JP5193769B2 - Method for producing polyurethane water dispersion for wood paint - Google Patents
Method for producing polyurethane water dispersion for wood paint Download PDFInfo
- Publication number
- JP5193769B2 JP5193769B2 JP2008241595A JP2008241595A JP5193769B2 JP 5193769 B2 JP5193769 B2 JP 5193769B2 JP 2008241595 A JP2008241595 A JP 2008241595A JP 2008241595 A JP2008241595 A JP 2008241595A JP 5193769 B2 JP5193769 B2 JP 5193769B2
- Authority
- JP
- Japan
- Prior art keywords
- polyol
- castor oil
- mass
- prepolymer
- dehydrated castor
- 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.)
- Active
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- 239000006185 dispersion Substances 0.000 title claims description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 66
- 239000002023 wood Substances 0.000 title claims description 52
- 239000003973 paint Substances 0.000 title claims description 42
- 239000004814 polyurethane Substances 0.000 title claims description 38
- 229920002635 polyurethane Polymers 0.000 title claims description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 27
- 229920005862 polyol Polymers 0.000 claims description 111
- 150000003077 polyols Chemical class 0.000 claims description 110
- 239000004359 castor oil Substances 0.000 claims description 77
- 235000019438 castor oil Nutrition 0.000 claims description 77
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 77
- 238000006243 chemical reaction Methods 0.000 claims description 50
- 238000000576 coating method Methods 0.000 claims description 33
- -1 diisocyanate compound Chemical class 0.000 claims description 32
- 150000004665 fatty acids Chemical class 0.000 claims description 25
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 22
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 21
- 239000000194 fatty acid Substances 0.000 claims description 21
- 229930195729 fatty acid Natural products 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 16
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 13
- 239000011630 iodine Substances 0.000 claims description 13
- 229910052740 iodine Inorganic materials 0.000 claims description 13
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 150000001718 carbodiimides Chemical class 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 34
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 32
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 30
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 27
- 239000011248 coating agent Substances 0.000 description 24
- 239000000203 mixture Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 19
- 239000003054 catalyst Substances 0.000 description 18
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- 239000003960 organic solvent Substances 0.000 description 16
- 239000002253 acid Substances 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000010992 reflux Methods 0.000 description 14
- 239000012298 atmosphere Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 12
- 239000012295 chemical reaction liquid Substances 0.000 description 12
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 12
- 150000002433 hydrophilic molecules Chemical class 0.000 description 11
- 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 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- 239000000654 additive Substances 0.000 description 10
- 238000004090 dissolution Methods 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 8
- 238000002845 discoloration Methods 0.000 description 8
- 238000006386 neutralization reaction Methods 0.000 description 8
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 7
- 239000005056 polyisocyanate Substances 0.000 description 7
- 229920001228 polyisocyanate Polymers 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- ARSRBNBHOADGJU-UHFFFAOYSA-N 7,12-dimethyltetraphene Chemical compound C1=CC2=CC=CC=C2C2=C1C(C)=C(C=CC=C1)C1=C2C ARSRBNBHOADGJU-UHFFFAOYSA-N 0.000 description 6
- VFZRZRDOXPRTSC-UHFFFAOYSA-N DMBA Natural products COC1=CC(OC)=CC(C=O)=C1 VFZRZRDOXPRTSC-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 125000005442 diisocyanate group Chemical group 0.000 description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 229920005906 polyester polyol Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 150000003512 tertiary amines Chemical class 0.000 description 5
- 238000004383 yellowing Methods 0.000 description 5
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000004970 Chain extender Substances 0.000 description 4
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 235000021388 linseed oil Nutrition 0.000 description 3
- 239000000944 linseed oil Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 235000012424 soybean oil Nutrition 0.000 description 3
- 239000003549 soybean oil Substances 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 2
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 239000002245 particle Substances 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
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 2
- 229960003656 ricinoleic acid Drugs 0.000 description 2
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- VKNBFINDVATXHU-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)nonanoic acid Chemical compound CCCCCCCC(CO)(CO)C(O)=O VKNBFINDVATXHU-UHFFFAOYSA-N 0.000 description 1
- UHAMPPWFPNXLIU-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)pentanoic acid Chemical compound CCCC(CO)(CO)C(O)=O UHAMPPWFPNXLIU-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- YHFGMFYKZBWPRW-UHFFFAOYSA-N 3-methylpentane-1,1-diol Chemical compound CCC(C)CC(O)O YHFGMFYKZBWPRW-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- JCELWOGDGMAGGN-UHFFFAOYSA-N N=C=O.N=C=O.C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 JCELWOGDGMAGGN-UHFFFAOYSA-N 0.000 description 1
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- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
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- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
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- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
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- 229960002887 deanol Drugs 0.000 description 1
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- 229940100539 dibutyl adipate Drugs 0.000 description 1
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- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
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- 150000002009 diols Chemical class 0.000 description 1
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- 238000004821 distillation Methods 0.000 description 1
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- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
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- 230000003301 hydrolyzing effect Effects 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
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- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000212 poly(isobutyl acrylate) Polymers 0.000 description 1
- 229920000196 poly(lauryl methacrylate) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
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- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Description
本発明は、木材塗料用ポリウレタン系水分散体の製造方法に関する。更に詳しくは、本発明は、木材用塗料の主成分として用いたときに、変色、特に黄変し難く、且つ優れた耐水性、耐溶剤性及び耐湿熱性等を有する皮膜を形成することができる木材塗料用ポリウレタン系水分散体の製造方法に関する。 The present invention relates to a method for producing a polyurethane-based aqueous dispersion for wood paint. More specifically, the present invention can form a film that is hardly discolored, particularly yellowed, and has excellent water resistance, solvent resistance, and moist heat resistance when used as a main component of a wood coating. The present invention relates to a method for producing a polyurethane-based aqueous dispersion for wood paint.
従来、ヒマシ油系ポリオール等のポリオールを用いて製造されたイソシアネート末端プレポリマーが水に分散されてなる各種のポリウレタン系水分散体が提案されており、塗料等の主成分として用いられている。例えば、不飽和脂肪酸エステルポリオール等のポリオール化合物と、有機ジイソシアネート化合物と、ジアルキルモノヒドロキシアルカン酸との反応生成物を必須成分とする水性ウレタン化アルキッド樹脂分散体が知られている(例えば、特許文献1参照。)。また、ポリイソシアネート化合物、ヒマシ油系ポリオール化合物、分子内に水酸基以外の親水性基を有し、且つ水酸基を2個以上有する化合物、を反応させて得られたイソシアネート末端プレポリマーに、活性水素を2個以上有する化合物を作用させて鎖延長反応させてなるウレタン系水性組成物が知られている(例えば、特許文献2参照。)。 Conventionally, various polyurethane-based aqueous dispersions in which an isocyanate-terminated prepolymer produced using a polyol such as a castor oil-based polyol is dispersed in water have been proposed and used as a main component of a paint or the like. For example, an aqueous urethanized alkyd resin dispersion containing a reaction product of a polyol compound such as an unsaturated fatty acid ester polyol, an organic diisocyanate compound, and a dialkyl monohydroxyalkanoic acid as an essential component is known (for example, Patent Documents). 1). In addition, active hydrogen is added to an isocyanate-terminated prepolymer obtained by reacting a polyisocyanate compound, a castor oil-based polyol compound, a compound having a hydrophilic group other than a hydroxyl group in the molecule and having two or more hydroxyl groups. A urethane-based aqueous composition obtained by reacting a compound having two or more compounds to cause a chain extension reaction is known (for example, see Patent Document 2).
上記のように、塗料等として用いられる各種のウレタン系水分散体などが知られている。しかし、特許文献1では、有機ジイソシアネート化合物が数多く例示されてはいるものの、皮膜の変色との関連で特定の有機ジイソシアネート化合物を選択することについては何ら着目されていない。また、実施例では、変色し易いトリレンジイソシアネートが用いられており、イソホロンジイソシアネートも用いられているが、このジイソシアネートであっても、特定のポリオールを用いないときは変色の問題がある。更に、特許文献2では、ポリオール原料として脱水ヒマシ油を用いること、及び塗膜を酸化重合により硬化させることについて何ら記載がなく、被膜の変色にも全く着目されていない。 As described above, various urethane-based aqueous dispersions used as paints and the like are known. However, although many organic diisocyanate compounds are exemplified in Patent Document 1, no attention is paid to selecting a specific organic diisocyanate compound in relation to discoloration of the film. Further, in the examples, tolylene diisocyanate which is easily discolored is used, and isophorone diisocyanate is also used, but even this diisocyanate has a problem of discoloration when a specific polyol is not used. Furthermore, in Patent Document 2, there is no description about using dehydrated castor oil as a polyol raw material and curing the coating film by oxidative polymerization, and no attention is paid to discoloration of the coating film.
本発明は上記の従来の状況に鑑みてなされたものであり、木材用塗料の主成分として用いたときに、木材に塗布された後、含有されるイソシアネート末端プレポリマー(以下、「プレポリマー」と略記することもある。)が酸化重合し、架橋されて、変色、特に黄変し難く、且つ優れた耐水性、耐溶剤性及び耐湿熱性等を有する皮膜を形成することができる木材塗料用ポリウレタン系水分散体(以下、「水分散体」と略記することもある。)の製造方法を提供することを目的とする。 The present invention has been made in view of the above-described conventional situation, and when used as a main component of a wood paint, an isocyanate-terminated prepolymer (hereinafter referred to as “prepolymer”) contained after being applied to wood. For wood coatings that are oxidatively polymerized and cross-linked to form a film that is resistant to discoloration, particularly yellowing, and that has excellent water resistance, solvent resistance, and moist heat resistance. It is an object of the present invention to provide a method for producing a polyurethane-based water dispersion (hereinafter sometimes abbreviated as “water dispersion”).
本発明は以下のとおりである。
1.脱水ヒマシ油及び/又は脱水ヒマシ油脂肪酸と、4官能以上のポリオールとの反応生成物であり、該脱水ヒマシ油及び/又は該脱水ヒマシ油脂肪酸と、該4官能以上のポリオールとの合計を100質量%とした場合に、該4官能以上のポリオールは5〜40質量%である脱水ヒマシ油脂肪酸骨格を有するポリオール(A)と、少なくとも2個のヒドロキシル基と、少なくとも1個のカルボキシル基とを有する親水性化合物と、2又は3個のシクロヘキシル基を有するジイソシアネート化合物(B)と、を反応させてイソシアネート末端プレポリマーを生成させ、その後、該イソシアネート末端プレポリマーが溶解した反応液と水とを混合することを特徴とする木材塗料用ポリウレタン系水分散体の製造方法。
2.上記ポリオール(A)のヨウ素価が80〜130である上記1.に記載の木材塗料用ポリウレタン系水分散体の製造方法。
3.上記反応液と上記水とを混合するのと同時に、又は該混合後に、混合液にカルボジイミドが添加され、該混合液に含有される固形分を100質量部とした場合に、該カルボジイミドは0.3〜3.0質量部である上記1.又は2.に記載の木材塗料用ポリウレタン系水分散体の製造方法。
4.上記1.乃至3.のうちのいずれか1項に記載の木材塗料用ポリウレタン系水分散体の製造方法により製造されたことを特徴とする木材塗料用ポリウレタン系水分散体。
The present invention is as follows.
1. A reaction product of dehydrated castor oil and / or dehydrated castor oil fatty acid and a tetrafunctional or higher polyol, and the total of the dehydrated castor oil and / or dehydrated castor oil fatty acid and the tetrafunctional or higher polyol is 100. In the case of mass%, the tetrafunctional or higher polyol is 5 to 40 mass% of a polyol (A) having a dehydrated castor oil fatty acid skeleton, at least two hydroxyl groups, and at least one carboxyl group. And a diisocyanate compound (B) having 2 or 3 cyclohexyl groups are reacted to form an isocyanate-terminated prepolymer, and then a reaction solution in which the isocyanate-terminated prepolymer is dissolved and water. A method for producing a polyurethane-based aqueous dispersion for wood paint, which comprises mixing.
2. 1. The iodine value of the polyol (A) is 80 to 130. The manufacturing method of the polyurethane-type water dispersion for wood coatings as described in any one of .
3. At the same time as or after the mixing of the reaction solution and the water, carbodiimide is added to the mixed solution, and when the solid content in the mixed solution is 100 parts by mass, the carbodiimide is 0. The above 1. which is 3 to 3.0 parts by mass. Or 2. The manufacturing method of the polyurethane-type water dispersion for wood coatings as described in any one of.
4). Above 1. To 3. A polyurethane-based aqueous dispersion for wood coatings produced by the method for producing a polyurethane-based aqueous dispersion for wood coatings according to any one of the above.
本発明の木材塗料用ポリウレタン系水分散体の製造方法によれば、酸化重合により塗膜が容易に硬化し、十分な硬度を有する皮膜を形成することができるイソシアネート末端プレポリマーを含有する水分散体を効率よく製造することができる。また、亜麻仁油、大豆油等の植物油由来の従来のポリオールを用いたときは、変色し易いが、本発明の製造方法では、特定の構造のポリオール(A)を使用することにより、変色を十分に抑えることができる。更に、1液型でありながら、ポリオール(A)を用いることにより、従来の2液型の塗料と同様に優れた耐水性及び耐溶剤性を有し、且つ十分な耐湿熱性等を備える皮膜を形成することができるイソシアネート末端プレポリマーを含有する水分散体を効率よく製造することができる。
また、ポリオール(A)が、脱水ヒマシ油及び/又は脱水ヒマシ油脂肪酸と、4官能以上のポリオールとの反応生成物であり、該脱水ヒマシ油及び/又は該脱水ヒマシ油脂肪酸と、該4官能以上のポリオールとの合計を100質量%とした場合に、該4官能以上のポリオールは5〜40質量%であるため、及びポリイソシアネート化合物(B)が、2個のシクロヘキシル基を有するジイソシアネート化合物であるため、これらを反応させ易く、プレポリマーを容易に生成させることができる。
更に、ポリオール(A)のヨウ素価が80〜130である場合は、木材用塗料として用いたときに、十分な硬度等を有する被膜を形成することができる。
また、反応液と水とを混合するのと同時に、又は混合後に、混合液にカルボジイミドが添加され、混合液に含有される固形分を100質量部とした場合に、カルボジイミドが0.3〜3.0質量部である場合は、カルボジイミドにより架橋が促進され、より容易に皮膜を形成することができる。
According to the method for producing a polyurethane-based water dispersion for wood paints of the present invention, an aqueous dispersion containing an isocyanate-terminated prepolymer capable of forming a film having sufficient hardness by easily curing the coating film by oxidative polymerization. The body can be manufactured efficiently. In addition, when conventional polyols derived from vegetable oils such as linseed oil and soybean oil are used, discoloration tends to occur. However, in the production method of the present invention, discoloration is sufficiently achieved by using a polyol (A) having a specific structure. Can be suppressed. Furthermore, by using the polyol (A) while having a one-component type, a film having excellent water resistance and solvent resistance as well as sufficient heat-and-moisture resistance, etc., as in the case of the conventional two-component paint. An aqueous dispersion containing an isocyanate-terminated prepolymer that can be formed can be efficiently produced.
Also, the polyol (A) is a reaction product of dehydrated castor oil and / or dehydrated castor oil fatty acid and a tetrafunctional or higher functional polyol, and the dehydrated castor oil and / or dehydrated castor oil fatty acid and the tetrafunctional when the total 100 mass% of the above polyols, for the tetra- or higher-functional polyol is from 5 to 40 wt%, and a polyisocyanate compound (B), in a diisocyanate compound having two cyclohexyl there therefore, easier to react them, the prepolymer can be readily produced.
Furthermore, when the polyol (A) has an iodine value of 80 to 130, a film having sufficient hardness and the like can be formed when used as a paint for wood.
Moreover, carbodiimide is 0.3-3, when carbodiimide is added to a liquid mixture simultaneously with mixing a reaction liquid and water or after mixing, and the solid content contained in a liquid mixture is 100 mass parts. In the case of 0.0 part by mass, crosslinking is promoted by carbodiimide, and a film can be formed more easily.
以下、本発明を詳しく説明する。
本発明の木材塗料用ポリウレタン系水分散体の製造方法は、脱水ヒマシ油及び/又は脱水ヒマシ油脂肪酸と、4官能以上のポリオールとの反応生成物であり、脱水ヒマシ油及び/又は脱水ヒマシ油脂肪酸と、4官能以上のポリオールとの合計を100質量%とした場合に、4官能以上のポリオールは5〜40質量%である脱水ヒマシ油脂肪酸骨格を有するポリオール(A)と、少なくとも2個のヒドロキシル基と、少なくとも1個のカルボキシル基とを有する親水性化合物と、2又は3個のシクロヘキシル基を有するジイソシアネート化合物(B)と、を反応させてイソシアネート末端プレポリマーを生成させ、その後、イソシアネート末端プレポリマーが溶解した反応液と水とを混合することを特徴とする。
The present invention will be described in detail below.
The method for producing a polyurethane-based aqueous dispersion for wood paint according to the present invention is a reaction product of dehydrated castor oil and / or dehydrated castor oil fatty acid and a tetra- or higher functional polyol, and dehydrated castor oil and / or dehydrated castor oil. When the total of the fatty acid and the tetrafunctional or higher functional polyol is 100% by mass, the tetrafunctional or higher functional polyol is 5 to 40% by mass of the polyol (A) having a dehydrated castor oil fatty acid skeleton, and at least two A hydrophilic compound having a hydroxyl group, at least one carboxyl group, and a diisocyanate compound (B) having 2 or 3 cyclohexyl groups are reacted to form an isocyanate-terminated prepolymer, and then an isocyanate-terminated prepolymer. The reaction solution in which the prepolymer is dissolved is mixed with water.
[1]脱水ヒマシ油脂肪酸骨格を有するポリオール(A)
上記「脱水ヒマシ油脂肪酸骨格を有するポリオール(A)」は、脱水ヒマシ油、脱水ヒマシ油脂肪酸等と4官能以上のポリオールとをエステル交換反応、又はエステル化反応させて生成させることができる。具体的な方法は特に限定されないが、例えば、攪拌装置、冷却器等を備える反応容器に、脱水ヒマシ油及び/又は脱水ヒマシ油脂肪酸、4官能以上のポリオール及び触媒を投入し、加熱しながら攪拌し、反応させて生成させることができる。反応雰囲気は窒素ガス雰囲気、及びアルゴンガス雰囲気等の不活性ガス雰囲気などの不活性雰囲気であることが好ましい。反応温度及び反応時間は特に限定されないが、反応温度は190〜250℃、特に200〜240℃とすることが好ましく、反応時間は2〜10時間、特に2.5〜8時間とすることが好ましい。
[1] Polyol (A) having a dehydrated castor oil fatty acid skeleton
The “polyol (A) having a dehydrated castor oil fatty acid skeleton” can be produced by transesterification or esterification of dehydrated castor oil, dehydrated castor oil fatty acid and the like with a tetrafunctional or higher functional polyol. Although the specific method is not particularly limited, for example, dehydrated castor oil and / or dehydrated castor oil fatty acid, a tetrafunctional or higher functional polyol and a catalyst are charged into a reaction vessel equipped with a stirrer, a cooler and the like, and stirred while heating. And can be made to react. The reaction atmosphere is preferably an inert atmosphere such as a nitrogen gas atmosphere or an inert gas atmosphere such as an argon gas atmosphere. The reaction temperature and reaction time are not particularly limited, but the reaction temperature is preferably 190 to 250 ° C, particularly 200 to 240 ° C, and the reaction time is preferably 2 to 10 hours, particularly 2.5 to 8 hours. .
脱水ヒマシ油は、ヒマシ油を構成するリシノール酸が有するヒドロキシル基を、触媒により隣接する炭素に結合する水素とともに引き抜くことにより脱水して二重結合に変化させた化合物である。リシノール酸は9位にヒドロキシル基、12位に二重結合を有しているため、脱水反応により生成する二重結合は他の二重結合と共役系になることもあるし、共役系にならないこともあり、脱水ヒマシ油には共役系と非共役系とが混在している。また、脱水ヒマシ油脂肪酸は、脱水ヒマシ油を加水分解しグリセリンを除去した化合物である。 Dehydrated castor oil is a compound in which a hydroxyl group of ricinoleic acid that constitutes castor oil is dehydrated and converted into a double bond by extracting together with hydrogen bonded to adjacent carbon by a catalyst. Since ricinoleic acid has a hydroxyl group at the 9-position and a double bond at the 12-position, the double bond produced by the dehydration reaction may be conjugated with other double bonds or not conjugated. In some cases, dehydrated castor oil contains a mixture of conjugated and non-conjugated systems. Dehydrated castor oil fatty acid is a compound obtained by hydrolyzing dehydrated castor oil and removing glycerin.
4官能以上のポリオールとしては、ペンタエリスリトール、ジトリメチロールプロパン、ジグリセリン、ジペンタエリスリトール、ソルビトール、シュルクゾール等が挙げられる。これらのうちでは、4官能のポリオールが好ましく、ペンタエリスリトールが多用される。4官能以上のポリオールは1種のみ用いてもよいし、2種以上を併用してもよい。また、官能基数の異なるポリオールを併用することもできる。 Examples of the tetrafunctional or higher functional polyol include pentaerythritol, ditrimethylolpropane, diglycerin, dipentaerythritol, sorbitol, and shulksol. Of these, tetrafunctional polyols are preferable, and pentaerythritol is frequently used. Only one tetrafunctional or higher functional polyol may be used, or two or more polyols may be used in combination. Also, polyols having different numbers of functional groups can be used in combination.
脱水ヒマシ油及び/又は脱水ヒマシ油脂肪酸と4官能以上のポリオールとの配合割合は、脱水ヒマシ油及び/又は脱水ヒマシ油脂肪酸と、4官能以上のポリオールとの合計を100質量%とした場合に、4官能以上のポリオールは5〜40質量%である。4官能以上のポリオールは、4官能以上のポリオール(M1モルとする。)と脱水ヒマシ油及び/又は脱水ヒマシ油脂肪酸(M2モルとする。併用する場合は合計量とする。)とのモル比(M1/M2)が0.40〜1.00、特に0.45〜0.90となる配合量とすることが好ましい。このモル比(M1/M2)が0.40〜1.00であれば、2官能を少し越えるポリオール(A)を容易に合成することができる。また、脱水ヒマシ油及び/又は脱水ヒマシ油脂肪酸と4官能以上のポリオールとのエステル交換反応/エステル化反応においては、他のポリオールとしてヒマシ油等を併用することができる。この他のポリオールの配合量は、ポリオールの全量を100質量%とした場合に、50質量%以下であることが好ましい。50質量%を越えると、脱水ヒマシ油及び/又は脱水ヒマシ油脂肪酸による酸化重合架橋の効果が低くなるため好ましくない。 The blending ratio of the dehydrated castor oil and / or dehydrated castor oil fatty acid and the tetrafunctional or higher polyol is when the total of the dehydrated castor oil and / or dehydrated castor oil fatty acid and the tetrafunctional or higher polyol is 100% by mass. The tetrafunctional or higher functional polyol is 5 to 40% by mass. The tetrafunctional or higher polyol is a tetrafunctional or higher polyol (M 1 mol) and dehydrated castor oil and / or dehydrated castor oil fatty acid (M 2 mol. When used in combination, the total amount). It is preferable to set the blending amount so that the molar ratio (M 1 / M 2 ) is 0.40 to 1.00, particularly 0.45 to 0.90. If this molar ratio (M 1 / M 2 ) is 0.40 to 1.00, a polyol (A) slightly exceeding bifunctionality can be easily synthesized. In the transesterification / esterification reaction of dehydrated castor oil and / or dehydrated castor oil fatty acid with a tetra- or higher functional polyol, castor oil or the like can be used in combination as another polyol. The blending amount of the other polyol is preferably 50% by mass or less when the total amount of the polyol is 100% by mass. If it exceeds 50% by mass, the effect of oxidative polymerization crosslinking by dehydrated castor oil and / or dehydrated castor oil fatty acid is undesirably reduced.
触媒としては、エステル交換反応/エステル化反応に一般に用いられる触媒を使用することができる。この触媒としては、ナトリウムメトキシド、ナトリウムエトキシド、カリウムメトキシド、カリウムエトキシド、カリウム−t−ブトキシド、テトラエトキシチタン、テトラブトキシチタン等のアルコキシド触媒、各種の酸化物触媒、各種の水酸化物触媒、及び各種のジアルキルスズ化合物触媒などが挙げられる。 As a catalyst, the catalyst generally used for transesterification / esterification reaction can be used. Examples of the catalyst include sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, potassium tert-butoxide, tetraethoxy titanium, tetrabutoxy titanium and other alkoxide catalysts, various oxide catalysts, various hydroxides. Examples thereof include catalysts and various dialkyltin compound catalysts.
ポリオール(A)のヨウ素価は特に限定されないが、80〜130、特に85〜125であることが好ましい。ヨウ素価が80〜130であれば、プレポリマーの酸化重合が十分になされ、優れた耐水性及び耐溶剤性を有し、且つ十分な耐湿熱性等を備える皮膜を形成することができる。また、酸価は、通常、1.5mgKOH/g以下、特に1.2mgKOH/g以下である。更に、水酸基価は、100〜200mgKOH/g、特に100〜170mgKOH/gである。また、25℃で測定した粘度は200〜600mPa・s、特に250〜550mPa・sである。この粘度が高すぎる場合は、プレポリマーの生成時、有機溶媒の質量割合を増加させることにより調整することができる。 Although the iodine value of a polyol (A) is not specifically limited, It is preferable that it is 80-130, especially 85-125. When the iodine value is 80 to 130, the prepolymer is sufficiently oxidatively polymerized, and it is possible to form a film having excellent water resistance and solvent resistance, and sufficient moisture and heat resistance. The acid value is usually 1.5 mgKOH / g or less, particularly 1.2 mgKOH / g or less. Furthermore, the hydroxyl value is 100 to 200 mgKOH / g, particularly 100 to 170 mgKOH / g. The viscosity measured at 25 ° C. is 200 to 600 mPa · s, particularly 250 to 550 mPa · s. When this viscosity is too high, it can be adjusted by increasing the mass ratio of the organic solvent during the production of the prepolymer.
[2]イソシアネート末端プレポリマーの生成
上記「親水性化合物」は、少なくとも2個のヒドロキシル基と、少なくとも1個のカルボキシル基とを有する。この親水性化合物は、イソシアネート末端プレポリマーの生成時、ポリオール(A)とともにポリイソシアネート化合物と反応し、カルボキシル基を有するプレポリマーを生成させることができる。この親水性化合物としては、ジメチロールプロピオン酸、ジメチロールブタン酸、ジメチロールペンタン酸、ジメチロールノナン酸等のジメチロールアルカン酸が挙げられる。親水性化合物は1種のみ用いてもよく、2種以上を併用してもよい。
[2] Formation of Isocyanate-Terminated Prepolymer The “hydrophilic compound” has at least two hydroxyl groups and at least one carboxyl group. This hydrophilic compound can react with the polyisocyanate compound together with the polyol (A) during the production of the isocyanate-terminated prepolymer to produce a prepolymer having a carboxyl group. Examples of the hydrophilic compound include dimethylol alkanoic acids such as dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolpentanoic acid, and dimethylolnonanoic acid. Only one hydrophilic compound may be used, or two or more hydrophilic compounds may be used in combination.
上記「ジイソシアネート化合物(B)」としては、皮膜の変色を抑えるという観点で、2又は3個のシクロヘキシル基を有するジイソシアネート化合物(B)が用いられる。このジイソシアネート化合物(B)としては、4,4’−ジフェニルメタンジイソシアネート(MDI)の水添物、トリジンジイソシアネートの水添物、トリフェニルメタンジイソシアネートの水添物、トリフェニルメタントリイソシアネートの水添物等が挙げられる。これらのうちでは、2個のシクロヘキシル基を有するジイソシアネート化合物、例えば、MDIの水添物が好ましい。また、このように2又は3個のシクロヘキシル基を有することで、シクロヘキシル基を1個有するジイソシアネート化合物、例えば、イソホロンジイソシアネートを用いたときと比べて、皮膜の耐溶剤性等を向上させることができる。更に、水添物ではない、例えば、MDIを用いたときは、反応性が高すぎ、粒子状のプレポリマーが水に分散する前に、反応が進みすぎて樹脂状になってしまい、水分散体とすることができないことがある。ジイソシアネート化合物(B)は1種のみ用いてもよいし、2種以上を併用してもよい。 Above-mentioned "di isocyanate compound (B)" is in terms of suppressing the discoloration of the coating, di- isocyanate compound having two or three cyclohexyl (B) is used. As the di-isocyanate compound (B), 4,4' hydrogenation product of diphenylmethane diisocyanate (MDI), tolidine diisocyanate hydrogenated product, triphenylmethane diisocyanate hydrogenation product, triphenylmethane triisocyanate hydrogenates Etc. Of these, diisocyanate compounds having two cyclohexyl groups, such as hydrogenated MDI, are preferred. Also, this way, by having two or three cyclohexyl group, di-isocyanate compound to one chromatic cyclohexyl, for example, than when using isophorone diisocyanate, to improve the solvent resistance of the film it can. Furthermore, when it is not a hydrogenated product, for example, MDI is used, the reactivity is too high, and before the particulate prepolymer is dispersed in water, the reaction proceeds too much to become a resinous state, resulting in water dispersion. You may not be able to make a body. Di isocyanate compound (B) may be used singly or in combination of two or more kinds.
更に、プレポリマーを生成させる際、ポリオールとして、ポリオール(A)と他のポリオール(但し、上記「親水性化合物は除く。)とを併用することもできる。この他のポリオールは特に限定されないが、例えば、(1)エチレングリコール、プロピレングリコール、1,4−ブタンジオール、3−メチルペンタンジオール、1,6ヘキサンジオール、ジエチレングリコール、ネオペンチルグリコール、グリセリン、ビスフェノールA、トリメチロールプロパン、ペンタエリスリトール等の短鎖ポリオール、及びダイマー酸ジオール等の長鎖ポリオール、(2)上記(1)の短鎖ポリオールのエチレンオキサイド及び/又はプロピレンオキサイド付加物、ポリテトラメチレングリコール等のポリエーテルポリオール、(3)アジピン酸、マロン酸、セバシン酸、アゼライン酸、フタル酸、テレフタル酸、イソフタル酸、無水フタル酸、トリメリット酸等の多塩基酸と、上記(1)の短鎖ポリオールとを公知の方法で反応させてなるポリエステルポリオール、及びカプロラクトン等の開環重合により得られるラクトン系ポリエステルポリオールなどのポリエステルポリオール、(4)上記(1)の短鎖ポリオールと、ジエチルカーボネート、ジメチルカーボネート等との脱アルコール反応によって合成されるポリカーボネートポリオール、(5)ポリブタジエンポリオール、ポリイソプレンポリオール等のポリオレフィンポリオール、などが挙げられる。これらの他のポリオールは1種のみ用いてもよいし、2種以上を併用してもよい。 Further, when the prepolymer is produced, the polyol (A) and other polyol (however, excluding the above-mentioned “hydrophilic compound”) can be used in combination as the polyol. The other polyol is not particularly limited, For example, (1) short of ethylene glycol, propylene glycol, 1,4-butanediol, 3-methylpentanediol, 1,6 hexanediol, diethylene glycol, neopentyl glycol, glycerin, bisphenol A, trimethylolpropane, pentaerythritol, etc. Long chain polyols such as chain polyols and dimer acid diols, (2) ethylene oxide and / or propylene oxide adducts of the short chain polyols of (1) above, polyether polyols such as polytetramethylene glycol, (3) adipic acid , Ma It is obtained by reacting a polybasic acid such as acid, sebacic acid, azelaic acid, phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, trimellitic acid and the short-chain polyol of (1) by a known method. Polyester polyols such as polyester polyols and lactone polyester polyols obtained by ring-opening polymerization such as caprolactone, and (4) synthesized by dealcoholization reaction of the short-chain polyol of (1) above with diethyl carbonate, dimethyl carbonate, etc. Polycarbonate polyol, (5) Polyolefin polyol such as polybutadiene polyol, polyisoprene polyol, etc. These other polyols may be used alone or in combination of two or more.
プレポリマー生成時の、ポリオール(A)(他のポリオールを併用する場合はポリオールの合計量)、親水性化合物及びポリイソシアネート化合物(B)の各々の配合割合は特に限定されないが、親水性化合物は、親水性化合物(M3mmolとする。)と、ポリオール(A)又はポリオールの合計量(M4gとする。)との比(M3/M4)が、0.25〜0.60、特に0.30〜0.50となる配合量であることが好ましい。この比(M3/M4)が0.25〜0.60であれば、プレポリマーに所要量のカルボキシル基を導入することができる。また、ポリオール(A)又はポリオールの合計量と、ポリイソシアネート化合物(B)との量比を表すイソシアネートインデックスは、1.10〜2.00、特に1.20〜1.70であることが好ましい。 The blending ratios of the polyol (A) (total amount of polyol when other polyols are used in combination), the hydrophilic compound and the polyisocyanate compound (B) at the time of prepolymer generation are not particularly limited, The ratio (M 3 / M 4 ) of the hydrophilic compound (M 3 mmol) and the total amount of polyol (A) or polyol (M 4 g) is 0.25 to 0.60. In particular, the blending amount is preferably 0.30 to 0.50. When this ratio (M 3 / M 4 ) is 0.25 to 0.60, a required amount of carboxyl groups can be introduced into the prepolymer. Moreover, it is preferable that the isocyanate index showing the amount ratio of a polyol (A) or the total amount of a polyol and a polyisocyanate compound (B) is 1.10-2.00, especially 1.20-1.70. .
プレポリマーの生成に用いる触媒としては、ジオクチルチンジラウレート、ジブチルチンジラウレート、ジブチルチンジアセテート、ジブチルチンジマレエート、オクテン酸鉛等の金属触媒、及びトリエチルアミン、トリエチレンジアミン、ジメチルアミノエタノール等のアミン触媒などが挙げられる。触媒は1種のみ用いてもよいし、2種以上を併用してもよく、金属触媒とアミン触媒とを併用することもできる。 Catalysts used to produce the prepolymer include metal catalysts such as dioctyltin dilaurate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dimaleate, lead octenoate, and amine catalysts such as triethylamine, triethylenediamine, and dimethylaminoethanol. Can be mentioned. Only one type of catalyst may be used, two or more types may be used in combination, and a metal catalyst and an amine catalyst may be used in combination.
プレポリマーは、有機溶媒を用いることなく生成させることもでき、有機溶媒を媒体として生成させることもできる。有機溶媒を用いる場合、この有機溶媒は、ポリオール(A)、親水性化合物、ポリイソシアネート化合物(B)等を室温(例えば、25〜35℃)以上の温度で溶解させることができ、且つ生成するプレポリマーを室温(例えば、25〜35℃)以上の温度で溶解させることができればよく、特に限定されない。有機溶媒としては、ウレタン化反応に不活性で水との親和性が高い溶媒が好ましく、メチルエチルケトン、アセトン、メチルイソブチルケトン等のケトン類、及びN−メチルピロリドン、ジメチルアセトアミド、ジメチルホルムアミド、テトラヒドロフラン等が挙げられ、中でも十分な溶解力を有し、且つ低沸点であるケトン類、特にメチルエチルケトンが好ましい。また、N−メチルピロリドン等の沸点が水よりも高い溶媒は、通常の有機溶媒を留去させるときの条件では留去させることができず、木材用塗料として基材に塗布した後も残留するが、プレポリマー粒子等の結合剤及び造膜助剤としても機能するため、併用することが好ましい。有機溶媒の使用量は、プレポリマーを100質量部とした場合に、10〜100質量部の範囲とすることができる。 The prepolymer can be produced without using an organic solvent, or can be produced using an organic solvent as a medium. When an organic solvent is used, this organic solvent can dissolve and generate a polyol (A), a hydrophilic compound, a polyisocyanate compound (B) and the like at a temperature of room temperature (for example, 25 to 35 ° C.) or higher. There is no particular limitation as long as the prepolymer can be dissolved at a temperature of room temperature (for example, 25 to 35 ° C.) or higher. The organic solvent is preferably a solvent that is inert to the urethanization reaction and has a high affinity with water, and ketones such as methyl ethyl ketone, acetone, and methyl isobutyl ketone, and N-methylpyrrolidone, dimethylacetamide, dimethylformamide, tetrahydrofuran, and the like. Among them, ketones having sufficient dissolving power and low boiling point, particularly methyl ethyl ketone is preferable. In addition, a solvent having a boiling point higher than that of water, such as N-methylpyrrolidone, cannot be distilled off under the conditions for distilling off a normal organic solvent, and remains after being applied to a substrate as a wood paint. However, since it also functions as a binder such as prepolymer particles and a film-forming aid, it is preferable to use them in combination. The usage-amount of an organic solvent can be made into the range of 10-100 mass parts, when a prepolymer is 100 mass parts.
また、プレポリマーの末端イソシアネート基の含有量は特に限定されないが、プレポリマーを100質量%とした場合に、1.5〜5.5質量%、特に2.0〜4.5質量%とすることができる。この末端イソシアネート基の含有量は、研磨性、硬度、光沢、耐薬品性等の所要物性を勘案し、設定することが好ましい。 Further, the content of the terminal isocyanate group of the prepolymer is not particularly limited, but when the prepolymer is 100% by mass, the content is 1.5 to 5.5% by mass, particularly 2.0 to 4.5% by mass. be able to. The content of the terminal isocyanate group is preferably set in consideration of required physical properties such as polishing properties, hardness, gloss, and chemical resistance.
[3]水分散体及び水分散体組成物
上記のようにして調製した、プレポリマーが溶解した反応液と水とを混合することにより水分散体とすることができる。また、上記の沸点が水よりも高い有機溶媒は、通常、水分散体に残留する。
上記「水」は特に限定されないが、蒸留水、イオン交換水、純水等の純度の高い水を用いることが好ましい。反応液と水とを混合する方法も特に限定されないが、大量の水と一時に混合するよりも、反応液に液滴として水を滴下する方法が好ましい。この滴下する方法であれば、水にプレポリマーをより均一に分散させることができ、より均質な水分散体とすることができる。
[3] Aqueous dispersion and aqueous dispersion composition A water dispersion can be obtained by mixing the reaction liquid prepared as described above and having the prepolymer dissolved therein and water. Moreover, the organic solvent whose boiling point is higher than that of water usually remains in the aqueous dispersion.
The “water” is not particularly limited, but it is preferable to use high-purity water such as distilled water, ion-exchanged water, or pure water. A method of mixing the reaction solution and water is not particularly limited, but a method of adding water as droplets to the reaction solution is preferable to mixing with a large amount of water at a time. If it is the method of dripping, a prepolymer can be more uniformly disperse | distributed to water and it can be set as a more homogeneous water dispersion.
また、反応液と水とを混合する前に、反応液に、プレポリマーに導入されたカルボキシル基を中和するための中和剤を添加することが好ましい。中和剤としては、塗膜硬化後、被膜内に残留しないため、アミン類が好ましく、第3級アミンがより好ましい。この第3級アミンは特に限定されないが、例えば、トリメチルアミン、トリエチルアミン、トリ−n−プロピルアミン、トリ−n−ブチルアミン等の脂肪族第3級アミン、及びN,N−ジメチルアニリン、N,N−ジエチルアニリン等の芳香族第3級アミンなどを用いることができる。第3級アミンは1種のみ用いてもよいし、2種以上を併用してもよい。この中和により、プレポリマーの親水性が向上し、より均質な水分散体とすることができる。 Moreover, it is preferable to add the neutralizing agent for neutralizing the carboxyl group introduce | transduced into the prepolymer to a reaction liquid before mixing a reaction liquid and water. As the neutralizing agent, amines are preferable and tertiary amines are more preferable because they do not remain in the coating after the coating is cured. The tertiary amine is not particularly limited, and examples thereof include aliphatic tertiary amines such as trimethylamine, triethylamine, tri-n-propylamine and tri-n-butylamine, and N, N-dimethylaniline, N, N- Aromatic tertiary amines such as diethylaniline can be used. Only one tertiary amine may be used, or two or more tertiary amines may be used in combination. By this neutralization, the hydrophilicity of the prepolymer is improved and a more homogeneous aqueous dispersion can be obtained.
中和剤として用いる第3級アミンは、プレポリマー中に導入したカルボキシル基と等モル量であることが好ましく、これによりプレポリマーの親水性がより向上し、プレポリマー粒子がより均一に分散した水分散体とすることができる。 The tertiary amine used as the neutralizing agent is preferably equimolar with the carboxyl group introduced into the prepolymer, whereby the hydrophilicity of the prepolymer is further improved and the prepolymer particles are more uniformly dispersed. It can be an aqueous dispersion.
更に、反応液と水とを混合するのと同時に、又は混合した後に、混合液に鎖延長剤を添加することが好ましい。また、プレポリマーの生成に有機溶媒を用いた場合、鎖延長剤は有機溶媒の留去の前に添加することがより好ましい。鎖延長剤としては、イソシアネート基と反応する活性水素を2個以上有する化合物を用いることができ、エチレンジアミン、プロピレンジアミン、イソホロンジアミン、ピペラジン、フェニレンジアミン等のジアミン、及び3官能以上のポリアミンなどが挙げられる。この鎖延長により、プレポリマー分子が結合されて鎖延長されるとともに、鎖延長された分子の末端がアミノ基又はヒドロキシル基となる。これにより、分子末端がイソシアネート基のままである場合、水と反応してしまうプレポリマーの反応を抑え、水分散体を安定化することができる。 Furthermore, it is preferable to add a chain extender to the mixed solution at the same time as or after mixing the reaction solution and water. Moreover, when an organic solvent is used for the production | generation of a prepolymer, it is more preferable to add a chain extender before distillation of an organic solvent. As the chain extender, a compound having two or more active hydrogens that react with an isocyanate group can be used. Examples thereof include diamines such as ethylenediamine, propylenediamine, isophoronediamine, piperazine, and phenylenediamine, and trifunctional or more polyamines. It is done. By this chain extension, the prepolymer molecule is bonded and chain extended, and the terminal of the chain extended molecule becomes an amino group or a hydroxyl group. Thereby, when the molecular terminal remains an isocyanate group, the reaction of the prepolymer that reacts with water can be suppressed, and the aqueous dispersion can be stabilized.
鎖延長剤として用いられるジアミンの使用量は、化学分析により測定されるプレポリマーのイソシアネート基含有量との当量比に基づいて設定することができる。ジアミンは、ジアミンのアミノ基当量(M5とする。)と、プレポリマーのイソシアネート基当量(M6とする)との比(M5/M6)が0.5〜1.0となる当量比で使用することが好ましい。鎖延長反応の反応条件は特に限定されないが、反応温度は30〜60℃、反応時間は30分〜4時間の条件で反応させることが好ましい。 The usage-amount of the diamine used as a chain extender can be set based on the equivalent ratio with the isocyanate group content of the prepolymer measured by chemical analysis. The diamine is equivalent in which the ratio (M 5 / M 6 ) of the amino group equivalent (referred to as M 5 ) of the diamine and the isocyanate group equivalent (referred to as M 6 ) of the prepolymer is 0.5 to 1.0. The ratio is preferably used. The reaction conditions for the chain extension reaction are not particularly limited, but the reaction temperature is preferably 30 to 60 ° C. and the reaction time is preferably 30 minutes to 4 hours.
鎖延長されたプレポリマーにおける脱水ヒマシ油及び/又は脱水ヒマシ油脂肪酸に由来する成分の、プレポリマーの全量に対する質量割合は特に限定されないが、プレポリマーの全量を100質量%とした場合に、脱水ヒマシ油等に由来する成分は20〜60質量%であることが好ましい。この成分の質量割合が20〜60質量%であれば、水分散体を含有する木材用塗料を基材に塗布した後、プレポリマーの酸化重合が容易になされ、十分な硬度等を有する被膜を形成することができる。 The mass ratio of the component derived from dehydrated castor oil and / or dehydrated castor oil fatty acid in the chain-extended prepolymer to the total amount of the prepolymer is not particularly limited, but dehydration is performed when the total amount of the prepolymer is 100% by mass. The component derived from castor oil or the like is preferably 20 to 60% by mass. If the mass ratio of this component is 20 to 60% by mass, a coating having sufficient hardness and the like can be obtained after the prepolymer is easily oxidized and polymerized after the wood coating containing the aqueous dispersion is applied to the substrate. Can be formed.
また、プレポリマーが中和され、鎖延長された後の混合液に、カルボジイミド化合物を添加することが好ましい。このカルボジイミド化合物は、分子中にカルボジイミド基を有する化合物であれば特に限定されないが、水溶性のカルボジイミド化合物であることがより好ましい。従って、より好ましいカルボジイミド化合物としては、ジイソシアネート化合物を脱二酸化炭素縮合反応により重合させた後、末端イソシアネート基をヒドロキシル基等の反応性を有する親水性基を備える有機化合物でキャップした化合物を挙げることができる。具体的には、日清紡績社製のカルボジライトシリーズ等の化合物が挙げられる。この製品は水溶性タイプとなっており固形分含有量は約40質量%である。カルボジイミド化合物の添加量は特に限定されないが、混合液(水分散体)に含有される固形分を100質量部とした場合に、0.3〜3.0質量部であることが好ましい。 Moreover, it is preferable to add a carbodiimide compound to the mixed solution after the prepolymer is neutralized and chain-extended. Although this carbodiimide compound will not be specifically limited if it is a compound which has a carbodiimide group in a molecule | numerator, It is more preferable that it is a water-soluble carbodiimide compound. Therefore, a more preferable carbodiimide compound includes a compound obtained by polymerizing a diisocyanate compound by a carbon dioxide condensation reaction and then capping the terminal isocyanate group with an organic compound having a hydrophilic group having reactivity such as a hydroxyl group. it can. Specific examples include compounds such as the Carbodilite series manufactured by Nisshinbo Industries. This product is a water-soluble type and has a solid content of about 40% by mass. The addition amount of the carbodiimide compound is not particularly limited, but is preferably 0.3 to 3.0 parts by mass when the solid content contained in the mixed liquid (aqueous dispersion) is 100 parts by mass.
上記「木材塗料用ポリウレタン系水分散体」には、必要に応じて各種の添加剤を配合して水分散体組成物とすることができる。この添加剤としては、例えば、(1)フタル酸ジエチル、フタル酸ジブチル、アジピン酸ジブチル等の可塑剤、(2)ロジン、テルペン樹脂、クマロン樹脂等の粘着付与樹脂、(3)炭酸カルシウム、シリカ、クレー、タルク、カーボンブラック等の無機充填剤、(4)酸化防止剤、紫外線吸収剤、紫外線防止剤等の安定剤、などの他、酸化重合促進剤、難燃剤、防黴剤、防錆剤等の各種の添加剤が挙げられる。 The above-mentioned “polyurethane aqueous dispersion for wood coatings” can be blended with various additives as necessary to obtain an aqueous dispersion composition. Examples of the additive include (1) plasticizers such as diethyl phthalate, dibutyl phthalate, and dibutyl adipate, (2) tackifying resins such as rosin, terpene resin, and coumarone resin, and (3) calcium carbonate and silica. In addition to inorganic fillers such as clay, talc and carbon black, (4) stabilizers such as antioxidants, UV absorbers and UV inhibitors, oxidation polymerization accelerators, flame retardants, antifungal agents, rust prevention Various additives such as an agent may be mentioned.
水分散体の具体的な製造方法及び製造条件は特に限定されないが、例えば、攪拌装置、冷却器等を備える反応容器に、有機溶媒、ポリオール(A)、親水性化合物、及び触媒を投入し、溶解後、ポリイソシアネート化合物(B)を仕込み、これらを加熱しながら攪拌し、反応させてプレポリマーを生成させ、次いで、反応液と水とを混合することにより製造することができる。また、有機溶媒を用いた場合、この有機溶媒を留去する方法は特に限定されず、温度は有機溶媒の沸点等により設定することが好ましい。また、減圧下に留去してもよく、常圧下に留去してもよいが、減圧下に留去することが好ましい。減圧下に留去すれば設定温度を低下させることもでき、プレポリマーに必要のない熱を加えることなく、且つ短時間で効率よく有機溶媒を留去することができる。 The specific production method and production conditions of the aqueous dispersion are not particularly limited. For example, an organic solvent, a polyol (A), a hydrophilic compound, and a catalyst are charged into a reaction vessel equipped with a stirrer, a cooler, and the like. After the dissolution, the polyisocyanate compound (B) is charged, and these are stirred while being heated and reacted to form a prepolymer, and then the reaction solution and water are mixed. When an organic solvent is used, the method for distilling off the organic solvent is not particularly limited, and the temperature is preferably set according to the boiling point of the organic solvent. Moreover, although it may distill off under reduced pressure and it may distill off under normal pressure, it is preferable to distill off under reduced pressure. If the solvent is distilled off under reduced pressure, the set temperature can be lowered, and the organic solvent can be efficiently distilled off in a short time without applying unnecessary heat to the prepolymer.
製造時の雰囲気は不活性雰囲気でも大気雰囲気でもよいが、窒素ガス雰囲気、及びアルゴンガス雰囲気等の不活性ガス雰囲気などの不活性雰囲気で反応させることが好ましい。また、プレポリマー生成時の反応温度及び反応時間は特に限定されないが、反応温度は60〜100℃、特に70〜90℃とすることが好ましく、反応時間は4〜10時間、特に5.5〜8.5時間とすることが好ましい。 The atmosphere during the production may be an inert atmosphere or an air atmosphere, but it is preferable to react in an inert atmosphere such as a nitrogen gas atmosphere or an inert gas atmosphere such as an argon gas atmosphere. Further, the reaction temperature and reaction time at the time of producing the prepolymer are not particularly limited, but the reaction temperature is preferably 60 to 100 ° C., particularly preferably 70 to 90 ° C., and the reaction time is 4 to 10 hours, particularly 5.5 to It is preferably 8.5 hours.
鎖延長されたプレポリマーの生成に用いられる脱水ヒマシ油等の原料の全量に対する脱水ヒマシ油及び/又は脱水ヒマシ油脂肪酸の質量割合は特に限定されないが、原料の全量を100質量%とした場合に、20〜60質量%、特に25〜55質量%であることが好ましい。脱水ヒマシ油等の質量割合が25〜60質量%であれば、水分散体を含有する木材用塗料を基材に塗布した後、プレポリマーの酸化重合が容易になされ、十分な硬度等を有する被膜を形成することができる。 The mass ratio of dehydrated castor oil and / or dehydrated castor oil fatty acid to the total amount of raw materials such as dehydrated castor oil used for the production of the chain-extended prepolymer is not particularly limited, but when the total amount of raw materials is 100% by mass It is preferable that it is 20-60 mass%, especially 25-55 mass%. If the mass ratio of dehydrated castor oil or the like is 25 to 60% by mass, the prepolymer is easily subjected to oxidative polymerization and has sufficient hardness and the like after applying the wood coating material containing the aqueous dispersion to the substrate. A film can be formed.
[5]木材用塗料
本発明の方法により製造された木材塗料用ポリウレタン系水分散体、及びこれに各種の添加剤を配合した水分散体組成物は、塗料として用いるための各種の添加剤等を配合して木材用塗料として使用することができる。
[5] Wood paints A polyurethane-based water dispersion for wood paints produced by the method of the present invention, and an aqueous dispersion composition in which various additives are blended with these, various additives for use as paints, etc. Can be used as a paint for wood.
水分散体は、25℃で測定した粘度が10〜200mPa・s、特に15〜170mPa・sであることが好ましい。この範囲の粘度であれば、木材用塗料の調製時、取り扱い易く、塗料の調製が容易である。また、水分散体の水素イオン指数(pH)は7.0〜9.0、特に7.0〜8.5であることが好ましい。この範囲のpHであれば、ポリウレタン系の水分散体として安定である。更に、水分散体における不揮発分は、水分散体を100質量%とした場合に、25〜60質量%、特に30〜55質量%であることが好ましい。この範囲の不揮発分であれば、低粘度であり、且つ塗料の樹脂分としても十分である。尚、水分散体組成物である場合も、その粘度、pH及び不揮発分は、それぞれ上記の水分散体と同様の範囲であることが好ましく、それにより、同様の作用効果が奏される。 The aqueous dispersion preferably has a viscosity measured at 25 ° C. of 10 to 200 mPa · s, particularly 15 to 170 mPa · s. When the viscosity is within this range, the wood paint is easy to handle and the paint is easy to prepare. Further, the hydrogen ion exponent (pH) of the aqueous dispersion is preferably 7.0 to 9.0, particularly preferably 7.0 to 8.5. If it is pH of this range, it will be stable as a polyurethane-type water dispersion. Further, the nonvolatile content in the aqueous dispersion is preferably 25 to 60% by mass, particularly 30 to 55% by mass, when the aqueous dispersion is 100% by mass. If the non-volatile content is within this range, the viscosity is low and the resin content of the paint is sufficient. Even in the case of an aqueous dispersion composition, the viscosity, pH, and non-volatile content are preferably in the same ranges as those of the aqueous dispersion described above, whereby the same effects can be achieved.
本発明の方法により製造された水分散体、及び水分散体組成物を主成分とする木材用塗料には、各種の添加剤が配合される。この添加剤としては、(1)(a)ポリプロピレングリコールを付加したポリメチルシロキサン、ポリフェニルメチルシロキサン等のシリコン系、(b)ポリビニルイソブチルエーテル等のエーテル系、(c)ポリイソブチルアクリレート等のアクリル系などのレベリング剤、(2)(a)プロピレングリコール、エステル化した植物油脂肪酸、セロソルブアセテート、ブチルセロソルブ、ブチルセロソルブアセテート等のセロソルブ系、(b)テキサノール、(c)ポリプロピレングリコールモノメチルエーテル等のグリコールエーテルなどの造膜助剤、(3)(a)ジメチルポリシロキサン等のシリコン系、ポリビニルイソブチルエーテル等のエーテル系、(b)ポリラウリルメタクリレート等のアクリル系などの消泡剤、(4)カーボンブラック、弁柄、炭酸カルシウム、紺青、亜鉛華、鉛丹等の無機顔料、及びアゾ系、アントラキノン系、フタロシアニン系等の有機顔料、などの各種の添加剤が挙げられる。これらの各種の添加剤は、それぞれ1種のみ用いてもよいし、2種以上を併用してもよい。これら添加剤の配合量の合計は、プレポリマーを100質量%とした場合に、5〜25質量%、特に10〜20質量%であることが好ましい。言い換えれば、プレポリマーは75〜95質量%、特に80〜90質量%であることが好ましい。 Various additives are blended in the water dispersion produced by the method of the present invention and the wood coating material mainly composed of the water dispersion composition. Examples of the additive include (1) (a) polymethylsiloxane to which polypropylene glycol is added, silicon-based polymethylsiloxane, polyphenylmethylsiloxane and the like, (b) ether-based such as polyvinyl isobutyl ether, and (c) acrylic such as polyisobutyl acrylate. (2) (a) propylene glycol, esterified vegetable oil fatty acid, cellosolve such as cellosolve acetate, butylcellosolve, butylcellosolve acetate, (b) texanol, (c) glycol ether such as polypropylene glycol monomethyl ether, etc. (3) (a) Silicon type such as dimethylpolysiloxane, ether type such as polyvinyl isobutyl ether, (b) acrylic type antifoaming agent such as polylauryl methacrylate, (4) carbon Black, red iron, calcium carbonate, Prussian blue, zinc white, inorganic pigments such as red lead, and azo, anthraquinone, organic phthalocyanine pigments such as, include various additives such. Each of these various additives may be used alone or in combination of two or more. The total amount of these additives is 5 to 25% by mass, particularly 10 to 20% by mass, when the prepolymer is 100% by mass. In other words, the prepolymer is preferably 75 to 95% by mass, particularly 80 to 90% by mass.
木材用塗料を基材に塗布する方法は特に限定されず、刷毛塗り、ローラーコート、スプレーコート、グラビアコート、リバースロールコート、エアナイフコート、バーコート、カーテンロールコート、ディップコート、ロッドコート、ドクターブレードコート等の各種の塗布方法により塗布することができる。また、木材用塗料を基材に塗布した後、塗膜を乾燥させ、硬化させて皮膜とする方法も特に限定されないが、大気雰囲気下、所定温度で所要時間静置し、水を揮散させ、鎖延長されたプレポリマーを酸化重合、及びカルボジイミド化合物を用いる場合は、この化合物による重合と併せて、重合させ硬化させることができる。温度及び時間は特に限定されないが、高温短時間であるよりも低温長時間であることが好ましく、温度は30〜60℃、特に35〜50℃とすることが好ましく、時間は、温度及びプレポリマーの反応性等にもよるが、48〜288時間、特に96〜240時間とすることが好ましい。 The method of applying the wood coating to the substrate is not particularly limited, and is applied by brush coating, roller coating, spray coating, gravure coating, reverse roll coating, air knife coating, bar coating, curtain roll coating, dip coating, rod coating, doctor blade. It can apply | coat by various application methods, such as a coat | court. Also, after applying the wood paint to the base material, the method of drying and curing the coating film to form a film is not particularly limited, but it is allowed to stand at a predetermined temperature for a required time in an air atmosphere to evaporate water, When a chain-extended prepolymer is used by oxidative polymerization and a carbodiimide compound, it can be polymerized and cured together with polymerization by this compound. The temperature and time are not particularly limited, but it is preferably a low temperature and a long time rather than a high temperature and a short time, the temperature is preferably 30 to 60 ° C., particularly 35 to 50 ° C., and the time is the temperature and the prepolymer. Although depending on the reactivity of the above, it is preferably 48 to 288 hours, particularly preferably 96 to 240 hours.
以下、実施例により本発明を具体的に説明する。
[1]脱水ヒマシ油の合成
攪拌機、温度計、窒素導入管、還流コンデンサ及び留出器を備える反応器に、ヒマシ油を1000g(0.93モル)、硫酸水素ナトリウムを4.0g及び水を4.0g投入し、徐々に減圧して5mmHgの圧力とし、240℃まで昇温させた。その温度を継続したままで3時間攪拌し、脱水反応をさせて反応水を系外に留出させた。反応終了後、100℃以下に冷却し、炭酸水素ナトリウム3.0gと水10gとを添加して触媒を中和し、再度減圧にして水分を取り除いた後、中和塩を除去した。得られた脱水ヒマシ油の酸価は3.0mgKOH/g、水酸基価は10mgKOH/g、25℃における粘度は150mPa・sであった。
Hereinafter, the present invention will be described specifically by way of examples.
[1] Synthesis of dehydrated castor oil In a reactor equipped with a stirrer, thermometer, nitrogen inlet tube, reflux condenser and distiller, 1000 g (0.93 mol) of castor oil, 4.0 g of sodium hydrogen sulfate and water were added. 4.0 g was added, the pressure was gradually reduced to 5 mmHg, and the temperature was raised to 240 ° C. While maintaining the temperature, the mixture was stirred for 3 hours to cause dehydration reaction, and the reaction water was distilled out of the system. After completion of the reaction, the reaction mixture was cooled to 100 ° C. or lower, and 3.0 g of sodium hydrogen carbonate and 10 g of water were added to neutralize the catalyst. The pressure was reduced again to remove moisture, and then the neutralized salt was removed. The obtained dehydrated castor oil had an acid value of 3.0 mgKOH / g, a hydroxyl value of 10 mgKOH / g, and a viscosity at 25 ° C. of 150 mPa · s.
[2]ポリオールの合成
合成例1
攪拌機、温度計、窒素導入管及び還流コンデンサを備える反応器に、脱水ヒマシ油を1500g(1.66モル)、ペンタエリスリトールを113g(0.83モル)、及びナトリウムメトキシドの28質量%メタノール溶液を2.4g投入し、窒素気流下、220℃で3時間攪拌し、反応させた。その後、100℃以下に冷却し、リン酸の75質量%水溶液を1.3g添加して、触媒を中和し、除去した。得られたヒマシ油系ポリオールのヨウ素価は123、酸価は1.0mgKOH/g、水酸基価は129mgKOH/g、25℃における粘度は500mPa・sであった(以下、「ポリオールA−1」という。また、表1、2でも「ポリオールA−1」と表記する。)。
[2] Synthesis of polyol Synthesis example 1
In a reactor equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser, 1500 g (1.66 mol) of dehydrated castor oil, 113 g (0.83 mol) of pentaerythritol, and a 28% by mass methanol solution of sodium methoxide 2.4 g was added, and the mixture was stirred at 220 ° C. for 3 hours under a nitrogen stream to react. Then, it cooled to 100 degrees C or less, added 1.3g of 75 mass% aqueous solution of phosphoric acid, and neutralized and removed the catalyst. The obtained castor oil-based polyol had an iodine value of 123, an acid value of 1.0 mgKOH / g, a hydroxyl value of 129 mgKOH / g, and a viscosity at 25 ° C. of 500 mPa · s (hereinafter referred to as “polyol A-1”). In Tables 1 and 2, it is expressed as “polyol A-1”.)
合成例2
脱水ヒマシ油を1200g(1.33モル)とし、ペンタエリスリトールに代えてペンタエリスリトールのプロピレンオキサイド付加物(水酸基価;410mgKOH/g)400g(0.73モル)を用いた他は、合成例1と同様にしてヒマシ油系ポリオールを製造した。得られたヒマシ油系ポリオールのヨウ素価は99、酸価は1.0mgKOH/g、水酸基価は111mgKOH/g、25℃における粘度は300mPa・sであった(以下、「ポリオールA−2」という。また、表1、2でも「ポリオールA−2」と表記する。)。
Synthesis example 2
Synthetic Example 1 except that 1200 g (1.33 mol) of dehydrated castor oil was used, and 400 g (0.73 mol) of a propylene oxide adduct of pentaerythritol (hydroxyl value: 410 mgKOH / g) was used instead of pentaerythritol. A castor oil-based polyol was produced in the same manner. The obtained castor oil-based polyol had an iodine value of 99, an acid value of 1.0 mgKOH / g, a hydroxyl value of 111 mgKOH / g, and a viscosity at 25 ° C. of 300 mPa · s (hereinafter referred to as “polyol A-2”). In Tables 1 and 2, it is expressed as “polyol A-2”.)
合成例3
脱水ヒマシ油を1040g(1.16モル)、ペンタエリスリトールのプロピレンオキサイド付加物を560g(1.02モル)とした他は、合成例2と同様にしてヒマシ油系ポリオールを製造した。得られたヒマシ油系ポリオールのヨウ素価は86、酸価は1.0mgKOH/g、水酸基価は147mgKOH/g、25℃における粘度は400mPa・sであった(以下、「ポリオールA−3」という。また、表1、2、3でも「ポリオールA−3」と表記する。)。
Synthesis example 3
A castor oil-based polyol was produced in the same manner as in Synthesis Example 2, except that 1040 g (1.16 mol) of dehydrated castor oil and 560 g (1.02 mol) of a propylene oxide adduct of pentaerythritol were used. The iodine value of the resulting castor oil-based polyol was 86, the acid value was 1.0 mgKOH / g, the hydroxyl value was 147 mgKOH / g, and the viscosity at 25 ° C. was 400 mPa · s (hereinafter referred to as “polyol A-3”). In Tables 1, 2, and 3, it is also expressed as “polyol A-3”.)
合成例4
脱水ヒマシ油を960g(1.07モル)とし、ポリオールとしてペンタエリスリトール96g(0.71モル)と、ヒマシ油544g(0.58モル)とを用いた他は、合成例1と同様にしてヒマシ油系ポリオールを製造した。得られたヒマシ油系ポリオールのヨウ素価106、酸価は1.0mgKOH/g、水酸基価は154mgKOH/g、25℃における粘度は500mPa・sであった(以下、「ポリオールA−4」という。また、表1、2でも「ポリオールA−4」と表記する。)。
Synthesis example 4
In the same manner as in Synthesis Example 1, except that 960 g (1.07 mol) of dehydrated castor oil was used and 96 g (0.71 mol) of pentaerythritol and 544 g (0.58 mol) of castor oil were used as polyols. An oil-based polyol was produced. The resulting castor oil-based polyol had an iodine value of 106, an acid value of 1.0 mgKOH / g, a hydroxyl value of 154 mgKOH / g, and a viscosity at 25 ° C. of 500 mPa · s (hereinafter referred to as “polyol A-4”). In Tables 1 and 2, it is expressed as “polyol A-4”.)
合成例5
攪拌機、温度計、窒素導入管及び検水管、還流コンデンサを備える反応器に、脱水ヒマシ油脂肪酸を590g(2モル)、ペンタエリスリトールのプロピレンオキサイド付加物138g(0.25モル)、トリイソプロピルチタネート0.2gを投入し、窒素気流下、220℃で6時間攪拌し、反応水を36g留出させ反応させ、その後、100℃以下に冷却し、減圧脱水した。得られたヒマシ油系ポリオールのヨウ素価は118、酸価は1.0mgKOH/g、水酸基価は101mgKOH/g、25℃における粘度は500mPa・sであった(以下、「ポリオールA−5」という。また、表1、2でも「ポリオールA−5」と表記する。)。
Synthesis example 5
In a reactor equipped with a stirrer, a thermometer, a nitrogen introduction tube and a water sampling tube, a reflux condenser, 590 g (2 mol) of dehydrated castor oil fatty acid, 138 g (0.25 mol) of propylene oxide adduct of pentaerythritol, triisopropyl titanate 0 .2 g was added and stirred at 220 ° C. for 6 hours under a nitrogen stream, and 36 g of reaction water was distilled to react, then cooled to 100 ° C. or lower and dehydrated under reduced pressure. The iodine value of the resulting castor oil-based polyol was 118, the acid value was 1.0 mgKOH / g, the hydroxyl value was 101 mgKOH / g, and the viscosity at 25 ° C. was 500 mPa · s (hereinafter referred to as “polyol A-5”). In Tables 1 and 2, “Polyol A-5” is also used.)
比較合成例1
脱水ヒマシ油に代えて亜麻仁油1500g(1.66モル)を使用し、ペンタエリスリトールを113g(0.83モル)とした他は合成例1と同様にしてヒマシ油系ポリオールを製造した。得られたヒマシ油系ポリオールのヨウ素価は166、酸価は1.0mgKOH/g、水酸基価116mgKOH/g、25℃における粘度は500mPa・sであった(以下、「ポリオールB」という。また、表1、3でも「ポリオールB」と表記する。)。
以上、合成例1〜4及び比較合成例1のポリオール(A−1〜5及びB)のヨウ素価、酸価、水酸基価及び25℃における粘度を表1に記載する。
尚、ヨウ素価はJIS K 0070−6に従って測定した。また、酸価はJIS K 0070−3に従って測定した。更に、水酸基価はJIS K 0070−7に従って測定した。また、粘度はJIS K 8803−8に従って測定した。
Comparative Synthesis Example 1
A castor oil-based polyol was produced in the same manner as in Synthesis Example 1, except that 1500 g (1.66 mol) of linseed oil was used instead of dehydrated castor oil and 113 g (0.83 mol) of pentaerythritol was used. The resulting castor oil-based polyol had an iodine value of 166, an acid value of 1.0 mgKOH / g, a hydroxyl value of 116 mgKOH / g, and a viscosity at 25 ° C. of 500 mPa · s (hereinafter referred to as “polyol B”. Tables 1 and 3 also indicate “polyol B”.)
The iodine value, acid value, hydroxyl value, and viscosity at 25 ° C. of the polyols (A-1 to 5 and B) of Synthesis Examples 1 to 4 and Comparative Synthesis Example 1 are described in Table 1.
The iodine value was measured according to JIS K 0070-6. The acid value was measured according to JIS K 0070-3. Furthermore, the hydroxyl value was measured according to JIS K 0070-7. The viscosity was measured according to JIS K 8803-8.
[2]木材塗料用ポリウレタン系水分散体の製造
実施例1
攪拌機、温度計、窒素導入管及び還流コンデンサを備える反応器に、ポリオールA−1を110g、MEKを80g、DMBAを10.9g、NMPを20g、及びDBTDLを0.06g投入し、溶解後、HMDIを68.3g仕込み、次いで、昇温させ、80℃で7時間反応させ、イソシアネート末端プレポリマー(プレポリマーを100質量%とした場合に、2.6質量%のイソシアネート基を有する。)を含有する反応液を得た。その後、40℃にてこの反応液にTEAを6.7g添加し、中和した。次いで、IPDAを6.0g配合したイオン交換水を420g滴下し、鎖延長反応させるとともに転相させ、その後、カルボジイミド化合物(日清紡績社製、商品名「カルボジライトSV−02」)を3.9g添加し、その後、十分攪拌して均一にし、次いで、減圧下、50℃でMEKを留去し、木材塗料用ポリウレタン系水分散体を製造した。
[2] Production of polyurethane-based aqueous dispersion for wood coating Example 1
In a reactor equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser, 110 g of polyol A-1, 80 g of MEK, 10.9 g of DMBA, 20 g of NMP, and 0.06 g of DBTDL were charged and dissolved. 68.3 g of HMDI was charged, and then the temperature was raised and reacted at 80 ° C. for 7 hours to give an isocyanate-terminated prepolymer (having 2.6% by mass of isocyanate groups when the prepolymer is 100% by mass). A containing reaction solution was obtained. Then, 6.7g of TEA was added to this reaction liquid at 40 degreeC, and it neutralized. Next, 420 g of ion-exchanged water containing 6.0 g of IPDA was dropped to cause chain extension reaction and phase inversion, and then 3.9 g of carbodiimide compound (trade name “Carbodilite SV-02” manufactured by Nisshinbo Industries, Inc.) was added. Thereafter, the mixture was sufficiently stirred to make it uniform, and then MEK was distilled off at 50 ° C. under reduced pressure to produce a polyurethane-based aqueous dispersion for wood paint.
実施例2
攪拌機、温度計、窒素導入管及び還流コンデンサを備える反応器に、ポリオールA−2を554g、MEKを300g、DMPAを61g、NMPを61g、及びDBTDLを0.15g投入し、溶解後、HMDIを328g仕込み、次いで、昇温させ、80℃で7時間反応させ、イソシアネート末端プレポリマー(プレポリマーを100質量%とした場合に、2.9質量%のイソシアネート基を有する。)を含有する反応液を得た。その後、40℃にて、この反応液にTEAを46g添加し、中和した。次いで、IPDAを46.0g配合したイオン交換水を2020g滴下し、鎖延長反応させるとともに転相させ、その後、カルボジイミド化合物(日清紡績社製、商品名「カルボジライトSV−02」)を19.8g添加し、その後、十分攪拌して均一にし、次いで、減圧下、50℃でMEKを留去し、木材塗料用ポリウレタン系水分散体を製造した。
Example 2
Into a reactor equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, 554 g of polyol A-2, 300 g of MEK, 61 g of DMPA, 61 g of NMP, and 0.15 g of DBTDL are charged, and after dissolution, HMDI is added. 328 g was charged, then heated, reacted at 80 ° C. for 7 hours, and a reaction liquid containing an isocyanate-terminated prepolymer (having 2.9 mass% isocyanate group when the prepolymer was 100 mass%). Got. Thereafter, 46 g of TEA was added to the reaction solution at 40 ° C. to neutralize it. Next, 2020 g of ion-exchanged water containing 46.0 g of IPDA was dropped to cause chain extension reaction and phase inversion, and then 19.8 g of carbodiimide compound (trade name “Carbodilite SV-02” manufactured by Nisshinbo Industries, Inc.) was added. Thereafter, the mixture was sufficiently stirred to make it uniform, and then MEK was distilled off at 50 ° C. under reduced pressure to produce a polyurethane-based aqueous dispersion for wood paint.
実施例3
攪拌機、温度計、窒素導入管及び還流コンデンサを備える反応器に、ポリオールA−3を83.6g、SA/MPDを20.8g、MEKを60g、DMPAを11.6g、NMPを28g、及びDOTDLを0.04g投入し、溶解後、HMDIを65.6g仕込み、次いで、昇温させ、80℃で7時間反応させ、イソシアネート末端プレポリマー(プレポリマーを100質量%とした場合に、2.3質量%のイソシアネート基を有する。)を含有する反応液を得た。その後、40℃にて、この反応液にTEAを8.7g添加し、中和した。次いで、IPDAを6.8g配合したイオン交換水を370g滴下し、鎖延長反応させるとともに転相させ、その後、カルボジイミド化合物(日清紡績社製、商品名「カルボジライトSV−02」)を3.8g添加し、その後、十分攪拌して均一にし、次いで、減圧下、50℃でMEKを留去し、木材塗料用ポリウレタン系水分散体を製造した。
Example 3
In a reactor equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, 83.6 g of polyol A-3, 20.8 g of SA / MPD, 60 g of MEK, 11.6 g of DMPA, 28 g of NMP, and DOTDL 0.04 g was added, and after dissolution, 65.6 g of HMDI was added, and then the temperature was raised and reacted at 80 ° C. for 7 hours to obtain an isocyanate-terminated prepolymer (2.3 when the prepolymer was 100% by mass). A reaction liquid containing a mass% isocyanate group) was obtained. Thereafter, at 40 ° C., 8.7 g of TEA was added to the reaction solution for neutralization. Next, 370 g of ion-exchanged water containing 6.8 g of IPDA was dropped to cause chain extension reaction and phase inversion, and then 3.8 g of carbodiimide compound (trade name “Carbodilite SV-02” manufactured by Nisshinbo Industries, Inc.) was added. Thereafter, the mixture was sufficiently stirred to make it uniform, and then MEK was distilled off at 50 ° C. under reduced pressure to produce a polyurethane-based aqueous dispersion for wood paint.
実施例4
攪拌機、温度計、窒素導入管及び還流コンデンサを備える反応器に、ポリオールA−4を113.6g、MEKを63g、DMPAを12.6g、NMPを30g、及びDBTDLを0.06g投入し、溶解後、HMDIを82.0g仕込み、次いで、昇温させ、80℃で7時間反応させ、イソシアネート末端プレポリマー(プレポリマーを100質量%とした場合に、2.9質量%のイソシアネート基を有する。)を含有する反応液を得た。その後、40℃にて、この反応液にTEAを9.5g添加し、中和した。次いで、IPDAを12g配合したイオン交換水を490g滴下し、鎖延長反応させるとともに転相させ、その後、カルボジイミド化合物(日清紡績社製、商品名「カルボジライトSV−02」)を4.4g添加し、その後、十分攪拌して均一にし、次いで、減圧下、50℃でMEKを留去し、木材塗料用ポリウレタン系水分散体を製造した。
Example 4
In a reactor equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, 113.6 g of polyol A-4, 63 g of MEK, 12.6 g of DMPA, 30 g of NMP, and 0.06 g of DBTDL are charged and dissolved. Thereafter, 82.0 g of HMDI was charged, and then the temperature was raised and reacted at 80 ° C. for 7 hours to have an isocyanate-terminated prepolymer (having 2.9% by mass of isocyanate groups when the prepolymer was 100% by mass). ) Containing was obtained. Thereafter, at 40 ° C., 9.5 g of TEA was added to the reaction solution for neutralization. Next, 490 g of ion-exchanged water containing 12 g of IPDA was dropped to cause chain extension reaction and phase inversion, and then 4.4 g of a carbodiimide compound (trade name “Carbodilite SV-02” manufactured by Nisshinbo Co., Ltd.) was added, Thereafter, the mixture was sufficiently stirred to make it uniform, and then MEK was distilled off at 50 ° C. under reduced pressure to produce a polyurethane-based aqueous dispersion for wood paint.
実施例5
攪拌機、温度計、窒素導入管及び還流コンデンサを備える反応器に、ポリオールA−5を132.1g、AP−2を9.3g、MEKを60g、DMPAを14.0g、NMPを30g、及びDBTDLを0.06g投入し、溶解後、HMDIを85.0g仕込み、次いで、昇温させ、80℃で7時間反応させ、イソシアネート末端プレポリマー(プレポリマーを100質量%とした場合に、2.6質量%のイソシアネート基を有する。)を含有する反応液を得た。その後、40℃にて、この反応液にTEAを9.5g添加し、中和した。次いで、ピペラジンを5.1g配合したイオン交換水を440g滴下し、鎖延長反応させるとともに転相させ、その後、カルボジイミド化合物(日清紡績社製、商品名「カルボジライトSV−02」)を4.8g添加し、その後、十分攪拌して均一にし、次いで、減圧下、50℃でMEKを留去し、木材塗料用ポリウレタン系水分散体を製造した。
Example 5
In a reactor equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, 132.1 g of polyol A-5, 9.3 g of AP-2, 60 g of MEK, 14.0 g of DMPA, 30 g of NMP, and DBTDL 0.06 g was added, and after dissolution, 85.0 g of HMDI was added, and then the temperature was raised and reacted at 80 ° C. for 7 hours to obtain an isocyanate-terminated prepolymer (2.6% when the prepolymer was 100% by mass). A reaction liquid containing a mass% isocyanate group) was obtained. Thereafter, at 40 ° C., 9.5 g of TEA was added to the reaction solution for neutralization. Next, 440 g of ion-exchanged water containing 5.1 g of piperazine was dropped to cause chain extension reaction and phase inversion, and then 4.8 g of carbodiimide compound (trade name “Carbodilite SV-02” manufactured by Nisshinbo Industries, Inc.) was added. Thereafter, the mixture was sufficiently stirred to make it uniform, and then MEK was distilled off at 50 ° C. under reduced pressure to produce a polyurethane-based aqueous dispersion for wood paint.
実施例6
攪拌機、温度計、窒素導入管及び還流コンデンサを備える反応器に、ポリオールA−1を77.0g、1,4−BDを4.5g、MEKを60g、DMBAを9.0g、NMPを23g、及びDBTDLを0.06g投入し、溶解後、HMDIを70.9g仕込み、次いで、昇温させ、80℃で7時間反応させ、イソシアネート末端プレポリマー(プレポリマーを100質量%とした場合に、3.6質量%のイソシアネート基を有する。)を含有する反応液を得た。その後、40℃にて、この反応液にTEAを4.9g添加し、中和した。次いで、IPDAを6.0g配合したイオン交換水を340g滴下し、鎖延長反応させるとともに転相させ、その後、カルボジイミド化合物(日清紡績社製、商品名「カルボジライトSV−02」)を3.3g添加し、その後、十分攪拌して均一にし、次いで、減圧下、50℃でMEKを留去し、木材塗料用ポリウレタン系水分散体を製造した。
Example 6
In a reactor equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, 77.0 g of polyol A-1, 4.5 g of 1,4-BD, 60 g of MEK, 9.0 g of DMBA, 23 g of NMP, And 0.06 g of DBTDL were added, and after dissolution, 70.9 g of HMDI was added, and then the temperature was raised and reacted at 80 ° C. for 7 hours to give an isocyanate-terminated prepolymer (3% when the prepolymer was 100% by mass). The reaction liquid containing 6 mass% isocyanate group) was obtained. Thereafter, 4.9 g of TEA was added to the reaction solution at 40 ° C. to neutralize it. Next, 340 g of ion-exchanged water containing 6.0 g of IPDA was dropped to cause chain extension reaction and phase inversion, and then 3.3 g of carbodiimide compound (trade name “Carbodilite SV-02” manufactured by Nisshinbo Industries, Inc.) was added. Thereafter, the mixture was sufficiently stirred to make it uniform, and then MEK was distilled off at 50 ° C. under reduced pressure to produce a polyurethane-based aqueous dispersion for wood paint.
実施例7
攪拌機、温度計、窒素導入管及び還流コンデンサを備える反応器に、ポリオールA−1を70.5g、1,4−BDを4.3g、AP−2を4.4g、MEKを60g、DMPAを7.8g、NMPを17g、及びDBTDLを0.06g投入し、溶解後、HMDIを73.5g仕込み、次いで、昇温させ、80℃で7時間反応させ、イソシアネート末端プレポリマー(プレポリマーを100質量%とした場合に、4.2質量%のイソシアネート基を有する。)を含有する反応液を得た。その後、40℃にて、この反応液にTEAを4.7g添加し、中和した。次いで、IPDAを4.0g配合したイオン交換水を380g滴下し、鎖延長反応させるとともに転相させ、その後、カルボジイミド化合物(日清紡績社製、商品名「カルボジライトSV−02」)を3.2g添加し、その後、十分攪拌して均一にし、次いで、減圧下、50℃でMEKを留去し、木材塗料用ポリウレタン系水分散体を製造した。
Example 7
In a reactor equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, 70.5 g of polyol A-1, 4.3 g of 1,4-BD, 4.4 g of AP-2, 60 g of MEK, DMPA 7.8 g, 17 g of NMP, and 0.06 g of DBTDL were added. After dissolution, 73.5 g of HMDI was added, and then the temperature was raised and reacted at 80 ° C. for 7 hours to obtain an isocyanate-terminated prepolymer (prepolymer of 100 A reaction liquid containing 4.2% by mass of isocyanate groups when the mass% was obtained) was obtained. Thereafter, at 40 ° C., 4.7 g of TEA was added to the reaction solution for neutralization. Next, 380 g of ion-exchanged water containing 4.0 g of IPDA was dropped to cause chain extension reaction and phase inversion, and then 3.2 g of carbodiimide compound (trade name “Carbodilite SV-02” manufactured by Nisshinbo Industries, Inc.) was added. Thereafter, the mixture was sufficiently stirred to make it uniform, and then MEK was distilled off at 50 ° C. under reduced pressure to produce a polyurethane-based aqueous dispersion for wood paint.
比較例1
攪拌機、温度計、窒素導入管及び還流コンデンサを備える反応器に、AA/HGを492g(0.246モル)、MEKを300g、DMBAを36.4g、NMPを50g、及びDBTDLを0.08g投入し、溶解後、HMDIを210g仕込み、次いで、昇温させ、80℃で7時間反応させ、イソシアネート末端プレポリマー(プレポリマーを100質量%とした場合に、3.7質量%のイソシアネート基を有する。)を含有する反応液を得た。その後、40℃にて、この反応液にTEAを24.8g添加し、中和した。次いで、IPDAを23.5g配合したイオン交換水を1200g滴下し、鎖延長反応させるとともに転相させ、その後、減圧下、50℃でMEKを留去し、木材塗料用ポリウレタン系水分散体を製造した。
Comparative Example 1
In a reactor equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, 492 g (0.246 mol) of AA / HG, 300 g of MEK, 36.4 g of DMBA, 50 g of NMP, and 0.08 g of DBTDL are charged. After dissolution, 210 g of HMDI was charged, and then the temperature was raised and reacted at 80 ° C. for 7 hours to give an isocyanate-terminated prepolymer (having 3.7% by mass of isocyanate groups when the prepolymer was taken as 100% by mass). .) Was obtained. Thereafter, 24.8 g of TEA was added to the reaction solution at 40 ° C. to neutralize it. Next, 1200 g of ion-exchanged water containing 23.5 g of IPDA was added dropwise to cause chain extension reaction and phase inversion, and then MEK was distilled off at 50 ° C. under reduced pressure to produce a polyurethane-based aqueous dispersion for wood paint. did.
比較例2
攪拌機、温度計、窒素導入管及び還流コンデンサを備える反応器に、AA/IPAを200g(0.10モル)、TMPを3g、MEKを150g、DMPAを39.0g、NMPを30g、及びDBTDLを0.06g投入し、溶解後、HMDIを184g仕込み、次いで、昇温させ、80℃で7時間反応させ、イソシアネート末端プレポリマー(プレポリマーを100質量%とした場合に、4.2質量%のイソシアネート基を有する。)を含有する反応液を得た。その後、40℃にて、この反応液にTEAを32g添加し、中和した。次いで、EDAを10g配合したイオン交換水を800g滴下し、鎖延長反応させるとともに転相させ、その後、減圧下、50℃でMEKを留去し、木材塗料用ポリウレタン系水分散体を製造した。
Comparative Example 2
In a reactor equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, AA / IPA 200 g (0.10 mol), TMP 3 g, MEK 150 g, DMPA 39.0 g, NMP 30 g, and DBTDL 0.06 g was added, and after dissolution, 184 g of HMDI was added, and then the temperature was raised and reacted at 80 ° C. for 7 hours to obtain an isocyanate-terminated prepolymer (4.2 mass% when the prepolymer was 100 mass%). A reaction solution containing an isocyanate group) was obtained. Thereafter, at 40 ° C., 32 g of TEA was added to the reaction solution for neutralization. Next, 800 g of ion-exchanged water containing 10 g of EDA was added dropwise to cause chain extension reaction and phase inversion, and then MEK was distilled off at 50 ° C. under reduced pressure to produce a polyurethane-based aqueous dispersion for wood coating.
比較例3
攪拌機、温度計、窒素導入管及び還流コンデンサを備える反応器に、ポリオールBを80.6g、1,4−BDを4.7g、MEKを60g、DMBAを9.5g、NMPを23g、及びDBTDLを0.06g投入し、溶解後、HMDIを70.9g仕込み、次いで、昇温させ、80℃で7時間反応させ、イソシアネート末端プレポリマー(プレポリマーを100質量%とした場合に、3.6質量%のイソシアネート基を有する。)を含有する反応液を得た。その後、40℃にて、この反応液にTEAを5.2g添加し、中和した。次いで、IPDAを6.0g配合したイオン交換水を340g滴下し、鎖延長反応させるとともに転相させ、その後、減圧下、50℃でMEKを留去し、木材塗料用ポリウレタン系水分散体を製造した。
Comparative Example 3
In a reactor equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, polyol B is 80.6 g, 1,4-BD is 4.7 g, MEK is 60 g, DMBA is 9.5 g, NMP is 23 g, and DBTDL. 0.06 g was added, and after dissolution, 70.9 g of HMDI was added, and then the temperature was raised and reacted at 80 ° C. for 7 hours to obtain an isocyanate-terminated prepolymer (3.6% when the prepolymer was 100% by mass). A reaction liquid containing a mass% isocyanate group) was obtained. Thereafter, at 40 ° C., 5.2 g of TEA was added to the reaction solution for neutralization. Next, 340 g of ion-exchanged water containing 6.0 g of IPDA was dropped to cause chain extension reaction and phase inversion, and then MEK was distilled off at 50 ° C. under reduced pressure to produce a polyurethane-based aqueous dispersion for wood paint. did.
比較例4
汎用大豆油系ポリウレタン系水分散体(市販品)を用いた。
Comparative Example 4
A general-purpose soybean oil-based polyurethane aqueous dispersion (commercially available product) was used.
比較例5
攪拌機、温度計、窒素導入管及び還流コンデンサを備える反応器に、ポリオールA−3を83.6g、SA/MPDを20.8g、MEKを60g、DMBAを11.6g、NMPを23g、及びDOTDLを0.04g投入し、溶解後、IPDIを55.6g仕込み、次いで、昇温させ、80℃で7時間反応させ、イソシアネート末端プレポリマー(プレポリマーを100質量%とした場合に、2.5質量%のイソシアネート基を有する。)を含有する反応液を得た。その後、40℃にて、この反応液にTEAを8.7g添加し、中和した。次いで、IPDAを6.8g配合したイオン交換水を370g滴下し、鎖延長反応させるとともに転相させ、その後、減圧下、50℃でMEKを留去し、木材塗料用ポリウレタン系水分散体を製造した。
Comparative Example 5
In a reactor equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, 83.6 g of polyol A-3, 20.8 g of SA / MPD, 60 g of MEK, 11.6 g of DMBA, 23 g of NMP, and DOTDL 0.04 g was added, and after dissolution, 55.6 g of IPDI was added, and then the temperature was raised and reacted at 80 ° C. for 7 hours. A reaction liquid containing a mass% isocyanate group) was obtained. Thereafter, at 40 ° C., 8.7 g of TEA was added to the reaction solution for neutralization. Next, 370 g of ion-exchanged water containing 6.8 g of IPDA was added dropwise to cause chain extension reaction and phase inversion, and then MEK was distilled off at 50 ° C. under reduced pressure to produce a polyurethane-based aqueous dispersion for wood paint. did.
尚、実施例及び比較例における略記の意味は以下のとおりである。
DMPA;ジメチロールプロピオン酸
DMBA;ジメチロールブタン酸
MEK;メチルエチルケトン
NMP;N−メチルピロリドン
DBTDL;ジブチルチンジラウレート
DOTDL;ジオクチルチンジラウレート
HMDI;MDIの水添物
IPDI;イソホロンジイソシアネート
TEA;トリエチルアミン
IPDA;イソホロンジアミン
EDA;エチレンジアミン
TMP;トリメチロールプロパン
1,4−BD;1,4−ブタンジオール
AP−2;ビスフェノールAのプロピレンオキサイド2モル付加物
SA/MPD;セバシン酸と3メチルペンタンジオールとの反応物であるポリエステルポリオール(重量平均分子量;3500、水酸基価;34mgKOH/g)
AA/HG;アジピン酸とヘキサンジオールとの反応物であるポリエステルポリオール(重量平均分子量;2000、水酸基価;56mgKOH/g)
AA/IPA=1/1(モル比)/HG;アジピン酸及びイソフタル酸(モル比で1/1)とヘキサンジオールとの反応物であるポリエステルポリオール(重量平均分子量;2000、水酸基価;56mgKOH/g)
In addition, the meaning of the abbreviation in an Example and a comparative example is as follows.
DMPA; dimethylolpropionic acid DMBA; dimethylolbutanoic acid MEK; methyl ethyl ketone NMP; N-methylpyrrolidone DBTDL; dibutyltin dilaurate DOTDL; dioctyltin dilaurate HMDI; hydrogenated product of MDI IPDI; isophorone diisocyanate TEA; Ethylenediamine TMP; trimethylolpropane 1,4-BD; 1,4-butanediol AP-2; propylene oxide 2-mol adduct of bisphenol A SA / MPD; polyester which is a reaction product of sebacic acid and 3-methylpentanediol Polyol (weight average molecular weight; 3500, hydroxyl value; 34 mgKOH / g)
AA / HG: polyester polyol which is a reaction product of adipic acid and hexanediol (weight average molecular weight: 2000, hydroxyl value: 56 mgKOH / g)
AA / IPA = 1/1 (molar ratio) / HG; polyester polyol which is a reaction product of adipic acid and isophthalic acid (1/1 by molar ratio) and hexanediol (weight average molecular weight; 2000, hydroxyl value; 56 mgKOH / g)
以上、実施例1〜7及び比較例1〜5の木材塗料用ポリウレタン系水分散体の粘度、pH、不揮発分及び脱水ヒマシ油含有量を、それぞれ表2、3に記載する。
尚、粘度はJIS K 8803−8に従って測定した。また、pHは堀場製作所製の「pH meter F−22」により測定した。更に、不揮発分(表2、3では「NV」と略記する。)はJIS K 0067−2−3に従い、125℃で3時間加熱したときの揮発残分とした算出した。
不揮発分(%)=[(加熱後の全重量−容器の重量)/(加熱前の全重量−容器の重量)]×100
また、表2、3における「脱水ヒマシ油の質量割合」は、鎖延長されたプレポリマーの生成に用いられた原料の合計量を100質量%とした場合の、脱水ヒマシ油の質量割合である。
脱水ヒマシ油の質量割合(%)=(脱水ヒマシ油の質量/原料の合計質量)×100
The viscosity, pH, non-volatile content, and dehydrated castor oil content of the polyurethane-based aqueous dispersions for wood coatings of Examples 1 to 7 and Comparative Examples 1 to 5 are described in Tables 2 and 3, respectively.
The viscosity was measured according to JIS K 8803-8. The pH was measured with “pH meter F-22” manufactured by Horiba. Further, the nonvolatile content (abbreviated as “NV” in Tables 2 and 3) was calculated as the volatile residue when heated at 125 ° C. for 3 hours in accordance with JIS K 0067-2-3.
Non-volatile content (%) = [(total weight after heating−weight of container) / (total weight before heating−weight of container)] × 100
The “mass ratio of dehydrated castor oil” in Tables 2 and 3 is the mass ratio of dehydrated castor oil when the total amount of raw materials used for the production of the chain-extended prepolymer is 100 mass%. .
Mass ratio (%) of dehydrated castor oil = (mass of dehydrated castor oil / total mass of raw materials) × 100
[3]塗装用及びフィルム作製用の各々の配合物の調製
実施例1〜7及び比較例1〜5の木材塗料用ポリウレタン系水分散体(表4では「PUD」と略記する。)の不揮発分(表4では「NV」と略記する。)を30質量%に調整し、この水分散体と、レベリング剤(サイテック社製、商品名「Additol XW395」)、造膜助剤(ダウ・ケミカル日本社製、商品名「ダワノールDPM」)及びイオン交換水とを表4に記載の塗料用及びフィルム作製用の各々の組成となるように配合し、試験片の作製に供した。
[3] Preparation of respective formulations for coating and film production Nonvolatiles of polyurethane-based aqueous dispersions for wood paints of Examples 1 to 7 and Comparative Examples 1 to 5 (abbreviated as “PUD” in Table 4). The minute amount (abbreviated as “NV” in Table 4) was adjusted to 30% by mass, and this water dispersion, leveling agent (trade name “Additol XW395” manufactured by Cytec Co., Ltd.), film-forming aid (Dow Chemical) Nippon Shokubai Co., Ltd., trade name “Dawanol DPM”) and ion-exchanged water were blended so as to have the respective compositions for coating and film production shown in Table 4, and used for the production of test pieces.
[4]性能評価
(1)塗膜の評価
縦200mm、横150mmのラワン合板の基材の一面に、実施例1〜7及び比較例1〜5の木材塗料用ポリウレタン系水分散体を用いて表4の組成になるように配合した塗料を4回重ね塗りし、一回につき塗布量が4.0〜6.0gになるように調整し、塗膜を形成した。各々の塗布の間隔は6時間以上(6〜10時間)とし、1〜3層は雰囲気温度(25℃)で乾燥させた。また、1〜3層は上層の塗布前に表面を240番のサンドペーパーで研磨した。一方、最上層、即ち、4層目は研磨せず、40℃で1週間養生させ、評価に供した。
尚、上記の研磨時の研磨性を目視により評価した。評価基準は、○;サンドペーパーの目詰まりがなく、良好である、△;少し目詰まりがみられるが、研磨することができる、である。
[4] Performance Evaluation (1) Evaluation of Coating Film Using the polyurethane-based aqueous dispersions for wood paints of Examples 1 to 7 and Comparative Examples 1 to 5 on one surface of a base material of Lauan plywood having a length of 200 mm and a width of 150 mm. The paint blended so as to have the composition shown in Table 4 was applied four times, and the coating amount was adjusted to 4.0 to 6.0 g at a time to form a coating film. Each application interval was 6 hours or more (6 to 10 hours), and the first to third layers were dried at an ambient temperature (25 ° C.). The layers 1 to 3 were polished with No. 240 sandpaper before the upper layer was applied. On the other hand, the uppermost layer, that is, the fourth layer was not polished and was cured at 40 ° C. for 1 week for evaluation.
In addition, the polishability at the time of the above polishing was visually evaluated. Evaluation criteria are: ○: Sandpaper is not clogged and is good, Δ: Clogging is slightly observed, but polishing is possible.
上記(1)のようにして基材の表面に形成した皮膜の性能を評価した。
(a)黄変性;養生後、30日経過した時点で皮膜の着色を目視で観察した。評価基準は、○;変色がなく良好、△;少し黄色に変色、×:黄変する、である。
(b)鉛筆硬度;JIS K 5600−5−4に従って評価した。
(c)光沢;堀場製作所製、型式「IG−331」を用いてJIS K 5600−4−7に従って60°鏡面光沢度を評価した。
(d)スポットテスト(耐薬品性):JIS K 5600−6−1[方法3(点滴法)]に従い、表5に記載の液体を皮膜に滴下し、過度の蒸発を防ぐために試験面をポリキャップにより覆い、24時間静置後、試験面の状態を目視で観察した。評価基準は、○;滴下跡が視認されず、良好である、△;滴下跡が視認され、液体に少し侵されている、×;滴下面に皺等がみられ、液体に侵されている、である。
尚、Na2CO3、酢酸及びEtOH(エタノール)は、いずれも水溶液である。また、洗剤はP&G社製、商品名「ジョイ」であり、ラッカーシンナーはJIS K 5538に定められた製品である。
(e)耐湿熱性;底面が直径100mmの円形のステンレス製容器に沸騰水を入れ、この容器を、水を流延させた皮膜面に静置し、30分間経過後、容器を取り除き、皮膜表面を目視で観察した。評価基準は、○;静置跡が視認されず、良好である、△;静置跡が視認され、湿度及び熱の影響を少し受けている、である。
以上、(a)〜(e)の評価結果を表5に記載する。
The performance of the film formed on the surface of the substrate as in (1) above was evaluated.
(A) Yellowing; Coloring of the film was visually observed when 30 days had elapsed after curing. The evaluation criteria are ○: good without any discoloration, Δ: slightly discolored to yellow, ×: discolored yellow.
(B) Pencil hardness; evaluated according to JIS K 5600-5-4.
(C) Glossiness: 60 ° specular glossiness was evaluated according to JIS K 5600-4-7 using a model “IG-331” manufactured by HORIBA, Ltd.
(D) Spot test (chemical resistance): In accordance with JIS K 5600-6-1 [Method 3 (Drip method)], the liquid shown in Table 5 is dropped onto the film, and the test surface is coated to prevent excessive evaporation. After covering with a cap and allowing to stand for 24 hours, the state of the test surface was visually observed. Evaluation criteria: ○: Drop marks are not visually recognized and good, Δ: Drop marks are visually recognized and slightly infiltrated with the liquid, X: Wrinkles are observed on the dropping surface, and the liquid is invaded .
Na 2 CO 3 , acetic acid and EtOH (ethanol) are all aqueous solutions. The detergent is a product name “Joy” manufactured by P & G, and the lacquer thinner is a product defined in JIS K 5538.
(E) Moisture and heat resistance; boiling water is put into a circular stainless steel container having a bottom surface of 100 mm in diameter, and this container is allowed to stand on the surface of the film on which water has been cast. After 30 minutes, the container is removed and the surface of the film is removed. Was visually observed. The evaluation criteria are ○: the standing trace is not visually recognized and good, and Δ: the standing trace is visually recognized and is slightly affected by humidity and heat.
The evaluation results of (a) to (e) are shown in Table 5 above.
表5の結果によれば、実施例1〜7の木材塗料用ポリウレタン系水分散体を用いた場合は、研磨性、黄変性及び耐湿熱性は全く問題なく、十分な硬度を有し、且つ光沢も81以上であり、優れている。また、エタノール、ラッカーシンナーに対する耐薬品性(耐溶剤性)が少し低いこともあるが、総体的に十分な耐薬品性を有していることが分かる。一方、比較例1〜5の木材塗料用ポリウレタン系水分散体を用いた場合は、研磨性、酢酸及び洗剤に対する耐薬品性に大きな問題はないものの、その他の評価で大きく劣っている項目があることが分かる。特に、汎用大豆油系ポリウレタン系水分散体を用いた比較例4では、脱水ヒマシ油に代えて乾性油である亜麻仁油を用いて合成したポリオールを使用した比較例3では黄変が激しい。また、脱水ヒマシ油を用いて合成したポリオールを使用しているものの、シクロヘキシル基が1個のイソホロンジイソシアネートを用いた比較例5では、耐溶剤性に劣ることが分かる。 According to the results of Table 5, when the polyurethane-based aqueous dispersions for wood paints of Examples 1 to 7 were used, there were no problems with polishing, yellowing and heat-and-moisture resistance, sufficient hardness, and gloss. Is 81 or more, which is excellent. Moreover, although chemical resistance (solvent resistance) with respect to ethanol and lacquer thinner may be a little low, it turns out that it has sufficient chemical resistance generally. On the other hand, when using the polyurethane-based aqueous dispersions for wood paints of Comparative Examples 1 to 5, there are no significant problems in chemical resistance against abrasiveness, acetic acid and detergent, but there are items that are greatly inferior in other evaluations. I understand that. In particular, in Comparative Example 4 using a general-purpose soybean oil-based polyurethane aqueous dispersion, yellowing is severe in Comparative Example 3 using a polyol synthesized using linseed oil which is a dry oil instead of dehydrated castor oil. Moreover, although the polyol synthesize | combined using dehydrated castor oil is used, it turns out that it is inferior to solvent resistance in the comparative example 5 using the isocyclohexylone diisocyanate with one cyclohexyl group.
(2)フィルムの評価
実施例1〜7及び比較例1〜5の木材塗料用ポリウレタン系水分散体を用いて表4の組成になるように配合したフィルム作製用配合物を用いて、金属製の型に流し込むようにして厚さ300μmのフィルムを作製し、このフィルムから縦100mm、横30mmの試験片を切り出し、この試験片を40℃の温水に浸漬し、48時間経過後、表面に付着した水をガーゼで拭き取り、重量変化率を算出し、外観を目視で評価した。
重量変化率(%)=[(浸漬後重量−浸漬前重量)/浸漬前重量]×100
結果を表6に記載する。
(2) Evaluation of film Using the compound for film preparation blended so as to have the composition shown in Table 4 using the polyurethane-based aqueous dispersions for wood paints of Examples 1 to 7 and Comparative Examples 1 to 5, the film was made of metal. A film having a thickness of 300 μm was produced by pouring into a mold of 100 mm, and a test piece having a length of 100 mm and a width of 30 mm was cut out from the film, and this test piece was immersed in warm water at 40 ° C. and adhered to the surface after 48 hours. The water was wiped off with gauze, the weight change rate was calculated, and the appearance was visually evaluated.
Weight change rate (%) = [(weight after immersion−weight before immersion) / weight before immersion] × 100
The results are listed in Table 6.
表6の結果によれば、実施例1〜7の木材塗料用ポリウレタン系水分散体を用いた場合は、重量変化率は+2.4%以下、即ち、重量増加率は2.4%以下であり、吸水性が極めて低く、外観も若干濁りがみられる程度であり、全く問題ないことが分かる。一方、比較例1〜5の木材塗料用ポリウレタン系水分散体を用いた場合、比較例1〜2及び4〜5では、重量増加率が大きく、比較例1、4、5、特に比較例4では、重量増加率が極めて大きく、問題である。また、比較例3では、重量増加率及び外観ともに全く問題ないが、前記の黄変性が劣っており、問題である。 According to the results of Table 6, when using the polyurethane-based aqueous dispersion for wood paints of Examples 1 to 7, the weight change rate is + 2.4% or less, that is, the weight increase rate is 2.4% or less. In addition, the water absorption is extremely low, and the appearance is only slightly turbid, indicating that there is no problem at all. On the other hand, when the polyurethane-based aqueous dispersion for wood paints of Comparative Examples 1 to 5 is used, Comparative Examples 1 to 2 and 4 to 5 have a large weight increase rate. Then, the rate of weight increase is extremely large, which is a problem. In Comparative Example 3, there is no problem in the weight increase rate and the appearance, but the yellowing is inferior, which is a problem.
本発明は、木質の床、壁、天井及び家具等の、木製であり、且つ美観を向上させるため表面に塗料を塗布し、皮膜を形成する必要のある各種の用途において利用することができる。 INDUSTRIAL APPLICABILITY The present invention can be used in various applications such as wooden floors, walls, ceilings, furniture, and the like that are made of wood and need to be coated with a paint to form a film in order to improve aesthetics.
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