JP6046328B2 - Colorant composition and method for producing the same, coloration method using the colorant composition, and method for producing a sealing material - Google Patents
Colorant composition and method for producing the same, coloration method using the colorant composition, and method for producing a sealing material Download PDFInfo
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- JP6046328B2 JP6046328B2 JP2010194072A JP2010194072A JP6046328B2 JP 6046328 B2 JP6046328 B2 JP 6046328B2 JP 2010194072 A JP2010194072 A JP 2010194072A JP 2010194072 A JP2010194072 A JP 2010194072A JP 6046328 B2 JP6046328 B2 JP 6046328B2
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- colorant composition
- group
- hydroxyl group
- isocyanate
- molecular weight
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims description 117
- 239000003086 colorant Substances 0.000 title claims description 90
- 239000003566 sealing material Substances 0.000 title claims description 32
- 238000000034 method Methods 0.000 title claims description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 79
- 229920000570 polyether Polymers 0.000 claims description 67
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 66
- -1 polyoxypropylene urethane Polymers 0.000 claims description 56
- 229920005862 polyol Polymers 0.000 claims description 40
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 38
- 150000003077 polyols Chemical class 0.000 claims description 35
- 239000000049 pigment Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 20
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 18
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 17
- 125000005442 diisocyanate group Chemical group 0.000 claims description 11
- 150000002513 isocyanates Chemical class 0.000 claims description 11
- 238000004040 coloring Methods 0.000 claims description 10
- 239000012948 isocyanate Substances 0.000 claims description 9
- 230000006698 induction Effects 0.000 claims 1
- 239000000565 sealant Substances 0.000 claims 1
- 230000018044 dehydration Effects 0.000 description 25
- 238000006297 dehydration reaction Methods 0.000 description 25
- 229920001451 polypropylene glycol Polymers 0.000 description 22
- 239000002585 base Substances 0.000 description 21
- 229920005989 resin Polymers 0.000 description 21
- 239000011347 resin Substances 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 20
- 239000000463 material Substances 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 238000002156 mixing Methods 0.000 description 16
- 238000007789 sealing Methods 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 239000000758 substrate Substances 0.000 description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 239000001060 yellow colorant Substances 0.000 description 11
- 239000011572 manganese Substances 0.000 description 10
- 239000003973 paint Substances 0.000 description 10
- 239000001062 red colorant Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- 239000000654 additive Substances 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 8
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- 238000003756 stirring Methods 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 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 7
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 7
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical class CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
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- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000002612 dispersion medium Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
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- 239000013008 thixotropic agent Substances 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 239000006096 absorbing agent Substances 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 238000011109 contamination Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- 239000004576 sand Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 150000001414 amino alcohols Chemical class 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
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- 235000014113 dietary fatty acids Nutrition 0.000 description 4
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
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- 238000000691 measurement method Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 4
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 3
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000515 polycarbonate Chemical group 0.000 description 3
- 239000004417 polycarbonate Chemical group 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000010454 slate Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
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- 239000010935 stainless steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 238000004078 waterproofing Methods 0.000 description 3
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 2
- OJPDDQSCZGTACX-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)anilino]ethanol Chemical compound OCCN(CCO)C1=CC=CC=C1 OJPDDQSCZGTACX-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
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- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
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- 238000009835 boiling Methods 0.000 description 2
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- ATOUXIOKEJWULN-UHFFFAOYSA-N 1,6-diisocyanato-2,2,4-trimethylhexane Chemical compound O=C=NCCC(C)CC(C)(C)CN=C=O ATOUXIOKEJWULN-UHFFFAOYSA-N 0.000 description 1
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- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- HNHVTXYLRVGMHD-UHFFFAOYSA-N n-butyl isocyanate Chemical compound CCCCN=C=O HNHVTXYLRVGMHD-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229950002083 octabenzone Drugs 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 229920000058 polyacrylate Chemical group 0.000 description 1
- 229920002647 polyamide Chemical group 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000921 polyethylene adipate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Chemical group 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- WPPDXAHGCGPUPK-UHFFFAOYSA-N red 2 Chemical compound C1=CC=CC=C1C(C1=CC=CC=C11)=C(C=2C=3C4=CC=C5C6=CC=C7C8=C(C=9C=CC=CC=9)C9=CC=CC=C9C(C=9C=CC=CC=9)=C8C8=CC=C(C6=C87)C(C=35)=CC=2)C4=C1C1=CC=CC=C1 WPPDXAHGCGPUPK-UHFFFAOYSA-N 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- JUYONNFUNDDKBE-UHFFFAOYSA-J tri(oct-2-enoyloxy)stannyl oct-2-enoate Chemical compound [Sn+4].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O JUYONNFUNDDKBE-UHFFFAOYSA-J 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- UJMBCXLDXJUMFB-UHFFFAOYSA-K trisodium;5-oxo-1-(4-sulfonatophenyl)-4-[(4-sulfonatophenyl)diazenyl]-4h-pyrazole-3-carboxylate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-UHFFFAOYSA-K 0.000 description 1
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、耐ブリード汚染性に優れ、調色が容易な着色剤組成物及びその製造方法、並びに当該着色剤組成物を用いた着色方法及びシーリング材の製造方法に関する。 The present invention relates to a colorant composition excellent in bleed stain resistance and easy toning and a method for producing the same, and a coloration method using the colorant composition and a method for producing a sealing material.
従来、シーリング材、防水材、接着剤、及び塗料などの調色において、ベース樹脂に粉体状の顔料を直接添加し混合する方法が知られている。 Conventionally, a method of directly adding and mixing a powdery pigment to a base resin is known for toning of sealing materials, waterproofing materials, adhesives, paints, and the like.
しかし、ベース樹脂に顔料を直接添加する場合、顔料の分散に時間を要する。そこで、有機溶剤や可塑剤などの液体（分散媒）に予め顔料を分散した着色剤組成物を使用することが多い。着色剤組成物は、分散媒に単色または数色の顔料を所望の割合で混合分散したもので、場合により他の配合剤と混合され、使用されているものである。着色剤組成物と、基材となるシーリング材、防水材、接着剤、又は塗料等を混合して、目的とする色調のシーリング材、防水材、接着剤、又は塗料等を製造する方法は、多数の色調のものを効率的に製造できるという利点がある。 However, when the pigment is added directly to the base resin, it takes time to disperse the pigment. Therefore, a colorant composition in which a pigment is previously dispersed in a liquid (dispersion medium) such as an organic solvent or a plasticizer is often used. The colorant composition is obtained by mixing and dispersing a single color or several colors of pigment in a dispersion medium at a desired ratio, and optionally used by mixing with other compounding agents. A method for producing a sealing material, a waterproof material, an adhesive, or a paint having a target color tone by mixing a colorant composition and a sealing material, a waterproof material, an adhesive, or a paint as a base material, There is an advantage that a large number of colors can be efficiently manufactured.
例えば、特許文献１には、外壁材のシーリングなどに使用される硬化性シリコーン組成物を製造するに際し、変成シリコーンポリマーなどのベース材と、硬化触媒と、着色剤組成物を調製して混合することが記載されている。特許文献１の実施例には、着色剤組成物としてカーボンブラックとフタル酸ジオクチル（ＤＯＰ）と２５：７５の比で混合したものが記載されている（段落００１４参照）。 For example, in Patent Document 1, when producing a curable silicone composition used for sealing an outer wall material, a base material such as a modified silicone polymer, a curing catalyst, and a colorant composition are prepared and mixed. It is described. In an example of Patent Document 1, a colorant composition mixed with carbon black and dioctyl phthalate (DOP) at a ratio of 25:75 is described (see paragraph 0014).
しかしながら、特許文献１に記載されたような従来技術の着色剤組成物を用いると、得られるシーリング材等の上塗り塗料（仕上げ塗料）に対してブリード汚染を引き起こすという問題があった。これは、分散媒として使用しているＤＯＰ等の高沸点の溶剤や可塑剤が、上塗り塗料の表面に移行していることが原因と考えられる。一方、分散媒として低沸点の有機溶剤を用いると、有機溶剤の揮散による環境汚染が問題となる。そこで、本発明が解決しようとする課題は、有機溶剤の大気中への揮散による環境汚染を発生させることなく、耐ブリード汚染性に優れた着色剤組成物を見出すことである。 However, when the colorant composition of the prior art as described in Patent Document 1 is used, there is a problem of causing bleed contamination to the top coating (finishing paint) such as a sealing material obtained. This is presumably because a high-boiling solvent such as DOP or a plasticizer used as a dispersion medium has migrated to the surface of the top coat. On the other hand, when an organic solvent having a low boiling point is used as the dispersion medium, environmental pollution due to volatilization of the organic solvent becomes a problem. Therefore, the problem to be solved by the present invention is to find a colorant composition having excellent resistance to bleed contamination without causing environmental pollution due to volatilization of the organic solvent into the atmosphere.
本発明者等が鋭意研究を重ねた結果、水酸基含有ポリエーテル及び／又は水酸基含有ポリエーテル誘導体と、顔料とを含有する着色剤組成物が上記の課題を解決することを見出し、本発明を完成するに至った。すなわち本発明は、以下の（１）〜（９）に関する。尚、本発明において、「着色」には「調色」の意味も含むものとする。
（１）水酸基含有ポリエーテル及び／又は水酸基含有ポリエーテル誘導体と、顔料とを含有する着色剤組成物。
（２）前記水酸基含有ポリエーテル誘導体が、水酸基含有ポリエーテルの水酸基と有機イソシアネートを反応させて得られるウレタン結合を有する化合物である、（１）に記載の着色剤組成物。
（３）前記水酸基含有ポリエーテル及び／又は水酸基含有ポリエーテル誘導体が、ポリオキシアルキレン鎖を有し、数平均分子量（Ｍｎ）が１，０００〜１０，０００である、（１）に記載の着色剤組成物。
（４）前記水酸基含有ポリエーテル及び／又は水酸基含有ポリエーテル誘導体の分子量分布（Ｍｗ／Ｍｎ）が１．６以下であることを特徴とする、（３）に記載の着色剤組成物。
（５）前記有機イソシアネートが脂肪族ジイソシアネート、脂環族ジイソシアネート、芳香脂肪族ジイソシアネートからなる群から選ばれる少なくとも１種以上の有機ジイソシアネートである、（２）に記載の着色剤組成物。
（６）含水率が０．０５質量％以下である、（１）〜（５）いずれかに記載の着色剤組成物。
（７）水酸基含有ポリエーテル及び／又は水酸基含有ポリエーテル誘導体に顔料を混合分散させた後に、当該組成物を脱水することによって、含水率を０．０５質量％以下にすることを特徴とする、（１）〜（６）のいずれかに記載の着色剤組成物の製造方法。
（８）（１）〜（６）のいずれかに記載の着色剤組成物を用いて基材を着色する方法。
（９）（１）〜（６）のいずれかに記載の着色剤組成物を用いることを特徴とするシーリング材の製造方法。
As a result of intensive studies by the present inventors, it has been found that a colorant composition containing a hydroxyl group-containing polyether and / or a hydroxyl group-containing polyether derivative and a pigment solves the above-mentioned problems, thereby completing the present invention. It came to do. That is, the present invention relates to the following (1) to (9). In the present invention, “coloring” includes the meaning of “toning”.
(1) A colorant composition containing a hydroxyl group-containing polyether and / or a hydroxyl group-containing polyether derivative and a pigment.
(2) The colorant composition according to (1), wherein the hydroxyl group-containing polyether derivative is a compound having a urethane bond obtained by reacting a hydroxyl group of a hydroxyl group-containing polyether with an organic isocyanate.
(3) The coloring according to (1), wherein the hydroxyl group-containing polyether and / or the hydroxyl group-containing polyether derivative has a polyoxyalkylene chain and has a number average molecular weight (Mn) of 1,000 to 10,000. Agent composition.
(4) The colorant composition according to (3), wherein the hydroxyl group-containing polyether and / or the hydroxyl group-containing polyether derivative has a molecular weight distribution (Mw / Mn) of 1.6 or less.
(5) The colorant composition according to (2), wherein the organic isocyanate is at least one organic diisocyanate selected from the group consisting of aliphatic diisocyanates, alicyclic diisocyanates, and araliphatic diisocyanates.
(6) The colorant composition according to any one of (1) to (5), wherein the water content is 0.05% by mass or less.
(7) After the pigment is mixed and dispersed in the hydroxyl group-containing polyether and / or the hydroxyl group-containing polyether derivative, the composition is dehydrated to reduce the water content to 0.05% by mass or less. (1) The manufacturing method of the coloring agent composition in any one of (6).
(8) A method of coloring a substrate using the colorant composition according to any one of (1) to (6).
(9) A method for producing a sealing material, wherein the colorant composition according to any one of (1) to (6) is used.
本発明の着色剤組成物を用いることにより、大気中への揮散による環境汚染を発生させることなく、耐ブリード汚染性に優れたシーリング材、防水材、接着剤、及び塗料等を得ることができる。 By using the colorant composition of the present invention, it is possible to obtain a sealing material, a waterproof material, an adhesive, a paint, and the like having excellent resistance to bleed contamination without causing environmental pollution due to volatilization into the atmosphere. .
以下、本発明を、実施形態に即して詳細に説明する。
［着色剤組成物］
本発明の着色剤組成物は、水酸基含有ポリエーテル及び／又は水酸基含有ポリエーテル誘導体と、顔料とを含有する。以下、本発明に係る着色剤組成物の構成成分について詳述する。
Hereinafter, the present invention will be described in detail according to embodiments.
[Colorant composition]
The colorant composition of the present invention contains a hydroxyl group-containing polyether and / or a hydroxyl group-containing polyether derivative and a pigment. Hereinafter, the components of the colorant composition according to the present invention will be described in detail.
（水酸基含有ポリエーテル）
水酸基含有ポリエーテルとしては、水酸基を少なくとも１個以上有するポリエーテル化合物であってポリオキシアルキレン系のポリオールやモノオール、ポリアセタール樹脂、フェノキシ樹脂（高分子量ポリヒドロキシポリエーテル）などを挙げることができる。尚、ポリオールとは複数のアルコール性水酸基をもつ化合物のことをいう。
(Hydroxyl-containing polyether)
Examples of the hydroxyl group-containing polyether include polyether compounds having at least one hydroxyl group, such as polyoxyalkylene polyols, monools, polyacetal resins, and phenoxy resins (high molecular weight polyhydroxy polyethers). The polyol means a compound having a plurality of alcoholic hydroxyl groups.
ポリオキシアルキレン系のポリオールやモノオールは、公知の製造方法で得られる。例えば、水酸化カリウムおよび水酸化セシウム等のアルカリ触媒、ジエチル亜鉛、塩化鉄、金属ポルフィリン、ならびに複合金属シアン化物錯体等からなる群から選ばれる少なくとも一種の触媒の存在下、開始剤にアルキレンオキシドを開環重合反応させて製造することができる。アルキレンオキシドは単独又は２種以上を組み合わせて開環付加重合させることができる。 Polyoxyalkylene polyols and monools can be obtained by known production methods. For example, an alkylene oxide is used as an initiator in the presence of at least one catalyst selected from the group consisting of alkali catalysts such as potassium hydroxide and cesium hydroxide, diethyl zinc, iron chloride, metal porphyrin, and double metal cyanide complexes. It can be produced by a ring-opening polymerization reaction. The alkylene oxide can be ring-opening addition polymerized alone or in combination of two or more.
開始剤としては、水酸基を１個以上含有する化合物などが挙げられる。例えば、メタノール、エタノール、ｎ−プロパノール、ｉｓｏ−プロパノール、ｎ−ブタノール、ｉｓｏ−ブタノール、ｔｅｒｔ−ブタノール、シクロヘキサノール等の、炭素数１〜１０のアルキルモノアルコール類、エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、ネオペンチルグリコール、１，４−ブタンジオール、１，６−ヘキサンジオール、グリセリン、トリメチロールプロパン、ペンタエリスリトール、ジグリセリン等の多価アルコール類、ソルビトール、シュークロース、グルコース、ラクトース、ソルビタン等の糖類系多価アルコール類、フェノール、クレゾール、ビスフェノールＡ、ビスフェノールＦ等のフェノール類、モノエタノールアミン、ジエタノールアミン、Ｎ−メチルジエタノールアミン、Ｎ−メチルジプロパノールアミン、Ｎ−フェニルジエタノールアミン等のアミノアルコール類などである。 Examples of the initiator include compounds containing one or more hydroxyl groups. For example, alkyl monoalcohols having 1 to 10 carbon atoms such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, tert-butanol, cyclohexanol, ethylene glycol, diethylene glycol, propylene glycol, Polyhydric alcohols such as dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, sorbitol, sucrose, glucose, lactose, sorbitan Sugar polyhydric alcohols such as phenol, cresol, bisphenol A, bisphenol F and other phenols, monoethanolamine, diethanolamine, N-me Le diethanolamine, N- methyl dipropanolamine, and the like amino alcohols such as N- phenyl diethanolamine.
アルキレンオキシドとしては、炭素数１〜１０（好ましくは炭素数１〜５）のアルキレンオキシド例えば、エチレンオキシド、プロピレンオキシド、ブチレンオキシド、テトラヒドロフランなどが挙げられる。 Examples of the alkylene oxide include alkylene oxides having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms) such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran.
ポリオキシアルキレン系のポリオールやモノオールとして、具体的には、ポリオキシエチレンのポリオールやモノオール、ポリオキシプロピレンのポリオールやモノオール、ポリテトラメチレンエーテルのポリオールやモノオール、ポリ（オキシエチレン）−ポリ（オキシプロピレン）−ランダム或いはブロック共重合のポリオールやモノオール、ポリ（オキシプロピレン）−ポリ（オキシブチレン）−ランダム或いはブロック共重合のポリオールやモノオールなどを挙げることができる。粘度が低く、耐ブリード汚染性に優れる点で、ポリオキシアルキレン系ポリオール、ポリオキシアルキレン系モノオールが好ましく、さらにポリオキシプロピレントリオール、ポリオキシプロピレンジオール、ポリオキシプロピレンモノオールが好ましい。 Specific examples of polyoxyalkylene polyols and monools include polyoxyethylene polyols and monools, polyoxypropylene polyols and monools, polytetramethylene ether polyols and monools, and poly (oxyethylene)- Poly (oxypropylene) -random or block copolymer polyols and monools, poly (oxypropylene) -poly (oxybutylene) -random or block copolymer polyols and monools, and the like. In terms of low viscosity and excellent bleed stain resistance, polyoxyalkylene polyols and polyoxyalkylene monools are preferred, and polyoxypropylene triols, polyoxypropylene diols, and polyoxypropylene monools are more preferred.
ポリオキシアルキレン系のポリオールやモノオールは、数平均分子量が５００〜５０，０００、更に１，０００〜２０，０００、特に１，０００〜１０，０００のものが好ましい。数平均分子量が５００未満では、得られる着色剤組成物の耐ブリード汚染性が低下し、５０，０００を超えると粘度が高くなるおそれがあり好ましくない。重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比＝Ｍｗ／Ｍｎが１．６以下、特に１．０〜１．３が好ましい。分子量分布が狭いものを用いると、着色剤組成物の粘度を低く抑えることができる。さらに、着色剤組成物や着色剤組成物を含むシーリング材などの作業性が優れる。重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）はポリスチレン換算でゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定された値である。 Polyoxyalkylene polyols and monools preferably have a number average molecular weight of 500 to 50,000, more preferably 1,000 to 20,000, and particularly preferably 1,000 to 10,000. When the number average molecular weight is less than 500, the bleed stain resistance of the resulting colorant composition decreases, and when it exceeds 50,000, the viscosity may increase, which is not preferable. Ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) = Mw / Mn is 1.6 or less, particularly preferably 1.0 to 1.3. If a material having a narrow molecular weight distribution is used, the viscosity of the colorant composition can be kept low. Furthermore, workability | operativity, such as a sealing material containing a coloring agent composition or a coloring agent composition, is excellent. The weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured by gel permeation chromatography (GPC) in terms of polystyrene.
ポリオキシアルキレン系のポリオールやモノオールの総不飽和度は０．１ｍｅｑ／ｇ以下、さらに０．０７ｍｅｑ／ｇ以下、特に０．０４ｍｅｑ／ｇ以下のものが好ましい。総不飽和度が０．１ｍｅｑ／ｇを超えると耐候性の低下や耐ブリード汚染性の低下が生じるおそれがあり好ましくない。総不飽和度はＪＩＳ Ｋ１５５７−３：２００７により測定される。 The total unsaturation degree of the polyoxyalkylene polyol or monool is 0.1 meq / g or less, more preferably 0.07 meq / g or less, and particularly preferably 0.04 meq / g or less. If the total degree of unsaturation exceeds 0.1 meq / g, the weather resistance and the bleed contamination resistance may be lowered, which is not preferable. The total degree of unsaturation is measured according to JIS K1557-3: 2007.
ポリオキシアルキレン系のポリオールやモノオールは、分子１モルの水酸基を除いた部分の５０質量％以上、更に８０質量％以上、特に好ましくは９０質量％以上がポリオキシアルキレンで構成されていれば、残りの部分がエーテル、ウレタン、エステル、ポリカーボネート、ポリアミド、ポリアクリレート、ポリオレフィンなどで変性されていてもよい。水酸基を除いた分子の９５質量％以上がポリオキシアルキレンからなるポリオールやモノオールが最も好ましい。 The polyoxyalkylene-based polyol or monool is 50% by mass or more, more preferably 80% by mass or more, particularly preferably 90% by mass or more of the portion excluding the hydroxyl group of 1 mol of the molecule. The remaining part may be modified with ether, urethane, ester, polycarbonate, polyamide, polyacrylate, polyolefin or the like. Most preferred are polyols and monools in which 95% by mass or more of the molecules excluding the hydroxyl group are composed of polyoxyalkylene.
（水酸基含有ポリエーテル誘導体）
水酸基含有ポリエーテル誘導体としては、前記水酸基含有ポリエーテルの水酸基をエーテル化やエステル化、ウレタン化等した、分子内にエーテル基、エステル基、ウレタン基などの極性基を有するものが挙げられる。極性基は誘導体中に１種類でもよいし、数種類でもよい。また、極性基の個数は誘導体中に１つでもよいし、複数でもよい。特に、貯蔵安定性の観点から、水分や酸素と反応して硬化しない化合物が好ましい。
(Hydroxyl-containing polyether derivative)
Examples of the hydroxyl group-containing polyether derivative include those having a polar group such as an ether group, an ester group or a urethane group in the molecule, wherein the hydroxyl group of the hydroxyl group-containing polyether is etherified, esterified or urethanized. The polar group may be one kind or several kinds in the derivative. Further, the number of polar groups may be one in the derivative or plural. In particular, from the viewpoint of storage stability, a compound that does not cure by reacting with moisture or oxygen is preferable.
具体的には、極性基としてウレタン基を導入した化合物が好ましい。ウレタン基を導入した化合物は、粘度が低く、着色剤組成物にした際に耐ブリード汚染性に優れる。また、イソシアネート基含有ウレタンプレポリマー及び架橋性シリル基含有樹脂と相溶性が良好である。さらに、イソシアネート基含有ウレタンプレポリマー及び架橋性シリル基含有樹脂を硬化成分とするシーリング材などに配合したときの作業性が良好である。 Specifically, a compound having a urethane group introduced as a polar group is preferable. A compound into which a urethane group has been introduced has a low viscosity and is excellent in bleed stain resistance when formed into a colorant composition. In addition, the compatibility with the isocyanate group-containing urethane prepolymer and the crosslinkable silyl group-containing resin is good. Furthermore, workability when blended with a sealing material containing an isocyanate group-containing urethane prepolymer and a crosslinkable silyl group-containing resin as a curing component is good.
極性基としてウレタン基を導入した化合物は、前記水酸基含有ポリエーテルと有機イソシアネートとを反応させることにより製造することができる。前記水酸基含有ポリエーテルはポリオキシアルキレン系のポリオールやモノオールであることが好ましい。具体的には、ポリオキシアルキレン系モノオールと有機ジイソシアネート、または、ポリオキシアルキレン系ポリオールと有機モノイソシアネートとを反応させることにより製造した、実質的にイソシアネート基又は水酸基を含有しないポリオキシアルキレン系ウレタン樹脂であることが好ましい。本発明において、前記「実質的にイソシアネート基又は水酸基を含有しない」とは、イソシアネート基又は水酸基を完全に含有しない場合のみに限定する意味ではない。すなわち、ポリオキシアルキレン系ウレタン樹脂の合成の際に、イソシアネート基と水酸基の当量比によっては、イソシアネート基又は水酸基が少量残存する場合があるが、当該残存量が、水酸基含有ポリエーテル誘導体としての効果と、これを配合して得られる着色剤組成物の各種性能に対する悪影響が無視できる範囲であれば、前記「実質的にイソシアネート基又は水酸基を含有しない」に含まれるものである。この様な、イソシアネート基又は水酸基の含有量として、例えば、ポリオキシアルキレン系ウレタン樹脂中に０．０５ｍｍｏｌ／ｇ未満である。 A compound having a urethane group introduced as a polar group can be produced by reacting the hydroxyl group-containing polyether with an organic isocyanate. The hydroxyl group-containing polyether is preferably a polyoxyalkylene polyol or monool. Specifically, a polyoxyalkylene-based urethane that is substantially free of isocyanate groups or hydroxyl groups, produced by reacting a polyoxyalkylene-based monool and an organic diisocyanate, or a polyoxyalkylene-based polyol and an organic monoisocyanate. A resin is preferred. In the present invention, the phrase “substantially does not contain an isocyanate group or a hydroxyl group” does not mean that the isocyanate group or the hydroxyl group is not completely contained. That is, when synthesizing a polyoxyalkylene urethane resin, a small amount of isocyanate group or hydroxyl group may remain depending on the equivalent ratio of isocyanate group to hydroxyl group, but the residual amount is effective as a hydroxyl group-containing polyether derivative. If the colorant composition obtained by blending these is in a range in which the adverse effects on various performances can be ignored, it is included in the above “substantially does not contain an isocyanate group or a hydroxyl group”. Such an isocyanate group or hydroxyl group content is, for example, less than 0.05 mmol / g in the polyoxyalkylene urethane resin.
イソシアネート基／水酸基の当量比は１．１／１．０以下となる範囲で反応させるのが好ましい。当量比が１．１／１．０を上回るとイソシアネート基の含有量が多くなり、保存中に空気中の水分と反応して増粘し作業性や貯蔵安定性を悪化させる。本発明の着色剤組成物を、イソシアネート基含有プレポリマーを含有するシーリング材などに用いる場合は、イソシアネート基／水酸基の当量比が０．９／１．０〜１．１／１．０となる範囲で反応させることが好ましく、１／１で反応させることがもっとも好ましい。当量比が０．９／１．０を下回ると水酸基の含有率が多くなるため、本発明の着色剤組成物をイソシアネート基含有プレポリマーに配合したとき、イソシアネート基と反応し増粘し、作業性や貯蔵安定性を悪化させる点で好ましくない。水酸基当量は、ＪＩＳ Ｋ１５５７−１：２００７により求められる。 The isocyanate group / hydroxyl group equivalent ratio is preferably 1.1 / 1.0 or less. When the equivalent ratio exceeds 1.1 / 1.0, the content of isocyanate groups increases, reacts with moisture in the air during storage, and thickens to deteriorate workability and storage stability. When the colorant composition of the present invention is used for a sealing material containing an isocyanate group-containing prepolymer, the equivalent ratio of isocyanate group / hydroxyl group is 0.9 / 1.0 to 1.1 / 1.0. The reaction is preferably performed within the range, and the reaction is most preferably 1/1. When the equivalent ratio is less than 0.9 / 1.0, the hydroxyl group content increases. Therefore, when the colorant composition of the present invention is blended with an isocyanate group-containing prepolymer, it reacts with the isocyanate group to increase the viscosity. It is not preferable in terms of deteriorating properties and storage stability. The hydroxyl equivalent is determined according to JIS K1557-1: 2007.
有機イソシアネートとしては、具体的には、有機ポリイソシアネート、有機モノイソシアネート、及びこれらの混合物が挙げられる。これらは、単独であるいは２種以上を組み合わせて使用できる。 Specific examples of the organic isocyanate include organic polyisocyanates, organic monoisocyanates, and mixtures thereof. These can be used alone or in combination of two or more.
有機ポリイソシアネートとしては、例えば、２，４−トルエンジイソシアネート、２，６−トルエンジイソシアネート等のトルエンジイソシアネート類、４，４′−ジフェニルメタンジイソシアネート、２，４′−ジフェニルメタンジイソシアネート、２，２′−ジフェニルメタンジイソシアネート等のジフェニルメタンジイソシアネート類、１，２−フェニレンジイソシアネート、１，３−フェニレンジイソシアネート、１，４−フェニレンジイソシアネート等のフェニレンジイソシアネート類、２，４，６−トリメチルフェニル−１，３−ジイソシアネート、２，４，６−トリイソプロピルフェニル−１，３−ジイソシアネート、１，４−ナフタレンジイソシアネート、１，５−ナフタレンジイソシアネート等のナフタレンジイソシアネート類、クロロフェニレン−２，４−ジイソシアネート、４，４′−ジフェニルエーテルジイソシアネート、３，３′−ジメチルジフェニルメタン−４，４′−ジイソシアネート、３，３′−ジメトキシジフェニル−４，４′−ジイソシアネートなどの芳香族ジイソシアネート、１，６−ヘキサメチレンジイソシアネート、１，４−テトラメチレンジイソシアネート、２，２，４−トリメチル−１，６−ヘキサメチレンジイソシアネート、２，４，４−トリメチル−１，６−ヘキサメチレンジイソシアネート、デカメチレンジイソシアネート、リジンジイソシアネートなどの脂肪族ジイソシアネート、ｏ−キシリレンジイソシアネート、ｍ−キシリレンジイソシアネート、ｐ−キシリレンジイソシアネート等のキシリレンジイソシアネート類などの芳香脂肪族ジイソシアネート、１，４−シクロヘキシルジイソシアネート、イソホロンジイソシアネート、水素添加トルエンジイソシアネート、水素添加キシリレンジイソシアネート、水素添加ジフェニルメタンジイソシアネートなどの脂環族ジイソシアネートが挙げられる。更に、ポリメチレンポリフェニルポリイソシアネート、クルードトルエンジイソシアネートなどの有機ポリイソシアネートも使用できる。また、これらの有機ポリイソシアネートを変性して得られる、ウレトジオン結合、イソシアヌレート結合、アロファネート結合、ビュレット結合、ウレトンイミン結合、カルボジイミド結合、ウレタン結合、ウレア結合などを１以上含有する変性イソシアネートも使用できる。 Examples of the organic polyisocyanate include toluene diisocyanates such as 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, and 2,2′-diphenylmethane diisocyanate. Diphenylmethane diisocyanates such as 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, phenylene diisocyanates such as 1,4-phenylene diisocyanate, 2,4,6-trimethylphenyl-1,3-diisocyanate, 2,4 Naphthalene diisocyanate such as 1,6-triisopropylphenyl-1,3-diisocyanate, 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate Chlorophenylene-2,4-diisocyanate, 4,4'-diphenyl ether diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate, etc. Aromatic diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,4,4-trimethyl-1,6-hexa Xylylene diisocyanates such as aliphatic diisocyanates such as methylene diisocyanate, decamethylene diisocyanate, lysine diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate What araliphatic diisocyanate, 1,4-cyclohexyl diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylylene diisocyanate, and alicyclic diisocyanates such as hydrogenated diphenylmethane diisocyanate. Furthermore, organic polyisocyanates such as polymethylene polyphenyl polyisocyanate and crude toluene diisocyanate can also be used. In addition, modified isocyanates containing one or more uretdione bonds, isocyanurate bonds, allophanate bonds, burette bonds, uretonimine bonds, carbodiimide bonds, urethane bonds, urea bonds and the like obtained by modifying these organic polyisocyanates can also be used.
有機モノイソシアネートとしては、例えば、ｎ−ブチルモノイソシアネート、ｎ−ヘキシルモノイソシアネート、ｎ−ヘキサデシルモノイソシアネート、ｎ−オクタデシルモノイソシアネート、ｐ−イソプロピルフェニルモノイソシアネート、ｐ−ベンジルオキシフェニルモノイソシアネートが挙げられる。 Examples of the organic monoisocyanate include n-butyl monoisocyanate, n-hexyl monoisocyanate, n-hexadecyl monoisocyanate, n-octadecyl monoisocyanate, p-isopropylphenyl monoisocyanate, and p-benzyloxyphenyl monoisocyanate. .
これらのうち、粘度を低くでき、黄変を防止する点で、芳香脂肪族ジイソシアネート、脂肪族ジイソシアネート、脂環族ジイソシアネートが好ましい。特に、ｍ−キシリレンジイソシアネートが好ましい。 Of these, araliphatic diisocyanate, aliphatic diisocyanate, and alicyclic diisocyanate are preferable in that the viscosity can be lowered and yellowing can be prevented. In particular, m-xylylene diisocyanate is preferable.
ポリオキシアルキレン系ウレタン樹脂の合成には、公知のウレタン化触媒を反応触媒として用いることができる。具体的には、オクチル酸第一錫、オクテン酸錫などの、亜鉛、錫、鉛、ジルコニウム、ビスマス、コバルト、マンガン、鉄などの金属とオクチル酸、オクテン酸、ナフテン酸などの有機酸との金属塩、ジブチル錫ジアセチルアセトナート、ジルコニウムテトラアセチルアセトナート、チタンテトラアセチルアセトナート、錫系キレート化合物であるＥＸＣＥＳＴＡＲ Ｃ−５０１（旭硝子社製）などの金属キレート化合物、ジブチル錫ジラウレート、ジオクチル錫ジラウレート等の有機金属化合物、トリエチレンジアミン、トリエチルアミン、トリ−ｎ−ブチルアミン等の有機アミンやその塩等を用いることができる。これらのうち金属有機酸塩や有機金属化合物が好ましい。また、水酸基やイソシアネート基と反応性を有しない公知の有機溶剤を反応溶媒として使用することは、大気中への揮散による環境汚染を発生させることとなり好ましくない。 A known urethanization catalyst can be used as a reaction catalyst in the synthesis of the polyoxyalkylene urethane resin. Specifically, between zinc, tin, lead, zirconium, bismuth, cobalt, manganese, iron and other metals and organic acids such as octylic acid, octenoic acid and naphthenic acid, such as stannous octylate and tin octenoate. Metal chelate compounds such as metal salts, dibutyltin diacetylacetonate, zirconium tetraacetylacetonate, titanium tetraacetylacetonate, tin-based chelate compound EXCESTAR C-501 (Asahi Glass Co., Ltd.), dibutyltin dilaurate, dioctyltin dilaurate, etc. Organic metal compounds, organic amines such as triethylenediamine, triethylamine, and tri-n-butylamine, salts thereof, and the like can be used. Of these, metal organic acid salts and organic metal compounds are preferred. Moreover, it is not preferable to use a known organic solvent that is not reactive with a hydroxyl group or an isocyanate group as a reaction solvent because it causes environmental pollution due to volatilization into the atmosphere.
なお、水酸基含有ポリエーテル誘導体の数平均分子量は、上記と同様の理由から、５００〜５０，０００、更に１，０００〜２０，０００、特に１，０００〜１０，０００のものが好ましい。また、重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比＝Ｍｗ／Ｍｎが１．６以下、特に１．０〜１．３が好ましい。 The number average molecular weight of the hydroxyl group-containing polyether derivative is preferably 500 to 50,000, more preferably 1,000 to 20,000, and particularly preferably 1,000 to 10,000 for the same reason as described above. Further, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) = Mw / Mn is 1.6 or less, particularly preferably 1.0 to 1.3.
（顔料）
本発明における顔料としては、特に限定されず、いずれも公知の顔料を使用できる。具体的には、白色、黄色、赤色、青色、緑色、黒色などの有色がある。本発明においては、単一の顔料からなるものであっても、複数の顔料を混合したものであってもよい。白色顔料としては、酸化チタン、亜鉛華、鉛白、リトポンなどが挙げられる。黄色顔料としては、酸化鉄イエロー、黄鉛、亜鉛黄、ベンジジンイエロー、オーラミンレーキなどが挙げられる。赤色顔料としては、鉛丹、酸化鉄レッド（ベンガラ）、塩基性クロム酸鉛、朱、カドミウム赤、ブリリアントスカーレットなどが挙げられる。青色顔料としては、コバルト青（アルミン酸コバルト）、群青、紺青、フタロシアニンブルーなどが挙げられる。緑色顔料としては、酸化クロム、クロムグリーン、ジンクグリーン、ピグメントグリーンなどが挙げられる。黒色顔料としては、カーボンブラック、ランプブラック、ボーンブラック、黒鉛などが挙げられる。顔料の配合量は、水酸基含有ポリエーテル又は水酸基含有ポリエーテル誘導体１００質量部に対して１０〜３００質量部が好ましく、特に２５〜１５０質量部が好ましい。
(Pigment)
The pigment in the present invention is not particularly limited, and any known pigment can be used. Specifically, there are colors such as white, yellow, red, blue, green, and black. In the present invention, it may be composed of a single pigment or a mixture of a plurality of pigments. Examples of white pigments include titanium oxide, zinc white, lead white, and lithopone. Examples of yellow pigments include iron oxide yellow, yellow lead, zinc yellow, benzidine yellow, and auramin lake. Examples of red pigments include red lead, iron oxide red (Bengara), basic lead chromate, vermilion, cadmium red, and brilliant scarlet. Examples of blue pigments include cobalt blue (cobalt aluminate), ultramarine blue, bitumen, and phthalocyanine blue. Examples of the green pigment include chromium oxide, chromium green, zinc green, and pigment green. Examples of black pigments include carbon black, lamp black, bone black, and graphite. The blending amount of the pigment is preferably 10 to 300 parts by mass, particularly preferably 25 to 150 parts by mass with respect to 100 parts by mass of the hydroxyl group-containing polyether or the hydroxyl group-containing polyether derivative.
［着色剤組成物の製造方法］
本発明の着色剤組成物の製造方法は、水酸基含有ポリエーテル及び／又は水酸基含有ポリエーテル誘導体中に顔料を均一に分散できる方法であればどの様な方法を用いてもよい。例えば、プラネタリーミキサー、ニーダー、アジター、ナウタミキサー、ラインミキサーなどステンレス製や鉄製の公知の攪拌、混合装置を用いて、顔料と水酸基含有ポリエーテル及び／又は水酸基含有ポリエーテル誘導体を混合、分散することにより製造される。
[Method for producing colorant composition]
As a method for producing the colorant composition of the present invention, any method may be used as long as the pigment can be uniformly dispersed in the hydroxyl group-containing polyether and / or the hydroxyl group-containing polyether derivative. For example, a pigment and a hydroxyl group-containing polyether and / or a hydroxyl group-containing polyether derivative are mixed and dispersed using a known stirring and mixing device made of stainless steel or iron such as a planetary mixer, a kneader, an agitator, a nauta mixer, or a line mixer. It is manufactured by.
必要に応じて着色剤組成物中の含水率を低くする為に脱水工程を加えても良い。水分量はカールフィッシャー法で測定することができる。脱水方法は、どのような方法を用いても良く、例えば、脱水した顔料を水酸基含有ポリエーテル及び／又は水酸基含有ポリエーテル誘導体に分散する方法、水酸基含有ポリエーテル及び／又は水酸基含有ポリエーテル誘導体中に顔料を分散した後に脱水する方法が挙げられる。後者の方法を用いる場合は、水酸基含有ポリエーテル中に顔料を分散した後に脱水し、有機イソシアネートなどを加えて反応させて水酸基含有ポリエーテルを誘導体化する方法、水酸基含有ポリエーテル及び／又は水酸基含有ポリエーテルの誘導体に顔料を分散した後に脱水する方法のどちらでもよい。取扱いが容易な点で水酸基含有ポリエーテル及び／又は水酸基含有ポリエーテル誘導体に顔料を分散した後に必要に応じて脱水する方法が好ましい。具体的には、顔料を分散した後に、減圧又は／及び加熱することによって脱水することができる。 If necessary, a dehydration step may be added to lower the water content in the colorant composition. The water content can be measured by the Karl Fischer method. Any method may be used as the dehydration method, for example, a method of dispersing a dehydrated pigment in a hydroxyl group-containing polyether and / or a hydroxyl group-containing polyether derivative, a hydroxyl group-containing polyether and / or a hydroxyl group-containing polyether derivative. And a method of dehydrating after dispersing the pigment. When using the latter method, the pigment is dispersed in the hydroxyl group-containing polyether and then dehydrated, and a method of derivatizing the hydroxyl group-containing polyether by adding organic isocyanate or the like to react, hydroxyl group-containing polyether and / or hydroxyl group-containing method Either of the methods of dehydrating after dispersing the pigment in the polyether derivative may be used. In view of easy handling, a method in which a pigment is dispersed in a hydroxyl group-containing polyether and / or a hydroxyl group-containing polyether derivative and then dehydrated as necessary is preferable. Specifically, after the pigment is dispersed, it can be dehydrated by reducing pressure and / or heating.
脱水工程を加える場合は、脱水工程後の着色剤組成物の含水率は１．０質量％以下、好ましくは０．１質量％以下、更に好ましくは０．０５質量％以下である。含水率を少なくすることにより、着色剤組成物の粘度を低くすることができる。着色剤の粘度を低くすると、従来用いられている着色剤組成物と同程度の粘度でも顔料の高濃度化が可能となり、同量の顔料を添加する場合に分散媒の量を低減することができるため、分散媒による基材の物性変化を少なくすることができると共に、該着色剤組成物を用いて着色する際に、攪拌、混合装置の制限を受けず、簡易に着色できるという利点がある。また、該着色剤組成物を湿気により硬化する一液型の樹脂組成物に加えた時の、貯蔵安定性を向上させることができる。 When the dehydration step is added, the water content of the colorant composition after the dehydration step is 1.0% by mass or less, preferably 0.1% by mass or less, and more preferably 0.05% by mass or less. By reducing the water content, the viscosity of the colorant composition can be lowered. By reducing the viscosity of the colorant, it becomes possible to increase the concentration of the pigment even when the viscosity is the same as that of a conventionally used colorant composition, and the amount of the dispersion medium can be reduced when the same amount of pigment is added. Therefore, it is possible to reduce the change in physical properties of the substrate due to the dispersion medium, and there is an advantage that when coloring with the colorant composition, it can be easily colored without being restricted by stirring and mixing devices. . In addition, the storage stability when the colorant composition is added to a one-component resin composition that is cured by moisture can be improved.
なお、本発明の着色剤組成物には、上記の成分に加え、例えば酸化防止剤や紫外線吸収剤や光硬化性化合物などの耐候性安定剤、貯蔵安定性改良剤、分散剤、充填剤、揺変剤等の各種添加剤を配合しても良い。これらの添加剤を配合する場合には、水酸基含有ポリエーテル又は水酸基含有ポリエーテル誘導体１００質量部に対して０．０１〜１０質量部が好ましく、特に０．１〜３．０質量部が好ましい。なお、これらの添加剤については、下記で詳述する。 In addition to the above components, the colorant composition of the present invention includes, for example, a weather resistance stabilizer such as an antioxidant, an ultraviolet absorber, and a photocurable compound, a storage stability improver, a dispersant, a filler, Various additives such as thixotropic agents may be blended. When mix | blending these additives, 0.01-10 mass parts is preferable with respect to 100 mass parts of hydroxyl-containing polyether or a hydroxyl-containing polyether derivative, and 0.1-3.0 mass parts is especially preferable. These additives will be described in detail below.
［基材の着色方法］
本発明の基材の着色方法は、上述の着色剤組成物を用いることを特徴とする。着色剤組成物を、基材となるシーリング材、防水材、接着剤、又は塗料等を混合して、シーリング材、防水材、接着剤、又は塗料等を目的とする色調にすることができる。なお、着色剤組成物は１種類でも数種類を混合して用いてもよい。また、本発明の着色剤組成物は、通常、基材１００質量部に対して、２０質量部以下、好ましくは１０質量部以下の範囲内で用いられる。
[Substrate coloring method]
The substrate coloring method of the present invention is characterized by using the above-described colorant composition. The colorant composition can be mixed with a sealing material, a waterproofing material, an adhesive, or a paint serving as a base material to obtain a color tone intended for the sealing material, the waterproofing material, the adhesive, or the coating. The colorant composition may be used alone or in combination. In addition, the colorant composition of the present invention is usually used within a range of 20 parts by mass or less, preferably 10 parts by mass or less with respect to 100 parts by mass of the base material.
［シーリング材の製造方法］
シーリング材の製造方法は、シーリング基材を本発明の着色剤組成物を用いて所望の色調に調色するものである。具体的な方法としては、着色剤組成物とシーリング基材を均一に混合、分散できる方法であればどの様な方法を用いてもよい。例えば、プラネタリーミキサー、ニーダー、アジター、ナウタミキサー、ラインミキサーなどステンレス製や鉄製の公知の攪拌、混合装置を用いて、着色剤組成物とシーリング基材を混合、分散することがあげられる。
[Method of manufacturing sealing material]
The manufacturing method of a sealing material adjusts a sealing base material to a desired color tone using the coloring agent composition of this invention. As a specific method, any method may be used as long as it can uniformly mix and disperse the colorant composition and the sealing substrate. For example, the colorant composition and the sealing substrate may be mixed and dispersed using a known stirring and mixing device made of stainless steel or iron such as a planetary mixer, a kneader, an agitator, a nauta mixer, or a line mixer.
シーリング基材としては特に限定されない。例えば、アクリル系基材、シリコーン系基材、変成シリコーン系基材、ポリサルファイド系基材、アクリルウレタン系基材、ポリウレタン系基材、ポリイソブチレン系基材、フッ素系基材および変性ポリサルファイド基材系などが挙げられる。これらは１成分型でも２成分型でもよい。 The sealing substrate is not particularly limited. For example, acrylic base, silicone base, modified silicone base, polysulfide base, acrylic urethane base, polyurethane base, polyisobutylene base, fluorine base and modified polysulfide base Etc. These may be one-component type or two-component type.
前記シーリング基材は、公知の方法によって製造されるが、プラネタリーミキサー、ニーダー、アジター、ナウタミキサー、ラインミキサーなどステンレス製や鉄製の公知の攪拌、混合装置を用いて、硬化性樹脂と添加剤等を混合、混練することにより製造される。なお、硬化性樹脂、添加剤はそれぞれ、１種であっても２種以上使用してもよい。 The sealing substrate is manufactured by a known method, but a curable resin and an additive using a known stirring and mixing device made of stainless steel or iron such as a planetary mixer, a kneader, an agitator, a nauta mixer, or a line mixer. Etc. are manufactured by mixing and kneading. The curable resin and the additive may be used alone or in combination of two or more.
硬化性樹脂は、公知のものを使用することができるが、湿気により硬化する一液型の樹脂が好ましく、架橋性シリル基含有樹脂又はイソシアネート基含有プレポリマーが最も好ましい。 A known resin can be used as the curable resin, but a one-pack type resin that is cured by moisture is preferable, and a crosslinkable silyl group-containing resin or an isocyanate group-containing prepolymer is most preferable.
架橋性シリル基含有樹脂は、一般に変成シリコーン樹脂と呼ばれているものであり、湿気（水）と反応してシロキサン結合を形成することにより架橋してゴム状硬化物を形成する、分子内にシリル基を１個以上含有する樹脂である。このような架橋性シリル基含有樹脂としては、例えば、特開昭５２−７３９９８号公報、特開昭５５−９６６９号公報、特開昭５９−１２２５４１号公報、特開昭６０−６７４７号公報、特開昭６１−２３３０４３号公報、特開昭６３−１１２６４２号公報、特開平３−７９６２７号公報、特開平４−２８３２５９号公報、特開平５−７０５３１号公報、特開平５−２８７１８６号公報、特開平１１−８０５７１号公報、特開平１１−１１６７６３号公報、特開平１１−１３０９３１号公報中に開示されているものを挙げることができる。本発明における架橋性シリル基含有樹脂としては具体的には、分子内に１個以上の架橋性シリル基を含有する、主鎖がそれぞれオルガノシロキサンを含有していてもよい、ポリオキシアルキレン重合体、ビニル変性ポリオキシアルキレン重合体、ビニル系重合体、ポリエステル重合体、アクリル酸エステル重合体、メタクリル酸エステル重合体、これらの共重合体等が挙げられる。架橋性シリル基は、シーリング材の硬化性や硬化後の物性等の点から、分子内に１〜５個含まれるのが好ましい。さらに、架橋性シリル基は、架橋しやすく製造しやすい次の一般式で示されるものが好ましい。 The crosslinkable silyl group-containing resin is generally called a modified silicone resin and forms a rubber-like cured product by cross-linking by forming a siloxane bond by reacting with moisture (water). It is a resin containing one or more silyl groups. Examples of such crosslinkable silyl group-containing resins include JP-A-52-73998, JP-A-55-9669, JP-A-59-122541, JP-A-60-6747, JP-A-61-233043, JP-A-63-112642, JP-A-3-79627, JP-A-4-283259, JP-A-5-70531, JP-A-5-287186, Examples thereof include those disclosed in JP-A-11-80571, JP-A-11-116763, and JP-A-11-130931. Specifically, as the crosslinkable silyl group-containing resin in the present invention, a polyoxyalkylene polymer containing one or more crosslinkable silyl groups in the molecule, and each main chain may contain an organosiloxane. , Vinyl-modified polyoxyalkylene polymers, vinyl polymers, polyester polymers, acrylic acid ester polymers, methacrylic acid ester polymers, and copolymers thereof. It is preferable that 1-5 crosslinkable silyl groups are contained in a molecule | numerator from points, such as the sclerosis | hardenability of a sealing material, and the physical property after hardening. Further, the crosslinkable silyl group is preferably one represented by the following general formula which is easily crosslinked and easy to produce.
（式中、Ｒは炭化水素基であり、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基又は炭素数７〜２０のアラルキル基が好ましく、メチル基が最も好ましい。Ｘで示される反応性基はハロゲン原子、水素原子、水酸基、アルコキシ基、アシルオキシ基、ケトキシメート基、アミド基、酸アミド基、メルカプト基、アルケニルオキシ基及びアミノオキシ基より選ばれる基であり、Ｘが複数の場合には、Ｘは同じ基であっても異なった基であってもよい。このうちＸはアルコキシ基が好ましく、メトキシ基又はエトキシ基が最も好ましい。ａは０、１又は２の整数であり、０又は１が最も好ましい。） Wherein R is a hydrocarbon group, preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and most preferably a methyl group. The reactive group is a group selected from a halogen atom, a hydrogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, a mercapto group, an alkenyloxy group, and an aminooxy group. In this case, X may be the same group or different groups, among which X is preferably an alkoxy group, most preferably a methoxy group or an ethoxy group, and a is an integer of 0, 1 or 2. , 0 or 1 is most preferred.)
架橋性シリル基含有樹脂の主鎖は、硬化後の引張接着性、モジュラス等の物性の点から、オルガノシロキサンを含有していてもよい。具体的には、ポリオキシアルキレン重合体及び／又はビニル変性ポリオキシアルキレン重合体が好ましい。ポリオキシアルキレン重合体としては、ポリオキシプロピレン重合体が好ましい。ビニル変性ポリオキシアルキレン重合体としては、アクリル変性ポリオキシプロピレン重合体、メタクリル変性ポリオキシプロピレン重合体が好ましい。ビニル変性ポリオキシアルキレン重合体は、分子内に１個以上の架橋性シリル基を含有する。ポリオキシアルキレン重合体の存在下で、ラジカル重合開始剤の添加あるいは紫外線照射などの通常のラジカル重合方法により、１種又は２種以上のビニル系単量体を重合させる等して得ることができる（特開昭５９−７８２２３号公報、特公平２−４２３６７号公報等参照）。 The main chain of the crosslinkable silyl group-containing resin may contain an organosiloxane from the viewpoint of physical properties such as tensile adhesiveness after curing and modulus. Specifically, a polyoxyalkylene polymer and / or a vinyl-modified polyoxyalkylene polymer is preferable. As the polyoxyalkylene polymer, a polyoxypropylene polymer is preferable. As the vinyl-modified polyoxyalkylene polymer, an acrylic-modified polyoxypropylene polymer and a methacryl-modified polyoxypropylene polymer are preferable. The vinyl-modified polyoxyalkylene polymer contains one or more crosslinkable silyl groups in the molecule. In the presence of a polyoxyalkylene polymer, it can be obtained by polymerizing one or more vinyl monomers by a normal radical polymerization method such as addition of a radical polymerization initiator or ultraviolet irradiation. (See JP-A-59-78223, JP-B-2-42367, etc.).
本発明において、架橋性シリル基含有樹脂の数平均分子量は１，０００以上、特に６，０００〜３０，０００がよい。分子量分布は１．６以下が好ましい。硬化前の粘度が低いので取り扱い易く、硬化後の強度、伸び、モジュラス等の物性が好適である。 In the present invention, the number average molecular weight of the crosslinkable silyl group-containing resin is 1,000 or more, particularly 6,000 to 30,000. The molecular weight distribution is preferably 1.6 or less. Since the viscosity before curing is low, it is easy to handle, and physical properties such as strength, elongation and modulus after curing are suitable.
イソシアネート基含有プレポリマーは、有機ポリイソシアネートと活性水素化合物とを活性水素（基）に対してイソシアネート基過剰、好ましくはイソシアネート基／活性水素（基）（当量比）が１．２〜４．０、更には１．３〜３．０、特に１．３〜２．０となるような割合で反応させて得られるものが好ましい。イソシアネート当量は上記と同様の方法で求めることができ、活性水素当量は水酸基価、アミン価等により求められる。 In the isocyanate group-containing prepolymer, the organic polyisocyanate and the active hydrogen compound are in excess of the isocyanate group with respect to the active hydrogen (group), and preferably the isocyanate group / active hydrogen (group) (equivalent ratio) is 1.2 to 4.0. Further, those obtained by reacting at a ratio of 1.3 to 3.0, particularly 1.3 to 2.0 are preferable. The isocyanate equivalent can be determined by the same method as described above, and the active hydrogen equivalent can be determined by the hydroxyl value, the amine value, and the like.
有機ポリイソシアネートとしては、例えば、フェニレンジイソシアネート、ジフェニルジイソシアネート、ナフタレンジイソシアネート、ジフェニルメタンジイソシアネート（ＭＤＩ）、トリレンジイソシアネート（ＴＤＩ）、ジフェニルエーテルジイソシアネートなどの芳香族ジイソシアネート、キシリレンジイソシアネートなどの芳香脂肪族ジイソシアネート、ヘキサメチレンジイソシアネート、ペンタメチレンジイソシアネート、プロピレンジイソシアネート、ブチレンジイソシアネートなどの脂肪族ジイソシアネート、シクロヘキサンジイソシアネート、メチレンビス（シクロヘキシルイソシアネート）、イソホロンジイソシアネートなどの脂環族ジイソシアネート、およびこれらジイソシアネートのカルボジイミド変性体、ビウレット変性体、アロファネート変性体、二量体、三量体、または、ポリメチレンポリフェニルポリイソシアネート（クルードＭＤＩ、ポリメリックＭＤＩ）などが挙げられる。これらのうち、芳香族ジイソシアネートが好ましく、ＭＤＩとＴＤＩが更に好ましい。 Examples of the organic polyisocyanate include aromatic diisocyanates such as phenylene diisocyanate, diphenyl diisocyanate, naphthalene diisocyanate, diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), diphenyl ether diisocyanate, and araliphatic diisocyanates such as xylylene diisocyanate, hexamethylene. Aliphatic diisocyanates such as diisocyanate, pentamethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, cyclohexane diisocyanate, methylene bis (cyclohexyl isocyanate), alicyclic diisocyanates such as isophorone diisocyanate, and carbodiimide modified products of these diisocyanates, biuret DOO modified products, allophanate modified products, dimers, trimers, or polymethylene polyphenyl polyisocyanate (crude MDI, polymeric MDI), and the like. Of these, aromatic diisocyanates are preferred, and MDI and TDI are more preferred.
前記活性水素化合物としては、ポリオール、アミノアルコール、ポリアミンなどが挙げられる。これらの化合物のうち、高分子のポリオールが好適である。 Examples of the active hydrogen compound include polyols, amino alcohols, and polyamines. Of these compounds, polymeric polyols are preferred.
高分子のポリオールとしては、ポリエステルポリオール、ポリエステルアミドポリオール、ポリエーテルポリオール、ポリエーテル・エステルポリオール、ポリカーボネートポリオール、炭化水素系ポリオール等が挙げられ、数平均分子量５００以上のものである。ポリエステルポリオール、ポリエステルアミドポリオールとしては、例えば、公知のコハク酸、アジピン酸、テレフタル酸等のジカルボン酸、それらの酸エステル、酸無水物等と、エチレングリコール、プロパンジオール、ブタンジオール、ペンタンジオール、ヘキサンジオール、ネオペンチルグリコール、トリメチロールプロパン、グリセリン、クオドロールあるいはビスフェノールＡのエチレンオキサイド又はプロピレンオキサイド付加物等の低分子ポリオール、あるいはエチレンジアミン、ジエチレントリアミン等の低分子ポリアミン、モノエタノールアミン等のアミノアルコール等の単独、又はこれらの混合物との脱水縮合反応で得られる化合物が挙げられる。さらに、ε−カプロラクトン等の環状エステル（すなわちラクトン）モノマーの開裂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等が挙げられる。ポリエーテルポリオールとしては、例えば、ポリオキシエチレンポリオール、ポリオキシプロピレンポリオール等が挙げられる。ポリエーテル・エステルポリオールとしては、例えば、前記のポリエーテルポリオールと前記のジカルボン酸、酸無水物等とから製造される化合物が挙げられる。ポリカーボネートポリオールとしては、例えば、前記のポリエステルポリオールの製造に用いる低分子ポリオールとジエチルカーボネート、ジフェニルカーボネート等との反応から得られる化合物が挙げられる。ポリオールとしては更に、前記ポリエステルポリオールの製造原料として挙げた数平均分子量５００未満の低分子ポリオールが挙げられる。 Examples of the polymer polyol include polyester polyols, polyester amide polyols, polyether polyols, polyether / ester polyols, polycarbonate polyols, hydrocarbon polyols, and the like, and those having a number average molecular weight of 500 or more. Examples of the polyester polyol and polyester amide polyol include known dicarboxylic acids such as succinic acid, adipic acid, and terephthalic acid, their acid esters, acid anhydrides, ethylene glycol, propanediol, butanediol, pentanediol, and hexane. Low molecular polyols such as diol, neopentyl glycol, trimethylolpropane, glycerin, quadrol or bisphenol A ethylene oxide or propylene oxide adducts, low molecular polyamines such as ethylenediamine and diethylenetriamine, amino alcohols such as monoethanolamine, etc. Or a compound obtained by a dehydration condensation reaction with a mixture thereof. Furthermore, a lactone polyester polyol obtained by cleavage polymerization of a cyclic ester (that is, lactone) monomer such as ε-caprolactone is exemplified. Examples of the polyether polyol include polyoxyethylene polyol and polyoxypropylene polyol. Examples of the polyether ester polyol include compounds produced from the above polyether polyol and the above dicarboxylic acid, acid anhydride and the like. Examples of the polycarbonate polyol include compounds obtained from a reaction between a low molecular polyol used for the production of the polyester polyol and diethyl carbonate, diphenyl carbonate, or the like. Examples of the polyol further include low molecular weight polyols having a number average molecular weight of less than 500, which are cited as the raw materials for producing the polyester polyol.
ポリアミンとしては、ポリプロピレングリコールの末端ジアミノ化物などの、数平均分子量５００以上でポリエーテルポリオールの末端がアミノ基となったポリエーテルポリアミン等の高分子ポリアミンが挙げられる。ポリアミンとしては更に、エチレンジアミン、ヘキサメチレンジアミン、イソホロンジアミン、ジアミノジフェニルメタン、ジエチレントリアミン等の数平均分子量５００未満の低分子ポリアミンが挙げられる。 Examples of the polyamine include polymer polyamines such as polyether polyamines having a number average molecular weight of 500 or more and a polyether polyol terminal having an amino group, such as a terminal diaminated product of polypropylene glycol. Examples of the polyamine further include low molecular weight polyamines having a number average molecular weight of less than 500, such as ethylenediamine, hexamethylenediamine, isophoronediamine, diaminodiphenylmethane, and diethylenetriamine.
アミノアルコールとしては、モノエタノールアミン、ジエタノールアミン、Ｎ−メチルジエタノールアミン、Ｎ−メチルジプロパノールアミン、Ｎ−フェニルジエタノールアミン等が挙げられる。 Examples of amino alcohols include monoethanolamine, diethanolamine, N-methyldiethanolamine, N-methyldipropanolamine, and N-phenyldiethanolamine.
また、一般にポリウレタン工業において公知の活性水素基を含有する、数平均分子量５００以上の、エポキシ樹脂、ポリアミド樹脂、ポリエステル樹脂等も挙げられる。 In addition, epoxy resins, polyamide resins, polyester resins and the like having an active hydrogen group generally known in the polyurethane industry and having a number average molecular weight of 500 or more are also included.
イソシアネート基含有プレポリマーのイソシアネート基（ＮＣＯ）濃度は、０．３〜３５質量％であることが好ましく、更には０．３〜１０質量％、特に０．３〜５質量％であることが好ましい。濃度が１０質量％を超えると、発泡、硬化物の物性低下を引き起こすおそれがあり、０．３質量％未満であると、高粘度化、作業性の低下等を招来するおそれがある。 The isocyanate group (NCO) concentration of the isocyanate group-containing prepolymer is preferably 0.3 to 35% by mass, more preferably 0.3 to 10% by mass, and particularly preferably 0.3 to 5% by mass. . If the concentration exceeds 10% by mass, foaming and physical properties of the cured product may be reduced, and if it is less than 0.3% by mass, viscosity may be increased and workability may be reduced.
添加剤としては、例えば酸化防止剤や紫外線吸収剤や光硬化性化合物などの耐候性安定剤、貯蔵安定性改良剤（脱水剤）、分散剤、充填剤、揺変剤等を挙げることができる。 Examples of additives include weather resistance stabilizers such as antioxidants, ultraviolet absorbers, and photocurable compounds, storage stability improvers (dehydrating agents), dispersants, fillers, thixotropic agents, and the like. .
耐候安定剤は、水酸基含有ポリエーテル及び／又は水酸基含有ポリエーテルの誘導体の酸化や光劣化、熱劣化を防止して、耐候性だけでなく耐熱性を向上させるためにも使用する。 The weathering stabilizer is used to prevent oxidation, photodegradation, and thermal degradation of the hydroxyl group-containing polyether and / or the derivative of the hydroxyl group-containing polyether, thereby improving not only the weather resistance but also the heat resistance.
酸化防止剤としては具体的には、ヒンダードアミン系やヒンダードフェノール系の酸化防止剤を挙げることができ、ヒンダードアミン系酸化防止剤としては、例えば、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）［［３，５−ビス（１，１−ジメチルエチル）−４−ヒドロキシフェニル］メチル］ブチルマロネート、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）セバケート、メチル−１，２，２，６，６−ペンタメチル−４−ピペリジルセバケート、４−ベンゾイルオキシ−２，２，６，６−テトラメチルピペリジンなどが挙げられる。また、三共社製の商品名サノールＬＳ−２９２などの他、旭電化工業社製の商品名アデカスタブシリーズのＬＡ−５２、ＬＡ−５７、ＬＡ−６２、ＬＡ−６７、ＬＡ−７７、ＬＡ−８２、ＬＡ−８７などの分子量１，０００未満の低分子量ヒンダードアミン系酸化防止剤、同じくＬＡ−６３Ｐ、ＬＡ−６８ＬＤ或いはチバ・スペシャルティ・ケミカルズ社製の商品名ＣＨＩＭＡＳＳＯＲＢシリーズの１１９ＦＬ、２０２０ＦＤＬ、９４４ＦＤ、９４４ＬＤなどの分子量１，０００以上の高分子量ヒンダードアミン系酸化防止剤なども挙げられる。 Specific examples of the antioxidant include hindered amine-based and hindered phenol-based antioxidants. Examples of the hindered amine-based antioxidant include bis (1,2,2,6,6-pentamethyl). -4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) Examples include sebacate, methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine. In addition to Sanyo LS-292, trade names manufactured by Sankyo Co., Ltd., trade names Adeka Stub series LA-52, LA-57, LA-62, LA-67, LA-77, LA- 82, LA-87 and other low molecular weight hindered amine antioxidants with a molecular weight of less than 1,000, also LA-63P, LA-68LD or Ciba Specialty Chemicals' product names CHIMASSORB series 119FL, 2020FDL, 944FD, 944LD And high molecular weight hindered amine antioxidants having a molecular weight of 1,000 or more.
ヒンダードフェノール系酸化防止剤としては、例えば、ペンタエリストール−テトラキス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、オクタデシル−３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、Ｎ，Ｎ′−ヘキサン−１，６−ジイルビス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニルプロピオナミド）］、ベンゼンプロパン酸３，５−ビス（１，１−ジメチルエチル）−４−ヒドロキシＣ７−Ｃ９側鎖アルキルエステル、２，４−ジメチル−６−（１−メチルペンタデシル）フェノールなどが挙げられる。 Examples of the hindered phenol antioxidant include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-). tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide)], benzenepropanoic acid Examples include 3,5-bis (1,1-dimethylethyl) -4-hydroxy C7-C9 side chain alkyl ester, 2,4-dimethyl-6- (1-methylpentadecyl) phenol, and the like.
紫外線吸収剤としては、例えば、２−（３，５−ジ−ｔｅｒｔ−ブチル−２−ヒドロキシフェニル）−５−クロロベンゾトリアゾール等のベンゾトリアゾール系紫外線吸収剤、２−（４，６−ジフェニル−１，３，５−トリアジン−２−イル）−５−［（ヘキシル）オキシ］−フェノール等のトリアジン系紫外線吸収剤、オクタベンゾン等のベンゾフェノン系紫外線吸収剤、２，４−ジ−ｔｅｒｔ−ブチルフェニル−３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンゾエート等のベンゾエート系紫外線吸収剤が挙げられる。 Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers such as 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, and 2- (4,6-diphenyl- Triazine-based UV absorbers such as 1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, benzophenone-based UV absorbers such as octabenzone, 2,4-di-tert-butylphenyl Examples include benzoate-based ultraviolet absorbers such as -3,5-di-tert-butyl-4-hydroxybenzoate.
光硬化性化合物としては、アクリロイル基やメタクリロイル基等の光によって反応硬化する基を分子内に１個以上含有する化合物が挙げられ、具体的には例えば、イソシアネート基含有ウレタン樹脂に水酸基含有アクリレート化合物や水酸基含有メタクリレート化合物を反応させたウレタンアクリレートやウレタンメタクリレート、トリメチロールプロパントリアクリレートやトリメチロールプロパントリメタクリレート等のエステルアクリレートやエステルメタクリレート、ポリエチレンアジペートポリオールのアクリレートやメタクリレート等のポリエステルアクリレートやポリエステルメタクリレート、ポリエーテルポリオールのアクリレートやメタクリレート等のポリエーテルアクリレートやポリエーテルメタクリレート、或いはポリケイ皮酸ビニル類、アジド化樹脂などが挙げられ、分子量１０，０００以下、更に分子量５，０００以下の単量体、オリゴマーが好ましく、特にアクリロイル基及び／又はメタクリロイル基を１分子当たり平均して２個以上含有する物が好ましい。 Examples of the photocurable compound include a compound containing one or more groups that are reactively cured by light such as an acryloyl group or a methacryloyl group in the molecule. Specifically, for example, a hydroxyl group-containing acrylate compound is added to an isocyanate group-containing urethane resin. And polyester acrylates such as urethane acrylate, urethane methacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, and other polyester acrylates, polyester methacrylates such as polyethylene adipate polyol acrylates and methacrylates. Polyether acrylate such as ether polyol acrylate or methacrylate, polyether methacrylate, or poly Examples thereof include vinyl cinnamates and azido resins, and monomers and oligomers having a molecular weight of 10,000 or less, and more preferably a molecular weight of 5,000 or less are preferred. Particularly, acryloyl groups and / or methacryloyl groups are averaged per molecule. The thing containing 2 or more is preferable.
貯蔵安定性改良剤（脱水剤）としては、水分と反応するビニルトリメトキシシランなどの低分子の架橋性シリル基含有化合物、ｐ−トルエンスルホニルイソシアネートなどが挙げられる。 Examples of the storage stability improver (dehydrating agent) include low-molecular crosslinkable silyl group-containing compounds such as vinyltrimethoxysilane that react with moisture, p-toluenesulfonyl isocyanate, and the like.
分散剤としてはアニオン系、カチオン系、両性、或いはノニオン系界面活性剤が挙げられる。 Examples of the dispersant include anionic, cationic, amphoteric, and nonionic surfactants.
充填剤としては、炭酸カルシウム、クレー、タルク、スレート粉、マイカ、カオリン、ゼオライト、珪藻土、有機、無機のバルーン等が挙げられ、粒径１〜１００μｍのものが好ましく、このうち炭酸カルシウムがさらに好ましい。 Examples of the filler include calcium carbonate, clay, talc, slate powder, mica, kaolin, zeolite, diatomaceous earth, organic and inorganic balloons, and those having a particle size of 1 to 100 μm are preferable, and among these, calcium carbonate is more preferable. .
揺変剤としては、コロイダルシリカ、石綿粉等の無機揺変剤、有機ベントナイト、変性ポリエステルポリオール、脂肪酸アマイド等の有機揺変剤が挙げられ、揺変剤兼充填剤として脂肪酸処理炭酸カルシウム等が挙げられ、このうち脂肪酸処理炭酸カルシウムが好ましい。 Examples of thixotropic agents include inorganic thixotropic agents such as colloidal silica and asbestos powder, organic thixotropic agents such as organic bentonite, modified polyester polyols, and fatty acid amides, and fatty acid-treated calcium carbonate and the like as thixotropic agents and fillers. Of these, fatty acid-treated calcium carbonate is preferred.
これらの添加剤の配合量は、硬化性樹脂１００質量部に対して、０．０１〜１０質量部、特に０．１〜３．０質量部の範囲が好ましい。 The compounding amount of these additives is preferably in the range of 0.01 to 10 parts by mass, particularly 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the curable resin.
上記のような、場合により各種添加剤が配合されたシーリング基材１００質量部に対し、本発明の着色剤組成物を、通常２０質量部以下、好ましくは１０質量部以下を混合分散させることにより、着色／調色されたシーリング材を製造することができる。着色剤組成物の配合量が２０質量部を超えると、耐ブリード汚染性の低下や硬化物物性の低下が生じるおそれがある。 By mixing and dispersing the colorant composition of the present invention in an amount of usually 20 parts by mass or less, preferably 10 parts by mass or less, with respect to 100 parts by mass of the sealing base material optionally mixed with various additives as described above. A colored / toned sealing material can be produced. When the blending amount of the colorant composition exceeds 20 parts by mass, the bleed stain resistance and the cured product properties may be deteriorated.
以下、本発明を実施例によりさらに詳細に説明するが、本発明はこれらに限定されるものではない。尚、各実施例において分子量の測定条件、イソシアネート基濃度の測定方法、粘度の測定条件、及び水分含有量の測定方法は以下のとおりである。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these. In each example, the measurement conditions of molecular weight, the measurement method of isocyanate group concentration, the measurement conditions of viscosity, and the measurement method of water content are as follows.
（分子量測定）
ＧＰＣ測定装置：東ソー社製、ＨＬＣ−８２２０ＧＰＣ
カラム：東ソー社製、ＴＳＫｇｅｌ ＳｕｐｅｒＨＭ−Ｍ、ＴＳＫｇｅｌ ＳｕｐｅｒＨ２０００
測定温度：４０℃
展開溶媒：ＴＨＦ
溶質濃度：１０ｍｇ／ｍｌ
流速：０．６ｍｌ／ｍｉｎ
検出装置：ＲＩ
標準試料：ポリスチレン
（イソシアネート基濃度の測定方法）
ＪＩＳ Ｋ１６０３−１：２００７のＢ法に準拠して測定した。
（粘度の測定条件）
Ｂ８Ｕ型回転粘度計（東機産業社製ＴＶ−２０、ローターＮｏ．７、５ｒｐｍ）を用いて２５℃における粘度を測定した。
（水分含有量の測定方法）
電量滴定法を用いたカールフィッシャー水分計（型式；ＭＫＣ−６１０型、京都電子工業社製）に水分気化装置（ＡＤＰ−６１１型、京都電子工業社製）を接続した装置により、カールフィッシャー試薬を、クーロマットＡ及びクーロマットＣＧとして、着色剤組成物中の水分量を求めた。
(Molecular weight measurement)
GPC measuring device: Tosoh Corporation, HLC-8220GPC
Column: manufactured by Tosoh Corporation, TSKgel SuperHM-M, TSKgel SuperH2000
Measurement temperature: 40 ° C
Developing solvent: THF
Solute concentration: 10 mg / ml
Flow rate: 0.6 ml / min
Detector: RI
Standard sample: Polystyrene (isocyanate group concentration measurement method)
It measured based on B method of JISK1603-1: 2007.
(Viscosity measurement conditions)
The viscosity at 25 ° C. was measured using a B8U type rotational viscometer (TV-20 manufactured by Toki Sangyo Co., Ltd., rotor No. 7, 5 rpm).
(Measurement method of water content)
A Karl Fischer moisture meter (ADP-611 type, manufactured by Kyoto Electronics Industry Co., Ltd.) connected to a Karl Fischer moisture meter (model; MKC-610 type, manufactured by Kyoto Electronics Industry Co., Ltd.) using a coulometric titration method was used. The water content in the colorant composition was determined as Coulomat A and Coulomat CG.
（１）水酸基含有ポリエーテル誘導体及びシーリング基材の合成例
合成例１；水酸基含有ポリエーテルの誘導体Ｕ−１の合成
攪拌機、温度計、窒素シール管及び加温・冷却装置の付いた反応容器に、窒素気流下で、ポリオキシプロピレンモノオール（旭硝子社製ＸＳ−Ｍ３０００、数平均分子量３，３００、分子量分布（Ｍｗ／Ｍｎ）１．０〜１．１）３００ｇ（ＯＨ当量：０．０９１）を仕込み、攪拌しながらジブチル錫ジラウレート０．１ｇとｍ−キシリレンジイソシアネート（三井武田ケミカル社製タケネート５００、分子量１８８）９．１ｇ（ＮＣＯ当量：０．０９６８）（Ｒ値（ＮＣＯ当量／ＯＨ当量）＝１．０６）を加えた後、加温して７０〜８０℃で４時間攪拌して、イソシアネート基含有量が理論値（０．０８質量％）以下となった時点で反応を終了し、ポリオキシプロピレン系ウレタン樹脂Ｕ−１を製造した。Ｕ−１は、滴定による実測イソシアネート基濃度０．０６質量％、粘度３，２００ｍＰａ・ｓ／２５℃、数平均分子量７０００、分子量分布（Ｍｗ／Ｍｎ）１．０５の常温で透明な液体であった。
(1) Synthesis example of hydroxyl group-containing polyether derivative and sealing substrate
Synthesis Example 1 Synthesis of Hydroxyl-Containing Polyether Derivative U-1 In a reaction vessel equipped with a stirrer, thermometer, nitrogen seal tube and heating / cooling device, polyoxypropylene monool (manufactured by Asahi Glass Co., Ltd.) in a nitrogen stream. XS-M3000, number average molecular weight 3,300, molecular weight distribution (Mw / Mn) 1.0 to 1.1) 300 g (OH equivalent: 0.091) were charged, and dibutyltin dilaurate 0.1 g and m- After adding 9.1 g (NCO equivalent: 0.0968) (R value (NCO equivalent / OH equivalent) = 1.06) of xylylene diisocyanate (Takenate 500 manufactured by Mitsui Takeda Chemical Co., Ltd., molecular weight 188), the mixture was heated. The reaction was terminated when the isocyanate group content was less than the theoretical value (0.08% by mass) after stirring at 70 to 80 ° C. for 4 hours, and a polyoxypropylene urethane resin was obtained. To produce a U-1. U-1 is a liquid that is transparent at room temperature with an isocyanate group concentration of 0.06% by mass, a viscosity of 3,200 mPa · s / 25 ° C., a number average molecular weight of 7000, and a molecular weight distribution (Mw / Mn) of 1.05 by titration. It was.
合成例２；ウレタンシーリング基材ＢＵ−１の合成
攪拌機、温度計、窒素シール管及び加温・冷却装置の付いた反応容器に、窒素気流下で、ポリオキシプロピレンジオール（旭硝子社製エクセノール−３０２１、数平均分子量３，３００）５９９．２ｇ（ＯＨ当量：０．３６３）と、ポリオキシプロピレントリオール（三井武田ケミカル社製ＭＮ−４０００、数平均分子量４，０００、分子量分布１．０〜１．１）２８４．５ｇ（ＯＨ当量：０．２１３）を仕込み、攪拌しながら４，４′−ジフェニルメタンジイソシアネート（日本ポリウレタン工業社製ミリオネートＭＴ、分子量２５０）１１６．２ｇ（ＮＣＯ当量：０．９３）（Ｒ値（ＮＣＯ当量／ＯＨ当量）＝１．６０）とジブチル錫ジラウレート０．１ｇを加えたのち、加温して７０〜８０℃で２時間攪拌して、イソシアネート基含有量が理論値（１．４７質量％）以下となった時点で常温まで冷却して反応を終了させて、イソシアネート基含有ポリオキシプロピレン系ウレタンプレポリマーＰ−１を製造した。Ｐ−１は、滴定による実測イソシアネート基含有量１．３８質量％の常温で粘稠な液体であった。
Synthesis Example 2 Synthesis of urethane sealing substrate BU-1 In a reaction vessel equipped with a stirrer, thermometer, nitrogen seal tube and heating / cooling device, a polyoxypropylene diol (EXENOL-3021 manufactured by Asahi Glass Co., Ltd.) was placed in a nitrogen stream. , Number average molecular weight 3,300) 599.2 g (OH equivalent: 0.363), polyoxypropylene triol (MN-4000 manufactured by Mitsui Takeda Chemical Co., Ltd., number average molecular weight 4,000, molecular weight distribution 1.0-1. 1) Charged 284.5 g (OH equivalent: 0.213) and stirred with stirring, 4,4′-diphenylmethane diisocyanate (Millionate MT, molecular weight 250, Nippon Polyurethane Industry Co., Ltd.) 116.2 g (NCO equivalent: 0.93) ( R value (NCO equivalent / OH equivalent) = 1.60) and 0.1 g of dibutyltin dilaurate, and then heated to 70 Stir at 80 ° C. for 2 hours, and when the isocyanate group content is less than the theoretical value (1.47% by mass), the reaction is terminated by cooling to room temperature, and the isocyanate group-containing polyoxypropylene urethane prepolymer P-1 was produced. P-1 was a viscous liquid at room temperature with a measured isocyanate group content of 1.38% by mass by titration.
調製混練装置（井上製作所社製、プラネタリーミキサーＰＬＭ型）に、前記イソシアネート基含有ポリオキシプロピレン系ウレタンプレポリマーＰ−１を４３６ｇ、ビニルトリメトキシシラン（チッソ社製、サイラエースＳ２１０）１０．５ｇ、ペンタエリストール−テトラキス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］（チバ・スペシャリティ・ケミカルズ社製、イルガノックス１０１０）５．５ｇ、脂肪酸（表面）処理炭酸カルシウム（丸尾カルシウム社製、カルファイン２００Ｍ）２６６ｇ、炭酸カルシウム２７４．５ｇを仕込み、３０〜４０℃で３０分間攪拌して、内容物が均一になるまで混合、分散してウレタンシーリング基材ＢＵ−１を得た。 In a preparation kneader (Inoue Seisakusho, Planetary Mixer PLM type), 436 g of the isocyanate group-containing polyoxypropylene urethane prepolymer P-1 and 10.5 g of vinyltrimethoxysilane (manufactured by Chisso, Silaace S210), Pentaerystole-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Ciba Specialty Chemicals, Irganox 1010) 5.5 g, fatty acid (surface) treated calcium carbonate (Maruo Calcium Co., Ltd., Calfine 200M) 266g, calcium carbonate 274.5g was charged, stirred at 30-40 ° C for 30 minutes, mixed and dispersed until the contents were uniform, urethane sealing substrate BU-1 Got.
合成例３；変成シリコーンシーリング基材ＢＳ−１の合成
前記合成例２において、イソシアネート基含有ポリオキシプロピレン系ウレタンプレポリマーＰ−１に替えて、架橋性シリル基含有ポリオキシプロピレン重合体（旭硝子社製、ＥＳ−Ｓ３６３０）を用いた以外は同様にして変成シリコーンシーリング基材ＢＳ−１を得た。
Synthesis Example 3 Synthesis of Modified Silicone Sealing Base Material BS-1 In Synthesis Example 2, instead of the isocyanate group-containing polyoxypropylene urethane prepolymer P-1, a crosslinkable silyl group-containing polyoxypropylene polymer (Asahi Glass Co., Ltd.) A modified silicone sealing substrate BS-1 was obtained in the same manner except that ES-S3630) was used.
（２）着色剤組成物の調製
実施例１（黒色の着色剤組成物１の調製）
混練装置（井上製作所社製、プラネタリーミキサーＰＬＭ型）に、ポリオキシプロピレンモノオール（旭硝子社製ＸＳ−Ｍ３０００、数平均分子量３，３００、分子量分布（Ｍｗ／Ｍｎ）１．０〜１．１）５００ｇ及びカーボンブラック（旭カーボン社製、サーマルブラック、黒色顔料）５００ｇを仕込み、３０〜４０℃で３０〜４０分間攪拌して、内容物が均一になるまで混合、分散した。この時の脱水前のカールフィッシャー法による水分は０.１０３質量％であった。次いで、１１０℃、２０ｍｍHg減圧下で１時間、攪拌・加熱し脱水操作を行った後、冷却して黒色着色剤組成物１（黒色１）を得た。脱水後の水分は０.０１２質量％であった。
(2) Preparation of colorant composition
Example 1 (Preparation of black colorant composition 1)
Polyoxypropylene monool (XS-M3000 manufactured by Asahi Glass Co., Ltd., number average molecular weight 3,300, molecular weight distribution (Mw / Mn) 1.0 to 1.1 in a kneader (Inoue Seisakusho, planetary mixer PLM type) ) 500 g and 500 g of carbon black (manufactured by Asahi Carbon Co., Ltd., thermal black, black pigment) were charged, stirred at 30 to 40 ° C. for 30 to 40 minutes, and mixed and dispersed until the contents were uniform. At this time, the water content by the Karl Fischer method before dehydration was 0.103% by mass. Next, the mixture was stirred and heated at 110 ° C. under a reduced pressure of 20 mmHg for 1 hour to perform a dehydration operation, and then cooled to obtain a black colorant composition 1 (black 1). The water content after dehydration was 0.012% by mass.
実施例２（黒色の着色剤組成物２の調製）
実施例１において、ポリオキシプロピレンモノオールに替えて合成例１の水酸基含有ポリエーテルの誘導体Ｕ−１を使用した以外は同様にして黒色着色剤組成物２（黒色２）を調製した。脱水後の水分は０.０１２質量％であった。
Example 2 (Preparation of black colorant composition 2)
A black colorant composition 2 (black 2) was prepared in the same manner as in Example 1, except that the hydroxyl group-containing polyether derivative U-1 of Synthesis Example 1 was used instead of polyoxypropylene monool. The water content after dehydration was 0.012% by mass.
実施例３（黒色の着色剤組成物３の調製）
実施例２において、脱水工程を行わない以外は同様にして黒色着色剤組成物３（黒色３）を調製した。水分は０．１０２重量％であった。
Example 3 (Preparation of black colorant composition 3)
In Example 2, a black colorant composition 3 (black 3) was prepared in the same manner except that the dehydration step was not performed. The water content was 0.102% by weight.
実施例４（赤色の着色剤組成物１の調製）
実施例１において、カーボンブラックに替えて酸化鉄レッド（バイエル社製、バイフェロックスレッド、赤色顔料）を使用した以外は同様にして赤色着色剤組成物１（赤色１）を調製した。脱水前の水分は０．１０４重量％、脱水後の水分は０.０１３質量％であった。
Example 4 (Preparation of red colorant composition 1)
A red colorant composition 1 (red 1) was prepared in the same manner as in Example 1 except that iron oxide red (Bayferlock thread, red pigment) was used instead of carbon black. The moisture before dehydration was 0.104% by weight, and the moisture after dehydration was 0.013% by mass.
実施例５（赤色の着色剤組成物２の調製）
実施例４において、ポリオキシプロピレンモノオールに替えて合成例１の水酸基含有ポリエーテルの誘導体Ｕ−１を使用した以外は同様にして赤色着色剤組成物２（赤色２）を調製した。脱水後の水分は０.０１２質量％であった。
Example 5 (Preparation of red colorant composition 2)
In Example 4, a red colorant composition 2 (red 2) was prepared in the same manner except that the hydroxyl group-containing polyether derivative U-1 of Synthesis Example 1 was used instead of polyoxypropylene monool. The water content after dehydration was 0.012% by mass.
実施例６（黄色の着色剤組成物１の調製）
実施例１において、カーボンブラックに替えて酸化鉄イエロー（バイエル社製、バイフェロックスイエロー、黄色顔料）を使用した以外は同様にして黄色着色剤組成物１（黄色１）を調製した。脱水前の水分は０．２９６重量％、脱水後の水分は０.０１８質量％であった。
Example 6 (Preparation of yellow colorant composition 1)
A yellow colorant composition 1 (yellow 1) was prepared in the same manner as in Example 1, except that iron oxide yellow (Bayferox Yellow, yellow pigment) was used instead of carbon black. The moisture before dehydration was 0.296% by weight, and the moisture after dehydration was 0.018% by mass.
実施例７（黄色の着色剤組成物２の調製）
実施例６において、ポリオキシプロピレンモノオールに替えて合成例１の水酸基含有ポリエーテルの誘導体Ｕ−１を使用した以外は同様にして黄色着色剤組成物２（黄色２）を調製した。脱水後の水分は０.０１６質量％であった。
Example 7 (Preparation of yellow colorant composition 2)
A yellow colorant composition 2 (yellow 2) was prepared in the same manner as in Example 6 except that the derivative U-1 of the hydroxyl group-containing polyether of Synthesis Example 1 was used instead of the polyoxypropylene monool. The water content after dehydration was 0.016% by mass.
実施例８（黄色の着色剤組成物３の調製）
実施例７において、脱水工程を行わない以外は同様にして黄色着色剤組成物３（黄色３）を調製した。水分は０．２９０重量％であった。
Example 8 (Preparation of yellow colorant composition 3)
In Example 7, a yellow colorant composition 3 (yellow 3) was prepared in the same manner except that the dehydration step was not performed. The water content was 0.290% by weight.
実施例９（白色の着色剤組成物１の調製）
実施例１において、カーボンブラックに替えて酸化チタン（石原産業社製、タイペークＲ−８３０、白色顔料）を使用した以外は同様にして白色着色剤組成物１（白色１）を調製した。脱水前の水分は０．３６３重量％、脱水後の水分は０.０１２質量％であった。
Example 9 (Preparation of white colorant composition 1)
A white colorant composition 1 (white 1) was prepared in the same manner as in Example 1 except that titanium oxide (Ishihara Sangyo Co., Ltd., Tyco R-830, white pigment) was used instead of carbon black. The moisture before dehydration was 0.363% by weight, and the moisture after dehydration was 0.012% by mass.
実施例１０（白色の着色剤組成物２の調製）
実施例９において、ポリオキシプロピレンモノオールに替えて合成例１の水酸基含有ポリエーテルの誘導体Ｕ−１を使用した以外は同様にして白色着色剤組成物２（白色２）を調製した。脱水後の水分は０.０１４質量％であった。
Example 10 (Preparation of white colorant composition 2)
A white colorant composition 2 (white 2) was prepared in the same manner as in Example 9 except that the hydroxyl group-containing polyether derivative U-1 of Synthesis Example 1 was used instead of the polyoxypropylene monool. The water content after dehydration was 0.014% by mass.
実施例１１（白色の着色剤組成物３の調製）
実施例１０において、脱水工程を行わない以外は同様にして白色着色剤組成物３（白色３）を調製した。水分は０．３６６重量％であった。
Example 11 (Preparation of white colorant composition 3)
A white colorant composition 3 (white 3) was prepared in the same manner as in Example 10 except that the dehydration step was not performed. The moisture was 0.366% by weight.
比較例１（黒色の着色剤組成物４の調製）
実施例１において、脱水工程を行わず、ポリオキシプロピレンモノオールに替えてフタル酸ジオクチルを使用した以外は同様にして黒色着色剤組成物４（黒色４）を調製した。
Comparative Example 1 (Preparation of black colorant composition 4)
A black colorant composition 4 (black 4) was prepared in the same manner as in Example 1 except that the dehydration step was not performed and dioctyl phthalate was used instead of polyoxypropylene monool.
比較例２（赤色の着色剤組成物３の調製）
実施例５において、脱水工程を行わず、ポリオキシプロピレンモノオールに替えてフタル酸ジオクチルを使用した以外は同様にして赤色着色剤組成物３（赤色３）を調製した。
Comparative Example 2 (Preparation of red colorant composition 3)
In Example 5, a red colorant composition 3 (red 3) was prepared in the same manner except that the dehydration step was not performed and dioctyl phthalate was used instead of polyoxypropylene monool.
比較例３（黄色の着色剤組成物４の調製）
実施例８において、脱水工程を行わず、ポリオキシプロピレンモノオールに替えてフタル酸ジオクチルを使用した以外は同様にして黄色着色剤組成物４（黄色４）を調製した。
Comparative Example 3 (Preparation of yellow colorant composition 4)
In Example 8, a yellow colorant composition 4 (yellow 4) was prepared in the same manner except that the dehydration step was not performed and dioctyl phthalate was used instead of polyoxypropylene monool.
比較例４（白色の着色剤組成物４の調製）
実施例１１において、脱水工程を行わず、ポリオキシプロピレンモノオールに替えてフタル酸ジオクチルを使用した以外は同様にして白色着色剤組成物４（白色４）を調製した。
Comparative Example 4 (Preparation of white colorant composition 4)
A white colorant composition 4 (white 4) was prepared in the same manner as in Example 11 except that the dehydration step was not performed and dioctyl phthalate was used instead of polyoxypropylene monool.
比較例５〜８（黒色の着色剤組成物５、赤色の着色剤組成物４、黄色の着色剤組成物５、白色の着色剤組成物５の調製）
比較例１〜４において、各顔料を１２５ｇ使用した以外は同様にして黒色の着色剤組成物５（黒色５）、赤色の着色剤組成物４（赤色４）、黄色の着色剤組成物５（黄色５）、白色の着色剤組成物５（白色５）を調製した。
Comparative Examples 5 to 8 (preparation of black colorant composition 5, red colorant composition 4, yellow colorant composition 5, and white colorant composition 5)
In Comparative Examples 1 to 4, a black colorant composition 5 (black 5), a red colorant composition 4 (red 4), and a yellow colorant composition 5 (except for using 125 g of each pigment) Yellow 5) and white colorant composition 5 (white 5) were prepared.
上記実施例１〜実施例１１及び比較例１〜比較例８の着色剤組成物の組成を色毎にまとめて表１及び表２に示す。 The compositions of the colorant compositions of Examples 1 to 11 and Comparative Examples 1 to 8 are summarized for each color and shown in Tables 1 and 2.
（３）シーリング材の調製方法
実施例１２ 調色したウレタンシーリング材（ＰＵ−１）
調製混練装置（井上製作所社製、プラネタリーミキサーＰＬＭ型）に、合成例３のウレタンシーリング基材ＢＵ−１を１，０００ｇ、実施例２で調製した黒色の着色剤組成物２を１０ｇ、実施例５で調製した赤色の着色剤組成物２を２０ｇ仕込み、実施例７で調製した黄色の着色剤組成物２を５０ｇ、実施例１０で調製した白色の着色剤組成物２を１２０ｇ加え、３０〜４０℃で３０〜４０分間攪拌して、内容物が均一になるまで混合、分散して調色したウレタンシーリング材（ＰＵ−１）を得た。
(3) Preparation method of sealing material
Example 12 Toned urethane sealing material (PU-1)
1,000 g of urethane sealing base material BU-1 of Synthesis Example 3 and 10 g of black colorant composition 2 prepared in Example 2 were prepared in a preparation kneading apparatus (Inoue Seisakusho, planetary mixer PLM type). 20 g of the red colorant composition 2 prepared in Example 5 was charged, 50 g of the yellow colorant composition 2 prepared in Example 7 was added, and 120 g of the white colorant composition 2 prepared in Example 10 was added. Stirring was carried out at ˜40 ° C. for 30 to 40 minutes to obtain a urethane sealing material (PU-1) which was mixed, dispersed and toned until the contents became uniform.
実施例１３〜１５（ＰＵ−２、ＭＳ−１，２）
前記実施例１２において、各シーリング基材及び各色の着色剤組成物の量を表３に示す配合量とした以外は同様にして、調色したウレタンシーリング材（ＰＵ−２）及び調色した変成シリコーンシーリング材（ＭＳ−１，２）を得た。
Examples 13 to 15 (PU-2, MS-1, 2)
In Example 12, the toned urethane sealing material (PU-2) and the toned modification were made in the same manner except that the amount of each sealing substrate and the colorant composition of each color was changed to the blending amount shown in Table 3. Silicone sealants (MS-1, 2) were obtained.
比較例９〜１２（ＰＵ−３，４、ＭＳ−３，４）
前記実施例１２において、各シーリング基材及び各色の着色剤組成物の量を表３に示す配合量とした以外は同様にして、調色したウレタンシーリング材（ＰＵ−３，４）及び調色した変成シリコーンシーリング材（ＭＳ−３，４）を得た。
Comparative Examples 9-12 (PU-3, 4, MS-3, 4)
In Example 12, the toned urethane sealing material (PU-3, 4) and the toning were performed in the same manner except that the amount of each sealing base material and the colorant composition of each color was changed to the blending amount shown in Table 3. The modified silicone sealant (MS-3, 4) was obtained.
（４）シーリング材の評価方法
（４−１）外観
目視観察により評価した。発泡、ブツがないかわずかに認められるとき○、発泡、ブツが多数認められるとき×とした。
（４−２）スランプ
ＪＩＳ Ａ１４３９：２００４「建築用シーリング材の試験方法」の「５．１スランプ試験」に準拠して、スランプ（縦）を測定した（試験温度２３℃）。２ｍｍ以内のスランプを○、２ｍｍを超えるスランプを×と評価した。
（４−３）Ｈ型物性
ＪＩＳ Ａ１４３９：２００４「建築用シーリング材の試験方法」の「５．２０引張接着性試験」に準拠して試験した（試験温度２３℃）。なお、試験体は、スレートをプライマー（ＯＰ２５３１、オート化学工業社製）で処理し、上記で製造したシーリング材を打設し、打設後の試験体を２３℃、５０％相対湿度で１４日間、３０℃で１４日間養生して作製した。
（４−４）耐ブリード汚染性
厚さ５ｍｍのスレート板を使用し、深さ５ｍｍ、幅２５ｍｍ、長さ１５０ｍｍの目地を作製した。その目地に上記で製造したシーリング材を打設し、余分のシーリング材をヘラでかきとり、表面を平らにしたものを、２３℃、５０％相対湿度で７日間養生硬化した。次に、目地上に水性アクリル塗料（日本ペイント社製、タイルラック 水性トップスーパーホワイト）を塗布し、２３℃、５０％相対湿度で更に７日間養生して、試験体を作製した。養生後の試験体を５０℃の恒温器に入れ、１０日間加熱処理した後、恒温器より取り出し、上塗りした塗料表面に黒色珪砂（粒径７０〜１１０μｍ）を振り掛け、直ちに試験体を裏返し、底面を手で軽く叩き余分な黒色珪砂を落とした。表面に付着して残った黒色珪砂（汚れ）の状態を目視で観察し、汚染性を判定した。
(4) Sealing material evaluation method (4-1) Appearance Evaluation was made by visual observation. When there was little or no foaming or blisters, it was marked with ◯.
(4-2) Slump The slump (longitudinal) was measured in accordance with “5.1 slump test” in JIS A1439: 2004 “Testing method of sealing material for building” (test temperature: 23 ° C.). The slump within 2 mm was evaluated as “◯” and the slump exceeding 2 mm was evaluated as “x”.
(4-3) H-type physical properties JIS A1439: 2004 Tested according to “5.20 tensile adhesion test” in “Testing method for building sealing material” (test temperature: 23 ° C.). The test specimen was treated with a slate with a primer (OP2531, manufactured by Auto Chemical Industry Co., Ltd.), the sealing material produced above was cast, and the test specimen after casting was placed at 23 ° C. and 50% relative humidity for 14 days. It was prepared by curing at 30 ° C. for 14 days.
(4-4) Bleed stain resistance A 5 mm thick slate plate was used to produce a joint having a depth of 5 mm, a width of 25 mm, and a length of 150 mm. The sealing material produced above was placed on the joint, the excess sealing material was scraped off with a spatula, and the surface was flattened and cured at 23 ° C. and 50% relative humidity for 7 days. Next, a water-based acrylic paint (manufactured by Nippon Paint Co., Ltd., tile rack water-based top super white) was applied to the surface of the joint, and further cured at 23 ° C. and 50% relative humidity for 7 days to prepare a test specimen. Place the test specimen after curing in a 50 ° C thermostat, heat-treat for 10 days, take out from the thermostat, sprinkle black silica sand (particle size 70-110 µm) on the surface of the overcoated paint, immediately turn the test specimen upside down, Lightly tapped with hand to remove excess black silica sand. The state of black silica sand (dirt) remaining on the surface was visually observed to determine the contamination.
判定基準：〇；シーリング材に上塗りした塗料の表面に黒色珪砂の付着がなくきれいな状態、×；シーリング材に上塗りした塗料の表面に黒色珪砂が多量に付着し黒く汚れた状態
表３に結果を示す。
Judgment criteria: 〇; Black silica sand is not adhered to the surface of the paint that has been overcoated on the sealing material; x; Black silica sand is abundantly adhered to the surface of the paint that has been overcoated on the sealing material; Table 3 shows the results. Show.
表３から明らかなとおり、同じ基材を使い、ほぼ同量の顔料を含有する実施例１３及び比較例９、並びに、実施例１５及び比較例１１を比較すると、比較例の方が５０％モジュラス（Ｍ５０）及び破断時強度（Ｔｂ）が低く、破断時伸び（Ｅｂ）が高くなっていることが分かる。 As is apparent from Table 3, when Example 13 and Comparative Example 9, and Example 15 and Comparative Example 11 using the same base material and containing almost the same amount of pigment were compared, Comparative Example 50 was found to have a 50% modulus. It can be seen that (M50) and the strength at break (Tb) are low and the elongation at break (Eb) is high.
また、それぞれ、実施例１３及び実施例１５の倍量の着色剤を使用した実施例１２及び１４においてもこれらの値に変化はほとんどみられず、本発明の実施例では硬化物の物性に与える影響が少ないことが分かる。 Further, in Examples 12 and 14 using the double amount of the colorant of Examples 13 and 15, respectively, these values hardly change, and in the examples of the present invention, the physical properties of the cured product are given. It turns out that there is little influence.
Claims (7)
前記水酸基含有ポリエーテル誘導体が、イソシアネート基／水酸基の当量比が０．９／１．０〜１．１／１．０となる範囲で、数平均分子量が５００〜５０，０００且つ重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比Ｍｗ／Ｍｎが１．６以下であるポリオキシアルキレン系ポリオール及び／またはポリオキシアルキレン系モノオールと有機イソシアネートとを反応させることにより得られるウレタン基を導入した化合物であり、
前記水酸基含有ポリエーテル誘導体中の前記イソシアネート基又は前記水酸基の含有量が、０．０５ｍｍｏｌ／ｇ未満であり、
前記着色顔料の配合量が、前記水酸基含有ポリエーテル誘導体１００質量部に対して２５〜１００質量部であり、
湿気により硬化するイソシアネート基含有ポリオキシプロピレン系ウレタンプレポリマーまたは架橋性シリル基含有ポリオキシアルキレン重合体を硬化成分とするシーリング材の着色用であることを特徴とする着色剤組成物。 A colorant composition containing a hydroxyl group-containing polyether derivative and a color pigment and having a water content of 0.05% by mass or less ,
The hydroxyl group-containing polyether derivative has a number average molecular weight of 500 to 50,000 and a weight average molecular weight ( with an isocyanate group / hydroxyl group equivalent ratio of 0.9 / 1.0 to 1.1 / 1.0 ). Mw) and the number average molecular weight (Mn) ratio Mw / Mn is a urethane group obtained by reacting a polyoxyalkylene polyol and / or polyoxyalkylene monool having an organic isocyanate with a polyoxyalkylene polyol having a ratio of 1.6 or less. Introduced compounds,
The isocyanate group or the hydroxyl group content in the hydroxyl group-containing polyether derivative is less than 0.05 mmol / g,
The amount of the coloring pigment, Ri 25 to 100 parts by mass der respect to the hydroxyl group-containing polyether derivative 100 parts by weight,
Isocyanate group-containing polyoxypropylene urethane prepolymer or crosslinkable silyl group-containing polyoxyalkylene polymer colorant composition characterized coloring der Rukoto sealant to cure component is cured by moisture.
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