JP2021123633A - Two component room temperature-curable urethane waterproof material composition for hand coating - Google Patents
Two component room temperature-curable urethane waterproof material composition for hand coating Download PDFInfo
- Publication number
- JP2021123633A JP2021123633A JP2020017169A JP2020017169A JP2021123633A JP 2021123633 A JP2021123633 A JP 2021123633A JP 2020017169 A JP2020017169 A JP 2020017169A JP 2020017169 A JP2020017169 A JP 2020017169A JP 2021123633 A JP2021123633 A JP 2021123633A
- Authority
- JP
- Japan
- Prior art keywords
- polyol
- room temperature
- curing agent
- waterproof material
- material composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 95
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000000203 mixture Substances 0.000 title claims abstract description 69
- 239000011248 coating agent Substances 0.000 title claims abstract description 52
- 238000000576 coating method Methods 0.000 title claims abstract description 52
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 175
- 229920005862 polyol Polymers 0.000 claims abstract description 85
- 150000003077 polyols Chemical class 0.000 claims abstract description 84
- 125000003118 aryl group Chemical group 0.000 claims abstract description 46
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229920000768 polyamine Polymers 0.000 claims abstract description 40
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 27
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 20
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 20
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims abstract description 11
- -1 tolylene isocyanate Chemical class 0.000 claims description 38
- 238000004078 waterproofing Methods 0.000 claims description 23
- 239000012948 isocyanate Substances 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 20
- 150000002009 diols Chemical class 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 16
- 150000002513 isocyanates Chemical group 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 12
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 5
- 229940043276 diisopropanolamine Drugs 0.000 claims description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- ZFECCYLNALETDE-UHFFFAOYSA-N 1-[bis(2-hydroxyethyl)amino]propan-2-ol Chemical compound CC(O)CN(CCO)CCO ZFECCYLNALETDE-UHFFFAOYSA-N 0.000 claims description 3
- CWKVFRNCODQPDB-UHFFFAOYSA-N 1-(2-aminoethylamino)propan-2-ol Chemical compound CC(O)CNCCN CWKVFRNCODQPDB-UHFFFAOYSA-N 0.000 claims description 2
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 abstract description 22
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 22
- 238000009472 formulation Methods 0.000 description 22
- 238000010276 construction Methods 0.000 description 17
- 230000000704 physical effect Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 229910000019 calcium carbonate Inorganic materials 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 241001112258 Moca Species 0.000 description 10
- 230000006866 deterioration Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 239000004014 plasticizer Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 239000011256 inorganic filler Substances 0.000 description 9
- 229910003475 inorganic filler Inorganic materials 0.000 description 9
- 229920001451 polypropylene glycol Polymers 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 5
- 229920006311 Urethane elastomer Polymers 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 4
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 4
- 150000007529 inorganic bases Chemical class 0.000 description 4
- VOEYXMAFNDNNED-UHFFFAOYSA-N metolcarb Chemical compound CNC(=O)OC1=CC=CC(C)=C1 VOEYXMAFNDNNED-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- PTPVMOFUJNOPCO-UHFFFAOYSA-N 2-(3-methylbutyl)benzoic acid Chemical compound CC(C)CCC1=CC=CC=C1C(O)=O PTPVMOFUJNOPCO-UHFFFAOYSA-N 0.000 description 3
- SVNWKKJQEFIURY-UHFFFAOYSA-N 2-methyl-1-(2-methylpropyl)imidazole Chemical compound CC(C)CN1C=CN=C1C SVNWKKJQEFIURY-UHFFFAOYSA-N 0.000 description 3
- SDQROPCSKIYYAV-UHFFFAOYSA-N 2-methyloctane-1,8-diol Chemical compound OCC(C)CCCCCCO SDQROPCSKIYYAV-UHFFFAOYSA-N 0.000 description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 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 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920005906 polyester polyol Polymers 0.000 description 3
- 239000004848 polyfunctional curative Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 2
- RQEOBXYYEPMCPJ-UHFFFAOYSA-N 4,6-diethyl-2-methylbenzene-1,3-diamine Chemical compound CCC1=CC(CC)=C(N)C(C)=C1N RQEOBXYYEPMCPJ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- UDSAIICHUKSCKT-UHFFFAOYSA-N bromophenol blue Chemical compound C1=C(Br)C(O)=C(Br)C=C1C1(C=2C=C(Br)C(O)=C(Br)C=2)C2=CC=CC=C2S(=O)(=O)O1 UDSAIICHUKSCKT-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 230000007670 carcinogenicity Effects 0.000 description 2
- 231100000260 carcinogenicity Toxicity 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 150000002483 hydrogen compounds Chemical class 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
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- 239000000080 wetting agent Substances 0.000 description 2
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
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- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
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- QJENIOQDYXRGLF-UHFFFAOYSA-N 4-[(4-amino-3-ethyl-5-methylphenyl)methyl]-2-ethyl-6-methylaniline Chemical compound CC1=C(N)C(CC)=CC(CC=2C=C(CC)C(N)=C(C)C=2)=C1 QJENIOQDYXRGLF-UHFFFAOYSA-N 0.000 description 1
- CBEVWPCAHIAUOD-UHFFFAOYSA-N 4-[(4-amino-3-ethylphenyl)methyl]-2-ethylaniline Chemical compound C1=C(N)C(CC)=CC(CC=2C=C(CC)C(N)=CC=2)=C1 CBEVWPCAHIAUOD-UHFFFAOYSA-N 0.000 description 1
- KZTROCYBPMKGAW-UHFFFAOYSA-N 4-[[4-amino-3,5-di(propan-2-yl)phenyl]methyl]-2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=C(N)C(C(C)C)=CC(CC=2C=C(C(N)=C(C(C)C)C=2)C(C)C)=C1 KZTROCYBPMKGAW-UHFFFAOYSA-N 0.000 description 1
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- 239000000539 dimer Substances 0.000 description 1
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Abstract
Description
本発明は、年間を通して可使時間を十分に確保することができ、しかも耐久性に優れた２液常温硬化型手塗り用ウレタン防水材組成物に関する。 The present invention relates to a two-component room temperature curable urethane waterproof material composition for hand coating, which can secure a sufficient pot life throughout the year and has excellent durability.
ウレタン防水材は、不定形状および狭小部分の施工に適していることより、新築工事あるいは改修工事を問わず、マンションなど集合住宅のベランダ、バルコニー、開放廊下や比較的大面積の屋上の平場部分、立面部分、パラペット、架台周りなどに使用されている。 Urethane waterproofing material is suitable for construction of irregular shapes and narrow parts, so regardless of new construction or renovation work, balconies, balconies, open corridors and relatively large rooftop flat roofs of condominiums, etc. It is used for elevations, parapets, and around pedestals.
一般的なウレタン防水材は、２液の液状物を攪拌機で混合した後、コテ、ヘラ、ローラー、刷毛などで手塗り施工するものであり、攪拌機で混合した後少なくとも３０分程度の使用可能時間（以下、「可使時間」と称す。）が必要とされている。可使時間については、２３℃において２液混合後から、粘度が６万ｍＰａ・ｓに到達するまでの時間とするのが一般的である。
手塗り用２液常温硬化型ウレタン防水材は、冬季の施工と夏季の施工では外気温が大幅に異なるため、夏季の３０℃以上での施工に適した夏用配合と、冬季の５℃以下の施工に適した冬用配合が用意されているのが一般的であり、平場用防水材においては、各季節の施工温度において、可使時間が３０分以上となるよう工夫されている（そのためには夏用配合においては、２３℃における可使時間として５５分以上程度が必要）。塗布作業において可使時間は長いほど好ましいが、一般的には可使時間を長くしようとすると硬化性が悪くなり、次工程を施工するために塗膜上に作業員が乗れるまでに時間（以下、「施工可能時間」と称す。）も長くなってしまう。通常の作業では、ウレタン防水材を夕方に塗布し翌朝には施工可能状態となることが望まれており、施工可能時間は年間を通して１７時間程度以内に調整できることが好ましいとされている。
A general urethane waterproof material is a material in which two liquids are mixed with a stirrer and then hand-painted with a trowel, spatula, roller, brush, etc., and after mixing with a stirrer, the usable time is at least about 30 minutes. (Hereinafter referred to as "potential time") is required. The pot life is generally the time from after mixing the two liquids at 23 ° C. until the viscosity reaches 60,000 mPa · s.
The two-component room temperature curable urethane waterproof material for hand coating has a significantly different outside temperature between winter construction and summer construction, so the summer formulation suitable for construction at 30 ° C or higher in summer and 5 ° C or lower in winter In general, a winter formulation suitable for the construction of is prepared, and the waterproof material for flat ground is devised so that the pot life is 30 minutes or more at the construction temperature of each season (for that reason). In the summer formulation, it is necessary to have a pot life of about 55 minutes or more at 23 ° C.). The longer the pot life is, the more preferable it is in the coating work, but in general, if the pot life is lengthened, the curability deteriorates, and it takes time for the worker to get on the coating film for the next process (hereinafter). , "Construction time") will also be long. In normal work, it is desired that the urethane waterproof material is applied in the evening and the work is ready for construction the next morning, and it is preferable that the workable time can be adjusted within about 17 hours throughout the year.
旧来、２液常温硬化型手塗用ウレタン防水材は、トリレンジイソシアナートとポリオキシプロピレンポリオールからなるイソシアナート基末端プレポリマーを主剤とし、一方の硬化剤中の活性水素として、比較的低反応性の芳香族ポリアミンである、３，３′−ジクロロ−４，４′−ジアミノジフェニルメタン（以下、「ＭＯＣＡ」と称す。）を主成分とし、低反応性の２級ポリオールであるポリオキシプロピレンポリオールを併用するのが一般的であった。また、低反応性のポリオキシプロピレンポリオールの反応を促進させるために、カルボン酸鉛を触媒として用いていた。カルボン酸鉛を使用しない場合は、ポリオールとの反応が十分に促進されないため、特に夏季においては主剤のイソシアナート基と水分との反応が進行してしまい、その結果副生する炭酸ガスにより発泡現象を起こし低物性化してしまう。
上記の防水材はＭＯＣＡ架橋型防水材と称せられている。ＭＯＣＡは結晶性が高くしかも溶解性に乏しい原料であるが、硬化剤に使用するポリオキシプロピレンポリオールにはある程度溶解し安定化させることができ、手塗施工に適した可使時間を有する防水材となるため、長い間汎用防水材として用いられてきた。
Traditionally, two-component room temperature curing urethane waterproofing materials for hand coating have a relatively low reaction as active hydrogen in one of the curing agents, with the main agent being an isocyanate group-terminated prepolymer composed of tolylene isocyanate and polyoxypropylene polyol. A polyoxypropylene polyol which is a low-reactivity secondary polyol containing 3,3'-dichloro-4,4'-diaminodiphenylmethane (hereinafter referred to as "MOCA") as a main component, which is a sexual aromatic polyamine. Was generally used in combination. In addition, lead carboxylate was used as a catalyst in order to accelerate the reaction of the low-reactivity polyoxypropylene polyol. When lead carboxylate is not used, the reaction with the polyol is not sufficiently promoted, so the reaction between the isocyanate group of the main agent and water proceeds, especially in summer, and as a result, the carbon dioxide gas produced as a by-product causes a foaming phenomenon. And the physical properties are reduced.
The above waterproofing material is referred to as a MOCA crosslinked waterproofing material. MOCA is a raw material with high crystallinity and poor solubility, but it is a waterproof material that can be dissolved and stabilized to some extent in the polyoxypropylene polyol used as a curing agent and has a pot life suitable for hand coating. Therefore, it has been used as a general-purpose waterproof material for a long time.
しかしながら、ＭＯＣＡ架橋型防水材には環境面での大きな問題があった。硬化剤に用いられているＭＯＣＡは労働安全衛生法で特定化学物質第２類物質に指定されており、硬化剤には上限値の１％を超えて使用されているため、特定化学物質など障害予防規則（以下、「特化則」と称す。）該当品となってしまう。また、ＭＯＣＡはＩＡＲＣ（国際がん研究機関）による発がん性評価でグループ１（ヒトに対して発がん性を示す）に分類されている。
さらに、促進剤として使用する必要があるカルボン酸鉛化合物は、世界的に使用が厳しく制限されている材料であり、化学物質排出把握管理促進法（通称、化管法）の特定第１種指定化学物質に指定されており、環境面からは使用を避けたい材料である。
However, the MOCA crosslinked waterproof material has a big environmental problem. MOCA used as a curing agent is designated as a Class 2 Specified Chemical Substance by the Industrial Safety and Health Act, and since it is used in a curing agent in excess of 1% of the upper limit, obstacles such as Specified Chemical Substances are impaired. It will be a product that falls under the preventive rules (hereinafter referred to as "specialization rules"). In addition, MOCA is classified into Group 1 (showing carcinogenicity to humans) in the carcinogenicity evaluation by IARC (International Agency for Research on Cancer).
Furthermore, the lead carboxylate compound that needs to be used as an accelerator is a material whose use is severely restricted worldwide, and is designated as the first specified type of the Chemical Substance Emission Control Promotion Law (commonly known as the Chemical Substances Control Law). It is designated as a chemical substance and is a material that should be avoided from the environmental point of view.
近年、ＭＯＣＡ架橋型防水材と同様にトリレンジイソシアナートとポリオキシプロピレンポリオールからなるイソシアナート基末端プレポリマーを主剤とし、硬化剤中の活性水素化合物として、ＭＯＣＡの替わりに高反応性の芳香族ポリアミンであるジエチルトルエンジアミン（以下、「ＤＥＴＤＡ」と称す。）を用いた、ＤＥＴＤＡ架橋型ウレタン防水材が開発されている。この方法は、ＤＥＴＤＡが高反応性であるため低温硬化性は良好であるが、夏季の可使時間を確保することに大きな問題があり、硬化剤にポリオールとウレタン化触媒である有機第２錫化合物または／および１位と２位に置換基を有するイミダゾール化合物を使用する方法（特許文献１）、硬化剤に反応性の穏やかな芳香族２級アミンとポリオールを併用する方法（特許文献２）、主剤に含まれるポリオールの２０当量％以上７５当量％以下がジオールであり、硬化剤に反応性の穏やかな芳香族２級アミンを併用する方法（特許文献３）などが提案されている。 In recent years, as with the MOCA crosslinked waterproofing material, the main agent is an isocyanate group-terminated prepolymer composed of tolylene diisocyanate and polyoxypropylene polyol, and as an active hydrogen compound in a curing agent, a highly reactive aromatic instead of MOCA. A DETDA crosslinked urethane waterproofing material using a polyamine, diethyltoluenediamine (hereinafter referred to as "DETDA"), has been developed. This method has good low-temperature curability because DETDA is highly reactive, but there is a big problem in securing the pot life in summer. A method of using a compound or / and an imidazole compound having substituents at the 1- and 2-positions (Patent Document 1), and a method of using a mildly reactive aromatic secondary amine and a polyol as a curing agent (Patent Document 2). , 20% or more and 75% or less of the polyol contained in the main agent is a diol, and a method of using a mildly reactive aromatic secondary amine in combination with a curing agent has been proposed (Patent Document 3).
ＤＥＴＤＡ架橋型防水材は、硬化剤に特定化学物質のＭＯＣＡを使用せず、さらにはカルボン酸鉛を使用しなくとも硬化性や発泡性に問題がないため、ＭＯＣＡ架橋型防水材に代わって主流となりつつある。 The DETDA cross-linked waterproof material is the mainstream in place of the MOCA cross-linked waterproof material because it does not use MOCA, which is a specific chemical substance, as a curing agent, and there is no problem in curability and foamability even if lead carboxylate is not used. Is becoming.
ＤＥＴＤＡ架橋型防水材で夏季の可使時間を確保するために、ポリオールや芳香族２級アミンを併用した場合、耐熱性や耐アルカリ性などの耐久性が必ずしも十分とは言えなかった。近年ウレタン防水材は１０年保証を要求されるのが一般的となってきており、初期性能だけでなく、耐久性能についても重要視する必要がある。耐久性については紫外線劣化と熱・アルカリ劣化が主な劣化要因となるが、紫外線劣化については通常ウレタン防水層の上に塗布するトップコートにより保護されているため、トップコートの性能に依存するところが大きい。一方の熱・アルカリ劣化についてはウレタン防水材組成物自体の性能に依存するため、ウレタン防水材を設計する上で非常に重要となる。熱劣化試験条件については、ＪＩＳ Ａ ６０２１では８０℃で１週間、アルカリ劣化試験条件については、ＪＩＳ Ａ ６０２１では２３℃で１週間の劣化処理と規定されているが、１０年保証が要求されるのが当然となった昨今においては、より過酷な劣化試験条件での評価を行い実用上の性能を担保しているのが現状である。 When a polyol or an aromatic secondary amine was used in combination with the DETDA crosslinked waterproof material to secure the pot life in summer, the durability such as heat resistance and alkali resistance was not always sufficient. In recent years, urethane waterproofing materials are generally required to have a 10-year warranty, and it is necessary to emphasize not only initial performance but also durability performance. Regarding durability, UV deterioration and thermal / alkaline deterioration are the main deterioration factors, but UV deterioration is usually protected by a top coat applied on the urethane waterproof layer, so it depends on the performance of the top coat. big. On the other hand, thermal / alkaline deterioration depends on the performance of the urethane waterproof material composition itself, and is therefore very important in designing the urethane waterproof material. JIS A 6021 stipulates a one-week deterioration treatment at 80 ° C., and JIS A 6021 stipulates a one-week deterioration treatment at 23 ° C., but a 10-year warranty is required. Nowadays, it is natural that the evaluation is performed under more severe deterioration test conditions to ensure the practical performance.
本発明者らはこれらの問題点を鑑み、ＤＥＴＤＡ架橋型防水材に関して鋭意検討した結果、トリレンジイソシアナートとポリオールからなるイソシアナート基末端プレポリマーを含む主剤と、芳香族ポリアミンと活性水素を３個以上有するポリアルカノールアミンを反応成分として含む硬化剤を使用することにより、年間を通して十分な可使時間を有し、かつ耐熱・耐アルカリ性に優れた２液常温硬化型手塗り用ウレタン防水材組成物が得られることを見出し、本発明を完成するに至った。
本発明は、ポリイソシアナートとポリオールからなるイソシアナート基末端プレポリマーを含む主剤と、芳香族ポリアミンおよびポリオールを反応成分として含む硬化剤とからなる２液常温硬化型手塗り用ウレタン防水材組成物であって、ポリイソシアナートがトリレンジイソシアナートを含み、芳香族ポリアミンがジエチルトルエンジアミンを含み、硬化剤中のポリオールが活性水素を３個以上有するポリアルカノールアミンを含むことを特徴とする。
In view of these problems, the present inventors diligently studied the DETDA crosslinked waterproofing material, and as a result, the main agent containing the isocyanate group-terminated prepolymer composed of tolylene isocyanate and polyol, and aromatic polyamine and active hydrogen were used as 3 By using a curing agent containing more than one polyalkanolamine as a reaction component, a two-component room temperature curing type urethane waterproofing material composition for hand coating that has sufficient pot life throughout the year and has excellent heat resistance and alkali resistance. We have found that a product can be obtained, and have completed the present invention.
The present invention is a two-component room temperature curing type urethane waterproofing material composition for hand coating, which comprises a main agent containing an isocyanate group-terminated prepolymer composed of a polyisocyanate and a polyol, and a curing agent containing an aromatic polyamine and a polyol as reaction components. The polyisocyanate contains tolylene diisocyanate, the aromatic polyamine contains diethyltoluenediamine, and the polyol in the curing agent contains polyalkanolamine having three or more active hydrogens.
本発明は、次の態様を含む。
［１］ポリイソシアナートとポリオールからなるイソシアナート基末端プレポリマーを含む主剤と、芳香族ポリアミンおよびポリオールを反応成分として含む硬化剤とからなる２液常温硬化型手塗り用ウレタン防水材組成物であって、ポリイソシアナートがトリレンジイソシアナートを含み、芳香族ポリアミンがジエチルトルエンジアミンを含み、硬化剤中のポリオールが活性水素を３個以上有するポリアルカノールアミンを含む、２液常温硬化型手塗り用ウレタン防水材組成物。
［２］活性水素を３個以上有するポリアルカノールアミンが、トリイソプロパノールアミン、トリエタノールアミン、１−［ビス（２−ヒドロキシエチル）アミノ）−２−プロパノール、ジイソプロパノールアミン、ジエタノールアミン、Ｎ，Ｎ，Ｎ′，Ｎ′−テトラキス（２−ヒドロキシプロピル）エチレンジアミンおよびＮ，Ｎ，Ｎ′，Ｎ′−テトラキス（２−ヒドロキシエチル）エチレンジアミンからなる群から選ばれる少なくとも１種である、［１］に記載の２液常温硬化型手塗り用ウレタン防水材組成物。
［３］ウレタン化触媒として有機第２錫化合物または／および１位と２位に置換基を有するイミダゾール化合物を含む［１］または［２］に記載の２液常温硬化型手塗り用ウレタン防水材組成物。
［４］硬化剤中の芳香族ポリアミンとポリオールの当量比が４０／６０〜９０／１０の範囲内にあり、硬化剤に含まれる活性水素化合物の４０当量％以上がジエチルトルエンジアミンを含む芳香族ポリアミンであり、５当量％以上が活性水素を３個以上有するポリアルカノールアミンである、［１］〜［３］のいずれか１つに記載の２液常温硬化型手塗り用ウレタン防水材組成物。
［５］ポリイソシアナートとポリオールとからなるイソシアナート基末端プレポリマーを構成するポリオールの７５当量％超がジオールである、［１］〜［４］のいずれか１つに記載の２液常温硬化型手塗り用ウレタン防水材組成物。
［６］ポリイソシアナートの７０当量％以上がトリレンジイソシアナートである、［１］〜［５］のいずれか１つに記載の２液常温硬化型手塗り用ウレタン防水材組成物。
The present invention includes the following aspects.
[1] A two-component room temperature curing type urethane waterproofing material composition for hand coating, which comprises a main agent containing an isocyanate group-terminated prepolymer composed of a polyisocyanate and a polyol, and a curing agent containing an aromatic polyamine and a polyol as reaction components. Two-component room temperature curing type hand coating, in which the polyisocyanate contains tolylene diisocyanate, the aromatic polyamine contains diethyltoluenediamine, and the polyol in the curing agent contains polyalkanolamine having three or more active hydrogens. Urethane waterproof material composition for.
[2] Polyalkanolamines having three or more active hydrogens are triisopropanolamine, triethanolamine, 1- [bis (2-hydroxyethyl) amino) -2-propanol, diisopropanolamine, diethanolamine, N, N, Described in [1], which is at least one selected from the group consisting of N', N'-tetrax (2-hydroxypropyl) ethylenediamine and N, N, N', N'-tetrax (2-hydroxyethyl) ethylenediamine. Two-component room temperature curable urethane waterproof material composition for hand coating.
[3] The two-component room temperature curing type urethane waterproofing material for hand coating according to [1] or [2], which contains an organic stannic compound or / and an imidazole compound having substituents at the 1- and 2-positions as a urethanization catalyst. Composition.
[4] The equivalent ratio of the aromatic polyamine to the polyol in the curing agent is in the range of 40/60 to 90/10, and 40 equivalent% or more of the active hydrogen compound contained in the curing agent is an aromatic containing diethyltoluenediamine. The two-component room temperature curing type urethane waterproofing material composition for hand coating according to any one of [1] to [3], which is a polyamine and has 5 equivalent% or more of polyalkanolamine having 3 or more active hydrogens. ..
[5] The two-component room temperature curing according to any one of [1] to [4], wherein more than 75 equivalent% of the polyol constituting the isocyanate group-terminated prepolymer composed of polyisocyanate and polyol is diol. Urethane waterproof material composition for mold hand coating.
[6] The two-component room temperature curing type urethane waterproof material composition for hand coating according to any one of [1] to [5], wherein 70 equivalent% or more of polyisocyanate is tolylene diisocyanate.
本発明の２液常温硬化型手塗り用ウレタン防水材は、年間を通して十分な可使時間を有し、かつ耐熱・耐アルカリ性などの耐久性にも優れる。 The two-component room temperature curing type urethane waterproof material for hand coating of the present invention has a sufficient pot life throughout the year and is also excellent in durability such as heat resistance and alkali resistance.
本発明は、２液常温硬化型手塗り用ウレタン防水材組成物に関する。ここで、２液とは、主剤と硬化剤の２つをいう。常温硬化型とは、外気温で硬化する性質を有するものであることをいい、すなわち敢えて熱を加えることをせずに周囲の自然環境に放置することによって硬化させるタイプであることをいう。手塗り用とは、コテ、ヘラ、ローラー、刷毛などを用いて人の手で塗って使用するものであることをいう。
本発明の２液常温硬化型手塗り用ウレタン防水材組成物は、トリレンジイソシアナートとポリオールからなるイソシアナート基末端プレポリマーを含む主剤と芳香族ポリアミンおよびポリオールを反応成分として含む硬化剤とからなり、硬化剤中の芳香族ポリアミンがジエチルトルエンジアミンを含み、硬化剤中のポリオールが活性水素を３個以上有するポリアルカノールアミンを含む。
The present invention relates to a two-component room temperature curable urethane waterproof material composition for hand coating. Here, the two liquids refer to two liquids, a main agent and a curing agent. The room temperature curing type means that it has the property of curing at outside air temperature, that is, it is a type that cures by leaving it in the surrounding natural environment without applying heat. Hand-painted means that it is applied by hand using a trowel, spatula, roller, brush, or the like.
The two-component room temperature curing type urethane waterproofing material composition for hand coating of the present invention is composed of a main agent containing an isocyanate group-terminated prepolymer composed of tolylene isocyanate and a polyol, and a curing agent containing an aromatic polyamine and a polyol as reaction components. The aromatic polyamine in the curing agent contains diethyltoluenediamine, and the polyol in the curing agent contains polyalkanolamine having three or more active hydrogens.
（主剤ポリイソシアナート）
主剤はポリイソシアナートとポリオールからなるイソシアナート基末端プレポリマーを含む。本発明は、ポリイソシアナートとしてトリレンジイソシアナートを含む必要があり、ポリイソシアナートの７０当量％以上がトリレンジイソシアナートであることが好ましく、８０当量％以上であることがより好ましく、９０当量％以上であることが最も好ましい。トリレンジイソシアナートとしては、２，４−異性体含有率が６５〜１００質量％のものが使用できる。具体的には市販のＴ−１００（２，４−異性体が約１００質量％）、Ｔ−８０（２，４−異性体が約８０質量％）およびＴ−６５（２，４−異性体が約６５質量％）あるいはこれらの混合物が用いられる。
(Main agent polyisocyanate)
The base agent contains an isocyanate group-terminated prepolymer consisting of polyisocyanate and polyol. The present invention needs to contain tolylene diisocyanate as polyisocyanate, and 70 equivalent% or more of polyisocyanate is preferably tolylene diisocyanate, more preferably 80 equivalent% or more, and 90 equivalents. Most preferably, it is% or more. As the tolylene isocyanate, one having a 2,4-isomer content of 65 to 100% by mass can be used. Specifically, commercially available T-100 (about 100% by mass of 2,4-isomer), T-80 (about 80% by mass of 2,4-isomer) and T-65 (about 80% by mass of 2,4-isomer). Is about 65% by mass) or a mixture thereof is used.
尚、一部その他のポリイソシアナートを併用することもできる。併用できるイソシアナートとしては、ヘキサメチレンジイソシアナート、イソホロンジイソシアナート、水添トリレンジイソシアナート、ノルボルナンジイソシアナート、水添ジフェニルメタンジイソシアナート、水添キシリレンジイソシアナートなどの脂肪族あるいは脂環族ポリイソシアナート、また、キシリレンジイソシアナート、テトラメチルキシリレンジイソシアナート、ジフェニルメタンジイソシアナートといった芳香族ポリイソシアナートおよびそれらのダイマー体、アロファネート体、ビウレット体、アダクト体、イソシアヌレート体などの誘導体およびそれらの混合物も一部使用することができる。 In addition, some other polyisocyanates can also be used in combination. Examples of isocyanates that can be used in combination include aliphatic or alicyclics such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, norbornan diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated xylylene diisocyanate. Group polyisocyanates, aromatic polyisocyanates such as xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate and derivatives such as dimer, allophanate, biuret, adduct, and isocyanurate. And some of their mixtures can also be used.
（主剤ポリオール）
主剤に用いるポリオールとしては、通常ウレタン防水材の主剤に用いられるポリオールを用いることができるが、低粘度で施工性のよい主剤とするためには、分子量が３００〜８０００のポリオキシプロピレンポリオールやポリオキシエチレンポリオキシプロピレンポリオールといったポリエーテル系ポリオールを用いることが好ましい。また、ポリエステル系などその他の高分子量ポリオールも一部であれば使用することができる。
さらに、１，４−ブタンジオール、３−メチル−１，５−ペンタンジオール、１，６−ヘキサンジオール、プロピレングリコール、ジプロピレングリコールといった短鎖ポリオールも使用することができる。
(Main agent polyol)
As the polyol used as the main agent, the polyol usually used as the main agent of urethane waterproofing material can be used, but in order to make the main agent having low viscosity and good workability, polyoxypropylene polyol or poly having a molecular weight of 300 to 8000 is used. It is preferable to use a polyether polyol such as oxyethylene polyoxypropylene polyol. Further, other high molecular weight polyols such as polyester can be used as long as it is a part.
Further, short chain polyols such as 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, propylene glycol and dipropylene glycol can also be used.
主剤に用いるポリオールの官能基数であるが、硬化剤にポリオールや芳香族２級アミンを併用した場合、耐熱性および耐アルカリ性が低下する傾向があり、この現象を防止するためには主剤に３官能基以上のポリオールを多めに用い分枝点を増やすことが必要であった。しかし、本発明では硬化剤に活性水素を３個以上有するポリアルカノールアミンを使用しているため、耐熱性および耐アルカリ性が顕著に改善されている。その結果、主剤中に３官能基以上のポリオールを多めに用いる必要はなくなり、可使時間の確保に有利となるジオールを多目に使うことが可能となった。したがって、主剤に用いるポリオールはジオールを７５当量％超とし、トリオール以上を２５当量％以下用いることが好ましく、ジオールを８０当量％以上使用し、トリオール以上を２０当量％以下用いることがより好ましい。ジオールが７５当量％以下では十分な可使時間を確保することが難しくなる。ジオールの割合の上限は限定されないが、好ましくは、ジオールを９５当量％未満使用し、トリオール以上を５当量％超使用する。 Regarding the number of functional groups of the polyol used as the main agent, when a polyol or an aromatic secondary amine is used in combination with the curing agent, the heat resistance and alkali resistance tend to decrease, and in order to prevent this phenomenon, the main agent is trifunctional. It was necessary to increase the number of branch points by using a large amount of polyols of groups or more. However, in the present invention, since polyalkanolamine having three or more active hydrogens is used as the curing agent, heat resistance and alkali resistance are remarkably improved. As a result, it is no longer necessary to use a large amount of polyol having a trifunctional group or more in the main agent, and it has become possible to use a large amount of diol, which is advantageous for securing the pot life. Therefore, the polyol used as the main agent preferably contains diol in an amount of more than 75 equivalent%, triol or more in an amount of 25 equivalent% or less, diol in an amount of 80 equivalent% or more, and triol or more in an amount of 20 equivalent% or less. If the diol is 75 equivalent% or less, it becomes difficult to secure a sufficient pot life. The upper limit of the proportion of diol is not limited, but preferably less than 95 equivalent% of diol is used and more than 5 equivalent% of triol is used.
（主剤ＮＣＯ含有量）
一般的に、可使時間を確保するためには、主剤のＮＣＯ含有量を少なくすることが効果的であるが、その結果硬化性が低下したりウレタン防水材として必要とされる強度や耐熱性・耐アルカリ性といった耐久性が低下するという問題が発生してしまう。
しかし、本発明のウレタン防水材組成物は、硬化剤にジエチルトルエンジアミンと活性水素を３個以上有するポリアルカノールアミンを含むため、比較的ＮＣＯ含有量が低い領域においてもウレタン防水材に必要とされる強度や耐久性を確保することができる。本発明において、主剤のＮＣＯ含有量は１．５〜３．５質量％の範囲にすることで、十分な可使時間を有した上でウレタン防水材に必要とされる強度や耐久性を確保することができるため好ましい。尚、可使時間確保および施工可能時間確保の面より、ＮＣＯ含有量が１．７〜３．３質量％であることがより好ましく、さらには１．９〜３．１質量％であることが最も好ましい。ＮＣＯ含有量が１．５質量％未満では、ウレタン防水材に必要とされる強度や耐久性を確保することが難しくなり、３．５質量％超では可使時間の確保が難しくなる。
(Main agent NCO content)
Generally, in order to secure the pot life, it is effective to reduce the NCO content of the main agent, but as a result, the curability is lowered and the strength and heat resistance required as a urethane waterproof material are reduced. -There is a problem that durability such as alkali resistance is reduced.
However, since the urethane waterproof material composition of the present invention contains diethyltoluenediamine and polyalkanolamine having three or more active hydrogens in the curing agent, it is required for the urethane waterproof material even in a region where the NCO content is relatively low. Strength and durability can be ensured. In the present invention, the NCO content of the main agent is set in the range of 1.5 to 3.5% by mass to ensure the strength and durability required for the urethane waterproof material while having a sufficient pot life. It is preferable because it can be used. From the viewpoint of securing the pot life and the workable time, the NCO content is more preferably 1.7 to 3.3% by mass, and further preferably 1.9 to 3.1% by mass. Most preferred. If the NCO content is less than 1.5% by mass, it becomes difficult to secure the strength and durability required for the urethane waterproof material, and if it exceeds 3.5% by mass, it becomes difficult to secure the pot life.
（主剤ＮＣＯ基／ＯＨ基当量比）
本発明で使用する主剤製造時のイソシアナート基とポリオールのＯＨ基との比である、ＮＣＯ基／ＯＨ基当量比は１．５〜２．５の範囲であることが好ましく、１．６以上２．３未満であることがより好ましく、１．７以上２．１未満であることが最も好ましい。
尚、ＮＣＯ基／ＯＨ基当量比が１．５未満になると主剤の増粘が激しくなり、２．５超では主剤中の遊離ＴＤＩ量を１質量％以下とすることが難しくなり、労働安全衛生法上特定化学物質として扱われる可能性が高くなるため好ましくない。
(Main agent NCO group / OH group equivalent ratio)
The NCO group / OH group equivalent ratio, which is the ratio of the isocyanate group used in the production of the main agent used in the present invention to the OH group of the polyol, is preferably in the range of 1.5 to 2.5, preferably 1.6 or more. It is more preferably less than 2.3, and most preferably 1.7 or more and less than 2.1.
If the NCO group / OH group equivalent ratio is less than 1.5, the thickening of the main agent becomes severe, and if it exceeds 2.5, it becomes difficult to reduce the amount of free TDI in the main agent to 1% by mass or less, and occupational safety and health. It is not preferable because it is more likely to be treated as a specific chemical substance legally.
（主剤の合成）
本発明のイソシアナート基末端プレポリマーは、トリレンジイソシアナートを含むポリイソシアナートとポリオールを６０〜１２０℃で２〜１２時間程度加熱・混合することにより合成できる。なお、反応が遅い場合は必要に応じて一般的なウレタン化反応促進剤を使用することもできる。
(Synthesis of main agent)
The isocyanate group-terminated prepolymer of the present invention can be synthesized by heating and mixing a polyisocyanate containing tolylene diisocyanate and a polyol at 60 to 120 ° C. for about 2 to 12 hours. If the reaction is slow, a general urethanization reaction accelerator can be used if necessary.
（硬化剤中の活性水素化合物）
本発明の硬化剤は、活性水素化合物として芳香族ポリアミンおよびポリオールを含む。芳香族ポリアミンはジエチルトルエンジアミン（ＤＥＴＤＡ）を含む。ＤＥＴＤＡには、３，５−ジエチル−２，４−トルエンジアミン、３，５−ジエチル−２，６−トルエンジアミンなどの異性体が存在するが、いずれの異性体を用いてもよく、またそれらの混合物を用いてもよい。工業用としては例えばアルベマール社製のエタキュア１００（２，４−異性体／２，６−異性体の質量比８０／２０）などが入手できる。
(Active hydrogen compound in curing agent)
The curing agent of the present invention contains aromatic polyamines and polyols as active hydrogen compounds. Aromatic polyamines include diethyl toluenediamine (DETDA). DETDA has isomers such as 3,5-diethyl-2,4-toluenediamine and 3,5-diethyl-2,6-toluenediamine, but any isomer may be used, and they may be used. You may use a mixture of. For industrial use, for example, EtaCure 100 (mass ratio of 2,4-isomer / 2,6-isomer 80/20) manufactured by Albemarle Corporation can be obtained.
また、硬化剤中の活性水素化合物の４０当量％以上がＤＥＴＤＡであることが好ましく、４５当量％以上であることがより好ましく、５０当量％以上であることが最も好ましい。高凝集性で高反応性でありしかも液状で溶解性の良いＤＥＴＤＡが４０当量％以上でないと、硬化性が良くしかも高物性の防水材とすることが難しい。
硬化剤中の芳香族ポリアミンのすべてがＤＥＴＤＡであることが好ましいが、硬化剤はＤＥＴＤＡ以外の芳香族ポリアミンを含むことができる。硬化剤がＤＥＴＤＡ以外の芳香族ポリアミンを含む場合、ＤＥＴＤＡは、芳香族ポリアミンの総量の５０当量％以上であることが好ましく、６０当量％以上であることがより好ましく、７０当量％以上であることがさらに好ましい。
Further, 40 equivalent% or more of the active hydrogen compound in the curing agent is preferably DETDA, more preferably 45 equivalent% or more, and most preferably 50 equivalent% or more. Unless DETDA, which is highly cohesive, highly reactive, liquid, and has good solubility, is 40 equivalent% or more, it is difficult to obtain a waterproof material having good curability and high physical characteristics.
It is preferable that all of the aromatic polyamines in the curing agent are DETDA, but the curing agent can include aromatic polyamines other than DETDA. When the curing agent contains an aromatic polyamine other than DETDA, the DETDA is preferably 50 equivalent% or more, more preferably 60 equivalent% or more, and 70 equivalent% or more of the total amount of the aromatic polyamine. Is even more preferable.
ＤＥＴＤＡと併用できる芳香族ポリアミンとしては、ＤＥＴＤＡと同様の高反応性であるクミアイ化学工業株式会社製のキュアハード（登録商標）ＭＥＤ（４，４′−メチレンビス（２−エチル−６−メチルアニリン））、日本化薬株式会社製のカヤハード（登録商標）ＡＡ（４，４′−メチレンビス（２−エチルアニリン））、日本化薬株式会社製のカヤボンド（登録商標）Ｃ−３００（４，４′−メチレンビス（２，６−ジエチルアニリン））、日本化薬株式会社製のカヤボンド（登録商標）Ｃ−４００（４，４′−メチレンビス（２，６−ジｉｓｏ−プロピルアニリン））などが挙げられる。 As an aromatic polyamine that can be used in combination with DETDA, Cure Hard (registered trademark) MED (4,4'-methylenebis (2-ethyl-6-methylaniline)) manufactured by Kumiai Chemical Industry Co., Ltd., which has the same high reactivity as DETDA. ), Kayahard (registered trademark) AA (4,4'-methylenebis (2-ethylaniline)) manufactured by Nippon Kayaku Co., Ltd., Kayabond (registered trademark) C-300 (4,4') manufactured by Nippon Kayaku Co., Ltd. -Methylenebis (2,6-diethylaniline)), Kayabond (registered trademark) C-400 (4,4'-methylenebis (2,6-diiso-propylaniline)) manufactured by Nippon Kayaku Co., Ltd., etc. ..
また、低反応性の芳香族ポリアミンである、アルベマール社製のエタキュア４２０（４，４′−メチレンビス（Ｎ−ｓｅｃ−ブチルアニリン））、アルベマール社製のエタキュア３００（ジメチルチオトルエンジアミン）、クミアイ化学株式会社製のエラスマー（登録商標）６５０Ｐ（ポリテトラメチレングリコールビス（ｐ−アミノベンゾエート））、クミアイ化学株式会社製のポレア（登録商標）ＳＬ−１００Ａ（ポリ（テトラメチレン／３−メチルテトラメチレンエーテル）グリコールビス（４−アミノベンゾエート））なども使用できる。その中で、エタキュア４２０はＤＥＴＤＡほど高凝集性ではないが、低反応性であるため可使時間を延長させる効果があり、しかも硬化性をあまり悪くさせないという特徴があるため、特に好ましく使用することができる。 In addition, low-reactive aromatic polyamines, Ethercure 420 (4,5'-methylenebis (N-sec-butylaniline)) manufactured by Albemar, Etacure 300 (dimethylthiotoluenediamine) manufactured by Albemar, Kumiai Chemistry. Erasmer (registered trademark) 650P (polytetramethylene glycol bis (p-aminobenzoate)) manufactured by Kumiai Chemical Co., Ltd., Porea (registered trademark) SL-100A (poly (tetramethylene / 3-methyltetramethylene ether)) manufactured by Kumiai Chemical Co., Ltd. ) Glycolbis (4-aminobenzoate)) and the like can also be used. Among them, EtaCure 420 is not as highly cohesive as DETDA, but it has the effect of prolonging the pot life because it has low reactivity, and it does not deteriorate the curability so much, so it is particularly preferably used. Can be done.
本発明の硬化剤は、活性水素化合物として芳香族ポリアミンおよびポリオールを含む。ポリオールは活性水素を３個以上有するポリアルカノールアミンを含む。ここで活性水素とは、具体的には水酸基およびアミノ基からなる活性水素のことを言う。活性水素を３個以上有するポリアルカノールアミンとしては、例えばＮ，Ｎ，Ｎ′，Ｎ′−テトラキス（２−ヒドロキシプロピル）エチレンジアミン、Ｎ，Ｎ，Ｎ′，Ｎ′−テトラキス（２−ヒドロキシエチル）エチレンジアミンなどの水酸基を４個有するテトラアルカノールジアミン、トリイソプロパノールアミン、トリエタノールアミン、１−［ビス（２−ヒドロキシエチル）アミノ）−２−プロパノールなどの水酸基を３個有するトリアルカノールアミン、ジイソプロパノールアミン、ジエタノールアミンなどの水酸基２個とアミノ基１個を有するジアルカノールアミンが使用できる。その中でもトリイソプロパノールアミン、トリエタノールアミン、ジイソプロパノールアミン、ジエタノールアミンが好ましく、トリイソプロパノールアミンが特に好ましく使用することができる。 The curing agent of the present invention contains aromatic polyamines and polyols as active hydrogen compounds. The polyol contains a polyalkanolamine having 3 or more active hydrogens. Here, the active hydrogen specifically refers to an active hydrogen composed of a hydroxyl group and an amino group. Examples of polyalkanolamines having three or more active hydrogens include N, N, N', N'-tetrakis (2-hydroxypropyl) ethylenediamine, N, N, N', N'-tetrakis (2-hydroxyethyl). Tetraalkanolamines having 4 hydroxyl groups such as ethylenediamine, triisopropanolamines, triethanolamines, trialkanolamines having 3 hydroxyl groups such as 1- [bis (2-hydroxyethyl) amino) -2-propanol, diisopropanolamines , Dialkanolamine having two hydroxyl groups and one amino group such as diethanolamine can be used. Among them, triisopropanolamine, triethanolamine, diisopropanolamine and diethanolamine are preferable, and triisopropanolamine can be particularly preferably used.
また、硬化剤中の活性水素化合物の５当量％以上が活性水素を３個以上有するポリアルカノールアミンであることが好ましく、１０当量％以上であることがより好ましく、１５当量％以上であることが最も好ましい。活性水素を３個以上有するポリアルカノールアミンが５当量％未満では、塗膜の耐熱性・耐アルカリ性などの耐久性を十分に確保した防水材とすることが難しい。
硬化剤中のポリオールのすべてが活性水素を３個以上有するポリアルカノールアミンであることが好ましいが、硬化剤は活性水素を３個以上有するポリアルカノールアミン以外のポリオールを含むことができる。硬化剤が活性水素を３個以上有するポリアルカノールアミン以外のポリオールを含む場合、活性水素を３個以上有するポリアルカノールアミンは、硬化剤中のポリオールの総量の２０当量％以上あることが好ましく、２５当量％以上であることがより好ましく、３０当量％以上であることがさらに好ましい。
Further, 5 equivalent% or more of the active hydrogen compound in the curing agent is preferably a polyalkanolamine having 3 or more active hydrogens, more preferably 10 equivalent% or more, and 15 equivalent% or more. Most preferred. If the amount of polyalkanolamine having 3 or more active hydrogens is less than 5 equivalent%, it is difficult to obtain a waterproof material having sufficient durability such as heat resistance and alkali resistance of the coating film.
It is preferable that all of the polyols in the curing agent are polyalkanolamines having 3 or more active hydrogens, but the curing agent can include polyols other than polyalkanolamines having 3 or more active hydrogens. When the curing agent contains a polyol other than the polyalkanolamine having 3 or more active hydrogens, the polyalkanolamine having 3 or more active hydrogens is preferably 20 equivalents or more of 20 equivalents or more of the total amount of the polyols in the curing agent. Equivalent% or more is more preferable, and 30 equivalent% or more is further preferable.
なお、活性水素を３個以上有するポリアルカノールアミンと併用できるポリオールとしてはポリエーテルポリオール、ポリエステルポリオール、アルキルポリオールなどが挙げられる。その中でもポリエステルポリオールが好ましく、ＭＰＤ（３−メチル−１，５−ペンタンジオール）、ＭＯＤ（２−メチル−１，８−オクタンジオール）などの側鎖を有するジオールを主成分としたポリオールとコハク酸、アジピン酸、アゼライン酸、セバシン酸、テトラヒドロ（無水）フタル酸、ヘキサヒドロ（無水）フタル酸などの脂肪族または脂環族ジカルボン酸との反応によって得られる低結晶性で耐加水分解性の良いポリエステルポリオールがより好ましい。さらには、ＭＰＤ、ＭＯＤ等といった側鎖を有するジオールとフタル酸や無水フタル酸等の芳香族ジカルボン酸との反応によって得られる低結晶性芳香族ポリエステルポリオールは耐加水分解性および機械的強度に優れるため、最も好ましい。具体的には、株式会社クラレ製のクラレポリオールＰ−５２０（数平均分子量５００）、クラレポリオールＰ−５３０（数平均分子量５００）などが挙げられる。 Examples of the polyol that can be used in combination with the polyalkanolamine having three or more active hydrogens include a polyether polyol, a polyester polyol, and an alkyl polyol. Among them, polyester polyol is preferable, and polyol and succinic acid mainly composed of diol having a side chain such as MPD (3-methyl-1,5-pentanediol) and MOD (2-methyl-1,8-octanediol). , Adipic acid, azelaic acid, sebacic acid, tetrahydro (anhydrous) phthalic acid, hexahydro (anhydrous) phthalic acid and other aliphatic or alicyclic dicarboxylic acids, which are low crystalline and highly hydrolysis resistant polyesters. Polyols are more preferred. Furthermore, the low crystalline aromatic polyester polyol obtained by reacting a diol having a side chain such as MPD or MOD with an aromatic dicarboxylic acid such as phthalic acid or phthalic anhydride is excellent in hydrolysis resistance and mechanical strength. Therefore, it is most preferable. Specific examples thereof include Kuraray polyol P-520 (number average molecular weight 500) and Kuraray polyol P-530 (number average molecular weight 500) manufactured by Kuraray Co., Ltd.
一方、硬化剤中の芳香族ポリアミン／ポリオールの当量比は４０／６０〜９０／１０の範囲が好ましく、４５／５５〜８０／２０であることがより好ましい。 On the other hand, the equivalent ratio of the aromatic polyamine / polyol in the curing agent is preferably in the range of 40/60 to 90/10, more preferably 45/55 to 80/20.
（主剤イソシアナート／硬化剤活性水素当量比）
主剤中の全イソシアナート基／硬化剤中の活性水素（アミノ基＋水酸基）の当量比は０．８〜１．６の範囲にすることが好ましく、０．９〜１．５にすることがより好ましく、０．９５〜１．４にすることが最も好ましい。主剤イソシアナート基／硬化剤活性水素当量比が０．８未満では活性水素が過剰であるため硬化物の高分子量化が不十分となり低物性化してしまい、１．６超では強度や耐久性が不十分になってしまい、硬化性も低下してしまう。
(Main agent isocyanate / curing agent active hydrogen equivalent ratio)
The equivalent ratio of all isocyanate groups in the main agent / active hydrogen (amino group + hydroxyl group) in the curing agent is preferably in the range of 0.8 to 1.6, preferably 0.9 to 1.5. More preferably, it is 0.95 to 1.4, and most preferably 0.95 to 1.4. If the main agent isocyanate group / curing agent active hydrogen equivalent ratio is less than 0.8, the amount of active hydrogen is excessive, so that the molecular weight of the cured product is insufficient and the physical properties are lowered. It becomes insufficient and the curability is also lowered.
（硬化促進剤）
本発明においては、硬化剤中の芳香族ポリアミンとしてイソシアナート基との反応性が高いＤＥＴＤＡを含んでいるため、硬化促進剤は特に使用しなくても構わないが、速硬化性を必要とする場面や施工温度が低い冬季用配合、硬化剤中のポリオール使用量が多い配合あるいは主剤イソシアナート／硬化剤活性水素当量比が高く過剰のイソシアナート基と水分との反応を促進させる必要がある場合などにおいて、必要に応じて硬化促進剤を使用することができる。
(Curing accelerator)
In the present invention, since DETDA, which has high reactivity with isocyanate groups, is contained as an aromatic polyamine in the curing agent, a curing accelerator may not be used in particular, but quick curing is required. When it is necessary to promote the reaction between the excess isocyanate group and water, which is used in winter when the construction temperature is low, when the amount of polyol used in the curing agent is large, or when the main agent isocyanate / curing agent active hydrogen equivalent ratio is high. In such cases, a curing accelerator can be used as needed.
本発明では、有機酸、有機酸金属塩、酸無水物、有機第２錫化合物、３級アミン化合物などの一般的なポリウレタン用硬化促進剤を用いることができる。その中でも有機第２錫化合物触媒が可使時間を短縮させることなしに硬化性を向上させることができるため好ましい。有機第２錫化合物触媒はあらかじめ主剤に添加することもできるが、主剤の貯蔵安定性を損ねる危険性があるため、硬化剤に配合する方が好ましく、硬化剤中に０．０００５質量％以上０．０３質量％未満添加することが好ましく、０．０３質量％以上添加すると水との反応を促進しすぎるため塗膜が発泡しやすくなると同時に耐熱性が低下し、０．０００５質量％未満では触媒効果が不十分である。 In the present invention, general curing accelerators for polyurethane such as organic acids, organic acid metal salts, acid anhydrides, organic stannic compounds and tertiary amine compounds can be used. Among them, the organic stannic compound catalyst is preferable because the curability can be improved without shortening the pot life. The organic stannicite compound catalyst can be added to the main agent in advance, but it is preferable to add it to the curing agent because there is a risk of impairing the storage stability of the main agent, and 0.0005% by mass or more is 0 in the curing agent. It is preferable to add less than 0.03% by mass, and if 0.03% by mass or more is added, the reaction with water is promoted too much, so that the coating film is easily foamed and at the same time the heat resistance is lowered. The effect is insufficient.
有機第２錫化合物の具体例としては、ジブチル錫オキサイド、ジオクチル錫オキサイド、ジブチル錫ジラウレート、ジブチル錫ジアセテート、ジブチル錫ジ２−エチルへキサノエート、ジオクチル錫ジアセテート、ジオクチル錫ジラウレート、ジブチル錫ジメルカプタイド、ジブチル錫ビスアセチルアセトネート、ジブチル錫オキシラウレート、ジオクチル錫ジネオデカネート、ジブチル錫ビスブチルマレート、ジオクチル錫２−エチルヘキシルマレート等が挙げられ、特に、ジブチル錫ジラウレート、ジオクチル錫ジラウレート、ジブチル錫ジメルカプタイドが好ましい。 Specific examples of the organic ditin compound include dibutyltin oxide, dioctyltin oxide, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin di2-ethylhexanoate, dioctyltin diacetate, dioctyltin dilaurate, and dibutyltin dimercaptide. Dibutyltin bisacetylacetonate, dibutyltin oxylaurate, dioctyltin dineodecanate, dibutyltin bisbutylmalate, dioctyltin 2-ethylhexylmalate, etc., and in particular, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dimercaptide preferable.
冬季用配合においては３級アミン系触媒を使用することが好ましい。３級アミン系触媒の中でも、イミダゾール化合物が好ましく、低温硬化性が良好な非発泡性の塗膜が提供できる。その中でも、１位と２位に置換基を有するイミダゾール触媒は低温時においてもＤＥＴＤＡ、ポリオール、湿気（水分）との反応をバランス良く促進し、冬季においても高強度で高耐熱性の塗膜を提供することができるより好ましい触媒である。１位と２位に置換基を有するイミダゾール触媒は有機金属触媒と併用することもでき、中でも有機第２錫化合物触媒と併用することが好ましく、トップコートとの接着性を低下させることなく、非常に硬化性の良い高物性・高耐熱性の防水材を提供できる。 It is preferable to use a tertiary amine-based catalyst in the winter formulation. Among the tertiary amine-based catalysts, the imidazole compound is preferable, and a non-foaming coating film having good low-temperature curability can be provided. Among them, the imidazole catalyst having substituents at the 1- and 2-positions promotes the reaction with DETDA, polyol, and moisture (moisture) in a well-balanced manner even at low temperatures, and provides a high-strength and highly heat-resistant coating film even in winter. It is a more preferred catalyst that can be provided. The imidazole catalyst having substituents at the 1- and 2-positions can be used in combination with an organometallic catalyst, and among them, it is preferable to use it in combination with an organic stannic compound catalyst, and it is extremely advantageous without deteriorating the adhesiveness with the top coat. It is possible to provide a waterproof material having high physical properties and high heat resistance with good curability.
また、１位と２位に置換基を有するイミダゾール触媒は可使時間を短縮させる傾向はあるが、年間を通しての硬化調整用触媒として配合することもできる。さらには年間を通しての現場添加型硬化促進剤として、施工現場で添加して使用することもできる。１位と２位に置換基を有するイミダゾール触媒としては、具体的には１，２−ジメチルイミダゾール、１−イソブチル−２−メチルイミダゾール、１−ベンジル−２−メチルイミダゾール、１−ベンジル−２−フェニルイミダゾール等が挙げられ、１，２−ジメチルイミダゾールと１−イソブチル−２−メチルイミダゾールが好ましく、常温で液体であり取扱いのしやすさから１−イソブチル−２−メチルイミダゾールがさらに好ましい。 Further, an imidazole catalyst having substituents at the 1-position and 2-position tends to shorten the pot life, but it can also be blended as a catalyst for curing adjustment throughout the year. Furthermore, it can be added and used at the construction site as an on-site addition type curing accelerator throughout the year. Specific examples of the imidazole catalyst having substituents at the 1- and 2-positions include 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-benzyl-2-methylimidazole, and 1-benzyl-2-. Examples thereof include phenylimidazole, and 1,2-dimethylimidazole and 1-isobutyl-2-methylimidazole are preferable, and 1-isobutyl-2-methylimidazole is more preferable because it is liquid at room temperature and easy to handle.
また、硬化剤中には、通常ウレタン防水材に用いる可塑剤、充填剤、消泡剤、湿潤剤、耐候性付与剤等を配合することができ、コロイダル炭酸カルシウムのようなチクソ性付与剤を配合することで立面部に施工可能なウレタン防水材とすることもできる。 Further, in the curing agent, a plasticizing agent, a filler, a defoaming agent, a wetting agent, a weather resistance imparting agent, etc., which are usually used for urethane waterproofing materials, can be blended, and a thixo property imparting agent such as colloidal calcium carbonate can be added. By blending it, it can be made into a urethane waterproof material that can be applied to the elevation.
（可塑剤）
本発明で用いる可塑剤としては、ウレタン樹脂に一般的に配合できる可塑剤を使用することができる。具体例として、ジイソノニルフタレート（ＤＩＮＰ）、ジオクチルフタレート（ＤＯＰ）、ブチルベンジルフタレート（ＢＢＰ）などのフタル酸エステル類、脂肪族二塩基酸エステル類、リン酸エステル類、トリメリット酸エステル類、セバシン酸エステル類、エポキシ脂肪酸エステル類、グリコールエステル類、動植物油系脂肪酸エステル類、石油・鉱物油系可塑剤、アルキレンオキシド重合系可塑剤等が挙げられる。中でも、引火点が２００℃以上である、ジイソノニルフタレート（ＤＩＮＰ）、ジオクチルフタレート（ＤＯＰ）は長期的にも質量減少を起こし難く、芳香族ポリエステルであり加水分解も起こし難いため、好ましく使用することができる。なお、硬化剤中に溶剤を使用することもできるが、施工後の揮発により収縮を起こす危険性や無機充填剤を沈降しやすくする傾向があり、環境面での問題もあるため５質量％以内で用いることが好ましく、使用しないことがより好ましい。
(Plasticizer)
As the plasticizer used in the present invention, a plasticizer that can be generally blended with urethane resin can be used. Specific examples include phthalates such as diisononyl phthalate (DINP), dioctyl phthalate (DOP), and butyl benzyl phthalate (BBP), aliphatic dibasic acid esters, phosphoric acid esters, trimellitic acid esters, and sebacic acid. Examples thereof include esters, epoxy fatty acid esters, glycol esters, animal and vegetable oil-based fatty acid esters, petroleum / mineral oil-based plasticizers, alkylene oxide polymerization-based plasticizers, and the like. Among them, diisononyl phthalate (DINP) and diisononyl phthalate (DOP), which have a flash point of 200 ° C. or higher, are less likely to cause mass loss even in the long term, and are aromatic polyesters, and are less likely to cause hydrolysis. Therefore, they are preferably used. can. A solvent can be used in the curing agent, but it is within 5% by mass because there is a risk of shrinkage due to volatilization after construction, the inorganic filler tends to settle easily, and there is an environmental problem. It is preferable to use it in, and it is more preferable not to use it.
本発明では、可塑剤の使用量は、主剤中のプレポリマー成分１００質量部に対し、可使時間確保および物性の面より１５〜９０質量部であることが好ましく、２０〜８０質量部であることがより好ましい。可塑剤量が１５質量部未満では、可使時間を十分確保した経済性のあるウレタン防水材とはなり難く、９０質量部を超えるとウレタン防水材に必要とされる強度や耐久性を確保することが難しくなり、可塑剤のブリードアウトも激しくなる。尚、可塑剤は硬化剤に配合することが原則であるが、一部主剤側に配合することもできる。 In the present invention, the amount of the plasticizer used is preferably 15 to 90 parts by mass with respect to 100 parts by mass of the prepolymer component in the main agent in terms of securing pot life and physical properties, and is 20 to 80 parts by mass. Is more preferable. If the amount of plasticizer is less than 15 parts by mass, it is difficult to obtain an economical urethane waterproof material with sufficient pot life, and if it exceeds 90 parts by mass, the strength and durability required for urethane waterproof material are secured. It becomes difficult and the bleed-out of the plasticizer becomes intense. In principle, the plasticizer is added to the curing agent, but it can also be added to the main agent side.
（無機充填剤）
また、本発明は、硬化剤に無機充填剤を配合することができる。無機充填剤を配合することで経済性に優れた汎用性のある防水材とすることができる。無機充填剤としては炭酸カルシウムが好ましい。炭酸カルシウムは経済効果が高いと同時に、硬化剤製造時の分散性が良好であり多量に配合しても増粘性が少なく、硬化剤貯蔵時の沈降性を少なくすることも容易であり、物性面での補強効果も高い。尚、炭酸カルシウムには、重質炭酸カルシウム、軽質炭酸カルシウム、表面処理コロイダル炭酸カルシウムなど種々の炭酸カルシウムがあるが、いずれの炭酸カルシウムも使用することができる。
(Inorganic filler)
Further, in the present invention, an inorganic filler can be added to the curing agent. By blending an inorganic filler, it is possible to obtain a highly economical and versatile waterproof material. Calcium carbonate is preferable as the inorganic filler. Calcium carbonate has a high economic effect, and at the same time, it has good dispersibility during the production of the curing agent, and even if it is blended in a large amount, the viscosity is small, and it is easy to reduce the settling property during the storage of the curing agent. The reinforcing effect is also high. The calcium carbonate includes various types of calcium carbonate such as heavy calcium carbonate, light calcium carbonate, and surface-treated colloidal calcium carbonate, and any calcium carbonate can be used.
また、シリカ、カオリン、タルク、ベントナイト、水酸化アルミニウム、水酸化バリウムなどの無機充填剤を一部使用することができる。尚、上記のような無機充填剤は付着水を含有し、この付着水がイソシアナート基と徐々に反応すると思われるが、付着水は活性水素とみなしていないのが一般的である。また、主剤と硬化剤を混合する際に巻き込まれる湿分（水分）や、防水材塗布後に塗膜表面より吸収される湿分（水分）もある程度イソシアナート基と反応するとされるのが一般的である。 In addition, some inorganic fillers such as silica, kaolin, talc, bentonite, aluminum hydroxide, and barium hydroxide can be used. Inorganic fillers as described above contain adhering water, and it is thought that the adhering water gradually reacts with the isocyanate group, but the adhering water is generally not regarded as active hydrogen. In addition, it is generally said that the moisture (moisture) involved when mixing the main agent and the curing agent and the moisture (moisture) absorbed from the coating film surface after applying the waterproof material also react with the isocyanate group to some extent. Is.
本発明は、硬化剤側に可塑剤を比較的多く配合することで、無機充填剤も多く配合することができ、それにより主剤／硬化剤の配合比１／２（質量比）も可能となるため、経済性に優れた汎用性のある防水材とすることができ、可使時間を確保した上でウレタン防水材に必要とされる強度や耐久性を十分にクリアーした防水材にすることができる。無機充填剤は硬化剤の総量を基準として２０〜８０質量％配合することが好ましい。２０質量％未満では補強効果が不十分でありまた経済性を損なってしまい、８０質量％を超えると増粘が高くなり施工性が悪化してしまう。 In the present invention, by blending a relatively large amount of plasticizer on the curing agent side, a large amount of inorganic filler can be blended, whereby the blending ratio of the main agent / curing agent can be halved (mass ratio). Therefore, it is possible to use a highly economical and versatile waterproof material, and it is possible to use a waterproof material that sufficiently clears the strength and durability required for urethane waterproof materials while ensuring the pot life. can. The inorganic filler is preferably blended in an amount of 20 to 80% by mass based on the total amount of the curing agent. If it is less than 20% by mass, the reinforcing effect is insufficient and the economic efficiency is impaired, and if it exceeds 80% by mass, the thickening becomes high and the workability deteriorates.
（その他添加剤）
その他、硬化剤には、湿潤剤、消泡剤、顔料、耐候性付与剤などの添加剤類を必要に応じて適量を配合することができる。
(Other additives)
In addition, an appropriate amount of additives such as a wetting agent, a defoaming agent, a pigment, and a weather resistance imparting agent can be added to the curing agent, if necessary.
（主剤／硬化剤 配合比）
主剤と硬化剤の配合比は特に限定はされないが、質量比で１／１〜１／３の範囲であることが好ましく、１／１〜１／２であることがより好ましい。
(Main agent / curing agent compounding ratio)
The blending ratio of the main agent and the curing agent is not particularly limited, but the mass ratio is preferably in the range of 1/1 to 1/3, and more preferably 1/1 to 1/2.
（防水工法）
また、本発明の２液常温硬化型手塗り用ウレタン防水材は、コンクリートなどの無機系下地に対し直接塗布することはできない。無機系下地の場合はウレタン防水材とは接着しないため、下地の水分をある程度遮蔽し接着性を確保することのできるプライマーを塗布した後に、施工することができる。また、改修時を含め、既存ウレタン防水層の上に場合によっては仲介プライマーを施し施工することができる。また、無機系下地に対し通気緩衝シート、塩ビシートなど高分子系シート、ゴムシート、不織布シートをプライマー、接着剤、機械固定、置き敷きなどで固定した上に施工することができる。さらに、金属系下地の場合も直接本願のウレタン防水材を塗布しても接着性は確保できないため、専用のプライマーを塗布した後に塗布することができる。
本発明は、アスファルト系防水層の改修を目的とはしておらず、コンクリートなどの無機下地、金属系下地、高分子系樹脂下地、ゴム下地の防水および保護を目的としたものである。また、本発明の２液常温硬化型手塗り用ウレタン防水材は日光が直接当たるような部分に使用する場合はトップコートを塗布することが原則となる。
(Waterproof method)
Further, the two-component room temperature curing type urethane waterproof material for hand coating of the present invention cannot be directly applied to an inorganic base such as concrete. In the case of an inorganic base, it does not adhere to the urethane waterproof material, so it can be applied after applying a primer that can block the moisture of the base to some extent and ensure adhesiveness. In addition, in some cases, an intermediary primer can be applied on the existing urethane waterproof layer, including at the time of repair. Further, it can be applied after fixing a polymer sheet such as a ventilation buffer sheet or a vinyl chloride sheet, a rubber sheet, or a non-woven fabric sheet to an inorganic base with a primer, an adhesive, mechanical fixing, or a laying. Further, even in the case of a metal-based substrate, since the adhesiveness cannot be ensured even if the urethane waterproof material of the present application is directly applied, it can be applied after applying a special primer.
The present invention does not aim at repairing an asphalt-based waterproof layer, but aims at waterproofing and protecting an inorganic base such as concrete, a metal-based base, a polymer-based resin base, and a rubber base. Further, in principle, the two-component room temperature curing type urethane waterproof material for hand coating of the present invention is to be applied with a top coat when it is used in a part exposed to direct sunlight.
尚、本発明では実用上の耐久性を考慮し、ＪＩＳ Ａ ６０２１に規定されている劣化処理条件より厳しい試験条件で耐久性を評価した。具体的には、ＪＩＳ Ａ ６０２１に準じて、加熱処理の場合は８０℃で４週間（ＪＩＳ Ａ ６０２１では１週間）、アルカリ処理の場合は６０℃（ＪＩＳ Ａ ６０２１では２３℃）で１週間の劣化処理を実施した。１０年保証を十分に担保する高耐久性の防水材としては、上記条件による加熱処理後の引張強さ比が９０％以上、破断時の伸び率が４００％以上、アルカリ処理後の引張強さ比が８０％以上、破断時の伸び率が４００％以上であることが好ましく、加熱処理後の引張強さ比が９５％以上、破断時の伸び率が４００％以上、アルカリ処理後の引張強さ比が８５％以上、破断時の伸び率が４００％以上であることがより好ましい。 In the present invention, in consideration of practical durability, the durability was evaluated under stricter test conditions than the deterioration treatment conditions specified in JIS A 6021. Specifically, according to JIS A 6021, heat treatment is performed at 80 ° C. for 4 weeks (JIS A 6021 is used for 1 week), and alkaline treatment is used at 60 ° C. (23 ° C. for JIS A 6021) for 1 week. Deterioration treatment was carried out. As a highly durable waterproof material that sufficiently guarantees a 10-year warranty, the tensile strength ratio after heat treatment under the above conditions is 90% or more, the elongation at break is 400% or more, and the tensile strength after alkaline treatment. The ratio is preferably 80% or more, the elongation at break is 400% or more, the tensile strength ratio after heat treatment is 95% or more, the elongation at break is 400% or more, and the tensile strength after alkali treatment. It is more preferable that the ratio is 85% or more and the elongation at break is 400% or more.
［原材料］
以下の実施例および比較例で用いた原材料は、次のとおりである。
コロネートＴ−８０： ２，４−トリレンジイソシアナート／２，６−トリレンジイソシアナート＝８０／２０（質量比）の混合物、ＮＣＯ含有量４８．３質量％、東ソー株式会社製
サンニックスＰＰ−２０００： ポリオキシプロピレンジオール、平均分子量２０００、ＯＨ価５６．１ｍｇＫＯＨ／ｇ、三洋化成工業株式会社製
サンニックスＧＡ−３０００： ポリオキシプロピレントリオール、平均分子量３０００、ＯＨ価：５６．１ｍｇＫＯＨ／ｇ、三洋化成工業株式会社製
ＭＣ−２０００ソルベント： 石油系炭化水素溶剤、ノルマルパラフィン、イソパラフィン混合物、三協化学株式会社製
ＤＥＴＤＡ： エタキュア１００、ジエチルトルエンジアミン、２，４−ジアミノ−３，５−ジエチルトルエン／２，６−ジアミノ−３，５−ジエチルトルエン＝８０／２０（質量比）の混合物、アルベマール社製
エタキュア４２０： ４，４′−メチレンビス（Ｎ−ｓｅｃ−ブチルアニリン）、芳香族２級ジアミン、アルベマール社製
クラレポリオールＰ−５３０： ３−メチル−１，５−ペンタンジオールとイソフタル酸との反応によって得られる芳香族系ポリエステルジオール、平均分子量５００、ＯＨ価：２２４．４ｍｇＫＯＨ／ｇ、株式会社クラレ製
トリイソプロパノールアミン： 試薬、東京化成工業株式会社製
ジイソプロパノールアミン： 試薬、東京化成工業株式会社製
ＤＩＮＰ： サンソサイザーＤＩＮＰ、ジイソノニルフタレート、新日本理化株式会社製
ジオクチル錫ジラウレート： ＫＳ−１２００Ａ−１、共同薬品株式会社製
ＮＣ−ＩＭ： １−イソブチル−２−メチルイミダゾール、エアープロダクツジャパン株式会社製
添加剤類： 楠本化成株式会社製
炭酸カルシウム： ＮＳ＃１００、日東粉化工業株式会社製
[raw materials]
The raw materials used in the following examples and comparative examples are as follows.
Coronate T-80: mixture of 2,4-tolylene diisocyanate / 2,6-tolylene diisocyanate = 80/20 (mass ratio), NCO content 48.3% by mass, Sanniks PP- manufactured by Toso Co., Ltd. 2000: Polyoxypropylene diol, average molecular weight 2000, OH value 56.1 mgKOH / g, Sanyo Kasei Kogyo Co., Ltd. Sanniks GA-3000: Polyoxypropylene triol, average molecular weight 3000, OH value: 56.1 mgKOH / g, Sanyo Made by Kasei Kogyo Co., Ltd. MC-2000 Solvent: Petroleum hydrocarbon solvent, normal paraffin, isocyanate paraffin mixture, manufactured by Sankyo Chemical Co., Ltd. DETDA: Etacure 100, diethyltoluenediamine, 2,4-diamino-3,5-diethyltoluene / 2,6-Diamino-3,5-diethyltoluene = 80/20 (mass ratio) mixture, Albemar EtaCure 420: 4,4'-methylenebis (N-sec-butylaniline), aromatic secondary diamine, Albemar's Clare polyol P-530: Aromatic polyesterdiol obtained by the reaction of 3-methyl-1,5-pentanediol with isocyanate, average molecular weight 500, OH value: 224.4 mgKOH / g, Clare Co., Ltd. Triisopropanolamine: Reagent, Tokyo Kasei Kogyo Co., Ltd. Diisopropanolamine: Reagent, Tokyo Kasei Kogyo Co., Ltd. DINP: Sansosizer DINP, Isocyanonylphthalate, Shinnihon Rika Co., Ltd. Dioctyltin dilaurate: KS-1200A-1, NC-IM manufactured by Kyodo Yakuhin Co., Ltd .: 1-isocyanate-2-methylimidazole, manufactured by Air Products Japan Co., Ltd. Additives: manufactured by Kusumoto Kasei Co., Ltd. Calcium carbonate: NS # 100, manufactured by Nitto Powder Industry Co., Ltd.
［主剤の調製］
表１〜４の配合に従って、四つ口フラスコにポリオールと溶剤を仕込み、次いでＴＤＩを仕込んだ。その後攪拌しながら１０５〜１１０℃で４〜８時間反応させて主剤を得た。
[Preparation of main agent]
According to the formulations shown in Tables 1 to 4, the four-necked flask was charged with the polyol and the solvent, and then with TDI. Then, the mixture was reacted at 105 to 110 ° C. for 4 to 8 hours with stirring to obtain a main agent.
［硬化剤の調製］
表１〜表４の配合に従って、ポリプロピレン製容器に液物を仕込み、攪拌機（ディゾルバー羽根）で低速混合し均一にした後、炭酸カルシウムを配合し１５００ｒｐｍで１０分間混合して硬化剤を得た。
[Preparation of curing agent]
According to the formulation shown in Tables 1 to 4, the liquid was charged in a polypropylene container, mixed at a low speed with a stirrer (dissolver blade) to make it uniform, and then calcium carbonate was added and mixed at 1500 rpm for 10 minutes to obtain a curing agent.
［実施例１、２］
実施例１、２は表１の配合に従って、主剤と硬化剤を得た。これら主剤と硬化剤を質量比１：２で混合しウレタン防水材組成物を得た。
主剤のジオール／トリオール当量比を８５／１５とし、硬化剤に芳香族ポリアミンとしてＤＥＴＤＡを、ポリオールとしてトリイソプロパノールアミンを用い、芳香族ポリアミンとポリオールの当量比がそれぞれ５５／４５、６０／４０である実施例１、２は、２３℃での可使時間はそれぞれ７２分、６１分と夏用配合として十分に長く、２３℃での施工可能時間はいずれも１５時間以内であり翌日施工が可能であった。さらに、得られた塗膜はいずれも高伸長形手塗り用ウレタン防水材として良好な初期物性と十分に高い耐熱・耐アルカリ性を示した。
[Examples 1 and 2]
In Examples 1 and 2, a main agent and a curing agent were obtained according to the formulation shown in Table 1. These main agent and curing agent were mixed at a mass ratio of 1: 2 to obtain a urethane waterproof material composition.
The diol / triol equivalent ratio of the main agent was 85/15, DETDA was used as the aromatic polyamine as the curing agent, and triisopropanolamine was used as the polyol, and the equivalent ratios of the aromatic polyamine and the polyol were 55/45 and 60/40, respectively. In Examples 1 and 2, the pot life at 23 ° C is 72 minutes and 61 minutes, respectively, which is sufficiently long for a summer compound, and the workable time at 23 ° C is within 15 hours, so that the next day can be carried out. there were. Furthermore, all of the obtained coating films showed good initial physical properties and sufficiently high heat resistance and alkali resistance as a urethane waterproof material for high elongation type hand coating.
［実施例３、４］
実施例３、４は表１の配合に従って、主剤と硬化剤を得た。これら主剤と硬化剤を質量比１：２で混合しウレタン防水材組成物を得た。
主剤のジオール／トリオール当量比を８５／１５とし、硬化剤に芳香族ポリアミンとしてＤＥＴＤＡとエタキュア４２０を併用し、ポリオールとしてトリイソプロパノールアミン用い、芳香族ポリアミンとポリオールの当量比がそれぞれ７０／３０、７５／２５である実施例３、４は、２３℃での可使時間はそれぞれ６３分、６５分と夏用配合として十分に長く、２３℃での施工可能時間はいずれも１５時間以内であり翌日施工が可能であった。さらに、得られた塗膜はいずれも高伸長形手塗り用ウレタン防水材として良好な初期物性と十分に高い耐熱・耐アルカリ性を示した。
[Examples 3 and 4]
In Examples 3 and 4, a main agent and a curing agent were obtained according to the formulation shown in Table 1. These main agent and curing agent were mixed at a mass ratio of 1: 2 to obtain a urethane waterproof material composition.
The diol / triol equivalent ratio of the main agent was 85/15, DETDA and EtaCure 420 were used together as the aromatic polyamine as the curing agent, triisopropanolamine was used as the polyol, and the equivalent ratios of the aromatic polyamine and the polyol were 70/30 and 75, respectively. In Examples 3 and 4, which are / 25, the pot life at 23 ° C is 63 minutes and 65 minutes, respectively, which is sufficiently long as a summer compound, and the workable time at 23 ° C is within 15 hours, respectively, and the next day. Construction was possible. Furthermore, all of the obtained coating films showed good initial physical properties and sufficiently high heat resistance and alkali resistance as a urethane waterproof material for high elongation type hand coating.
［実施例５］
実施例５は表１の配合に従って、主剤と硬化剤を得た。これら主剤と硬化剤を質量比１：２で混合しウレタン防水材組成物を得た。
主剤のジオール／トリオール当量比を８５／１５とし、硬化剤に芳香族ポリアミンとしてＤＥＴＤＡとエタキュア４２０を併用し、ポリオールとしてトリイソプロパノールアミンとクラレポリオールＰ−５３０を併用し、芳香族ポリアミンとポリオールの当量比が７０／３０である実施例５は、２３℃での可使時間はそれぞれ６７分と夏用配合として十分に長く、２３℃での施工可能時間は１５時間以内であり翌日施工が可能であった。さらに、得られた塗膜は高伸長形手塗り用ウレタン防水材として良好な初期物性と十分に高い耐熱・耐アルカリ性を示した。
[Example 5]
In Example 5, a main agent and a curing agent were obtained according to the formulation shown in Table 1. These main agent and curing agent were mixed at a mass ratio of 1: 2 to obtain a urethane waterproof material composition.
The diol / triol equivalent ratio of the main agent was set to 85/15, DETDA and EtaCure 420 were used in combination as the aromatic polyamine, and triisopropanolamine and Clare polyol P-530 were used in combination as the polyol, and the equivalent of the aromatic polyamine and the polyol was used. In Example 5 having a ratio of 70/30, the pot life at 23 ° C is 67 minutes each, which is sufficiently long for a summer compound, and the workable time at 23 ° C is within 15 hours, so that the next day can be carried out. there were. Furthermore, the obtained coating film showed good initial physical properties and sufficiently high heat resistance and alkali resistance as a urethane waterproof material for high elongation type hand coating.
［実施例６］
実施例６は表２の配合に従って、主剤と硬化剤を得た。これら主剤と硬化剤を質量比１：２で混合しウレタン防水材組成物を得た。
主剤のジオール／トリオール当量比を８０／２０とし、硬化剤に芳香族ポリアミンとしてＤＥＴＤＡとエタキュア４２０を併用し、ポリオールとしてトリイソプロパノールアミンを用い、芳香族ポリアミンとポリオールの当量比が７５／２５である実施例６は、２３℃での可使時間はそれぞれ７０分と夏用配合として十分に長く、２３℃での施工可能時間は１５時間以内であり翌日施工が可能であった。さらに、得られた塗膜は高伸長形手塗り用ウレタン防水材として良好な初期物性と十分に高い耐熱・耐アルカリ性を示した。
[Example 6]
In Example 6, a main agent and a curing agent were obtained according to the formulation shown in Table 2. These main agent and curing agent were mixed at a mass ratio of 1: 2 to obtain a urethane waterproof material composition.
The diol / triol equivalent ratio of the main agent is 80/20, DETDA and EtaCure 420 are used in combination as the aromatic polyamine as the curing agent, triisopropanolamine is used as the polyol, and the equivalent ratio of the aromatic polyamine to the polyol is 75/25. In Example 6, the pot life at 23 ° C. was 70 minutes each, which was sufficiently long for the summer compound, and the workable time at 23 ° C. was within 15 hours, so that the work could be carried out the next day. Furthermore, the obtained coating film showed good initial physical properties and sufficiently high heat resistance and alkali resistance as a urethane waterproof material for high elongation type hand coating.
［実施例７〜１０］
実施例７〜１０は表２の配合に従って、主剤と硬化剤を得た。これら主剤と硬化剤を質量比１：２で混合しウレタン防水材組成物を得た。
主剤のジオール／トリオール当量比をそれぞれ８０／２０、９０／１０、９５／５、１００／０とし、硬化剤に芳香族ポリアミンとしてＤＥＴＤＡを、ポリオールとしてトリイソプロパノールアミン用い、芳香族ポリアミンとポリオールの当量比がそれぞれ５５／４５、６５／３５、７０／３０、７５／２５である実施例７〜１０は、２３℃での可使時間はそれぞれ６４分、５８分、６４分、５７分と夏用配合として十分に長く、２３℃での施工可能時間はいずれも１５時間以内であり翌日施工が可能であった。さらに、得られた塗膜はいずれも高伸長形手塗り用ウレタン防水材として良好な初期物性と十分に高い耐熱・耐アルカリ性を示した。
[Examples 7 to 10]
In Examples 7 to 10, a main agent and a curing agent were obtained according to the formulation shown in Table 2. These main agent and curing agent were mixed at a mass ratio of 1: 2 to obtain a urethane waterproof material composition.
The diol / triol equivalent ratio of the main agent was 80/20, 90/10, 95/5, 100/0, respectively, DETDA was used as the aromatic polyamine as the curing agent, and triisopropanolamine was used as the polyol, and the equivalents of the aromatic polyamine and the polyol were used. Examples 7 to 10 having ratios of 55/45, 65/35, 70/30, and 75/25 have a pot life at 23 ° C. of 64 minutes, 58 minutes, 64 minutes, and 57 minutes, respectively, for summer use. The composition was sufficiently long, and the workable time at 23 ° C. was within 15 hours, and the work could be carried out the next day. Furthermore, all of the obtained coating films showed good initial physical properties and sufficiently high heat resistance and alkali resistance as a urethane waterproof material for high elongation type hand coating.
［実施例１１、１２］
実施例１１．１２は表３の配合に従って、主剤と硬化剤を得た。これら主剤と硬化剤を質量比１：２で混合しウレタン防水材組成物を得た。
硬化剤のポリオールとしてトリイソプロパノールアミンの代わりに、それぞれトリエタノールアミンあるいはジイソプロパノールアミンを用いた以外は実施例６と同様に行った。実施例１１、１２は、２３℃での可使時間はそれぞれ５５分、６８分と夏用配合として十分に長く、２３℃での施工可能時間は１５時間以内であり翌日施工が可能であった。さらに、得られた塗膜はいずれも高伸長形手塗り用ウレタン防水材として良好な初期物性と十分に高い耐熱・耐アルカリ性を示した。
[Examples 11 and 12]
In Example 11.12, a main agent and a curing agent were obtained according to the formulation shown in Table 3. These main agent and curing agent were mixed at a mass ratio of 1: 2 to obtain a urethane waterproof material composition.
The same procedure as in Example 6 was carried out except that triethanolamine or diisopropanolamine was used instead of triisopropanolamine as the polyol of the curing agent. In Examples 11 and 12, the pot life at 23 ° C. was 55 minutes and 68 minutes, respectively, which were sufficiently long for the summer formulation, and the workable time at 23 ° C. was within 15 hours, so that the work could be carried out the next day. .. Furthermore, all of the obtained coating films showed good initial physical properties and sufficiently high heat resistance and alkali resistance as a urethane waterproof material for high elongation type hand coating.
［実施例１３］
実施例１３は表３の配合に従って、主剤と硬化剤を得た。これら主剤と硬化剤を質量比１：２で混合しウレタン防水材組成物を得た。
硬化剤にウレタン化触媒としてＮＣ−ＩＭを０．０６質量％添加した以外は実施例６と同様に行った。実施例１３は、２３℃での可使時間はそれぞれ４４分と冬用配合として十分に長く、２３℃での施工可能時間は８時間であり翌日施工が可能であった。さらに、得られた塗膜は高伸長形手塗り用ウレタン防水材として良好な初期物性と十分に高い耐熱・耐アルカリ性を示した。
[Example 13]
In Example 13, a main agent and a curing agent were obtained according to the formulation shown in Table 3. These main agent and curing agent were mixed at a mass ratio of 1: 2 to obtain a urethane waterproof material composition.
The same procedure as in Example 6 was carried out except that 0.06% by mass of NC-IM was added to the curing agent as a urethanization catalyst. In Example 13, the pot life at 23 ° C. was 44 minutes each, which was sufficiently long for the winter formulation, and the workable time at 23 ° C. was 8 hours, so that the work could be carried out the next day. Furthermore, the obtained coating film showed good initial physical properties and sufficiently high heat resistance and alkali resistance as a urethane waterproof material for high elongation type hand coating.
［比較例１］
比較例１は表４の配合に従って、主剤と硬化剤を得た。これら主剤と硬化剤を質量比１：２で混合しウレタン防水材組成物を得た。
硬化剤活性水素として活性水素を３個以上有するポリアルカノールアミンを使用せずＤＥＴＤＡのみを使用した以外は実施例１と同様に行った。比較例１は、２３℃での可使時間は３２分と短く、気温の高い夏季などは作業性に問題が生ずると思われた。
[Comparative Example 1]
In Comparative Example 1, a main agent and a curing agent were obtained according to the formulation shown in Table 4. These main agent and curing agent were mixed at a mass ratio of 1: 2 to obtain a urethane waterproof material composition.
The same procedure as in Example 1 was carried out except that DETDA was used without using polyalkanolamine having three or more active hydrogens as the curing agent active hydrogen. In Comparative Example 1, the pot life at 23 ° C. was as short as 32 minutes, and it was considered that a problem would occur in workability in summer when the temperature was high.
［比較例２］
比較例２は表４の配合に従って、主剤と硬化剤を得た。これら主剤と硬化剤を質量比１：２で混合しウレタン防水材組成物を得た。
硬化剤活性水素として活性水素を３個以上有するポリアルカノールアミンを使用せずクラレポリオールＰ−５３０とＤＥＴＤＡのみを使用し、芳香族ポリアミンとポリオールの当量比を６０／４０とした以外は実施例１と同様に行った。比較例２は、２３℃での可使時間は６３分と夏用配合として十分に長いが、２３℃での施工可能時間は１８時間であり翌日施工はできなかった。さらに、得られた塗膜は高伸長形手塗り用ウレタン防水材として良好な初期物性を示したが、加熱処理後およびアルカリ処理後の引張強さ比は、それぞれ８９％、７９％と、活性水素を３個以上有するポリアルカノールアミンを使用した実施例１〜１３に比べて低く、高耐久性の防水材としては不十分なものであった。
[Comparative Example 2]
In Comparative Example 2, a main agent and a curing agent were obtained according to the formulation shown in Table 4. These main agent and curing agent were mixed at a mass ratio of 1: 2 to obtain a urethane waterproof material composition.
Example 1 except that Kuraray polyol P-530 and DETDA were used without using polyalkanolamine having three or more active hydrogens as the curing agent active hydrogen, and the equivalent ratio of aromatic polyamine to polyol was set to 60/40. I went in the same way. In Comparative Example 2, the pot life at 23 ° C. was 63 minutes, which was sufficiently long for the summer formulation, but the construction time at 23 ° C. was 18 hours, and the construction could not be performed the next day. Further, the obtained coating film showed good initial physical properties as a high-elongation type hand-coated urethane waterproofing material, but the tensile strength ratios after the heat treatment and the alkali treatment were 89% and 79%, respectively, which were active. It was lower than in Examples 1 to 13 using polyalkanolamines having 3 or more hydrogens, and was insufficient as a highly durable waterproof material.
［比較例３］
比較例３は表４の配合に従って、主剤と硬化剤を得た。これら主剤と硬化剤を質量比１：２で混合しウレタン防水材組成物を得た。
硬化剤活性水素として活性水素を３個以上有するポリアルカノールアミンを使用せず、ＤＥＴＤＡとエタキュア４２０を併用し、芳香族ポリアミンとポリオールの当量比が１００／０とした以外は実施例１と同様に行った。比較例３は、２３℃での可使時間は７９分と夏用配合として十分に長く、２３℃での施工可能時間は１５時間以内であり翌日施工が可能であった。さらに、得られた塗膜は高伸長形手塗り用ウレタン防水材として良好な初期物性を示したが、加熱処理後およびアルカリ処理後の引張強さ比は、それぞれ７１％、５２％と、活性水素を３個以上有するポリアルカノールアミンを使用した実施例１〜１３に比べて低く、高耐久性の防水材としては不十分なものであった。
[Comparative Example 3]
In Comparative Example 3, a main agent and a curing agent were obtained according to the formulation shown in Table 4. These main agent and curing agent were mixed at a mass ratio of 1: 2 to obtain a urethane waterproof material composition.
The same as in Example 1 except that polyalkanolamine having three or more active hydrogens was not used as the curing agent active hydrogen, DETDA and EtaCure 420 were used in combination, and the equivalent ratio of aromatic polyamine to polyol was set to 100/0. went. In Comparative Example 3, the pot life at 23 ° C. was 79 minutes, which was sufficiently long for the summer formulation, and the workable time at 23 ° C. was within 15 hours, so that the work could be carried out the next day. Further, the obtained coating film showed good initial physical properties as a high-elongation type hand-coated urethane waterproofing material, but the tensile strength ratios after the heat treatment and the alkali treatment were 71% and 52%, respectively, which were active. It was lower than in Examples 1 to 13 using polyalkanolamines having 3 or more hydrogens, and was insufficient as a highly durable waterproof material.
［比較例４］
比較例４は表４の配合に従って、主剤と硬化剤を得た。これら主剤と硬化剤を質量比１：２で混合しウレタン防水材組成物を得た。
硬化剤活性水素として活性水素を３個以上有するポリアルカノールアミンを使用せず、硬化剤に芳香族ポリアミンとしてＤＥＴＤＡとエタキュア４２０を併用し、ポリオールとしてクラレポリオールＰ−５３０を使用し、芳香族ポリアミンとポリオールの当量比が７５／２５とした以外は実施例１と同様に行った。比較例４は、２３℃での可使時間は６６分と夏用配合として十分に長く、２３℃での施工可能時間は１５時間以内であり翌日施工が可能であった。さらに、得られた塗膜は高伸長形手塗り用ウレタン防水材として良好な初期物性を示したが、加熱処理後およびアルカリ処理後の引張強さ比は、それぞれ８６％、７１％と、活性水素を３個以上有するポリアルカノールアミンを使用した実施例１〜１３に比べて低く、高耐久性の防水材としては不十分なものであった。
[Comparative Example 4]
In Comparative Example 4, a main agent and a curing agent were obtained according to the formulation shown in Table 4. These main agent and curing agent were mixed at a mass ratio of 1: 2 to obtain a urethane waterproof material composition.
Hardener: Do not use polyalkanolamine having 3 or more active hydrogens as active hydrogen, use DETDA and Etacure 420 as hardener in combination with DETDA and EtaCure 420 as hardener, use Clare polyol P-530 as polyol, and use aromatic polyamine. The same procedure as in Example 1 was carried out except that the equality ratio of the polyol was 75/25. In Comparative Example 4, the pot life at 23 ° C. was 66 minutes, which was sufficiently long for the summer formulation, and the workable time at 23 ° C. was within 15 hours, so that the work could be carried out the next day. Further, the obtained coating film showed good initial physical properties as a high-elongation type hand-coated urethane waterproofing material, but the tensile strength ratios after the heat treatment and the alkali treatment were 86% and 71%, respectively, which were active. It was lower than in Examples 1 to 13 using polyalkanolamines having 3 or more hydrogens, and was insufficient as a highly durable waterproof material.
なお、各評価項目の測定方法は次のとおりである。 The measurement method for each evaluation item is as follows.
［ＮＣＯ（質量％）］
２００ｍＬの三角フラスコに主剤約１ｇを精秤し、これに０．５Ｎジ−ｎ−ブチルアミン（トルエン溶液）１０ｍＬ、トルエン１０ｍＬおよび適量のブロムフェノールブルーを加え溶解後メタノール約１００ｍＬを加える。この混合液を０．２５Ｎ塩酸溶液で滴定する。ＮＣＯ（質量％）は以下の式によって求められる。
ＮＣＯ（質量％）＝（ブランク滴定値−０．５Ｎ塩酸溶液滴定値）×４．２０２×０．２５Ｎ塩酸溶液のファクター×０．２５÷サンプル重量
[NCO (mass%)]
About 1 g of the main agent is precisely weighed in a 200 mL Erlenmeyer flask, and 10 mL of 0.5 N-n-butylamine (toluene solution), 10 mL of toluene and an appropriate amount of bromphenol blue are added thereto, and after dissolution, about 100 mL of methanol is added. The mixture is titrated with a 0.25N hydrochloric acid solution. NCO (mass%) is calculated by the following formula.
NCO (mass%) = (blank titration value-0.5N hydrochloric acid solution titration value) x 4.202 x 0.25N hydrochloric acid solution factor x 0.25 / sample weight
［遊離ＴＤＩ（質量％）］
主剤をナス型フラスコに約１０ｇ精秤し、イソアミル安息香酸を１００ｍＬ加えて溶解させ、ロータリーエバポレーターによって蒸留する（イソアミル安息香酸とＴＤＩを共沸させる）。蒸発がとまったところでイソアミル安息香酸を５０ｍＬ追加してさらに蒸留する。回収した蒸留分に０．５Ｎジ−ｎ−ブチルアミン（トルエン溶液）１０ｍＬと適量のブロムフェノールブルーを加えた後メタノール約３００ｍＬを加える。この混合液を０．２５Ｎ塩酸溶液で滴定する。遊離ＴＤＩは以下の式によって求められる。
遊離ＴＤＩ（質量％）＝［（ブランク滴定値−回収した蒸留分の滴定値）×０．２５Ｎ塩酸溶液のファクター×０．２５÷（主剤重量×ＴＤＩ１ｇあたりの当量）］×１００
[Free TDI (mass%)]
Approximately 10 g of the main agent is precisely weighed in an eggplant-shaped flask, 100 mL of isoamylbenzoic acid is added to dissolve it, and the mixture is distilled by a rotary evaporator (isoamylbenzoic acid and TDI are azeotroped). When evaporation has stopped, add 50 mL of isoamylbenzoic acid and further distill. To the recovered distillation, add 10 mL of 0.5 N-n-butylamine (toluene solution) and an appropriate amount of bromphenol blue, and then add about 300 mL of methanol. The mixture is titrated with a 0.25N hydrochloric acid solution. The free TDI is calculated by the following formula.
Free TDI (% by mass) = [(blank titration value-titration value of recovered distillation) x 0.25N hydrochloric acid solution factor x 0.25 ÷ (base weight x equivalent per 1 g of TDI)] x 100
［可使時間（分）］
２３℃、湿度５０％の空気循環型環境試験室内において、主剤と硬化剤を所定の割合で混合し攪拌開始から、ＢＨ型粘度計で２ｒｐｍにおける粘度が６０，０００ｍＰａ・ｓになるまでの時間を測定した。（夏用配合は５５分以上が目安）
[Available time (minutes)]
In an air circulation type environmental test room at 23 ° C. and 50% humidity, the time from the start of stirring by mixing the main agent and the curing agent at a predetermined ratio until the viscosity at 2 rpm reaches 60,000 mPa · s with a BH type viscometer. It was measured. (For summer, 55 minutes or more is a guide)
［施工可能時間（硬化性）］
２３℃または５℃、湿度５０％の空気循環式型環境試験室内において、主剤と硬化剤を所定の割合で攪拌・混合した防水材を２ｋｇ／ｍ２塗布し、完全には硬化していないが、塗膜上を靴で歩行が可能となり、次工程の作業を開始できるまでの時間を測定した。（１７時間以内を翌日施工可能とした。）
[Construction time (curability)]
In an air circulation type environmental test room at 23 ° C or 5 ° C and 50% humidity, a waterproof material in which the main agent and the curing agent were stirred and mixed at a predetermined ratio was applied at 2 kg / m 2 and not completely cured. , The time until it became possible to walk on the coating film with shoes and the work of the next step could be started was measured. (Construction was possible the next day within 17 hours.)
［引張強さ（Ｎ／ｍｍ２）］
養生条件を２３℃、湿度５０％で７日とした試験片について、ＪＩＳ Ａ ６０２１に基づいて測定を行った（ＪＩＳ Ａ ６０２１のウレタンゴム系高伸長形では引張強さ規格は２．３Ｎ／ｍｍ２以上）。
[Tensile strength (N / mm 2 )]
Measurements were made based on JIS A 6021 for the test pieces whose curing conditions were 23 ° C. and humidity 50% for 7 days (the tensile strength standard of the urethane rubber-based high elongation type of JIS A 6021 is 2.3 N / mm). 2 or more).
［破断時の伸び率（％）］
養生条件を２３℃、湿度５０％で７日とした試験片について、ＪＩＳ Ａ ６０２１に基づいて測定を行った（ＪＩＳ Ａ ６０２１のウレタンゴム系高伸長形では破断時の伸び率規格は４５０％以上）。
[Elongation rate at break (%)]
Measurements were made based on JIS A 6021 for the test pieces whose curing conditions were 23 ° C. and humidity 50% for 7 days (the urethane rubber-based high elongation type of JIS A 6021 has an elongation rate standard of 450% or more at break. ).
［引裂き強さ（Ｎ／ｍｍ）］
養生条件を２３℃、湿度５０％で７日とした試験片について、ＪＩＳ Ａ ６０２１に基づいて測定を行った（ＪＩＳ Ａ ６０２１のウレタンゴム系高伸長形では引裂き強さ規格は１４Ｎ／ｍｍ以上）。
[Tear strength (N / mm)]
Measurements were made based on JIS A 6021 for the test pieces whose curing conditions were 23 ° C. and humidity 50% for 7 days (the tear strength standard for the urethane rubber-based high elongation type of JIS A 6021 is 14 N / mm or more). ..
［加熱処理後の引張強さ比（％）および破断時の伸び率（％）（耐熱性）］
２３℃、湿度５０％で７日養生後、８０℃の乾燥機に２８日（ＪＩＳ Ａ ６０２１では８０℃で７日）入れて加熱処理した試験片について、ＪＩＳ Ａ ６０２１に基づいて行い、処理前に対する引張強さ比および破断時の伸び率を測定し、引張強さ比９０％以上かつ破断時の伸び率４００％以上を高耐久性とした（ＪＩＳ Ａ ６０２１のウレタンゴム系高伸長形規格では８０℃、７日で引張強さ比８０％以上、破断時の伸び率４００％以上）。
[Tensile strength ratio (%) after heat treatment and elongation at break (%) (heat resistance)]
After curing at 23 ° C. and 50% humidity for 7 days, the test piece was heat-treated by putting it in a dryer at 80 ° C. for 28 days (7 days at 80 ° C. for JIS A 6021), and performed based on JIS A 6021 before treatment. The tensile strength ratio and the elongation at break were measured, and the tensile strength ratio of 90% or more and the elongation at break of 400% or more were set as high durability (in the JIS A 6021 urethane rubber high elongation type standard). Tensile strength ratio of 80% or more at 80 ° C. in 7 days, elongation at break of 400% or more).
［アルカリ処理後の引張強さ比（％）（耐アルカリ性）］
２３℃、湿度５０％で７日養生後、アルカリ処理条件を６０℃、７日（ＪＩＳ Ａ ６０２１では２３℃で７日）に変えた以外は、ＪＩＳ Ａ ６０２１に基づいて行い、処理前に対する引張強さ比および破断時の伸び率を測定し、引張強さ比８０％以上かつ破断時の伸び率４００％以上を高耐久性とした（ＪＩＳ Ａ ６０２１のウレタンゴム系高伸長形規格では２３℃、７日で引張強さ比６０％以上、破断時の伸び率４００％以上）。
[Tensile strength ratio (%) after alkali treatment (alkali resistance)]
After curing at 23 ° C. and 50% humidity for 7 days, the treatment was performed based on JIS A 6021 except that the alkali treatment conditions were changed to 60 ° C. and 7 days (7 days at 23 ° C. for JIS A 6021). The strength ratio and the elongation at break were measured, and the tensile strength ratio of 80% or more and the elongation at break of 400% or more were set as high durability (JIS A 6021 urethane rubber-based high elongation type standard 23 ° C. , Tensile strength ratio 60% or more in 7 days, elongation rate at break 400% or more).
本発明の２液常温硬化型手塗り用ウレタン防水材組成物は、高耐久性防水材として、建築物の屋上やマンションなどの集合住宅のベランダなどの防水層に好適に使用することができる。 The two-component room temperature curing type urethane waterproof material composition for hand coating of the present invention can be suitably used as a highly durable waterproof material for a waterproof layer such as a roof of a building or a veranda of an apartment house such as an apartment.
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