay mineral dispersion A prepared in Production Example 3 were mixed and stirred uniformly with a homodisper. An aqueous dispersion composition obtained by dispersing a polyhydroxyurethane resin and a clay mineral was obtained. When the stability of the obtained water dispersion composition was preserve | saved in a 50 degreeC thermostat and evaluated by the method mentioned later, favorable stability was shown.
上記で得たポリヒドロキシウレタン水分散体組成物を、厚み４０μｍの無延伸ポリプロピレンフィルム（ＣＰＰフィルム）〔東洋紡製、パイレンＰ１１１１（商品名）、酸素透過率実測値：１５００ｍＬ２０μｍ／ｍ2・ｄａｙ・ａｔｍ）を用い、そのコロナ処理面上に、乾燥時の膜厚が５μｍになるように塗布し、１００℃にて乾燥することで、基材上に被覆層を形成して複層フィルムを得た。水分散体組成物の保存安定性を評価すると共に、上記で得られたフィルムを用いて塗膜外観、光線透過率、表面光沢、ガスバリア性を評価した。それぞれの測定方法については、後述する。結果を表２に示した。
The polyhydroxyurethane aqueous dispersion composition obtained above was applied to an unstretched polypropylene film (CPP film) having a thickness of 40 μm [Toyobo, Pyrene P1111 (trade name), measured oxygen permeability: 1500
［実施例２］
先に説明した実施例用の樹脂合成例１で得られた樹脂溶液１００部に、トリエチルアミン２．９部を加え、実施例１と同様にして転相乳化を行って、ポリヒドロキシウレタン樹脂の水分散体（固形分２３％）を得た。次いで、得られたポリヒドロキシウレタン樹脂の水分散体１０部と、製造例３で調製した粘土鉱物分散液Ａの１０部を混合し、ホモディスパーで均一に撹拌することにより、本実施例のポリヒドロキシウレタン水分散体組成物を得た。そして、得られた水分散体組成物を用い、実施例１で使用したと同様の基材及び条件にて複層フィルムを作製した。上記で得た本実施例の水分散体組成物及びフィルムにて、実施例１と同様の評価を行い、結果を表２に示した。
[Example 2]
2.9 parts of triethylamine was added to 100 parts of the resin solution obtained in Resin Synthesis Example 1 for the examples described above, and phase inversion emulsification was performed in the same manner as in Example 1 to obtain water of polyhydroxyurethane resin. A dispersion (solid content 23%) was obtained. Next, 10 parts of the aqueous dispersion of the obtained polyhydroxyurethane resin and 10 parts of the clay mineral dispersion A prepared in Production Example 3 were mixed and stirred uniformly with a homodisper to obtain the polydisperse of this example. A hydroxyurethane aqueous dispersion composition was obtained. And the multilayer film was produced on the same base material and conditions as used in Example 1 using the obtained water dispersion composition. The same evaluation as in Example 1 was performed with the aqueous dispersion composition and film of this example obtained above, and the results are shown in Table 2.
［実施例３］
先に説明した実施例用の樹脂合成例１で得られた樹脂溶液１００部に、トリエチルアミン２．９部を加え、実施例１と同様にして転相乳化を行って、ポリヒドロキシウレタン樹脂の水分散体を得た。次いで、得られたポリヒドロキシウレタン樹脂の水分散体２０部と、製造例３で調製した粘土鉱物分散液Ａの１０部を混合し、ホモディスパーで均一に撹拌することにより、本実施例の、水中にポリヒドロキシウレタン樹脂と粘土鉱物とが分散してなる水分散体（固形分２３％）を得た。そして、得られた水分散体を用い、実施例１で使用したと同様の基材及び条件にて複層フィルムを作製した。上記で得た本実施例の水分散体組成物及びフィルムにて、実施例１と同様の評価を行い、結果を表２に示した。
[Example 3]
2.9 parts of triethylamine was added to 100 parts of the resin solution obtained in Resin Synthesis Example 1 for the examples described above, and phase inversion emulsification was performed in the same manner as in Example 1 to obtain water of polyhydroxyurethane resin. A dispersion was obtained. Next, 20 parts of the obtained polyhydroxyurethane resin aqueous dispersion and 10 parts of the clay mineral dispersion A prepared in Production Example 3 were mixed and stirred uniformly with a homodisper. An aqueous dispersion (solid content: 23%) obtained by dispersing polyhydroxyurethane resin and clay mineral in water was obtained. And the multilayer film was produced on the same base material and conditions as used in Example 1 using the obtained water dispersion. The same evaluation as in Example 1 was performed with the aqueous dispersion composition and film of this example obtained above, and the results are shown in Table 2.
［実施例４］
先に説明した実施例用の樹脂合成例１で得られた樹脂溶液１００部に、トリエチルアミン２．９部を加え、実施例１と同様にして転相乳化を行って、ポリヒドロキシウレタン樹脂の水分散体（固形分２３％）を得た。次いで、得られたポリヒドロキシウレタン樹脂の水分散体４０部と、製造例３で調製した粘土鉱物分散液Ａの１０部を混合し、ホモディスパーで均一に撹拌することにより、本実施例の、水中に、ポリヒドロキシウレタン樹脂と粘土鉱物とが分散してなる水分散体組成物を得た。そして、得られた水分散体組成物を用い、実施例１で使用したと同様の基材及び条件にて複層フィルムを作製した。上記で得た本実施例の水分散体組成物及びフィルムにて、実施例１と同様の評価を行い、結果を表２に示した。
[Example 4]
2.9 parts of triethylamine was added to 100 parts of the resin solution obtained in Resin Synthesis Example 1 for the examples described above, and phase inversion emulsification was performed in the same manner as in Example 1 to obtain water of polyhydroxyurethane resin. A dispersion (solid content 23%) was obtained. Next, 40 parts of the obtained polyhydroxyurethane resin aqueous dispersion and 10 parts of the clay mineral dispersion A prepared in Production Example 3 were mixed and stirred uniformly with a homodisper. An aqueous dispersion composition obtained by dispersing a polyhydroxyurethane resin and a clay mineral in water was obtained. And the multilayer film was produced on the same base material and conditions as used in Example 1 using the obtained water dispersion composition. The same evaluation as in Example 1 was performed with the aqueous dispersion composition and film of this example obtained above, and the results are shown in Table 2.
［実施例５］
先に説明した実施例用の樹脂合成例２で得られた樹脂溶液１００部に、トリエチルアミン１．４部を加え、実施例１と同様にして転相乳化を行って、ポリヒドロキシウレタン樹脂の水分散体（固形分２３％）を得た。水分散体中のポリマー分散粒子の粒度分布（日機装製 ＵＰＡ−ＥＸ１５０にて測定）はｄ５０＝０．０８０４０μｍであった。次いで、得られたポリヒドロキシウレタン樹脂の水分散体２０部と、製造例３で調製した粘土鉱物分散液Ａの１０部を混合し、ホモディスパーで均一に撹拌することにより、本実施例の、水中に、ポリヒドロキシウレタン樹脂と粘土鉱物とが分散してなる水分散体組成物（固形分２３％）を得た。そして、得られた水分散体組成物を用い、実施例１で使用したと同様の基材及び条件にて複層フィルムを作製した。上記で得た本実施例の水分散体組成物及びフィルムにて、実施例１と同様の評価を行い、結果を表２に示した。
[Example 5]
1.4 parts of triethylamine was added to 100 parts of the resin solution obtained in Resin Synthesis Example 2 for the examples described above, and phase inversion emulsification was performed in the same manner as in Example 1 to obtain water of polyhydroxyurethane resin. A dispersion (solid content 23%) was obtained. The particle size distribution (measured with Nikkiso UPA-EX150) of the polymer dispersed particles in the aqueous dispersion was d50 = 0.08040 μm. Next, 20 parts of the obtained polyhydroxyurethane resin aqueous dispersion and 10 parts of the clay mineral dispersion A prepared in Production Example 3 were mixed and stirred uniformly with a homodisper. An aqueous dispersion composition (solid content: 23%) obtained by dispersing polyhydroxyurethane resin and clay mineral in water was obtained. And the multilayer film was produced on the same base material and conditions as used in Example 1 using the obtained water dispersion composition. The same evaluation as in Example 1 was performed with the aqueous dispersion composition and film of this example obtained above, and the results are shown in Table 2.
［実施例６］
先に説明した実施例用の樹脂合成例３で得られた樹脂溶液１００部に、トリエチルアミン４．７部を加え、実施例１と同様にして転相乳化を行って、ポリヒドロキシウレタン樹脂の水分散体（固形分２３％）を得た。水分散体中のポリマー分散粒子の粒度分布（日機装製 ＵＰＡ−ＥＸ１５０にて測定）はｄ５０＝０．０１２７μｍであった。次いで、得られたポリヒドロキシウレタン樹脂の水分散体２０部と、製造例４で調製した粘土鉱物分散液Ｂの１０部を混合し、ホモディスパーで均一に撹拌することにより、本実施例の、水中に、ポリヒドロキシウレタン樹脂と粘土鉱物とが分散してなる水分散体組成物を得た。そして、得られた水分散体組成物を用い、実施例１で使用したと同様の基材及び条件にて複層フィルムを作製した。上記で得た本実施例の水分散体組成物及びフィルムにて、実施例１と同様の評価を行い、結果を表２に示した。
[Example 6]
4.7 parts of triethylamine was added to 100 parts of the resin solution obtained in Resin Synthesis Example 3 for the examples described above, and phase inversion emulsification was performed in the same manner as in Example 1 to obtain water of polyhydroxyurethane resin. A dispersion (solid content 23%) was obtained. The particle size distribution (measured with Nikkiso UPA-EX150) of the polymer dispersed particles in the aqueous dispersion was d50 = 0.127 μm. Next, 20 parts of the obtained polyhydroxyurethane resin aqueous dispersion and 10 parts of the clay mineral dispersion B prepared in Production Example 4 were mixed and stirred uniformly with a homodisper. An aqueous dispersion composition obtained by dispersing a polyhydroxyurethane resin and a clay mineral in water was obtained. And the multilayer film was produced on the same base material and conditions as used in Example 1 using the obtained water dispersion composition. The same evaluation as in Example 1 was performed with the aqueous dispersion composition and film of this example obtained above, and the results are shown in Table 2.
［実施例７］
先に説明した実施例用の樹脂合成例４で得られた樹脂溶液１００部に、トリエチルアミン６．４部を加え、実施例１と同様にして転相乳化を行って、ポリヒドロキシウレタン樹脂の水分散体（固形分２３％）を得た。水分散体中のポリマー分散粒子の粒度分布（日機装製 ＵＰＡ−ＥＸ１５０にて測定）はｄ５０＝０．００７１μｍであった。次いで、得られたポリヒドロキシウレタン樹脂の水分散体２０部と、製造例４で調製した粘土鉱物分散液Ｂの１０部を混合し、ホモディスパーで均一に撹拌することにより、本実施例の、水中に、ポリヒドロキシウレタン樹脂と粘土鉱物とが分散してなる水分散体組成物を得た。そして、得られた水分散体組成物を用い、実施例１で使用したと同様の基材及び条件にて複層フィルムを作製した。上記で得た本実施例の水分散体組成物及びフィルムにて、実施例１と同様の評価を行い、結果を表２に示した。
[Example 7]
6.4 parts of triethylamine was added to 100 parts of the resin solution obtained in Resin Synthesis Example 4 for the examples described above, and phase inversion emulsification was performed in the same manner as in Example 1 to obtain water of polyhydroxyurethane resin. A dispersion (solid content 23%) was obtained. The particle size distribution of the polymer dispersed particles in the aqueous dispersion (measured with UPA-EX150 manufactured by Nikkiso) was d50 = 0.711 μm. Next, 20 parts of the obtained polyhydroxyurethane resin aqueous dispersion and 10 parts of the clay mineral dispersion B prepared in Production Example 4 were mixed and stirred uniformly with a homodisper. An aqueous dispersion composition obtained by dispersing a polyhydroxyurethane resin and a clay mineral in water was obtained. And the multilayer film was produced on the same base material and conditions as used in Example 1 using the obtained water dispersion composition. The same evaluation as in Example 1 was performed with the aqueous dispersion composition and film of this example obtained above, and the results are shown in Table 2.
［比較例１］
比較例用の樹脂合成例ａで得た樹脂溶液に、反応時に既に使用しているトリエチルアミンを加えないこと以外は、実施例１と同様にして、濃度２３％に調整した、ポリヒドロキシウレタン樹脂の水分散体を得た。水分散体中のポリマー分散粒子の粒度分布（日機装製 ＵＰＡ−ＥＸ１５０にて測定）は、ｄ５０＝０．０１７９μｍであった。次いで、得られたポリヒドロキシウレタン樹脂の水分散体２０部と、製造例３で調製した粘土鉱物分散液Ａの１０部を混合し、ホモディスパーで均一に撹拌することにより、比較例の、水中に、ポリヒドロキシウレタン樹脂と粘土鉱物とが分散してなる水分散体組成物を得た。そして、得られた水分散体組成物を用い、実施例１で使用したと同様の基材及び条件にて複層フィルムを作製した。上記で得た比較例の水分散体及びフィルムにて、実施例１と同様の評価を行い、結果を表３に示した。
[Comparative Example 1]
The polyhydroxyurethane resin was adjusted to a concentration of 23% in the same manner as in Example 1 except that the triethylamine already used in the reaction was not added to the resin solution obtained in Resin Synthesis Example a for Comparative Example. An aqueous dispersion was obtained. The particle size distribution (measured with Nikkiso UPA-EX150) of the polymer dispersed particles in the aqueous dispersion was d50 = 0.0179 μm. Next, 20 parts of the obtained polyhydroxyurethane resin aqueous dispersion and 10 parts of the clay mineral dispersion A prepared in Production Example 3 were mixed and stirred uniformly with a homodisper to obtain the comparative example underwater. An aqueous dispersion composition obtained by dispersing a polyhydroxyurethane resin and a clay mineral was obtained. And the multilayer film was produced on the same base material and conditions as used in Example 1 using the obtained water dispersion composition. The same evaluation as in Example 1 was performed on the aqueous dispersion and film of Comparative Example obtained above, and the results are shown in Table 3.
［比較例２］
比較用の樹脂合成例ｂで得た樹脂溶液に、反応時に既に使用しているトリエチルアミンを加えないこと以外は実施例１と同様にして転相乳化を行って、濃度２３％に調整した、ポリヒドロキシウレタン樹脂の水分散体を得た。水分散体中のポリマー分散粒子の粒度分布（日機装製 ＵＰＡ−ＥＸ１５０にて測定）はｄ５０＝０．００１μｍであった。次いで、得られたポリヒドロキシウレタン樹脂の水分散体２０部と、製造例３で調製した粘土鉱物分散液Ａの１０部を混合し、ホモディスパーで均一に撹拌することにより、比較例の、水中に、ポリヒドロキシウレタン樹脂と粘土鉱物とが分散してなる水分散体組成物を得た。そして、得られた水分散体組成物を用い、実施例１で使用したと同様の基材及び条件にて複層フィルムを作製した。上記で得た比較例の水分散体組成物及びフィルムにて、実施例１と同様の評価を行い、結果を表３に示した。
[Comparative Example 2]
The resin solution obtained in Comparative Resin Synthesis Example b was subjected to phase inversion emulsification in the same manner as in Example 1 except that triethylamine already used during the reaction was not added, and adjusted to a concentration of 23%. An aqueous dispersion of a hydroxyurethane resin was obtained. The particle size distribution (measured with Nikkiso UPA-EX150) of the polymer dispersed particles in the aqueous dispersion was d50 = 0.001 μm. Next, 20 parts of the obtained polyhydroxyurethane resin aqueous dispersion and 10 parts of the clay mineral dispersion A prepared in Production Example 3 were mixed and stirred uniformly with a homodisper to obtain the comparative example underwater. An aqueous dispersion composition obtained by dispersing a polyhydroxyurethane resin and a clay mineral was obtained. And the multilayer film was produced on the same base material and conditions as used in Example 1 using the obtained water dispersion composition. The same evaluation as in Example 1 was performed with the comparative aqueous dispersion composition and film obtained above, and the results are shown in Table 3.
［比較例３］
比較用の樹脂合成例ｃで得たカルボキシル基を含まないヒドロキシポリウレタン樹脂溶液１００部に、イオン交換水１００部を徐々に加えながら転相乳化を試みた。しかし、３０部を加えた時点で樹脂が分離したため中止した。
[Comparative Example 3]
Phase inversion emulsification was attempted while gradually adding 100 parts of ion-exchanged water to 100 parts of a hydroxy polyurethane resin solution not containing a carboxyl group obtained in Comparative Resin Synthesis Example c. However, when 30 parts were added, the resin separated and was stopped.
（評価）
上記で得た実施例１〜７及び比較例１、２の各水分散体組成物の特性、及び、各水分散体組成物を用いて得た塗料で作製した各フィルムの評価は、以下の方法及び基準で行った。結果を表２、３にまとめて示した。
(Evaluation)
The characteristics of each aqueous dispersion composition of Examples 1 to 7 and Comparative Examples 1 and 2 obtained above, and the evaluation of each film prepared with the paint obtained using each aqueous dispersion composition were as follows. Performed by methods and standards. The results are summarized in Tables 2 and 3.
［安定性］
実施例１〜７及び比較例１、２の各水分散体組成物を、密閉したポリ容器に入れ、５０℃の恒温槽で保存した。そして、それぞれ、一ヶ月、三か月、六か月後の状態を観察し、それぞれ、以下の基準で評価し、結果を表２、３中に示した。
＜評価基準＞
〇：ポリマー粒子及び粘土鉱物の沈降は無く、外観上の変化が見られない。
△：ポリマー粒子及び粘土鉱物が沈降しているが撹拌により簡単に再分散する。
×：乳化粒子が破壊され樹脂分が沈降。撹拌しても再分散できない。
[Stability]
The aqueous dispersion compositions of Examples 1 to 7 and Comparative Examples 1 and 2 were placed in a sealed plastic container and stored in a thermostatic bath at 50 ° C. And the state after 1 month, 3 months, and 6 months was observed, respectively, and evaluated according to the following criteria, respectively, and the results are shown in Tables 2 and 3.
<Evaluation criteria>
◯: There is no sedimentation of polymer particles and clay minerals, and no change in appearance is observed.
(Triangle | delta): Although polymer particle and clay mineral have settled, it re-disperses easily by stirring.
X: The emulsified particles are broken and the resin is settled. It cannot be redispersed even with stirring.
［塗膜外観］
実施例１〜７及び比較例１、２で作製した各複層フィルムについて、塗布面（コーティング層）の外観を目視にて観察し、以下の基準で評価した。結果を表２、３中に示した。
＜評価基準＞
〇：透明〜半透明均一な被膜が形成されており、目視で確認できる凝集物が無い
×：凝集物によるスジ引き等と被膜が不均一、或いは目視できる凝集物がある
[Appearance of coating film]
About each multilayer film produced in Examples 1-7 and Comparative Examples 1 and 2, the external appearance of the coating surface (coating layer) was observed visually, and the following references | standards evaluated. The results are shown in Tables 2 and 3.
<Evaluation criteria>
◯: A transparent to translucent uniform film is formed, and there are no aggregates that can be visually confirmed.
［表面光沢］
実施例１〜７及び比較例１、２で作製した各複層フィルムについて、光沢計（スガ試験機製 ＵＧＡ−５Ｄ）を使用し、入射角６０°における光沢値を標準版の光沢値を９２とした相対値として測定した。結果を表２、３中に示した。
[Surface gloss]
For each of the multilayer films prepared in Examples 1 to 7 and Comparative Examples 1 and 2, a gloss meter (UGA-5D manufactured by Suga Test Instruments Co., Ltd.) was used, and the gloss value at an incident angle of 60 ° was the gloss value of the standard plate as 92. Measured as a relative value. The results are shown in Tables 2 and 3.
［耐水性］
実施例１〜７及び比較例１、２で作製した各複層フィルムについて、フィルムを水に浸漬し、室温で１時間後の塗膜表面状態を目視で観察し、以下の規準で評価した。結果を表２、３中に示した。
＜評価基準＞
〇：変化は見られない
△：塗膜の一部が白化している
×：塗膜が膨潤している
[water resistant]
About each multilayer film produced in Examples 1-7 and Comparative Examples 1 and 2, the film was immersed in water, the coating-film surface state after 1 hour was observed visually at room temperature, and the following references | standards evaluated. The results are shown in Tables 2 and 3.
<Evaluation criteria>
○: No change is observed Δ: Part of the coating is whitened ×: The coating is swollen
［ガスバリア性］
実施例１〜７及び比較例１、２で作製した表面に塗膜（コート層）を有する各フィルムについて、ＪＩＳ Ｋ−７１２６に準拠して酸素の透過度を測定し、これをガスバリア性の評価値とした。すなわち、この値が低いほどガスバリア性に優れると判断できる。具体的には、酸素透過率測定装置（ＭＯＣＯＮ社製、ＯＸ−ＴＲＡＮ ２／２１ＭＬ）を使用して、温度２３℃で、湿度６５％の恒温恒湿条件下にて、酸素透過度（酸素透過率）を測定した。なお、先に表１中に示した実施例用の樹脂合成例１〜４で作製したフィルムの酸素透過率は、膜厚２０μｍに換算した値であるのに対し、表２、３に示した実施例１〜７、比較例１、２のフィルムのガスバリア性の測定値は、表面に塗膜（コート層）を有するフィルム構成体としての酸素透過度である。該フィルムにおける実施例或いは比較例の塗料を塗布して得られたコート層の厚みは、精密厚み測定器（尾崎製作所製）を使用して実測し、５μｍであることを確認している。結果を表２、３中に示した。
比較のため、各水分散体組成物の調製に使用した樹脂の水分散体を用い、上記と同様にコート層の厚みを５μｍにした表面に塗膜（コート層）を形成したフィルムについて、ガスバリア性を評価した。その結果を表２中に示した。
[Gas barrier properties]
About each film which has a coating film (coat layer) on the surface produced in Examples 1-7 and Comparative Examples 1 and 2, the oxygen permeability was measured according to JIS K-7126, and this was evaluated for gas barrier properties. Value. That is, it can be judged that the lower the value, the better the gas barrier property. Specifically, using an oxygen permeability measuring device (MOCON, OX-TRAN 2 / 21ML), the oxygen permeability (oxygen permeability) at a temperature of 23 ° C. and a humidity of 65% under constant temperature and humidity conditions. Rate). In addition, while the oxygen permeability of the film produced in the resin synthesis examples 1 to 4 for the examples shown in Table 1 above is a value converted to a film thickness of 20 μm, it is shown in Tables 2 and 3. The measured values of the gas barrier properties of the films of Examples 1 to 7 and Comparative Examples 1 and 2 are oxygen permeability as a film structure having a coating film (coat layer) on the surface. The thickness of the coating layer obtained by applying the paints of Examples or Comparative Examples on the film was measured using a precision thickness measuring instrument (manufactured by Ozaki Seisakusho) and confirmed to be 5 μm. The results are shown in Tables 2 and 3.
For comparison, a gas barrier was used for a film in which a coating film (coating layer) was formed on the surface having a coating layer thickness of 5 μm as described above, using the aqueous dispersion of the resin used for the preparation of each aqueous dispersion composition. Sex was evaluated. The results are shown in Table 2.
表２から明らかなように、本発明の技術により粘土鉱物とポリヒドロキシウレタン樹脂が均一に分散された水分散体組成物を得ることができる。特に、従来処方で製造した比較例のヒドロキシウレタン樹脂の水分散体を用いた場合と比べて、粘土鉱物の分散性安定性に優れており、これは、本発明で使用したポリヒドロキシウレタン樹脂中に、アミド結合を介してカルボキシル基が導入されていることに由来していると考えられる。すなわち、アニオン性のカルボキシル基のみで親水化したポリヒドロキシウレタン樹脂のポリマー鎖は、粘土鉱物の層間に侵入しにくいことに比べて、本発明に使用したポリヒドロキシウレタン樹脂は、このアミド結合の存在により、粘土鉱物の層間へのポリマー鎖の侵入が阻害されず、均一な分散体を製造することができたと考えられる。この結果、表２に示されているように、粘土鉱物を利用したものでありながら、実施例の水分散体組成物を用いて形成した塗膜（被膜層）は、いずれも凝集物のない、粘度鉱物が微分散していることによってもたらされる光沢度を示す外観に優れたものになることが確認された。 As is apparent from Table 2, an aqueous dispersion composition in which clay mineral and polyhydroxyurethane resin are uniformly dispersed can be obtained by the technique of the present invention. In particular, the dispersion stability of clay minerals is excellent compared to the case of using an aqueous dispersion of a hydroxyurethane resin of a comparative example produced by a conventional formulation. This is because of the polyhydroxyurethane resin used in the present invention. It is thought that this is derived from the fact that a carboxyl group is introduced through an amide bond. In other words, the polyhydroxyurethane resin used in the present invention has the presence of this amide bond, compared to the polymer chain of the polyhydroxyurethane resin hydrophilicized only with an anionic carboxyl group, which is less likely to enter between layers of clay minerals. Thus, it is considered that the polymer chain intrusion into the interlayer of the clay mineral was not inhibited and a uniform dispersion could be produced. As a result, as shown in Table 2, none of the coating films (coating layers) formed using the aqueous dispersion compositions of the examples had agglomerates while using clay minerals. It was confirmed that the appearance showing the glossiness caused by the fine dispersion of the viscosity mineral was excellent.
また、従来ヒドロキシウレタン樹脂にカルボキシル基を導入する際のエステル結合と比較して、アミド結合は耐加水分解性に勝るため、ポリマー分散粒子の安定性も良好であった。さらに、本発明の、粘土鉱物とポリヒドロキシウレタン樹脂が均一に分散された水分散体組成物を使用して被膜を形成することで、簡易に、粘土鉱物−ポリヒドロキシウレタン樹脂の複合被膜を得ることができ、粘土鉱物の分散状態が良好なことから、高いガスバリア性を実現できることも確認された。 Moreover, compared with the ester bond at the time of introduce | transducing a carboxyl group into a hydroxy urethane resin conventionally, since the amide bond is excellent in hydrolysis resistance, the stability of the polymer dispersed particle was also favorable. Furthermore, a clay mineral-polyhydroxyurethane resin composite coating can be easily obtained by forming a coating using the aqueous dispersion composition in which the clay mineral and the polyhydroxyurethane resin are uniformly dispersed according to the present invention. It was also confirmed that a high gas barrier property can be realized because the dispersion state of the clay mineral is good.
本発明によれば、工業的に要求される長期間の保存が可能なポリヒドロキシウレタン樹脂−粘土鉱物の水分散体組成物を提供することができる。更に、該水分散体組成物を使用して、簡易にポリヒドロキシウレタン−粘土鉱物複合被膜の形成が可能であり、この被膜はガスバリア層として使用できる。また、形成される被膜は、粘土鉱物を利用したものでありながら、凝集物のない、粘度鉱物が微分散していることによってもたらされる光沢度を示す外観に優れたものになることから、広範な分野での利用が期待される。さらに、本発明を特徴づけるポリヒドロキシウレタン樹脂は、その原料に二酸化炭素を使用することができるものであるので、地球環境保護の面からも期待される技術である。 ADVANTAGE OF THE INVENTION According to this invention, the aqueous dispersion composition of the polyhydroxy urethane resin-clay mineral which can be preserve | saved for a long period which is required industrially can be provided. Furthermore, it is possible to easily form a polyhydroxyurethane-clay mineral composite coating by using the aqueous dispersion composition, and this coating can be used as a gas barrier layer. In addition, although the coating film is formed using clay mineral, it has excellent appearance showing glossiness caused by finely dispersed viscous minerals without agglomerates. It is expected to be used in various fields. Furthermore, since the polyhydroxyurethane resin characterizing the present invention can use carbon dioxide as a raw material, it is a technology expected from the viewpoint of protecting the global environment.
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